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COMPOSITIONS OF MATTER: SYSTEM II
BACKGROUND OF THE INVENTION
According to modem quantum theory, the chemical and physical
properties of substances arise fundamentally from electrodynamic
interactions. Modifying these interactions can alter electronic structures and
thereby endow the elements of the periodic table and their compounds with
new properties.
United States Patent No. 6,572,792 to
Christopher J. Nagel describes a process for modifying the
electronic structure of a material and of the products that are produced by
the
process. For example, this patent describes metals, such as copper, cobalt,
nickel, and alloys thereof, that possess novel properties, such as novel XRF
patterns and magnetic properties. However, it is desired to further amplify or
modify the effects achieved by the process.
SUMMARY OF THE INVENTION
The present invention relates to improved methods of modifying the
electronic structure of a material. The process includes the iterative and/or
cyclic addition of energy to a material.
In one embodiment, the present invention includes a method of
processing a metal or an alloy of metals, comprising the steps of:
(1.) Melting the material;
(2.) Adding a carbon source to the material; and
(3.) Varying the temperature of the material between two temperatures over one
or
more cycles, wherein the material remains at a temperature above the melting
point
during the entire step.
The process can further comprise one or more of the steps, in one or more
iterations or cycles:
(4.) Adding a flow of a gas (such as nitrogen, hydrogen and/or a noble gas)
through
the material;
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(5.) Varying the temperature of the material between two temperatures over one
or
more cycles, wherein the material remains at a temperature above the melting
point
during the entire step;
(6.) Adding a carbon source to the material; and/or
(7.) Holding the material with optional gas addition.
The process in a preferred embodiment involves one or more iterations or
cycles of adding energy to a material in a supersaturated state with carbon.
In this
embodiment, the process comprises, or further comprises, one or more of the
steps,
in one or more iterations or cycles:
(8.) Lowering the temperature of a molten material, wherein the material
becomes
supersaturated with carbon;
(9.) Varying the temperature of the material between two temperatures over one
or
more cycles, wherein supersaturation with carbon is maintained and the
material
remains at a temperature above the melting point during the entire step,
optionally in
the presence of gas addition during the entire step or any portion of the step
(e.g.,
during one or more or all of the steps wherein temperature increases or
decreases);
(10.) Holding the material at a selected temperature, optionally in the
presence of gas
addition;
(11.) Cooling the material, such that the material continues to be
supersaturated with
carbon and the material remains at a temperature above the melting point,
optionally
in the presence of gas addition; and/or
(12.) Cooling the material to room temperature, thereby obtaining a solidified
manufactured material.
In one embodiment, steps 8 and 9 (or 9 and 11) are performed and repeated
1, 2, 3, 4 or more times, preferably 4 or more times.
In preferred embodiments, the improvement in the processes of the invention
comprises at least one of the following:
(a) the gas or gaseous addition (e.g., nitrogen, hydrogen, and/or noble gas)
is added
to the material through a lance set at a level above the liquid level;
(b) at least one of the gases or gaseous additions comprises a gas mixture;
(c) at least one of the gases has been exposed to radiation;
(d) current, e.g., AC or DC current, is added to the material in a further
step or
during one or more of the above steps;
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(e) during the cooling step, a gas is added to the material; and/or
(f) during the cooling step, the material is quenched with water wherein the
water is
not stirred;
(g) at least one form of radiation has been filtered;
(h) the material is exposed to radiation in a further step or during one or
more of the
above steps; and/or
(i) varying the reactor power (e.g., above normal holding power) between two
power
levels over'/, one or more cycles.
Advantages of the present invention include a method of processing metals
into new compositions of matter and producing and characterizing compositions
of
matter with altered physical and/or electrical properties.
DETAILED DESCRIPTION OF THE INVENTION
United States Patent No. 6,572,792 to Christopher J. Nagel describes a
process for modifying the electronic structure of a material and to the
products that
are produced by the process. For example, this patent, which is incorporated
herein
by reference in its entirety, describes metals, such as copper, cobalt,
nickel, and
alloys thereof, that are induced by the process to acquire novel properties,
such as
novel XRF patterns and magnetic properties. As described in that patent,
electromagnetic chemistry is the science that affects the transfer and
circulation of
energy in many forms when induced by changes in electromagnetic energy. In
empty space, a constant speed for light, independent of the frame of reference
(i.e.,
"each ray of light moves in the coordinate system `at rest' with the definite
velocity
V independent of whether this ray of light is emitted by a body at rest or a
body in
[uniform] motion") as advanced in "The Theory of Electrodynamics of Moving
Bodies" (Einstein, 1905) implicitly embeds a discrete partition between its
associated coordinate system at rest and the reference systems that are
relative to it.
A topological description of this partition, satisfying the postulates
advanced in the
above referenced paper, requires that when the electrodynamic components of
matter
are manipulated, discrete changes in energy exchange occur between meromorphic
constructions while continuous changes in energy exchange occur along
holomorphic mappings. Harmonics governing the redistribution of energy are the
vehicles by which changes in (material) properties, such as the magnitude
and/or the
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orientation, can occur. Alignment of the electrodynamic component induces
effects
that may result in significant changes in the underlying material species: (1)
alignment of atoms with the resulting directionality of physical properties;
(2)
alignment of energy levels and the capability to modify harmonic structure,
may
establish physical properties conducive for energy transfer; (3) alignment of
the
electrodynamic component includes the opening of pathways for free electron
flow,
and; (4) alignment of electrodynamic field phase orientation.
The present invention relates to new materials and compositions of matter,
and includes manufactured, or tailored, metals or alloys of metals. A
"manufactured" or "tailored" metal or alloy is a metal or alloy, which
exhibits a
change in electronic structure, such as that seen in a fluid or adjustable XRF
spectrum. The American Heritage College Dictionary, Third Edition defines
"fluid"
as changing or tending to change.
Metals of the present invention are generally p, d, or f block metals. Metals
include transition metals such as Group 3 metals (e.g., scandium, yttrium,
lanthanum), Group 4 metals (e.g., titanium, zirconium, hafnium), Group 5
metals
(vanadium, niobium, tantalum), Group 6 metals (e.g., chromium, molybdenum,
tungsten), Group 7 metals (e.g., manganese, technetium, rhenium), Group 8
metals
(e.g., iron, ruthenium, osmium), Group 9 metals (e.g., cobalt, rhodium,
iridium),
Group 10 metals (nickel, palladium, platinum), Group 11 metals (e.g., copper,
silver,
gold), and Group 12 metals (e.g., zinc, cadmium, mercury). Metals of the
present
invention also include alkali metals (e.g., lithium, sodium, potassium,
rubidium, and
cesium) and alkaline earth metals (e.g., beryllium, magnesium, calcium,
strontium,
barium). Additional metals include aluminum, gallium, indium, tin, lead,
boron,
germanium, arsenic, antimony, tellurium, bismuth, thallium, polonium,
astatine, and
silicon.
The present invention also includes alloys of metals. Alloys are typically
mixtures of metals. Alloys of the present invention can be formed, for
example, by
melting together two or more of the metals listed above. Preferred alloys
include
those comprised of copper, gold, and silver; tin, zinc, and lead; tin, sodium,
magnesium, and potassium; iron, vanadium, chromium, and manganese; nickel,
tantalum, hafnium, and tungsten; copper and ruthenium; nickel and ruthenium;
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cobalt and ruthenium; cobalt, vanadium and ruthenium; and nickel, vanadium and
ruthenium.
The material can be added, or charged, to the reactor in a variety of forms.
For example, where the material is a metal, it can be convenient to add the
material
as powder, flakes, pellets or ingots. The material can be charged all at once
or in
stages, including continuously during the initial melt or energy addition
step.
The backspace of the reactor can be advantageously purged by a gas, such as
a gas, as described below, or other gas. Nitrogen is a convenient gas for this
purpose. In one example, a nitrogen flow is maintained throughout an entire
method, such that a nitrogen pressure of about 0.4-0.6 psig or about 0.5 psig
is
maintained. Alternatively, other gases, such as argon may be used for such
purposes.
Carbon sources of the present invention include materials that are partially,
primarily, or totally comprised of carbon. Suitable carbon sources include
graphite
rods, graphite powder, graphite flakes, fullerenes, amorphous carbon,
diamonds,
natural gas, methane, ethane, propane, butane, pentane, and combinations
thereof. A
preferred carbon source has a high purity (<50 ppm, such as <10 ppm,
preferably <5
ppm impurities). The carbon source is selected, in part, based on the system
to
which it is added. In one example, graphite rods and graphite flakes are added
in a
sequential manner. In another example, the carbon source can be added as a
gas,
such as through the introduction of methane.
Carbon sources can be contacted with the material for variable periods of
time. The period of time the carbon source is in contact with the material is
the time
between adding the carbon source and removing the undissolved carbon source.
The
period of time can be from about 0.5 hours to about 12 hours, about 1 hour to
about
10 hours, about 2 hours to about 8 hours, about 3 hours to about 6 hours,
about 3.5
hours to about 4.5 hours, or about 3.9 hours to about 4.1 hours.
Alternatively, the
period of time can be from about 5 minutes to about 300 minutes, about 10
minutes
to about 200 minutes, about 20 minutes to about 120 minutes, about 30 minutes
to
about 90 minutes, about 40 minutes to about 80 minutes, about 50 minutes to
about
70 minutes, or about 59 minutes to about 61 minutes. As can be seen above, the
process of the invention relies in part upon the cyclic, iterative and/or
harmonic
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addition of energy to the material. In general, the carbon contact period will
coincide with a cycle, series of cycles or iteration of steps.
A cycle of the present invention includes a period of time where the energy
of a material is varied between a first and second selected energy endpoints
with a
return to the first energy endpoint. A half cycle is the completion of a
single sweep
or variant between a first and second energy endpoint. A full cycle is the
completion
of two sweeps between the first and second energy endpoints. A cyclic step
refers to
the repetition of two or more cycles without substantially changing the
endpoints of
each sweep. Iterations generally refer to the repeating of two or more steps,
such as
a cyclic step in combination with a cooling step.
An energy level, such as an endpoint, can often be conveniently measured by
the material's (e.g., metal's) temperature and/or the degree to which a
material (e.g.,
metal) is saturated with a second component (e.g. carbon). Over a period of
time,
varying the temperature involves a period of raising (or increasing) the
temperature
of a material (e.g., metal or alloy) and a period when the temperature of a
material
(e.g., metal or alloy) decreases (either passively, such as by convection or
heat
transfer to the surrounding environment, or actively, such as by a mechanical
means
or cooling, e.g., quenching). The time period of each sweep can be selected to
produce a harmonic energy pattern. The time period is also, in part, dictated
by the
rate of heating and cooling which is practical by the equipment (e.g.,
induction
furnace) used, the material selected and the mass of material being processed.
In
some experiments, a cycle comprising a 7 minute period to increase the energy
level
(sweep up) and a 7 minute period to decrease the energy level (sweep down) was
used. However, other time periods (e.g., 2, 3, 4, 5, 6, 8, 9, 10, 20 or more
minutes)
can be used. Further, combinations can be used (7 minutes up and 5 minutes
down).
Where energy is added to a material by other means (e.g., ultraviolet or
infrared
radiation, current or reactor power), the time periods are not limited by the
rate of
heating or cooling the material.
Increasing the temperature of the metal or alloy increases the amount of
carbon that can be dissolved into that metal or alloy, which therefore
decreases the
degree to which the metal or alloy is saturated with carbon (relative to the
temperature and degree of carbon saturation when graphite saturation
assemblies are
removed the first time). Similarly, decreasing the temperature of the metal or
alloy
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increases the (relative) degree to which the metal or alloy is saturated with
carbon.
Thus, carbon saturation levels of a material can also be used to measure or
determine
energy endpoints. Where the material to be modified is a non-metal (e.g.,
carbon,
gas), the energy endpoints are better measured by temperature or associated
emission
spectra.
A cycle can also include, or be interrupted or ended with, a holding step.
Thus, the material can be held at an energy level (as measured, for example,
by the
temperature or degree of carbon saturation) for a selected period of time. The
holding period can be several minutes to several hours or more. In one
example, the
material was held for 60 minutes. In another example, the material was held
for 5
minutes. More than one hold step can be incorporated into the process and can
be
included in an iteration of steps.
The degree to which a metal is saturated with carbon varies over the course
of the process, as well as within a step. For example, the degree of carbon
saturation
can vary between 70% and 95% in the first cycling step, between 80% and 95% in
the second cycling step, between 101% and 103% in the third cycling step,
between
104% and 107% in the fourth cycling step, between 108% and 118% in the fifth
cycling step, and between 114% and 118% in the sixth cycling step. It is
preferred
to conduct 4 or more supersaturation steps. Supersaturation is defined herein
as
follows:
+n%wt represents the weight percent above the equilibrium saturation
value of the material in its natural state. For example, +l%Wt
represents 1%Wt above the saturation value as defined in its natural or
naturally occurring state.
[n]egsat represents the equilibrium saturation of "n" in its natural
state. For example, [C]egsat represents the equilibrium saturation of
carbon for the thermodynamic state specified (e.g., T, P,
composition) when the composition is in its natural, or naturally
occurring, state.
Gas, such as nitrogen, hydrogen or a noble gas, can be added during a cycle,
except where it is specified that gas addition is ceased prior to that cycle.
The gas
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provides a third body effect for the reaction facilitating energy exchange.
For
example, hydrogen, helium, nitrogen, neon, argon, krypton, xenon and carbon
monoxide can be added. In a preferred embodiment, the gas is added as a
mixture.
A preferred mixture comprises argon, helium, neon and/or krypton. Preferably,
at
least 50%, more preferably at least 80% such as at least 90% by volume argon,
helium or hydrogen is present in the mixture. Particularly preferred mixtures,
by
volume, include (1) 93% argon, 5% helium and 2% neon; (2) 92% argon, 5% helium
and 3% neon; (3) 95% argon and 5% helium or neon; (4) 95% helium and 5%
krypton; (5) 95% nitrogen and 5% helium; (6) 97% helium and 3% neon
(optionally
trace amounts of krypton); (7) 97% argon and 3% neon; (8) 60% argon and 40%
helium (optionally trace amounts of neon, hydrogen and/or krypton); (9) 49.5%
hydrogen, 49.5% helium and 1% neon. In selecting the specific combination and
concentrations of the gases, the following factors should be considered:
emission
profile, Hodge spectral character and required momentum/energy exchange.
In each embodiment, the gas can be added at various rates. In general, the
gas is added in terms of the resulting agitation on the material and exchange
with the
material. As such, the gas can be added at a low rate, resulting in low
agitation/exchange; at a modest, moderate or high or vigorous rate. The gases
can be
mixed prior to adding or added individually. Using conventional fluid dynamic
scaling models and assuming a crucible size of 3.75 inches I.D., with a 14.5
inch
height, holding 20 lbs of cobalt, examples of low agitation can be achieved by
adding about 0.25 SLPM; modest agitation can be achieved by adding between
about 1.25 SLPM; moderate agitation can be achieved by adding between about
2.5
SLPM and high agitation can be achieved agitation by adding between about 5.0
SLPM. Selecting low agitation generally results in clearly defined bubbles in
a
quiescent bath. High agitation generally results in a turbulent well-mixed
bath.
Modest and moderate agitation rates enables mixing and exchange to be adjusted
between these extremes. In some instances, the rate of addition can begin at
one
level and be changed during the step to a different level (e.g., from a low
rate to a
vigorous rate). In general, it is desirable to add the gas at a rate of excess
to assist in
controlling the reaction and ensuring that rate limiting steps are not
associated with
mass transfer diffusion. Flow rates for a crucible size of 8.875 inches, with
a 16.5
inch height, holding 100 lbs of copper can be determined using standard
scaling
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techniques based on bubble size and residence time distributions to achieve
similar
transport phenomena.
The gas can be added to the material either below or above (including
across) the surface level of the material. When the gas is added below the
surface
level, it can be added via injection ports from the bottom or sides of the
reactor.
However, it is often preferred to add the gas via a lance. The lance can be
positioned
to provide gas entry below the surface level, e.g. at the bottom of the
reactor,
midpoint or near the surface of the material. When the lance is to be
submerged, it
is often desirable to position the lance prior to or during the initial
charging of the
reactor with the material (e.g., as the reactor is being packed with metal
pellets).
Where the lance is not submerged, the lance can be placed to direct the gas
across
the surface of the material or toward at the surface. Where the gas is
directed toward
the material, the gas can be directed at a force that creates an indentation
in the
surface. The lance can be placed along the centerline of the reactor. However,
it is
often desirable to place the lance off center, e.g., at about two thirds
radius point as
measured from the center. Lance placement involves consideration of
mass/energy
transfer, interaction of multiple lances, and harmonic character of the
reactants being
added.
The material can be subjected or exposed to the gas either during the entire
process or a cycle or series of cycles or alternating cycles, during the
cooling step or
thereafter as a post treatment step.
Superior results in controlling the reaction have been achieved by exposing
at least one gas to radiation. The exposure can be applied in a continuous or
batch
mode. For example, the radiation source can be applied as the gas moves
through a
conduit for the gas source to the reactor. The conduit is preferably not
opaque and is
more preferably translucent or transparent. The radiation can be applied in an
open
or closed system. A closed system entails exposing the gas to the specified
radiation
in the substantial absence of other radiation sources (e.g., visible light,
magnetic
fields above background). This can be easily accomplished by building a black
box
surrounding a segment of the conduit and placing the radiation source(s)
within the
black box. An open system can also be employed where the radiation source(s)
are
not shielded from ambient light.
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In yet other embodiments, the material itself can be subjected to radiation,
either during or after the processes described herein. For example, a tailored
metal
can be subjected to radiation to further modify the properties of the metal.
The radiation sources can be selected to provide a broad range of emitted
wavelengths. For example, the radiation can range from infrared to ultraviolet
wavelengths. In one embodiment, examples of preferred radiation sources emit
into
the range of 160 nm to 1000 nm; in another embodiment, examples of preferred
radiation sources emit and into the range of 180 nm to 1100 nm; and in a more
preferred embodiment examples of preferred radiation sources emit into the
range of
400 nm to 700 nm. The radiation can be conveniently supplied by short arc
lamps,
high intensity discharge lamps, pencil lamps, lasers, light emitting diodes,
incandescent, fluorescent, and/or halogens for example. Examples of suitable
high
intensity discharge lamps include mercury vapor, sodium vapor and/or metal
halide.
Short arc lamps include mercury, xenon or mercury-xenon lamps. Pencil lamps
include neon, argon, krypton, xenon, short wave ultraviolet, long wave
ultraviolet,
mercury, mercury/argon, mercury/neon, and the like. The radiation can also
include
(or exclude), incandescent or fluorescent light and/or natural sources of
light, such as
electromagnetic radiation emitted by celestial bodies.
The radiation sources can optionally be used in combination with light
shields or wavelength filters. Examples of suitable shields and filters can be
obtained from UVP, Inc. (Upland, CA). The filters and shields can direct or
modify
the emission output. Examples of UVP Pen-Ray Filters include the G-275 filter
which absorbs visible light while transmitting ultraviolet at 254 nm and the G-
278
filter which converts shortwave radiation to longwave radiation at 365 nm. Pen-
Ray
Shields include Shield A which has a 0.04 inch ID hole for point-like source,
Shield
B which has a 0.31 x 0.63 inch window, and Shield C which has a 0.19 x 1.5
inch
window. Filters and shields can also be obtained from Newport Corp. (Irvine,
CA).
The Newport 6041 Short Wave Filter absorbs visible lines; the 6042 Long Wave
Conversion Filter attenuates the 253.7nm Hg line and fluoresces from 300-400
nm;
and the 6057 Glass Safety Filter absorbs the 253.7 nm Hg line and attenuates
the
312.6 nm line. The Aperture Shields offered by Newport include the 6038
Pinhole
Shield which has a 0.040 inch (1mm) diameter, the 6039 Small Aperture Shield
which has a 0.313 x 0.375 inch window and the 6040 Large Aperture Shield with
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0.188 x 1.50 inch window. Filters and shields can also be obtained from Edmund
Industrial Optics Inc. (Barrington, NJ). The Edmund UV Light Shield A has a
1mm
inner diameter drilled hole; Shield B has a 7.9mm x 15.9mm aperture; and
Shield C
has a 4.8 mm x 38.2 mm aperture.
The orientation of the lamp can also impact upon the result obtained. Thus,
in the embodiment where a gas is subjected to a radiation source, the
radiation
source can be fixed to direct the radiation directly towards, perpendicular,
away or
parallel to the conduit directing the gas, or its entry or exit point. The
gases can be
those discussed above or other gases, such as air or oxygen. The radiation
source
can be positioned horizontally, vertically and/or at an angle above, below
across
from the conduit. For example, the base of a pencil lamp (or other radiation
source)
can be set at the same height of the conduit and the tip of the lamp directed
or
pointed toward the conduit. Alternatively, the base of the pencil lamp (or
other
radiation source) can be set at the height of the conduit and the lamp
directed at a
30 (40 , 45 , 50 , 55 , 60 , or 90 ) angle above (below) the conduit.
Alternatively,
the base of the pencil lamp can be fixed above or below the level of the
conduit.
The tip of the pencil lamp can be pointed up or down, in the direction of the
gas flow
or against the gas flow or at another angle with respect to any of the above.
Further,
more than one of the same or different pencil lamps alone or in combination
with
other radiation sources can be used, set at the same or different heights,
orientations
and angles. The lamps can be presented in alternative orders (first xenon,
then
mercury or vice versa).
In an embodiment wherein the material to be treated is subjected to the
radiation source, similar positions can be achieved as above with respect to
the gas
conduit. The radiation source can be fixed to direct the radiation directly
towards,
perpendicular, away or parallel to the material. The radiation source can be
positioned horizontally, vertically and/or at an angle above, below across
from the
material. As above, the base of a pencil lamp (or other radiation source) can
be set
at the same height of the material and the tip of the lamp directed or pointed
toward
the material. Alternatively, the base of the pencil lamp (or other radiation
source)
can be set at the height of the material and the lamp directed at a 30 (40 ,
45 , 50 ,
55 , 60 , or 90 ) angle above (below) the material. Alternatively, the base of
the
pencil lamp can be fixed above or below the level of the material. The tip of
the
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pencil lamp can be pointed up or down, in the direction of the gas flow or
against the
gas flow or at another angle with respect to any of the above. Further, more
than one
of the same or different pencil lamps alone or in combination with other
radiation
sources can be used, set at the same or different heights, orientations and
angles.
In a preferred embodiment, the radiation source is a high intensity discharge
lamp positioned to direct the radiation towards the material. The high
intensity
discharge lamp is combined with one or more pencil lamps positioned proximal
to
the high intensity discharge lamp. Often, high intensity discharge lamps are
equipped with a hood or reflector to direct the radiation. In some instances,
one or
more pencil lamps can be placed inside and/or behind the reflector.
Further, the distance between the radiation source and the material and/or
gas conduit can impact the results achieved. For example, the lamps can be
placed
between about 5 and 100 cm or more from the conduit and/or material. In other
embodiments, the distance between the radiation source and the material and/or
gas
conduit can be between about 100 cm and 5 meters or more.
In other instances, the radiation can be filtered. Filters, such as colored
glass
filters, available from photography supply shops, for example, can be used. In
yet
other embodiments, the filter can be other materials, such as water, gas (air
or other
gas), a manufactured or tailored material, such as those materials described
or made
herein, or a material of selected density, chemical make-up, properties or
structure.
In one embodiment, the filter can be placed between the radiation source(s)
and the
target metal or alloy or gas used in the method. Filters can also be called
"(harmonic)
forcing functions." Forcing functions can be used in conjunction with
electromagnetic radiation sources to affect a change in a material. In
addition, gases
may be injected into apparatus containing a forcing function to modify the
performance of the assembly.
In one embodiment, the radiation source has an environment which is
different from that of the material. This can be accomplished by directing a
gas flow
into the lamp environment. Where the radiation source is a pencil lamp within
a box
to radiate a gas, this can be accomplished by direct gas flow into the box. In
other
embodiments, the radiation source can be a short arc lamp or a short arc lamp
assembly. In such embodiments, the gas can be introduced into the reflector
proximate to the lamp. The gas includes those gases discussed above.
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The radiation can be applied continuously or discontinuously (e.g. pulsed or
toggled) and its intensity can be modulated. Where the radiation is applied
continuously, the radiation can begin prior to introduction of the gas into
the conduit
or after. It can be applied for the duration of a cycle or series of cycles.
Where the
radiation is pulsed, the length of each pulse can be the same or different.
Generally,
the radiation is applied to induce harmonic change, altering the gas or target
materials prior to their introduction into the reactor. This is conveniently
accomplished by controlling the lamps with a computer. The factors to be
considered in radiation source placement, exposure and sequence include the
desired
wavelength, intensity, and energy characteristics, the angle of incidence, and
the
harmonic profile to be injected into the targeted material (e.g. gas, metal,
tailored
metal, radiated gas and the like).
In some instances, the radiation source and/or pencil lamp(s) and/or filters
and/or target material or gas are advantageously cooled. For example, where a
high
intensity discharge lamp is used in combination with a pencil lamp(s), it may
be
advantageous to cool the pencil lamp to prevent damage. Alternatively, where a
short arc lamp is used in combination with pencil lamps and/or glass filters
it may be
advantageous to cool the pencil lamps to prevent damage as well as the glass
filter to
prevent breakage.
Other sources of energy can be used to further tailor the materials of the
invention. For example, DC current can be applied continuously or the amperage
varied, for example between 0-300 amps, such as 0-150 amps. AC current can be
applied continuously or varied, e.g., in a wave pattern, such as a sinusoidal
wave,
square wave, or triangle wave pattern of a selected frequency and amplitude.
Typically, 10 volts, peak to peak, is used at 0-3.5 MHz, 0-28 MHz, or 0-50
MHz. In
other embodiments, the peak to peak voltage was less that about 15 vdc, 10
vdc, 8
vdc, 7.2 vdc, 5 vdc, 1.7 vdc, and 1 vdc. In one embodiment, electrodes can be
placed in the reactor, such as below the surface of the material, and current
applied.
As with the radiation discussed above, the current can be applied to coincide
with a
cycle or series of cycles or during all or a part of a single step of the
process. Often
the power supply is turned on prior to attachment to the electrodes to avoid
any
power surge impacts.
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Further, the cooling step can alter the results of the process. Such cooling
can include gradual and/or rapid cooling steps. Gradual cooling typically
includes
cooling due to heat exchange with air or other gas over 1 to 72 hours, 2 to 50
hours,
3 to 30 hours, or 8 to 72 hours. Rapid cooling, also known as quenching,
typically
includes an initial cooling with air or other gas to below the solidus
temperature,
thereby forming a solid mass, and placing the solid mass into a bath
comprising a
suitable fluid such as tap water, distilled water, deionized water, other
forms of
water, gases (as defined above), liquid nitrogen or other suitable liquified
gases, a
thermally-stable oil (e.g., silicone oil) or organic coolant, and combinations
thereof.
The bath should contain a suitable quantity of liquid at a suitable
temperature, such
that the desired amount of cooling occurs. The ingot can be removed from the
crucible before or after completing the cooling. While the material is
cooling, the
environment can be stirred, mixed or agitated. This can be accomplished by
maintaining a flow of coolant over the material, or agitating the cooling bath
or
environment. Alternatively, the coolant is not disturbed or agitated and
circulation
of the coolant is minimized.
In one embodiment, the material is cooled in a different vessel (cooling or
quench chamber). The cooling chamber can be, for example, a polyethylene (or
other plastic) container. The ingot can be placed directly, or indirectly,
into the
cooling vessel (e.g., in a vertical or horizontal orientation). Generally, the
ingot can
be placed at least about 6 inches from the inside wall of the container. The
height of
the coolant can be at least about 12 inches above and below the surface of the
ingot.
A refractory material (e.g., a ceramic block rinsed with coolant (e.g., DI
water) and,
optionally dried or allowed to dry) may be used to support the ingot in the
quench
chamber.
Where the material is cooled in a different vessel from the reactor or
induction furnace, the material can be removed, manually or robotically, to a
clean,
protected surface. This removal may be accomplished manually using a pair of
tongs (e.g. cast iron, steel, stainless steel, nickel, titanium, tungsten or
other high
temperature melting transition metal). Manual removal can also be accomplished
by
donning heavy, insulated, heat resistant gloves.
Where the crucible is removed from the reactor with the material, the
crucible should be removed before or after cooling. The crucible can be
removed by
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gently peeling it away from the material. A hammer, ram or wedge can be used
to
perform this function. However, care should be used to avoid striking the
material
hard with the hammer or otherwise causing a substantial impact upon or metal
contact with the material. In one embodiment, the crucible removal can be
performed in the presence of air at about 350 75 F, 750 250 F, 1100 250 F, or
at
Ts lidus -75 F, Ts I1dus -5 F.
One example of the base method can be described in terms of carbon
saturation values. After a metal or alloy is added to a suitable reactor,
establish the
dissolved carbon level at 70% to 95% of the equilibrium saturation of carbon
for the
thermodynamic state specified (e.g., T, P, composition) when the composition
is in
its natural state (hereinafter the equilibrium saturation of carbon is
referred to as
"[C]egsat"). Identify temperature set points for 80% and 95% [C]egsat. Vary
the
temperature between the predetermined set points, such that the temperature is
decreased for 7 minutes and increased over 7 minutes per cycle, for 15 cycles.
Next,
establish a flow of argon. Vary the temperature between the predetermined set
points, such that the temperature is decreased for 7 minutes and increased
over 7
minutes per cycle, for 5 cycles; the temperature should be maintained above
70%
[C]egsat at all times and maintained below 95% [C]egsat at all times. The
carbon level
is raised to saturation (i.e., [C]egsat) with continued argon addition. Hold
for 60
minutes at saturation (i.e., [C]egsat) with continued argon addition. Raise
the carbon
level to +I%wt (i.e., +1%wt represents 1% wt above the saturation value as
defined in
its natural equilibrium state, [C]egsat) of [C]egsat with continued argon
addition and
hold for 5 minutes. Vary the temperature for 20 cycles between +1%Wt and
+3%,,,t of
[C]egsat, such that the temperature is decreased over 9 minutes and increased
over 9
minutes per cycle. Cease argon addition. Cool the metal to +4%,vt of [C]egsat=
Vary
the temperature for 4.5 cycles between +4%,,,t and +7%,,,t of [C]egsat, such
that the
temperature is decreased over 3 minutes and increased over 5 minutes. Argon is
added as the carbon saturation increases and nitrogen is added as carbon
saturation
decreases. Cool the metal to obtain +8%,,,t with continued argon addition.
Vary the
temperature over 15.5 cycles between +8%,,,t and +18%,,,t of [C]egsat, such
that the
temperature is decreased over 15 minutes and increased over 15 minutes. Argon
is
added as the carbon saturation increases and nitrogen is added as carbon
saturation
decreases. After the 15.5 cycles are complete, gas addition is halted. Perform
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complete cycle by varying the temperature between +18%,,,t to +14%,t of
[C]egsat
(ending at +18%,,), such that the temperature is increased over 15 minutes and
decreased over 15 minutes. Proceed immediately to a cool down that leads to
solidification. The present process also includes one or more of the further
improvements described above.
Cycles of the present invention can vary in duration. The duration of a cycle
can vary among cycles in a step. A cycle duration is, for example, about 2
minutes
to about 90 minutes, about 3 minutes to about 67 minutes, about 5 minutes to
about
45 minutes, about 8 minutes to about 30 minutes, about 10 minutes to about 20
minutes, about 14 minutes to about 18 minutes, about 7 minutes to about 9
minutes,
about 13 minutes to about 15 minutes, about 17 minutes to about 19 minutes,
about
28 minutes to about 32 minutes, or about 29 minutes to about 31 minutes.
A cycle can be symmetric or asymmetric. In a symmetric cycle, the period
of increasing the metal or alloy temperature is equal to the period of
decreasing the
metal or alloy temperature. In an asymmetric cycle, the period of increasing
the
metal or alloy temperature is different than the period of decreasing the
metal or
alloy temperature. For an asymmetric cycle, the period of increasing the metal
or
alloy temperature can be longer than or shorter than the period of decreasing
the
metal or alloy temperature.
For example, in a cycle lasting about 7 minutes to about 9 minutes, the
temperature can be increased for about 3 minutes and the temperature can be
decreased for about 5 minutes. If the cycle lasts about 13 minutes to about 15
minutes, the temperature can be increased for about 7 minutes and the
temperature
can be decreased for about 7 minutes. If the cycle lasts about 17 minutes to
about 19
minutes, the temperature can be increased for about 9 minutes and the
temperature
can be decreased for about 9 minutes. If the cycle lasts about 29 minutes to
about 31
minutes, the temperature can be increased for about 15 minutes and the
temperature
can decreased for about 15 minutes.
The number of cycles in a step is generally an integer or half-integer value.
For example, the number of cycles in a step can be one or more, one to forty,
or one
to twenty. The number of cycles can be 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12,
13, 14, 15,
16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34,
35, 36, 37,
38, 39, or 40 or more. Alternatively, the number of cycles in a step can be
0.5, 1.5,
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2.5, 3.5, 4.5, 5.5, 6.5, 7.5, 8.5, 9.5, 10.5, 11.5, 12.5, 13.5, 14.5, 15.5,
16.5, 17.5, 18.5,
19.5, 20.5, 21.5, 22.5, 23.5, 24.5, 25.5, 26.5, 27.5, 28.5, 29.5, or 30.5 or
more. In a
step comprising a half-integer or a non-integer quantity of cycles, either
heating or
cooling can occur first.
After the initial heating step, the temperature of a metal or an alloy is
sufficiently high, such that the temperature is equal to or greater than the
solidus
temperature. The solidus temperature varies depending on the metal or the
alloy,
and the amount of carbon dissolved therein. The temperature at the end of Step
(F.)
of the third paragraph of the summary is typically about 900 F to about 3000
F, but
varies from metal to metal. For example, the temperature at the end of Step
(F.) can
be about 1932 F to about 2032 F, about 1957 F to about 2007 F, or about 1932 F
to
about 2467 F for copper; about 2368 F to about 2468 F, about 2393 F to about
2443 F, or about 2368 F to about 2855 F for nickel; about 2358 F to about 2458
F
or about 2373 F to about 2423 F, or about 2358 F to about 2805 F for cobalt;
about
1932 F to about 2032 F, about 1957 F to about 2007 F, or about 1932 F to about
2467 F for a copper/gold/silver alloy; about 399 F to about 499 F, about 424 F
to
about 474 F, or about 399 F to about 932 F for a tin/lead/zinc alloy; about
399 F to
about 499 F, about 424 F to about 474 F, or about 399 F to 932 F for a
tin/sodium/potassium/magnesium alloy; about 2550 F to about 2650 F, about
2575 F to about 2625 F, or about 2550 F to about 2905 F for silicon; about
2058 F
to about 2158 F, about 2073 F to about 2123 F, or about 2058 F to about 2855 F
for iron; about 2058 F to about 2158 F, about 2073 F to about 2123 F, or about
2058 F to about 2855 F for an iron/vanadium/chromium/manganese alloy; or
2368 F to about 2468 F, about 2393 F to about 2443 F, or about 2368 F to about
2855 F for a nickel/tantalum/hafnium/ tungsten alloy.
Methods of the present invention are carried out in a suitable reactor.
Suitable reactors are selected depending on the amount of metal or alloy to be
processed, mode of heating, extent of heating (temperature) required, and the
like. A
preferred reactor in the present method is an induction furnace reactor, which
is
capable of operating in a frequency range of 0 Hz to about 10,000 Hz, 0 Hz to
about
3,000 Hz, or 0 Hz to about 1,000 Hz. Reactors operating at lower frequencies
are
desirable for larger metal charges, such that a reactor operating at 0-3,000
Hz is
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generally suitable for 20 pound metal charges and a reactor operating at 0-
1,000 Hz
is generally suitable for 5000 pound metal charges.
Typically, reactors of the present method are lined with a suitable crucible
and appropriately sealed from the external environment enabling very tight
control
of the internal chemical environment (e.g., part per thousand, part per
million, or the
like). Crucibles are selected, in part, based on the amount of metal or alloy
to be
heated and the temperature of the method. Crucibles selected for the present
method
typically have a capacity from about five pounds to about five tons. One
preferred
crucible is comprised of 89.07% A1203, 10.37% Si02, 0.16% Ti02, 0.15% Fe203,
0.03% CaO, 0.01% MgO, 0.02% Na203, and 0.02% K20, and has a 9 inch outside
diameter, a 7.75 inch inside diameter, and a 14 inch depth. A second preferred
crucible is comprised of 99.68% A1203, 0.07% Si02, 0.08% Fe203, 0.04% CaO, and
0.12% Na203, and has a 4.5 inch outside diameter, a 3.75 inch inside diameter
and a
10 inch depth.
A new composition of matter of the present invention can manifest itself as a
transient, adjustable, or permanent change in energy and/or associated
properties, as
broadly defined. Property change can be exhibited as or comprise a change in:
(1)
structural atomic character (e.g., XES/XRF peak creation, peak fluidity, peak
intensity, peak centroid, peak profile or shape as a function of
material/sample
orientation, atomic energy level(s), and TEM, STM, MFM scans); (2) electronic
character (e.g., SQUID, scanning SQUID,scanning magnetoresistive microscopy,
scanning magnetic microscope, magnetometer, non-contact MFM, electron
electromagnetic interactions, quantum (or topological) order'' 2, quantum
entanglement3, Jahn-Teller effect, ground state effects, electromagnetic field
position/orientation, energy gradients, Hall effect, voltage, capacitance,
voltage
decay rate, voltage gradient, voltage signature including slope of decay
and/or
change of slope decay, voltage magnitude, voltage orientation); (3) structural
molecular or atomic character (e.g., SEM, TEM, STM, AFM, LFM, and MFM
scans, optical microscopy images, and structural orientation, ordering, long
range
alignment/ordering, anisotropy); (4) physical constants (e.g., color,
crystalline form,
specific rotation, emissivity, melting point, boiling point, density,
refractive index,
solubility, hardness, surface tension, dielectric, magnetic susceptibility,
coefficient
of friction, x-ray wavelengths); (5) physical properties (e.g., mechanical,
chemical,
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electrical, thermal, engineering, and the like); and, (6) other changes that
differentiate naturally occurring materials from manufactured materials
created by
inducing a change in matter.
A preferred analytical method is x-ray fluorescence spectrometry. X-ray
fluorescence spectrometry is described in "X-Ray Fluorescence Spectrometry",
by
George J. Havrilla in "Handbook of Instrumental Techniques for Analytical
Chemistry," Frank A. Settle, Ed., Prentice-Hall, Inc: 1997, which is
incorporated
herein by reference. XRF spectrometry is a well-known and long-practiced
method,
which has been used to detect and quantify or semi-quantify the elemental
composition (for elements with Z > 11) of solid and liquid samples. This
technique
benefits from minimal sample preparation, wide dynamic range, and being
nondestructive. Typically, XRF data are not dependent on which dimension
(e.g.,
axial or radial) of a sample was analyzed. Accuracy of less than 1 % error can
generally be achieved with XRF spectrometry, and the technique can have
detection
limits of parts per million.
XRF spectrometry first involves exciting an atom, such that an inner shell
electron is ejected. Upon ejection of an electron, an outer shell electron
will "drop"
down into the lower-energy position of the ejected inner shell electron. When
the
outer shell electron "drops" into the lower-energy inner shell, x-ray energy
is
released. Typically, an electron is ejected from the K, L, or M shell and is
replaced
by an electron from the L, M, or N shell. Because there are numerous
combinations
of ejections and replacements possible for any given element, x-rays of
several
energies are emitted during a typical XRF experiment. Therefore, each element
in
the Periodic Table has a standard pattern of x-ray emissions after being
excited by a
sufficiently energetic source, since each such element has its own
characteristic
electronic state. By matching a pattern of emitted x-ray energies to values
found in
tables, such as those on pages 10-233 to 10-271 of "Handbook of Chemistry and
Physics, 73'" Edition," edited by D. R. Lide, CRC Press, 1992, which is
incorporated
herein by reference, one can identify which elements are present in a sample.
In
addition, the intensity of the emitted x-rays allows one to quantify the
amount of an
element in a sample.
There are two standard variations of the XRF technique. First, as an energy-
dispersive method (EDXRF), the XRF technique uses a detector such as a Si(Li)
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detector, capable of simultaneously measuring the energy and intensity of x-
ray
photons from an array of elements. EDXRF is well-suited for rapid acquisition
of
data to determine gross elemental composition. Typically, the detection limits
for
EDXRF are in the range of tens to hundreds of parts-per-million. A wavelength-
dispersive technique (WDXRF) is generally better-suited for analyses requiring
high
accuracy and precision. WDXRF uses a crystal to disperse emitted x-rays, based
on
Bragg's Law. Natural crystals, such as lithium fluoride and germanium, are
commonly used for high-energy (short wavelength) x-rays, while synthetic
crystals
are commonly used for low-energy (longer wavelength) x-rays. Crystals are
chosen,
in part, to achieve desired resolution, so that x-rays of different energies
are
dispersed to distinguishable 20 angles. WDXRF can either measure x-rays
sequentially, such that a WDXRF instrument will step through a range of 20
angles
in recording a spectrum, or there will be detectors positioned at multiple 20
angles,
allowing for more rapid analysis of a sample. Detectors for WDXRF commonly
include gas ionization and scintillation detectors. A further description of
the use of
WDXRF technique in the present invention can be found in Example 1. Results
from EDXRF and results from WDXRF can be compared by determining the
relationship between a 20 angle and the wavelength of the corresponding x-ray
(e.g.,
using Bragg's Law) and converting the wavelength into energy (e.g., energy
equals
the reciprocal of the wavelength multiplied by Planck's constant and the
velocity of
light).
Analysis of emitted x-rays can be carried out automatically or semi-
automatically, such as by using a software package (e.g., UniQuant, which is
sold by
Omega Data Systems BY, Veldhoven, The Netherlands) for either EDXRF or
WDXRF. UniQuant is used for standard-less, semi-quantitative to quantitative
XRF
analysis using the intensities measured by a sequential x-ray spectrometer.
The
software package unifies all types of samples into one analytical program. The
UniQuant software program is highly effective for analyzing samples for which
no
standards are available. Sample preparation is usually minimal or not required
at all.
Samples can be of very different natures, sizes and shapes. Elements from
fluorine
or sodium up to uranium, or their oxide compounds, can be analyzed in samples
such as a piece of glass, a screw, metal drillings, lubricating oil, loose fly
ash
powder, polymers, phosphoric acid, thin layers on a substrate, soil, paint,
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rings of trees, and, in general, those samples for which no standards are
available.
The reporting is in weight % along with an estimated error for each element.
In software packages such as UniQuant, an XRF spectrum is composed of
data channels. Each data channel corresponds to an energy range and contains
information about the number of x-rays emitted at that energy. The data
channels
can be combined into one coherent plot to show the number or intensity of
emitted
x-rays versus energy or 20 angle (the 20 angle is related to the wavelength of
an x-
ray), such that the plot will show a series of peaks. An analysis of the peaks
by one
skilled in the art or the software package can identify the correspondence
between
the experimentally-determined peaks and the previously-determined peaks of
individual elements. For an element, peak location (i.e., the centroid of the
peak
with respect to energy or 20 angle), peak profile/ shape, peak creation, and
peak
fluidity would be expected to be essentially the same, within experimental
error, for
any sample containing the element. If the same quantity of an element is
present in
two samples, intensity will also be essentially the same, excepting
experimental error
and matrix effects.
A typical software package is programmed to correlate certain data channels
with the emitted x-rays of elements. Quantification of the intensity of
emitted x-rays
is accomplished by integrating the XRF spectrum over a number of data
channels.
Based on the measured intensities and the previously-compiled data on
elements, the
software package will integrate over all data channels, correlate the emitted
x-ray
intensities, and will then calculate the relative abundance or quantity of
elements
which appear to be present in a sample, based upon comparison to the
standards.
Composition of matter changes produced by the present invention will generally
be
characterized by an XRF spectrum that reports: (1) the presence of an element
which was not present in the starting material and was not added during the
process;
(2) an increased amount of an element that was not added to the process in the
amount measured; or, (3) a decreased amount of an element that was not removed
during the process in the amount indicated. Examples of (3) include a
reduction in
identifiable spectra referencing the sum before normalization and/or
reappearance of
an element upon combustion. Products of the present invention can also be
characterized by the difference between XRF Uniquant analysis such as by
burning
the sample (e.g., LECO analysis), described in more detail below.
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A "LECO" analysis is meant to include an analysis conducted by the CS-300
Carbon/Sulfur determinator supplied by a LECO computer. The CS-300
Carbon/Sulfur determinator is a microprocessor based, software driven
instrument
for measurement of carbon and sulfur content in metals, ores, ceramics and
other
inorganic materials.
Analysis begins by weighing out a sample (1 g nominal) into a ceramic
crucible on a balance. Accelerator material is added, the crucible is placed
on the
loading pedestal, and the ANALYZE key is pressed. Furnace closure is performed
automatically, then the combustion chamber is purged with oxygen to drive off
residual atmospheric gases. After purging, oxygen flow through the system is
restored and the induction furnace is turned on. The inductive elements of the
sample and accelerator couple with the high frequency field of the furnace.
The pure
oxygen environment and the heat generated by this coupling cause the sample to
combust. During combustion all elements of the sample oxidize. Carbon bearing
elements are reduced, releasing the carbon, which immediately binds with the
oxygen to form CO and C02, the majority being C02. Also, sulfur bearing
elements are reduced, releasing sulfur, which binds with oxygen to form S02-
Sample gases are swept in the carrier stream. Sulfur is measured as sulfur
dioxide in the first IR cell. A small amount of carbon monoxide is converted
to
carbon dioxide in the catalytic heater assembly while sulfur trioxide is
removed from
the system in a cellulose filter. Carbon is measured as carbon dioxide in the
IR cells,
as gases flow trough the IR cells.
Ideally, the relative abundances will total 100% prior to normalization.
However, for a variety of reasons, such as improper or insufficient
calibration,
and/or non-planar sample surface the relative abundances will not total 100%
prior
to normalization. Another reason that the relative abundances of elements do
not
total 100% prior to normalization is that a portion of the XRF spectrum falls
outside
of the data channels that the software package correlates with an element
(i.e., a
portion of the XRF spectrum is not recognized as belonging to an element and
is not
included in the relative abundance calculation). In this case, the relative
abundances
will likely total less than 100% prior to normalization. Further, the samples
will
often have anisotropic characteristics whereby an axial scan is distinct from
a radial
scan. Thus, products of the invention may be characterized by an XRF spectrum
that
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is not recognized by the Uniquant software (e.g., sum of known concentrations
before normalization is less than 100%) described herein in an amount, for
example,
of less than 98%, such as less than 90%, such as less than 80%. In additional
embodiments, the software package reports or detects one or more elements not
detected by other methods or are detected in different quantities.
X-ray emission spectrometry (XES), a technique analogous to XRF, also
provides electronic information about elements. In XES, a lower-energy source
is
used to eject electrons from a sample, such that only the surface (to several
micrometers) of the sample is analyzed. Similar to XRF, a series of peaks is
generated, which corresponds to outer shell electrons replacing ejected inner
shell
electrons. The peak shape, peak fluidity, peak creation, peak intensity, peak
centroid, and peak profile are expected to be essentially the same, within
experimental error and matrix effects, for two samples having the same
composition.
Thus, XES analysis of the control standard compared to the atomically
altered (i.e., manufactured or tailored) state can also be analyzed.
Manufactured
copper in the axial direction exhibits similar composition to natural copper
(i.e.,
99.98%wt), but radial scans exhibit new peaks in the region close to naturally
occurring S, Cl, and K. The shifting centroid of the observed peaks from the
natural
species (i.e., S, Cl, and K) confirms electronic change in the atomic state of
the base
element. Conventional chemical analysis performed using a LECO (IR) analyzer
to
detect SOX in the vapor phase post sample combustion confirmed the absence of
sulfur at XES lower detection limits.
Non-contact, magnetic force microscopy image or scanning tunneling
microscopy (STM) scan can also confirm the production of a new composition of
matter or manufactured or tailored material, identified by an altered and
aligned
electromagnetic network. Individually, and from differing vantage points,
these
scans show the outline of the changed electromagnetic energy network.
New compositions of matter can be electronically modified to induce long
range ordering/alignment. Optical microscopy and SEM imaging of the material
verifies the degree and extent of long range ordering achieved.
Non-contact, magnetic force microscopy image or scanning tunneling
microscopy (STM) scans can also confirm the production of a new composition of
matter or manufactured or tailored material, identified by an altered and
aligned
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electromagnetic network. Individually, and from differing vantage points,
these
scans can show the outline of the changed electromagnetic energy network. Non-
contact MFM imaging can show that products of the invention often possess
clear
pattern repetition and intensity of the manufactured material when compared to
the
natural material, or starting material. Products of the invention can be
characterized
by the presence of magnetic properties in high purity, non-magnetic metals,
such as
elemental copper (e.g., 99.98 %,,,t).
Products can also be characterized by color changes. The variation in color
of copper products ranged from black, copper, gold, silver and red. Other
visual
variations included translucency and near transparency at regions. While not
being
bound by theory, the alteration of copper's electronic state along the
continuum
enables the new composition of matter's color to be adjusted along the
continuum.
In several examples of the present invention, the ingots obtained by the
process possess a substantial internal void and absence of a crown of material
on the
top surface. In other examples of the invention, the ingot is characterized by
essentially no void, with a crown of material on the top.
Other products of the processes are characterized by changes in hardness.
The variation in diamond pyramid hardness between different manufactured
copper
samples ranged from about 25 to 90 (or 3 to 9 times higher than natural
copper).
Hardness change can be anisotropic.
The operations described in the embodiments presented herein did not result
merely from empirical explorations. Rather, guidance was obtained from
theoretical
considerations regarding the topological aspects of electrodynamics. These
enabled
specification of the range and duration of temperature cycles, the selection
of
specific combinations and concentrations of gases to be used, geometric
factors
affecting the lance placement, and all other chief features of the
experimental
protocols. While not being bound by theory, the Applicant believes the
application
of topological principles4 5,6,7,8,9,10 when applied to electrodynamics
provides a
powerful means for altering the properties of materials.
As noted in US.09/416,720, the theoretical analysis can be formulated in
terms of an allowed set of mathematical poles, defined as the zurn operator,
and
further characterized by the set of mathematical poles coalesced, defined as
the
isozurn value. Adjusting or manipulating the zurn causes the isozurn value to
differ
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from its starting or naturally occurring value, thereby modifying the
electronic
structure from that of the natural state.
The products produced by the process have utilities readily apparent to those
skilled in the art. Indeed, materials which comprise metals can be used to
manufacture products having adjustable chemical properties (e.g.,
regioselectivity,
regiospecificity, or reaction rate), electronic properties (e.g., band gap,
susceptibility,
resistivity, or magnetism), mechanical properties (e.g., ductility or
hardness) and/or
optical properties (e.g., color).
The invention further relates to the apparatus used to produce the materials.
The apparatus of the invention includes a reactor comprising an induction
furnace
characterized by a gas source and at least one radiation source arranged to
expose the
gas and/or the contents of the reactor, in the manner discussed above,
optional filters
and optional environmental controls. As such, the invention includes an
apparatus
comprising a combination of the following: (a) a first and a second pencil
lamp; (b)
at least one short arc lamp within a housing; (c) a gas source proximal to (b)
and an
induction furnace.
In one embodiment, the radiation source is proximate to a gas source which
is adapted to control the environment of the radiation source. In another
embodiment, the short arc lamp housing further comprises at least one pencil
lamp,
such as those discussed above. In another embodiment, the apparatus further
comprises a filter, such as those described herein.
EXEMPLIFICATION
EXAMPLE 1:
EXPERIMENTAL PROCEDURE FOR COPPER Method "AB" RUN 14-03-02
A cylindrical alumina-based crucible (99.68% A1203, 0.07% SiO2, 0.08% Fe203,
0.04% CaO, 0.12% Na203i 4.5 inches O.D. X 3.75 inches I.D. X 14.5 inches
depth) of a
100 pound induction furnace reactor (Inductotherm) fitted with a 73-30R
Powertrak
power supply was charged with 9080 g copper (99.98% purity) through its
charging
port. Prior to charging a gas addition lance was placed inside the reactor at
the reactor
centerline and placed two inches from the bottom of the bath. The reactor was
fitted
with a graphite cap and a ceramic liner (i.e., the crucible, from Engineering
Ceramics).
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During the entire procedure, a slight positive pressure of 97% argon and 3%
hydrogen
(-0.5 psig) was maintained in the reactor using a continuous backspace purge.
The
reactor was heated to the metal charge liquidus point plus at least 300 F, at
a rate no
greater than 300 F/hr, as limited by the integrity of the crucible. The
induction furnace
operated in the frequency range of 0 Hz to 3000 Hz, with frequency determined
by a
temperature-controlled feedback loop implementing an Omega Model CN3000
temperature controller. The temperature was increased to 2462 F again using a
rate no
greater than 300 F/hour. When this temperature was reached, graphite
saturation
assemblies (3/8 inches OD, 36 inches long high purity (<5 ppm impurities)
graphite
rods) were inserted to the bottom of the copper charge through ports located
in the top
plate. The copper was held at 2462 F for 2 hours. Every 30 minutes during the
hold
period, an attempt was made to lower the graphite saturation assemblies as
dissolution
occurred. As the copper became saturated with carbon, the graphite saturation
assemblies were consumed. After the 2-hour hold period was complete, the
graphite
saturation assemblies were removed.
The reactor temperature was increased to 2515 F over 7 minutes. The
temperature was then varied between 2476 F and 2515 F for 16.5 cycles. Each
cycle
consisted of raising the temperature continuously over 7 minutes and lowering
the
temperature continuously over 7 minutes. After the 15 cycles were completed,
the gas
flow rate was started in a bypass mode at a rate of 0.3 L/min of 97% argon and
3% neon
(all gas compositions are constant unless stated otherwise). Five minutes into
the 15.51
cycle, a xenon radiation source is activated within the sealed enclosure. At 6
minutes
into the 15.5t" cycle, a long wave ultraviolet radiation source was activated
in the sealed
enclosure. At sweep count 15.5, the gas flow was redirected to direct bath
addition. At
sweep count 16, a short wave ultraviolet radiation source was initiated in the
sealed
enclosure. At sweep count 16.5, the xenon radiation source was remotely
rotated within
the sealed enclosure. The temperature of the copper was varied over another 5
cycles
between 2476 F and 2515 F. After the fifth cycle, the reactor temperature was
lowered
to 2462 F over a 10-minute period.
The graphite saturation assemblies were reinstalled in the copper and remained
there for 1 hour. The graphite saturation assemblies were removed. The reactor
temperature was lowered to 2459 F over 5 minutes. The reactor was held at this
temperature for 5 minutes with continued gas addition. The temperature was
then
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varied between 2453 F and 2459 F over 20 cycles. Each cycle consisted of
lowering
the temperature continuously over 9 minutes and raising the temperature
continuously
over 9 minutes. After the 20"' cycle, third body addition (gas addition) was
changed to a
flow rate of 9 mL/min of 100% neon. The bath was then cooled to 2450 F over 10
minutes.
The temperature was then varied between 2441 F and 2450 F over 4.5 cycles.
Each cycle consisted of lowering the temperature continuously over 5 minutes
and
raising the temperature continuously over 3 minutes. In addition, while
raising the
temperature, a 0.15 L/min flow of 40%helium, 60% argon and trace neon was
added,
and while lowering the temperature, a 0.3 L/min flow of 40% argon, 60% helium,
trace
neon, trace hydrogen, and trace krypton was added. After the 4.5 cycles, the
short wave
radiation source within the sealed enclosure was terminated. The reactor
temperature
was then lowered to 2438 F over 1 minute. The temperature was varied between
2406 F and 2438 F for 15.5 cycles. Each cycle consisted of lowering the
temperature
continuously over 15 minutes and raising the temperature continuously over 15
minutes.
In addition, while raising the temperature, a 0.15 L/min flow of 40%helium,
60% argon
and trace neon was added, and while lowering the temperature, a 0.3 L/min flow
of 40%
argon, 60% helium, trace neon, trace hydrogen, and trace krypton was added.
After the
final cycle (sweep), gas flow was changed to trace neon only.
The temperature was then varied between 2419 F and 2406 F for one cycle.
The cycle consisted of raising the temperature continuously over 15 minutes
and
lowering the temperature continuously over 15 minutes. At the completion of
this
temperature sweep, the reactor temperature was lowered to Ts lsdu5 plus 11 F
over 45
minutes.
Upon reaching TS iidu, plus 11 F, gas addition was changed to 0.3 L/min of
100%
hydrogen and trace neon and held for five minutes. The reactor was then cooled
to
TS I;du, plus 10 F over five minutes. Upon reaching TS lidus plus 10 F, the
gas addition
lance was relocated into the headspace of the reactor, such that a quarter
inch (1/4
inches) dimple could be observed on the bath surface. The bath was held at TS
tidus plus
10 F for an additional 5 minutes for conditioning and equilibrization. The
reactor was
then cooled to Ts lidu, plus 8 F while maintaining a temperature lowering rate
of no more
than 3 F/hr. Upon reaching TS udus plus 8 F a manual power pulse of 2 kW was
introduced with a single continuous up/down sweep from normal holding power.
The
27
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reactor was then cooled to Ts iidus plus 2 F while maintaining a temperature
lowering
rate of no more than 3 F/hr. Upon reaching Ts lidus plus 2 F a manual power
pulse of 1.5
kW was introduced with a single continuous up/down sweep from normal holding
power. Furthermore, immediately following the manual power pulse the gas flow
rate
was changed to 0.15 L/min of 49.5% hydrogen, 49.5% helium and 1% neon. The
reactor was then cooled to Ts iidus again maintaining a temperature-lowering
rate of no
more than 3 F/hr. Upon reaching Ts lidus, the reactor temperature was lowered
to TS iidus
minus 75 F over five hours. Upon reaching TS iidus minus 75 F, the flow rate
was
changed to 30 ml/min of 60% helium, 40% hydrogen and trace neon. The induction
furnace power supply was then lowered to 0.75 kW and the reactor was allowed
to cool
to 1000 F. Upon reaching 1000 F, the flow rate was changed to 30 ml/min of
100%
helium and trace neon. The induction furnace power supply was lowered to 0.50
kW
and the reactor was allowed to cool to 350 F. Upon reaching 350 F, the
induction
furnace power supply was shut down. A timer was initiated. At a time of 5
minutes,
the long wave radiation source within the sealed enclosure was terminated. At
a time of
9 minutes, the xenon radiation source within the sealed enclosure was
terminated. At a
time of 15 minutes, the trace neon gas addition was terminated. At a time of
30
minutes, the helium gas addition was terminated. At a time of 45 minutes, the
ingot and
crucible were removed from the reactor in the presence of radiation sources
(metal
halide light sources) utilizing tongs.
Upon removal, the crucible was stripped from the metal ingot via a gentle
wedging action. Immediately following removal, the ingot was transferred into
a
quench chamber containing water, ensuring that the top of the ingot surface
was covered
by at least 6 inches of water. The ingot was allowed to stay in the quench
vessel for 6
hours prior to its removal from the quench vessel.
Note: An identical experimental program except for the use of pencil lamps --
which
provided a source of electromagnetic radiation to the third-body gases -- was
also
performed verifying the efficacy of the improved process (See 14-03-03 in
Table 1 and
attending discussions).
EXAMPLE 2:
EXPERIMENTAL PROCEDURE FOR COPPER Method "HA" RUN 14-02-06
A cylindrical alumina-based crucible (99.68% A12O3, 0.07% SiO2, 0.08% Fe2O3,
0.04% CaO, 0.12% Na2O3; 4.5 inches O.D. X 3.75 inches I.D. X 14.5 inches
depth) of a
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100 pound induction furnace reactor (Inductortherm) fitted with a 73-3 OR
Powertrak
power supply was charged with 9080 g copper (99.98% purity) through its
charging
port. The reactor was fitted with a graphite cap and a ceramic liner (i.e.,
the crucible,
from Engineering Ceramics). During the entire procedure, a slight positive
pressure of
nitrogen (-0.5 psig) was maintained in the reactor using a continuous
backspace purge.
The reactor was heated to the metal charge liquidus point plus at least 300 F,
at a rate
no greater than 300 F/hr, as limited by the integrity of the crucible. The
induction
furnace operated in the frequency range of 0 Hz to 3000 Hz, with frequency
determined
by a temperature-controlled feedback loop implementing an Omega Model CN3000
temperature controller. The temperature was increased to 2462 F again using a
rate no
greater than 300 F/hour. When this temperature was reached, graphite
saturation
assemblies (3/8 inch OD, 36 inch long high purity (<5 ppm impurities) graphite
rods)
were inserted to the bottom of the copper charge through ports located in the
top plate.
The copper was held at 2462 F for 2 hours. Every 30 minutes during the hold
period,
an attempt was made to lower the graphite saturation assemblies as dissolution
occurred. As the copper became saturated with carbon, the graphite saturation
assemblies were consumed. After the 2 hour hold period was complete, the
graphite
saturation assemblies were removed.
The reactor temperature was increased to 2539 F over 14 minutes. At this
point,
a gas addition lance was lowered into the molten metal to a position
approximately 2
inches from the bottom of the reactor and a 4.8 L/min flow of gas was begun.
The gas
composition was 92% argon, 3% neon, and 5% helium. The temperature was then
lowered to 2515 F over 10 minutes. Flow rate was then lowered to 2.4 L/min
with the
same ratio of gases (argon, neon, and helium). The temperature was then varied
between 2476 F and 2515 F for 15 cycles. Each cycle consisted of raising the
temperature continuously over 7 minutes and lowering the temperature
continuously
over 7 minutes. After the 15 cycles were completed, the gas flow rate was
altered again
to 1.4 L/min (all gas compositions are constant unless stated otherwise). The
temperature of the copper was varied over another 5 cycles between 2476 F and
2515 F. After the fifth cycle, the reactor temperature was lowered to 2462 F
over a 30
minute period with a lowered gas addition rate of 0.8 L/min.
The graphite saturation assemblies were reinstalled in the copper and remained
there for 1 hour. The graphite saturation assemblies were removed. Flow rate
was
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increased to 1.2 L/min. The reactor temperature was lowered to 2459 F over 5
minutes.
The reactor was held at this temperature for 5 minutes with continued gas
addition.
The temperature was then varied between 2453 F and 2459 F over 20 cycles. Each
cycle consisted of lowering the temperature continuously over 9 minutes and
raising the
temperature continuously over 9 minutes. During the temperature lowering
portion of
the cycle, gas addition was at the rate of 1.4 L/min with a gas composition of
95%
argon, 3% neon, 2% krypton. During the temperature increasing portion of the
cycle,
gas addition was at the rate of 2.8 L/min with a gas composition of 95% argon,
5%
neon. After the 20th cycle, third body addition (gas addition) was changed to
a flow rate
of 0.15 L/min with a gas composition of 95% helium, 5% krypton. The bath was
then
cooled to 2450 F over 13 minutes.
The temperature was then varied between 2441 F and 2450 F over 4.5 cycles.
Each cycle consisted of lowering the temperature continuously over 5 minutes
and
raising the temperature continuously over 3 minutes. In addition, while
raising the
temperature, a 1.2 L/min flow of 95% helium, 5% krypton was added, and while
lowering the temperature, a 2.4 L/min flow of 95% argon, 5% neon was added.
After
the 4.5 cycles, the reactor temperature was lowered to 2438 F over 1 minute.
The
temperature was varied between 2406 F and 2438 F for 15.5 cycles. Each cycle
consisted of lowering the temperature continuously over 15 minutes and raising
the
temperature continuously over 15 minutes. In addition, while raising the
temperature, a
1.2 L/min flow of 95% nitrogen, 5% helium was added, and while lowering the
temperature, a 2.4 L/min flow of 95% argon, 5% neon was added. After the final
cycle
(sweep), gas flow was changed to 0.15 L/min with a gas composition of 95%
helium,
5% argon. The reactor was then held for 16 minutes at 2406 F.
The temperature was then varied between 2419 F and 2406 F for one cycle.
The cycle consisted of raising the temperature continuously over 15 minutes
and
lowering the temperature continuously over 15 minutes. In addition, while
raising the
temperature, a 2.4 L/min flow of 95% helium, 5% argon was added, and while
lowering
the temperature, a 1.2 L/min flow of 95% argon, 5% nitrogen was added. At the
completion of this temperature sweep, the reactor temperature was lowered to
Tsolidus
plus 10 F.
The gas addition lance was relocated into the headspace of the reactor, such
that
a quarter inch (1/4 inches) dimple could be observed on the bath surface (1.2
L/min
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flow of 95% argon, 5% nitrogen). The bath was held at TS Iidus plus 10 F for
an
additional 5 minutes for conditioning and equilibrization. The reactor was
then cooled
to Ts Iiaus plus 8 F while maintaining a temperature lowering rate of no more
than 3 F/hr.
Upon reaching TS Iidus plus 8 F a manual power pulse of 2 kW was introduced
with a
single continuous up/down sweep from normal holding power. The reactor was
then
cooled to T, Iidus plus 2 F while maintaining a temperature lowering rate of
no more than
3 F/hr. Upon reaching T, Itdus plus 2 F a manual power pulse of 1.5 kW was
introduced
with a single continuous up/down sweep from normal holding power. The reactor
was
then cooled to TS Iidus again maintaining a temperature lowering rate of no
more than
3 F/hr. Upon reaching TS Itaus, the induction furnace power supply was lowered
to 1 kW
and the reactor was allowed to cool from Tsoiidus to Ts Iidus minus 20 F. Upon
reaching
TS Iidus minus 20 F, the induction furnace power supply was lowered to 0.75 kW
and the
reactor was allowed to cool to 1000 F. Upon reaching 1000 F, the induction
furnace
power supply was lowered to 0.50 kW and the reactor was allowed to cool to 350
F.
Immediately after setting the power to 0.5 kW, the gas flow rate was changed
to 0.15
L/min with a gas composition of 95% argon, 5% nitrogen. Upon reaching 350 F,
the
induction furnace power supply was shut down. Thirty minutes were allowed to
pass.
The ingot and crucible were removed from the reactor using titanium metal
tongs in the
presence of light supplied by metal halide ceiling lamps.
Upon removal, the crucible was stripped fr om the metal ingot via a gentle
wedging action. Immediately following removal, the ingot was transferred into
a
quench chamber containing deionized water, ensuring that the top of the ingot
surface
was covered by at least 6 inches of DI water. Upon entrance into the quench
chamber, a
timer was established. At a time of 10 hours and 30 minutes, the ingot was
removed
from the quench system using the titanium metal tongs and transferred to a
clean
surface. Exposure to external radiation sources included the metal halide
light and
placement directly under a skylight (which added filtered sunlight to the
irradiation
sources). The timer was then reset to zero. The ingot was irradiated for 10
minutes at
which point an additional radiation source (krypton lamp) was initiated. At 18
minutes,
two orthogonal fluorescent lamp racks were turned on. At 30 minutes, two
angled
metal halide lights were simultaneously turned on. At this point the timer was
again
reset. At a time of 6 hours, the krypton lamp, two orthogonal fluorescent lamp
racks,
and the two angled metal halide lights were sequentially turned off. The timer
was
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again reset to zero. At a time of 6 hours, 30 minutes, normal lab lighting
(metal halides)
was turned off. The timer was reset to zero. For 48 hours, the ingot was
allowed to
stabilize with no manual intervention (i.e., no handling).
EXAMPLE 3:
EXPERIMENTAL PROCEDURE FOR ALUMINIUM Method "HA" RUN 14-04-
02
A cylindrical alumina-based crucible (99.68% A12O3, 0.07% SiO2, 0.08% Fe2O3,
0.04% CaO, 0.12%Na203; 4.5 inches O.D. X 3.75 inches I.D. X 14.5 inches depth)
of a
100 pound induction furnace reactor (Inductortherm) fitted with a 73-3 OR
Powertrak
power supply was charged with 4540 g Aluminum (99.99% purity) through its
charging
port. The reactor was fitted with a graphite cap and a ceramic liner (i.e.,
the crucible,
from Engineering Ceramics). During the entire procedure, a slight positive
pressure of
nitrogen (-'0.5 psig) was maintained in the reactor using a continuous
backspace purge.
The reactor was heated to the metal charge liquidus point plus at least 300 F,
at a rate
no greater than 300 F/hr, as limited by the integrity of the crucible. The
induction
furnace operated in the frequency range of 0 Hz to 3000 Hz, with frequency
determined
by a temperature-controlled feedback loop implementing an Omega Model CN3000
temperature controller. The temperature was increased to 1650 F again using a
rate no
greater than 300 F/hour. When this temperature was reached, graphite
saturation
assemblies (3/8 inch OD, 36 inch long high purity (<5 ppm impurities) graphite
rods)
were inserted to the bottom of the aluminum charge through ports located in
the top
plate. The aluminum was held at 1650 F for 2 hours. Every 30 minutes during
the hold
period, an attempt was made to lower the graphite saturation assemblies as
dissolution
occurred. As the aluminum became saturated with carbon, the graphite
saturation
assemblies were consumed. After the 2 hour hold period was complete, the
graphite
saturation assemblies were removed.
The reactor temperature was increased to 1690 F over 14 minutes. At this
point,
a gas addition lance was lowered into the molten metal to a position
approximately 2
inches from the bottom of the reactor and a 4.8 L/min flow of gas was begun.
The gas
composition was 92% argon, 3% neon, and 5% helium. The temperature was then
lowered to 1678 F over 10 minutes. Flow rate was then lowered to 2.4 L/min
with the
same ratio of gases (argon, neon, and helium). The temperature was then varied
between 1657 F and 1678 F for 15 cycles. Each cycle consisted of raising the
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temperature continuously over 7 minutes and lowering the temperature
continuously
over 7 minutes. After the 15 cycles were completed, the gas flow rate was
altered again
to 1.4 L/min (all gas compositions are constant unless stated otherwise). The
temperature of the aluminum was varied over another 5 cycles between 1657 F
and
1678 F. After the fifth cycle, the reactor temperature was lowered to 1650 F
over a 30
minute period with a lowered gas addition rate of 0.8 L/min.
The graphite saturation assemblies were reinstalled in the aluminum and
remained there for 1 hour. The graphite saturation assemblies were removed.
Flow rate
was increased to 1.2 L/min. The reactor temperature was lowered to 1648 F over
5
minutes. The reactor was held at this temperature for 5 minutes with continued
gas
addition. The temperature was then varied between 1646 F and 1644 F over 20
cycles.
Each cycle consisted of lowering the temperature continuously over 9 minutes
and
raising the temperature continuously over 9 minutes. During the temperature
lowering
portion of the cycle, gas addition was at the rate of 1.4 L/min with a gas
composition of
95% argon, 3% neon, 2% krypton. During the temperature increasing portion of
the
cycle, gas addition was at the rate of 2.8 L/min with a gas composition of 95%
argon,
5% neon. After the 20th cycle, third body addition (gas addition) was changed
to a flow
rate of 0.15 L/min with a gas composition of 95% helium, 5% krypton. The bath
was
then cooled to 1643 F over 13 minutes.
The temperature was then varied between 1639 F and 1643 F over 4.5 cycles.
Each cycle consisted of lowering the temperature continuously over 5 minutes
and
raising the temperature continuously over 3 minutes. In addition, while
raising the
temperature, a 1.2 L/min flow of 95% helium, 5% krypton was added, and while
lowering the temperature, a 2.4 L/min flow of 95% argon, 5% neon was added.
After
the 4.5 cycles, the reactor temperature was lowered to 1637 F over 1 minute.
The
temperature was varied between 1620 F and 1637 F for 15.5 cycles. Each cycle
consisted of lowering the temperature continuously over 15 minutes and raising
the
temperature continuously over 15 minutes. In addition, while raising the
temperature, a
1.2 L/min flow of 95% nitrogen, 5% helium was added, and while lowering the
temperature, a 2.4 L/min flow of 95% argon, 5% neon was added. After the final
cycle
(sweep), gas flow was changed to 0.15 L/min with a gas composition of 95%
helium,
5% argon. The reactor was then held for 16 minutes at 1620 F.
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The temperature was then varied between 1627 F and 1620 F for one cycle.
The cycle consisted of raising the temperature continuously over 15 minutes
and
lowering the temperature continuously over 15 minutes. In addition, while
raising the
temperature, a 2.4 L/min flow of 95% helium, 5% argon was added, and while
lowering
the temperature, a 1.2 L/min flow of 95% argon, 5% nitrogen was added. At the
completion of this temperature sweep, the reactor temperature was lowered to
Tsoiidus
plus 10 F.
The gas addition lance was relocated into the headspace of the reactor, such
that
a quarter inch (1/4 inches) dimple could be observed on the bath surface (1.2
L/min
flow of 95% argon, 5% nitrogen). The bath was held at Tsolidus plus 10 F for
an
additional 5 minutes for conditioning and equilibration. The reactor was then
cooled to
Tsolidus plus 8 F while maintaining a temperature lowering rate of no more
than 3 F/hr.
Upon reaching Tsoiidus plus 8 F a manual power pulse of 2 kW was introduced
with a
single continuous up/down sweep from normal holding power. The reactor was
then
cooled to Tsolidus plus 2 F while maintaining a temperature lowering rate of
no more than
3 F/hr. Upon reaching Tsolidus plus 2 F a manual power pulse of 1.5 kW was
introduced
with a single continuous up/down sweep from normal holding power. The reactor
was
then cooled to T,ofidus again maintaining a temperature lowering rate of no
more than
3 F/hr. Upon reaching Tsolidus, the induction furnace power supply was lowered
to 1 kW
and the reactor was allowed to cool from Tsolidus to Ts fidus minus 20 F. Upon
reaching
Tsolidu, minus 20 F, the induction furnace power supply was lowered to 0.75 kW
and the
reactor was allowed to cool to 1000 F. Upon reaching 1000 F, the induction
furnace
power supply was lowered to 0.50 kW and the reactor was allowed to cool to 350
F.
Immediately after setting the power to 0.5 kW, the gas flow rate was changed
to 0.15
L/min with a gas composition of 95% argon, 5% nitrogen. Upon reaching 350 F,
the
induction furnace power supply was shut down. Thirty minutes were allowed to
pass.
The ingot and crucible were removed from the reactor using titanium metal
tongs in the
presence of light supplied by metal halide ceiling lamps.
Upon removal, the crucible was stripped from the metal ingot via a gentle
wedging action. Immediately following removal, the ingot was transferred into
a
quench chamber containing deionized water, ensuring that the top of the ingot
surface
was covered by at least 6 inches of DI water. Upon entrance into the quench
chamber, a
timer was established. At a time of 10 hours and 30 minutes, the ingot was
removed
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from the quench system using the titanium metal tongs and transferred to a
clean
surface. Exposure to external radiation sources included the metal halide
light and
placement directly under a skylight (which added filtered sunlight to the
irradiation
sources). The timer was then reset to zero. The ingot was irradiated for 10
minutes at
which point an additional radiation source (krypton lamp) was initiated. At 18
minutes,
two orthogonal fluorescent lamp racks were turned on. At 30 minutes, two
angled
metal halide lights were simultaneously turned on. At this point the timer was
again
reset. At a time of 6 hours, the krypton lamp, two orthogonal fluorescent lamp
racks,
and the two angled metal halide lights were sequentially turned off. The timer
was
again reset to zero. At a time of 6 hours, 30 minutes, normal lab lighting
(metal halides)
was turned off. The timer was reset to zero. For 48 hours, the ingot was
allowed to
stabilize with no manual intervention (i.e., no handling).
EXAMPLE 4:
EXPERIMENTAL PROCEDURE FOR COBALT, VANADIUM, RHENIUM
Method "HD" RUN 14-01-20
A cylindrical alumina-based crucible (99.68% A1203, 0.07% Si02, 0.08% Fe203,
0.04% CaO, 0.12% Na203i 4.5 inches O.D. X 3.75 inches I.D. X 14.5 inches
depth) of a
100 pound induction furnace reactor (Inductotherm) fitted with a 73-30R
Powertrak
power supply. A gas addition lance was installed to a position approximately
1/4 inches
from the bottom of the reactor. The reactor was charged with 8899 g cobalt
(99.5%
purity), 182 g vanadium (99.5% purity) and 7 g rhenium (99.997% purity)
through its
charging port. The reactor was fitted with a graphite cap and a ceramic liner
(i.e., the
crucible, from Engineering Ceramics). During the entire procedure, a slight
positive
pressure of 97% argon, 3% hydrogen (-0.5 psig) was maintained in the reactor
using a
continuous backspace purge. Bypass injection of gas addition was commenced
(i.e., gas
flow diverted around the reactor was initiated) at a rate of 0.15 L/min of
argon. The
incoming gas line for the gas addition lance passes through a sealed, light-
tight
enclosure whereby irradiation of the gas with precise radiation sources (e.g.,
wavelength, intensity, etc) could be achieved. When the entire gas line had
been
completely purged (assuming a plug flow model), a neon radiation source was
activated
within the sealed enclosure. A timer was set to zero. Bypass flow was adjusted
to
100% argon at a flow rate of 0.15 L/min with trace neon present (trace can be
defined as
< 0.005% vol. to < 5%). At a time of 3 minutes, an argon radiation source was
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WO 2007/106094 PCT/US2006/009560
activated within the sealed enclosure. After completion of another gas line
purge
(assuming a plug flow model), the gas line was switched from bypass to direct
injection
through the gas addition lance.
The induction furnace power was then initiated. The reactor was heated to
450 F, at a rate no greater than 300 F/hr, as limited by the integrity of the
crucible. The
induction furnace operated in the frequency range of 0 Hz to 3000 Hz, with
frequency
determined by a temperature-controlled feedback loop implementing an Omega
Model
CN3000 temperature controller. Upon reaching 450 F, the gas addition lance was
repositioned to 2 inches from the bottom of the reactor. The timer was again
set to zero.
At a time of 2 minutes, the gas composition was changed to 0.15 L/min of 66%
nitrogen, 34% hydrogen with trace neon present. After completion of another
gas line
purge (assuming a plug flow model), a krypton radiation source was initiated
in the
sealed enclosure. Continue reactor heat up at a rate no greater than 300 F/hr,
as limited
by the integrity of the crucible, until TS iidus minus 30 F was achieved. The
gas flow rate
was then increased to 0.3 L/min with a constant gas composition. At Ts lidus a
second
argon radiation source was activated within the sealed enclosure. Approach TS
lidus plus
8 F over a 3 to 5 minute time span. From TS iidus plus 8 F to Tsolidus plus 15
F, reduce the
gas flow rate to 0.15 L/min with a constant gas composition. Immediately upon
reaching TS lidus plus 15 F, a second neon radiation source was initiated in
the sealed
enclosure. Immediately after the second neon radiation source was initiated,
the gas
composition was adjusted to 75% hydrogen, 22% nitrogen, 3% argon and trace
neon.
The molten bath was held at this condition for 5 minute for stabilization.
After the 5 minute hold, the gas composition was adjusted to 20% helium, 63%
nitrogen, 17% argon, and trace neon. The bath was held under these conditions
for an
additional 15 minutes. Again, following the hold, the gas composition and flow
rate
were adjusted to 100% argon with trace neon at a rate of 0.3 L/min. The
reactor was
held at this condition for 3 minutes. The timer was reset to zero. At a time
of 65
minutes, graphite saturation assemblies (3/8 inches OD, 36 inches long high
purity (<5
ppm impurities) graphite rods) were inserted to the bottom of the cobalt alloy
charge
through ports located in the top plate. The cobalt was heated to 2504 F over a
one hour
period. The bath was then held at this condition for 2 hours. Every 30 minutes
during
the hold period, an attempt was made to lower the graphite saturation
assemblies as
dissolution occurred. As the cobalt became saturated with carbon, the graphite
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saturation assemblies were consumed. After the 2 hour hold period was
complete, the
graphite saturation assemblies were removed. An additional 47 grams of
graphite
powder was charged into the reactor through the charging port. The bath was
then
heated to 3194 F over three hours. Upon achieving 3194 F, the gas composition
and
flow rate were adjusted to 100% nitrogen with trace neon at a rate of 0.3
L/min. Hold
reactor conditions for five minutes. Reduce the gas flow rate to 0.15 L/min
with
constant composition. Immediately following this reduction in gas flow, the
krypton
radiation source in the sealed enclosure was turned off. The timer was reset
to zero. At
a time of 3 minutes, the gas flow rate was reduced to 37.5 ml/min with
constant
composition. One of the argon radiation sources inside the sealed enclosure
was turned
off. At a time of 5 minutes, the nitrogen component of the gas flow was
discontinued,
while maintaining the flow of trace neon. At a time of 10 minutes, remotely
rotate one
of the neon radiation sources within the sealed enclosure. The reactor
temperature was
lowered to 3064 F over 7 minutes.
The temperature was then varied between 2851 F and 3064 F for 16 cycles.
Each cycle consisted of raising the temperature continuously over 7 minutes
and
lowering the temperature continuously over 7 minutes. After completion of the
14.5
cycles, argon was reintroduced at a flow rate of 0.15 L/min with trace neon.
Five
minutes into the 15th cycle, a xenon radiation source was activated within the
sealed
enclosure. At 6 minutes into the 15th cycle, a long wave ultraviolet radiation
source was
activated in the sealed enclosure. At sweep count 15.5, a short wave
ultraviolet
radiation source was initiated in the sealed enclosure. At sweep count 16,
remotely
rotate the xenon radiation source within the sealed enclosure. The temperature
of the
cobalt was varied over another 5 cycles between 2851 F and 3064 F. After the
fifth
cycle, the reactor temperature was lowered to 2775 F over a 10 minute period.
Upon
achieving the target temperature of 2775, the graphite saturation assemblies
were
reinstalled in the cobalt and remained there for 1 hour. The graphite
saturation
assemblies were then removed.
Two voltage probes (source and ground probe) were then installed in the
headspace of the reactor and allowed to equilibrate for 5 minutes. Upon
completion of
the five minute hold the voltage probes were lowered into the bath. The source
probe
should be positioned 2 inches below the axial center and 1 inch from the
radial center.
The ground probe was positioned 0.75 inches above the axial position of the
source
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probe and 1 inch from the radial center (180 from the source probe). Once the
probes
are installed a five minute hold at this condition is done to allow the bath
to
electronically equilibrate with the probes. Voltage was then applied to the
probes and
varied between multiple voltage set points. This voltage application was in a
continuous up/down sweep between two predetermined voltages. The first voltage
cycle was varied between 17 and 18 volts for 24 cycles. Each cycle consisted
of raising
the voltage continuously over 45 seconds and lowering the voltage continuously
over 45
seconds. The second voltage cycle was varied between 13.25 and 14.75 volts for
20
cycles. Each cycle consisted of raising the voltage continuously over 45
seconds and
lowering the voltage continuously over 45 seconds. The third voltage cycle was
varied
between 8.75 and 10.25 volts for 17 cycles. Each cycle consisted of raising
the voltage
continuously over 45 seconds and lowering the voltage continuously over 45
seconds.
The fourth voltage cycle was varied between 4.00 and 7.00 volts for 14 cycles.
Each
cycle consisted of raising the voltage continuously over 45 seconds and
lowering the
voltage continuously over 45 seconds. The fifth voltage cycle was varied
between 1.50
and 5.00 volts for 10 cycles. Each cycle consisted of raising the voltage
continuously
over 45 seconds and lowering the voltage continuously over 45 seconds. The
sixth
voltage cycle was varied between 0.50 and 2.00 volts for 3 cycles. Each cycle
consisted
of raising the voltage continuously over 45 seconds and lowering the voltage
continuously over 45 seconds. When the final cycle was completed the voltage
was set
onto a constant 1 volt setting. This voltage remained constant until a later
step during
which the leads were removed.
The reactor temperature was then lowered to 2759 F over 5 minutes. The
reactor was held at this temperature for 5 minutes with continued gas
addition. The
temperature was then varied between 2727 F and 2759 F over 20 cycles. Each
cycle
consisted of lowering the temperature continuously over 9 minutes and raising
the
temperature continuously over 9 minutes. After the 20th cycle, third body gas
addition
was changed by turning off the argon component of the gas leaving only trace
neon gas
flow. The bath was then cooled to 2711 F over 5 minutes. Upon reaching 2711 F,
one
of the neon radiation sources within the sealed enclosure was remotely
rotated.
The temperature was then varied between 2662 F and 2711 F over 4.5
cycles. Each cycle consisted of lowering the temperature continuously over 5
minutes and raising the temperature continuously over 3 minutes. In addition,
while
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raising the temperature, a 0.15 L/min flow of 60% argon, 40% helium, and trace
neon was added, and while lowering the temperature, a 0.3 L/min flow of 100%
helium, trace neon, and trace krypton was added. At sweep count 0.5, a krypton
radiation source was initiated in the sealed enclosure. At sweep count 1.0, an
argon
radiation source was initiated in the sealed enclosure. At sweep count 4.5,
the short
wave ultraviolet radiation source was terminated in the sealed enclosure. The
reactor temperature was lowered to 2645 F over 5 minutes. The temperature was
varied between 2467 F and 2645 F for 15.5 cycles. Each cycle consisted of
lowering the temperature continuously over 15 minutes and raising the
temperature
continuously over 15 minutes. In addition, while raising the temperature, a
0.15
L/min flow of 60% argon, 40% helium, and trace neon was added, and while
lowering the temperature, a 0.3 L/min flow of 100% helium, trace neon, and
trace
krypton was added. After the 15.5th cycle, third body gas addition was changed
by
turning off all gas components except the trace neon gas flow.
After the 15.5th cycle, a timer was established. At a time of 3 minutes, the
xenon
radiation source within the sealed enclosure was remotely rotated. The timer
was then
reset to zero. At 60 minutes, flow rates were adjusted to 0.3 L/min of 100%
argon and
trace neon. At 65 minutes, flow rates were adjusted to 3.0 ml/min of 60%
argon, 40%
helium, and trace neon. Immediately after the flow was adjusted, one of the
neon
radiation sources within the sealed enclosure was remotely rotated. At 68
minutes, flow
rates were adjusted to 0.15 L/min of 100% helium, trace neon and trace
krypton. At 68
minutes 20 seconds, the 1 volt power was brought to zero output and the
voltage power
leads removed from the voltage probes. At 68 minutes 30 seconds, the long wave
ultraviolet radiation source was turned off in the sealed enclosure. At 71
minutes 15
seconds, the voltage probes were repositioned to three inches above the bath
surface.
At 75 minutes, the source and ground probe were completely removed from the
reactor.
After the voltage probes had been removed from the reactor, flow rates were
adjusted to 0.15 L/min of 77% argon, 18% nitrogen, 5% helium and trace neon.
The
reactor was then held at temperature and flow rate for 15 minutes. After the
15 minute
hold, an argon radiation source was turned off in the sealed enclosure. The
flow rates
were immediately readjusted to 0.15 L/min of 77% argon, 12% nitrogen, 11%
helium
and trace neon. The reactor was then held at temperature and flow rate for 25
minutes.
After the 25 minute hold, the krypton radiation source was turned off in the
sealed
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enclosure. The flow rates were immediately readjusted to 0.30 L/min of 10%
argon,
90% helium and trace neon. The reactor was then held at temperature and flow
rate for
3 minutes. After the 3 minute hold, flow rates were adjusted to 0.15 L/min of
10%
argon, 90% helium and trace neon and held for 2 minutes. After the 2 minute
hold,
flow rates were adjusted to 0.30 L/min of 7% hydrogen, 93% nitrogen and trace
neon
and held for 10 minutes. After the 10 minute hold, flow rates were adjusted to
0.15
L/min of 7% hydrogen, 93% nitrogen and trace neon and held for 3 minutes.
After the
3 minute hold, flow rates were adjusted to 30 ml/min of 7% hydrogen, 93%
nitrogen
and trace neon and held for 2 minutes. After the 2 minute hold, flow rates
were
adjusted to 0.15 L/min of 87% argon, 10% nitrogen, 3% helium and trace neon
and held
for 5 minutes. After the 5 minute hold, flow rates were adjusted to 0.6 L/min
of 90%
argon, 10% nitrogen and trace neon and held for 7 minutes. After the 7 minute
hold,
flow rates were adjusted to 30 ml/min of 90% argon, 10% nitrogen and trace
neon and
held for 2 minutes. After the 2 minute hold, flow rates were adjusted to 0.60
L/min of
95% argon, 5% nitrogen and trace neon and held for 15 minutes. After the 15
minute
hold, flow rates were adjusted to 0.30 L/min of 95% argon, 5% nitrogen and
trace neon
and held for 5 minutes.
The reactor temperature was then lowered to 2541 F over 21 minutes. The
temperature was then varied between 2467 F and 2541 F for three cycles. The
cycles
consisted of raising the temperature continuously over 27 minutes and lowering
the
temperature continuously over 27 minutes. After the third cycle, the bath was
held at
2541 F for 5 minutes. The reactor temperature was then lowered to 2467 F over
2
minutes 30 seconds. The temperature was then varied between 2541 F and 2467 F
for
two cycles. The cycles consisted of raising the temperature continuously over
11
minutes and lowering the temperature continuously over 7 minutes.
After the completion of the 2nd cycle, the induction power supply was placed
into manual control. The power was then instantaneously increased 5 kW above
the
steady state power level and immediately upon hitting the 5kW increase the
power was
instantaneously decreased back to the steady state power level. The power
level was
then varied up 3.7 kW and down 3.7 kW over 6 cycles. The cycles consisted of
raising
power 3.7 kW above the steady state power level over 25 seconds. Once raised,
the
power level was held at the additional 3.7 kW setting for 45 seconds.
Following the 45
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second hold, the power was lowered back to the steady state power level over a
15
second time frame.
After the 6t'' power cycle, the gas flows were adjusted to 0.60 L/min of 100%
argon and trace neon and held for 7 minutes. Following the seven minute hold,
the
argon flow was secured leaving only the trace neon flow. Once the argon flow
was
secured, a second lance was positioned inside the reactor. This lance was
placed at a
distance 2/3 from the radial center and 1.5 inches from the bottom of the
bath. The
centerline lance was then repositioned to t/4 inch from the bottom. Once the
centerline
lance was repositioned, flow was started in the off-centerline lance at a rate
of 30
mlhnin of 100% argon and trace neon. A timer was initiated. At a time of 2
minutes,
the trace neon flow in the centerline lance was secured. At a time of 2
minutes 30
seconds, flow was initiated in the centerline lance at a flow rate of 30
ml/min of 100%
carbon monoxide and held for 3 minutes. After the 3 minute hold, flow rates
were
adjusted in the off-centerline lance to 0.15 L/min of 100% argon and trace
neon and
held for 15 minutes. After the 15 minute hold, flow rates were adjusted in the
off-
centerline lance to trace neon only. Furthermore, the flow rate was adjusted
in the
centerline lance to 0.60 L/min of 100% carbon monoxide and held for 10
minutes.
After the 10 minute hold, the carbon monoxide in the centerline lance was
secured. The
reactor temperature was then lowered to Ts Iidus plus 18 F over 30 minutes.
Upon
reaching the Tsolidus plus 18 F, flow was adjusted in the centerline lance to
0.30 L/min of
100% carbon monoxide and held for 20 minutes. After the 20 minute hold, all
now was
secured in the centerline lance and the lance was removed.
After the centerline lance was removed, adjust flow rates in the off-
centerline
lance to 30 ml/min of 88% argon, 12% nitrogen and trace neon, and held for 3
minutes.
After the 3 minute hold, flow rates were adjusted to 0.30 L/min of 25% helium,
75%
argon and trace neon and held for 10 minutes. After the 10 minute hold, flow
rates were
adjusted to 0.30 L/min of 88% argon, 12% nitrogen and trace neon and held for
10
minutes. After the 10 minute hold, flow rates were adjusted to 0.15 L/min of
88%
argon, 12% nitrogen and trace neon and held for 5 minutes. After the 5 minute
hold,
flow rates were adjusted to 30 ml/min of 88% argon, 12% nitrogen and trace
neon and
held for 2 minutes. After the 2 minute hold, flow rates were adjusted to 0.15
L/min of
88% argon, 12% nitrogen and trace neon. Once the flow rates were adjusted, the
reactor
temperature was lowered to Ts Iidus plus 15 F over 45 minutes. Upon reaching
the T, lidus
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plus 15 F, flow was adjusted in the off-centerline lance to 0.30 L/min of 100%
argon
and trace neon and held for 5 minutes.
At the completion of the five minute hold, the reactor temperature was lowered
to TS iidus plus 11 F while maintaining a temperature lowering rate of no more
than
3 F/hr. Upon reaching Ts lidus plus 11 F, adjust flow rate in the off-
centerline lance to
0.30 L/min of 100% hydrogen and trace neon. At the completion of flow
adjustment,
the reactor temperature was lowered to TS udus plus 10 F while maintaining a
temperature lowering rate of no more than 3 F/hr. Upon reaching TS lidus plus
10 F,
adjust flow rate in the off-centerline lance to 30 ml/min of 100% hydrogen and
trace
neon. At the completion of flow adjustment, the reactor temperature was
lowered to
Ts lidus plus 9 F while maintaining a temperature lowering rate of no more
than 3 F/hr.
Upon reaching TS iidus plus 9 F, the gas addition lance was relocated into the
headspace
of the reactor, such that a quarter inch dimple (e.g., a quarter inch
depression) could be
observed on the bath surface. The bath was held at TS lidus plus 9 F for an
additional 5
minutes for conditioning and equilibration. The reactor was then cooled to TS
iidus plus
8 F while maintaining a temperature lowering rate of no more than 3 F/hr. Upon
reaching TS udus plus 8 F a manual power pulse of 2 kW was introduced with a
single
continuous up/down sweep from normal holding power. The reactor was then
cooled to
TS lidu, plus 2 F while maintaining a temperature lowering rate of no more
than 3 F/hr.
Upon reaching TS lidus plus 2 F a manual power pulse of 1.5 kW was introduced
with a
single continuous up/down sweep from normal holding power. Immediately after
the
1.5 kW power pulse, flow was adjusted in the off-centerline lance to 0.15
L/min of 50%
hydrogen, 50% helium and trace neon. The reactor was then cooled to Ts iidus
again
maintaining a temperature-lowering rate of no more than 3 F/hr. Upon reaching
Ts tidus,
the induction furnace power supply was lowered to 1 kW and the reactor was
allowed to
cool from Tsoiidus to Ts iidus minus 75 F. Upon reaching TS iidus minus 75 F,
flow rate in
the off-centerline lance was adjusted to 30 ml/min of 60% helium, 40% hydrogen
and
trace neon. Following the flow adjustment, the induction furnace power supply
was
lowered to 0.75 kW and the reactor was allowed to cool to 1000 F. Upon
reaching
1000 F, flow rate in the off-centerline lance was adjusted to 30 ml/min of
100% helium
and trace neon. Following the flow adjustment, the induction furnace power
supply was
lowered to 0.50 kW and the reactor was allowed to cool to 350 F. Upon reaching
350 F, the induction furnace power supply was shut down and a timer initiated.
At time
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of 5 minutes, flow rate in the off-centerline lance was adjusted to 0.60 L/min
of 100%
helium and trace neon. At time of 9 minutes, a neon radiation source within
the sealed
enclosure was remotely rotated. Upon completion of the rotation, flow in the
off-
centerline lance was adjusted to 0.30 L/min of 88% argon, 12% nitrogen and
trace neon.
Following the flow adjustment, the timer was reinitiated. At a time of 25
seconds, a neon radiation source within the sealed enclosure was remotely
rotated. At a
time of 1 minute 30 seconds, a neon radiation source within the sealed
enclosure was
terminated. At a time of 5 minutes an argon radiation source within the sealed
enclosure was terminated. At a time of 6 minute 30 seconds, flow rate was
adjusted to
0.30 L/min of 100% helium and trace neon. At a time of 7 minute, the second
neon
radiation source within the sealed enclosure was terminated.
The timer was reset to zero and restarted. At a time of 15 minutes, the trace
neon gas flow in the off-centerline lance was terminated. At a time of 17
minutes 25
seconds, the xenon radiation source within the sealed enclosure was remotely
rotated.
At a time of 30 minutes, the trace helium gas flow in the off-centerline lance
was
terminated. The timer was reset to zero and restarted. At a time of 15
minutes, the
xenon radiation source inside the sealed enclosure was terminated. Thirty
minutes were
allowed to pass. The ingot and crucible were removed from the reactor in the
presence
of radiation sources (metal halide light sources) utilizing titanium metal
tongs.
Upon removal, the crucible was stripped from the metal ingot via a gentle
wedging action. Immediately following removal, the ingot was transferred into
a
quench chamber containing deionized water, ensuring that the top of the ingot
surface
was covered by at least 6 inches of DI water. Upon entrance into the quench
chamber, a
timer was established. At a time of 2 hours 15 minutes, a long wave
ultraviolet
radiation source located above the quench vessel was initiated. At a time of 4
hours 7
minutes, a short wave ultraviolet radiation source located above the quench
vessel was
initiated. At a time of 5 hours 59 minutes 30 seconds the short wave
ultraviolet
radiation source located above the quench vessel was rotated to a tip up
position.
At a time of 6 hours, the ingot was removed from the quench system using the
titanium metal tongs and transferred to a clean radiation surface countertop.
Exposure
to external radiation sources included the metal halide light and placement
directly
under a skylight (which added filtered sunlight to the irradiation sources).
The ingot
was pat dried. Upon completion of the drying, the long wave ultraviolet
radiation
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source located above the quench vessel was rotated vertically and moved up 1
inch.
The timer was then reset to zero. The ingot was irradiated for 10 minutes at
which point
an additional radiation source (krypton lamp) was initiated. At 12 minutes 30
seconds,
the long wave ultraviolet radiation source located above the quench vessel was
rotated
to horizontal and moved down to its original position. At 13 minutes, a xenon
radiation
source located above the quench vessel was initiated. At 18 minutes, two
orthogonal
fluorescent lamp racks located next to the countertop were turned on. At 30
minutes,
two angled metal halide lights located next to the countertop were
simultaneously
turned on. At this point the timer was again reset. At 13 minutes 15 seconds,
a neon
radiation source located next to the countertop was turned on. At 15 minutes
30
seconds, an argon radiation source located next to the countertop was turned
on. At 23
minutes 45 seconds, the argon radiation source located next to the countertop
was
rotated to an angle of 35 . At 37 minutes 30 seconds the short wave
ultraviolet
radiation source located above the quench vessel was rotated to 35 . At 47
minutes 30
seconds, the xenon radiation source located above the quench vessel was
rotated to
horizontal. At 52 minutes 45 seconds, the long wave ultraviolet radiation
source
located above the quench vessel was rotated to 35 . At 58 minutes 30 seconds,
the short
wave ultraviolet radiation source located above the quench vessel was rotated
to 55 . At
77 minutes, the krypton radiation source located next to the countertop was
rotated to
vertical. At 89 minutes, the krypton radiation source located next to the
countertop was
rotated to 78 . At 97 minutes, the krypton radiation source located next to
the
countertop was rotated to 88 .
At this point the timer was again reset. At a time of 6 hours, the krypton
lamp,
short wave ultraviolet, long wave ultraviolet, argon (located over quench
vessel), xenon,
argon (located next to countertop), neon, two orthogonal fluorescent lamp
racks, and the
two angled metal halide lights were sequentially terminated in the given
order. The
timer was again reset. At a time of 6 hours, 30 minutes, normal lab lighting
(metal
halides) was turned off. The timer was reset. For 48 hours, the ingot was
allowed to
stabilize with no manual intervention (i.e., no handling).
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EXAMPLE 5:
EXPERIMENTAL PROCEDURE FOR NICKEL, RHENIUM Method "HD" RUN
14-01-21
A cylindrical alumina-based crucible (99.68% A1203, 0.07% Si02, 0.08% Fe2O3,
0.04% CaO, 0.12% Na203; 4.5 inches O.D. X 3.75 inches I.D. X 14.5 inches
depth) of a
100-pound induction furnace reactor (Inductotherm) fitted with a 73-30R
Powertrak
power supply. A gas addition lance was installed to a position approximately
1/4 inches
from the bottom of the reactor. The reactor was charged with 9080 g nickel
(99.9%
purity) and 5 g rhenium (99.997% purity) through its charging port. The
reactor was
fitted with a graphite cap and a ceramic liner (i.e., the crucible, from
Engineering
Ceramics). During the entire procedure, a slight positive pressure of 97%
argon, 3%
hydrogen (-0.5 psig) was maintained in the reactor using a continuous
backspace purge.
Bypass injection of gas addition was commenced (i.e., gas flow diverted around
the
reactor was initiated) at a rate of 0.15 L/min of argon. The incoming gas line
for the gas
addition lance passed through a sealed, light-tight enclosure whereby
irradiation of the
gas with precise radiation sources (e.g., wavelength, intensity, etc) was
achieved. When
the entire gas line had been completely purged (assuming a plug flow model), a
neon
radiation source was activated within the sealed enclosure. A timer was
initiated.
Bypass flow was adjusted to 100% argon at a flow rate of 0.15 L/min with trace
neon
present (trace can be defined as < 0.005% vol. to < 5%). At a time of 3
minutes, an
argon radiation source was activated within the sealed enclosure. After
completion of
another gas line purge (assuming a plug flow model), the gas line was switched
from
bypass to direct injection through the gas addition lance.
The induction furnace power was then initiated. The reactor was heated to
450 F, at a rate no greater than 300 F/hr, as limited by the integrity of the
crucible. The
induction furnace operated in the frequency range of 0 Hz to 3000 Hz, with
frequency
determined by a temperature-controlled feedback loop implementing an Omega
Model
CN3000 temperature controller. Upon reaching 450 F, the gas addition lance was
repositioned to 2 inches from the bottom of the reactor. The timer was
reinitiated. At a
time of 2 minutes, the gas composition was changed to 0.15 L/min of 66%
nitrogen,
34% hydrogen and trace neon. After completion of another gas line purge
(assuming a
plug flow model), a krypton radiation source was initiated in the sealed
enclosure. The
reactor continued to heat up at a rate no greater than 300 F/hr, as limited by
the integrity
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of the crucible, until TS lidus minus 30 F was achieved. The gas flow rate was
then
increased to 0.3 L/min with a constant gas composition. At TS lidus a second
argon
radiation source was activated within the sealed enclosure. Approach Ts lidus
plus 8 F
over a 3 to 5 minute time span. From Ts lidus plus 8 F to TS <<dus plus 15 F,
reduce the gas
flow rate to 0.15 L/min with a constant gas composition. Immediately upon
reaching
Ts lidus plus 15 F, a second neon radiation source was initiated in the sealed
enclosure.
Immediately after the second neon radiation source was initiated, the gas
composition
was adjusted to 75% hydrogen, 22% nitrogen, 3% argon, and trace neon. The
molten
bath was held at this condition for 5 minutes for stabilization.
After the 5-minute hold, the gas composition was adjusted to 20% helium, 63%
nitrogen, 17% argon, and trace neon. The bath was held under these conditions
for an
additional 15 minutes. Again, following the hold, the gas composition and flow
rate
were adjusted to 100% argon with trace neon at a rate of 0.3 L/min. The
reactor was
held at this condition for 3 minutes. The timer was reinitiated. At a time of
65 minutes,
graphite saturation assemblies (3/8 inches OD, 36 inches long high purity (<5
ppm
impurities) graphite rods) were inserted to the bottom of the nickel alloy
charge through
ports located in the top plate. The nickel was heated to 2540 F over a one-
hour period.
The bath was then held at this condition for 2 hours. Every 30 minutes during
the hold
period, an attempt was made to lower the graphite saturation assemblies as
dissolution
occurred. As the nickel became saturated with carbon, the graphite saturation
assemblies were consumed. After the 2-hour hold period was complete, the
graphite
saturation assemblies were removed. An additional 40 grams of graphite powder
was
charged into the reactor through the charging port. The bath was then heated
to 3390 F
over three hours. Upon achieving 3390 F, the gas composition and flow rate
were
adjusted to 100% nitrogen with trace neon at a rate of 0.3 L/min. The reactor
conditions
were held for 5 minutes and the gas flow rate was reduced to 0.15L/min with
constant
composition. Immediately following this reduction in gas flow, the krypton
radiation
source in the sealed enclosure was turned off. The timer was reinitiated. At a
time of 3
minutes, the gas flow rate was reduced to 37.5 ml/min with constant
composition. One
of the argon radiation sources inside the sealed enclosure was turned off. At
a time of 5
minutes, the nitrogen component of the gas flow was discontinued, while
maintaining
the flow of the trace neon. At a time of 10 minutes, one of the neon radiation
sources
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within the sealed enclosure was remotely rotated. The reactor temperature was
lowered
to 3193 F over 7 minutes.
The temperature was then varied between 2897 F and 3193 F for 16 cycles.
Each cycle consisted of raising the temperature continuously over 7 minutes
and
lowering the temperature continuously over 7 minutes. After completion of the
14.5
cycles, argon is reintroduced at a flow rate of 0.15 L/min with trace neon.
Five minutes
into the 15th cycle, a xenon radiation source was activated within the sealed
enclosure.
At 6 minutes into the 15th cycle, a long wave ultraviolet radiation source was
activated
in the sealed enclosure. At sweep count 15.5, a short wave ultraviolet
radiation source
was initiated in the sealed enclosure. At sweep count 16, remotely rotate the
xenon
radiation source within the sealed enclosure. The temperature of the nickel
was varied
over another 5 cycles between 2897 F and 3193 F. After the fifth cycle, the
reactor
temperature was lowered to 2800 F over a 60-minute period. Upon achieving the
target
temperature of 2800 F, the graphite saturation assemblies were reinstalled in
the nickel
and remained there for 1 hour. The graphite saturation assemblies were then
removed.
Two voltage probes (source and ground probe) were then installed in the
headspace of the reactor and allowed to equilibrate for 5 minutes. Upon
completion of
the five-minute hold, the voltage probes are lowered into the bath. The source
probe
was positioned 2 inches below the axial center and 1 inch from the radial
center. The
ground probe was positioned 0.75 inches above the axial position of the source
probe
and 1 inch from the radial center (180 from the source probe). Once the
probes were
installed, a five-minute hold at this condition was done to allow the bath to
electronically equilibrate with the probes. Voltage was then applied to the
probes and
varied between multiple voltage set points. This voltage was in a continuous
up/down
sweep between two predetermined voltages. The first voltage cycle was varied
between
17 and 18 volts for 24 cycles. Each cycle consisted of raising the voltage
continuously
over 45 seconds and lowering the voltage continuously over 45 seconds. The
second
voltage cycle was varied between 13.25 and 14.75 volts for 20 cycles. Each
cycle
consisted of raising the voltage continuously over 45 seconds and lowering the
voltage
continuously over 45 seconds. The third voltage cycle was varied between 8.75
and
10.25 volts for 17 cycles. Each cycle consisted of raising the voltage
continuously over
45 seconds and lowering the voltage continuously over 45 seconds. The fourth
voltage
cycle was varied between 4.00 and 7.00 volts for 14 cycles. Each cycle
consisted of
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raising the voltage continuously over 45 seconds and lowering the voltage
continuously
over 45 seconds. The fifth voltage cycle was varied between 1.50 and 5.00
volts for 10
cycles. Each cycle consisted of raising the voltage continuously over 45
seconds and
lowering the voltage continuously over 45 seconds. The sixth voltage cycle was
varied
between 0.50 and 2.00 volts for 3 cycles. Each cycle consisted of raising the
voltage
continuously over 45 seconds and lowering the voltage continuously over 45
seconds.
When the final cycle was completed the voltage was set onto a constant 1-volt
setting.
This voltage remained constant until a later step during which the leads were
removed.
The reactor temperature was then lowered to 2780 F over 5 minutes. The
reactor was held at this temperature for 5 minutes with continued gas
addition. The
temperature was then varied between 2741 F and 2780 F over 20 cycles. Each
cycle
consisted of lowering the temperature continuously over 9 minutes and raising
the
temperature continuously over 9 minutes. After the 20th cycle, turning off the
argon
component of the gas leaving only traces of neon gas flow changed third body
gas
addition. The bath was then cooled to 2722 F over 5 minutes. Upon reaching
2722 F,
one of the neon radiation sources within the sealed enclosure was remotely
rotated.
The temperature was then varied between 2664 F and 2722 F over 4.5 cycles.
Each cycle consisted of lowering the temperature continuously over 5 minutes
and
raising the temperature continuously over 3 minutes. In addition, while
raising the
temperature, a 0.15 L/min flow of 60% argon, 40% helium, and trace neon was
added,
and while lowering the temperature, a 0.3 L/min flow of 100% helium, trace
neon, and
trace krypton was added. At sweep count 0.5, a krypton radiation source was
initiated
in the sealed enclosure. At sweep count 1.0, an argon radiation source was
initiated in
the sealed enclosure. At sweep count 4.5, a short wave ultraviolet radiation
source was
terminated in the sealed enclosure. The reactor temperature was lowered to
2645 F
over 5 minutes. The temperature was varied between 2451 F and 2645 F for 15.5
cycles. Each cycle consisted of lowering the temperature continuously over 15
minutes
and raising the temperature continuously over 15 minutes. In addition, while
raising the
temperature, a 0.15 L/min flow of 60% argon, 40% helium, and trace neon was
added,
and while lowering the temperature, a 0.3 L/min flow of 100% helium, trace
neon, and
trace krypton was added. After the 15.5th cycle, turning off all gas
components except
the trace neon gas flow changed third body gas addition.
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After the 15.5th cycle, a timer was initiated. At a time of 3 minutes, the
xenon
radiation source within the sealed enclosure was remotely rotated. The timer
was
reinitiated. At 60 minutes, flow rates were adjusted to 0.3 L/min of 100%
argon and
trace neon. At 65 minutes, flow rates were adjusted to 3.0 ml/min of 60%
argon, 40%
helium, and trace neon. Immediately after the flow was adjusted, remotely
rotate one of
the neon radiation sources within the sealed enclosure. At 68 minutes, flow
rates were
adjusted to 0.15 L/min of 100% helium, trace neon and trace krypton. At 68
minutes 20
seconds, the 1-volt power was brought to zero output and the voltage power
leads
removed from the voltage probes. At 68 minutes 30 seconds, the long wave
ultraviolet
radiation source was turned off in the sealed enclosure. At 71 minutes 15
seconds,
reposition the voltage probes to three inches above the bath surface. At 75
minutes,
remove the source and ground probes completely from the reactor.
After the voltage probes had been removed from the reactor, flow rates were
adjusted to 0.15 L/min of 77% argon, 18% nitrogen, 5% helium, and trace neon.
The
reactor was then held at temperature and flow rate for 15 minutes. After the
15-minute
hold, an argon radiation source was turned off in the sealed enclosure. The
flow rates
were immediately readjusted to the flow rate 0.15 L/min of 77% argon, 12%
nitrogen,
11 % helium, and trace neon. The reactor was then held at temperature and flow
rate for
minutes. After the 25-minute hold, the krypton radiation source was turned off
in
20 the sealed enclosure. The flow rates were immediately readjusted to the
flow rate 0.30
L/min of 10% argon, 90% helium and trace neon. The reactor was then held at
temperature and flow rate for 3 minutes. After the 3-minute hold, flow rates
were
adjusted to 0.15 L/min of 10% argon, 90% helium and trace neon and held for 2
minutes. After the 2-minute hold, flow rates were adjusted to 0.30 L/min of 7%
25 hydrogen, 93% nitrogen and trace neon and held for 10 minutes. After the 10-
minute
hold, flow rates were adjusted to the flow rate of 0.15 L/min of 7% hydrogen,
93%
nitrogen and trace neon and held for 3 minutes. After the 3-minute hold, flow
rates
were adjusted to 30 ml/min of 7% hydrogen, 93% nitrogen and trace neon and
held for
2 minutes. After the 2-minute hold, flow rates were adjusted to 0.15 L/min of
87%
argon, 10% nitrogen, 3% helium, and trace neon and held for 5 minutes. After
the 5-
minute hold, flow rates were adjusted to 0.6 L/min of 90% argon, 10% nitrogen
and
trace neon and held for 7 minutes. After the 7-minute hold, flow rates were
adjusted to
30 ml/min of 90% argon, 10% nitrogen and trace neon and held for 2 minutes.
After
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the 2-minute hold, flow rates were adjusted to 0.60 L/min of 95% argon, 5%
nitrogen
and trace neon and held for 15 minutes. After the 15-minute hold, flow rates
were
adjusted to 0.30 L/min of 95% argon, 5% nitrogen and trace neon and held for 5
minutes.
The reactor temperature was lowered to 2529 F over 21 minutes. The
temperature was then varied between 2451 F and 2529 F for three cycles. The
cycle
consisted of raising the temperature continuously over 27 minutes and lowering
the
temperature continuously over 27 minutes. After the third cycle, the bath was
held at
2529 F for 5 minutes. The reactor temperature was then lowered to 2451 F over
2
minutes 30 seconds. The temperature was then varied between 2529 F and 2451 F
for
two cycles. The cycles consisted of raising the temperature continuously over
11
minutes and lowering the temperature continuously over 7 minutes.
After completion of the 2nd cycle, the induction power supply was placed into
manual control. The power was then instantaneously increased 5 kW above the
steady
state power level and immediately upon hitting the 5 kW increase the power was
instantaneously decreased back to the steady state power level. The power
level was
then varied up 3.7 kW and down 3.7 kW over 6 cycles. The cycles consisted of
raising
power 3.7 kW above the steady state power level over 25 seconds. Once raised,
the
power level was held at the additional 3.7 kW setting for 45 seconds.
Following the 45
second hold, the power was lowered back to the steady state power level over a
15
second time frame.
After the 6th power cycle, the gas flows were adjusted to 0.60 L/min of 100%
argon and trace neon and held for 7 minutes. Following the seven-minute hold,
the
argon flow was secured leaving only the trace neon flow. Once the argon flow
was
secured, a second lance was positioned inside the reactor. This lance was
placed at a
distance 2/3 from the radial center and 1.5 inches from the bottom of the
bath. The
centerline lance was then repositioned to 1/4 inch from the bottom. Once the
centerline
lance was repositioned, flow was started in the off-centerline lance at a rate
of 30
ml/min of 100% argon and trace neon. A timer was reinitiated. At a time of 2
minutes,
the trace neon flow in the centerline lance was secured. At a time of 2
minutes 30
seconds, flow was initiated in the centerline lance at a flow rate of 30
ml/min of 100%
carbon monoxide and held for 3 minutes. After the 3-minute hold, flow rates
were
adjusted in the off-centerline lance to 0.15 L/min of 100% argon and trace
neon and
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held for 15 minutes. After the 15-minute hold, flow rates were adjusted in the
off-
centerline lance to trace neon only. Furthermore, the flow rate was adjusted
in the
centerline lance to 0.60 L/min of 100% carbon monoxide and held for 10
minutes.
After the 10-minute hold, the carbon monoxide in the centerline lance was
secured. The
reactor temperature was then lowered to TS <<aus plus 18 F over 30 minutes.
Upon
reaching the TS I;aus plus 18 F, flow was adjusted in the centerline lance to
0.30 L/min of
100% carbon monoxide and held for 20 minutes. After the 20-minute hold, all
flow
was secured in the centerline lance and the lance was removed.
After the centerline lance was removed, flow rates in the off-centerline lance
were adjusted to 30 ml/min of 88% argon, 12% nitrogen and trace neon, and held
for 3
minutes. After the 3-minute hold, flow rates were adjusted to 0.30 L/min of
25%
helium, 75% argon and trace neon and held for 10 minutes. After the 10-minute
hold,
flow rates were adjusted to 0.30 L/min of 88% argon, 12% nitrogen and trace
neon and
held for 10 minutes. After the 10-minute hold, flow rates were adjusted to
0.15 L/min
of 88% argon, 12% nitrogen and trace neon and held for 5 minutes. After the 5-
minute
hold, flow rates were adjusted to 30 ml/min of 88% argon, 12% nitrogen and
trace neon
and held for 2 minutes. After the 2-minute hold, flow rates were adjusted to
0.15 L/min
of 88% argon, 12% nitrogen and trace neon. Once the flow rate was adjusted,
the
reactor temperature was lowered to TS iidus plus 15 F over 45 minutes. Upon
reaching
the T,0lId s plus 15 F, flow was adjusted in the off-centerline lance to 0.30
L/min of
100% argon and trace neon and held for 5 minutes.
At the completion of the five minute hold, the reactor temperature was lowered
to TS jidus plus 11 F while maintaining a temperature lowering rate of no more
than
3 F/hr. Upon reaching Tsolidus plus 11 F, flow rate in the off-centerline
lance was
adjusted to 0.30 L/min of 100% hydrogen and trace neon. At the completion of
flow
adjustment, the reactor temperature was lowered to Ts lidus plus 10 F while
maintaining
a temperature lowering rate of no more than 3 F/hr. Upon reaching TS fidus
plus 10 F,
flow rate in the off-centerline lance was adjusted to 30 ml/min of 100%
hydrogen and
trace neon. At the completion of the flow adjustment, the reactor temperature
was
lowered to Tsolidus plus 9 F while maintaining a temperature-lowering rate of
no more
than 3 F/hr. Upon reaching Tsolidus plus 9 F, the gas addition lance was
relocated into
the headspace of the reactor, such that a quarter inch (1/4 inches) dimple
could be
observed on the bath surface. The bath was held at Tsolidus plus 9 F for an
additional 5
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minutes for conditioning and equilibration. The reactor was then cooled to
Ts0lidus plus
8 F while maintaining a temperature lowering rate of no more than 3 F/hr. Upon
reaching TS lldus plus 8 F a manual power pulse of 2 kW was introduced with a
single
continuous up/down sweep from normal holding power. The reactor was then
cooled to
TS iidus plus 2 F while maintaining a temperature lowering rate of no more
than 3 F/hr.
Upon reaching TS edus plus 2 F a manual power pulse of 1.5 kW was introduced
with a
single continuous up/down sweep from normal holding power. Immediately after
the
1.5 kW power pulse, flow was adjusted in the off-centerline lance to 0.15
L/min of 50%
hydrogen, 50% helium and trace neon. The reactor was then cooled to Tsoiidus
again
maintaining a temperature-lowering rate of no more than 3 F/hr. Upon reaching
Ts lidus,
the induction furnace power supply was lowered to 1 kW and the reactor was
allowed to
cool from Ts iidus to Ts lidus minus 75 F. Upon reaching TS iid s minus 75 F,
adjust flow
rate in the off-centerline lance to 30 ml/min of 60% helium, 40% hydrogen and
trace
neon. Following the flow adjustment, the induction furnace power supply was
lowered
to 0.75 kW and the reactor was allowed to cool to 1000 F. Upon reaching 1000
F, flow
rate in the off-centerline lance was adjusted to 30 ml/min of 100% helium and
trace
neon. Following the flow adjustment, the induction furnace power supply was
lowered
to 0.50 kW and the reactor was allowed to cool to 350 F. Upon reaching 350 F,
the
induction furnace power supply was shut down and a timer initiated. At a time
of 5
minutes, flow rate in the off-centerline lance was adjusted to 0.60 L/min of
100%
helium and trace neon. At a time of 9 minutes, a neon radiation source within
the
sealed enclosure was remotely rotated. Upon completion of the rotation, now in
the
off-centerline lance was adjusted to 0.30 L/min of 88% argon, 12% nitrogen and
trace
neon.
Following the flow adjustment, the timer was reinitiated. At a time of 25
seconds, a neon radiation source within the sealed enclosure was remotely
rotated. At a
time of 1 minute 30 seconds, a neon radiation source within the sealed
enclosure was
terminated. At a time of 5 minutes, an argon radiation source within the
sealed
enclosure was terminated. At a time of 6 minutes 30 seconds, flow rate was
adjusted to
0.30 L/min of 100% helium and trace neon. At a time of 7 minute, the second
neon
radiation source within the sealed enclosure was terminated.
The timer was reinitiated. At a time of 15 minutes, the trace neon gas flow in
the off-centerline lance was terminated. At a time of 17 minutes 25 seconds,
the xenon
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radiation source within the sealed enclosure was remotely rotated. At a time
of 30
minutes, the trace helium gas flow in the off-centerline lance was terminated.
The timer
was reinitiated. At a time of 15 minutes, the xenon radiation source inside
the sealed
enclosure was terminated. Thirty minutes were allowed to pass. The ingot and
crucible
were removed from the reactor in the presence of radiation sources (metal
halide light
sources) utilizing titanium metal tongs.
Upon removal, the crucible was stripped from the metal ingot via a gentle
wedging action. Immediately following removal, the ingot was transferred into
a
quench chamber containing deionized water, ensuring that the top of the ingot
surface
was covered by at least 6 inches of DI water. Upon entrance into the quench
chamber, a
timer was established. At a time of 2 hours 15 minutes, a long wave
ultraviolet
radiation source located above the quench vessel was initiated. At a time of 4
hours 7
minutes, a short wave ultraviolet radiation source located above the quench
vessel was
initiated. At a time of 5 hours 59 minutes 30 seconds, the short wave
ultraviolet
radiation source located above the quench vessel was rotated to a vertical
position.
At a time of 6 hours, the ingot was removed from the quench system using the
titanium metal tongs and transferred to a clean radiation surface countertop.
Exposure
to external radiation sources included the metal halide light and placement
directly
under a skylight (which added filtered sunlight to the irradiation sources).
The ingot
was pat dried. Upon completion of the drying, the long wave ultraviolet
radiation
source located above the quench vessel was rotated vertical and moved up 1
inch. The
timer was then reinitiated. The ingot was irradiated for 10 minutes at which
point an
additional radiation source (krypton lamp) was initiated. At 12 minutes 30
seconds, the
long wave ultraviolet radiation source located above the quench vessel was
rotated
horizontal and moved down to its original position. At 13 minutes, a xenon
radiation
source located above the quench vessel was initiated. At 18 minutes, two
orthogonal
fluorescent lamp racks located next to the countertop were turned on. At 30
minutes,
two angled metal halide lights located next to the countertop were
simultaneously
turned on. At this point the timer was again reinitiated. At 13 minutes 15
seconds, a
neon radiation source located next to the countertop was turned on. At 15
minutes 30
seconds, an argon radiation source located next to the countertop was turned
on. At 23
minutes 45 seconds, the argon radiation source located next to the countertop
was
rotated to an angle of 35 . At 37 minutes 30 seconds, the short wave
ultraviolet
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radiation source located above the quench vessel was rotated to 35 . At 47
minutes 30
seconds, the xenon radiation source located above the quench vessel was
rotated to
horizontal. At 52 minutes 45 seconds, the long wave ultraviolet radiation
source
located above the quench vessel was rotated to 35 . At 58 minutes 30 seconds,
the short
wave ultraviolet radiation source located above the quench vessel was rotated
to 55 . At
77 minutes, the krypton radiation source located next to the countertop was
rotated to
vertical. At 89 minutes, the krypton radiation source located next tot eh
countertop was
rotated 78 . At 93 minutes, the ingot was lifted using composite black rubber
gloves
and a tailored material that acts as an energy filter was placed under the
ingot. The
tailored material used as an energy filter has an XRF as depicted in the
Appendix 1.
The ingot was then lowered onto the tailored energy filter.
At this point the timer was again reset. At a time of 6 hours, the krypton
lamp,
short wave ultraviolet, long wave ultraviolet, argon (located over quench
vessel), xenon,
argon (located next to countertop), neon, two orthogonal fluorescent lamp
racks, and the
two angled metal halide lights were sequentially terminated in the given
order. The
timer was again reset. At a time of 6 hours, 30 minutes, normal lab lighting
(metal
halides) was turned off. The timer was reset. For 48 hours, the ingot was
allowed to
stabilize with no manual intervention (i.e., no handling).
EXAMPLE 6:
EXPERIMENTAL PROCEDURE FOR IRON, VANADIUM, CHROMIUM,
MANGANESE Method "HD" RUN 14-01-13
A cylindrical alumina-based crucible (99.68% A1203, 0.07% SiO2, 0.08% Fe203,
0.04% CaO, 0.12% Na203; 4.5 inches O.D. X 3.75 inches I.D. X 14.5 inches
depth) of a
100-pound induction furnace reactor (Inductotherm) fitted with a 73-30R
Powertrak
power supply. A gas addition lance was installed to a position approximately
1/4 inches
from the bottom of the reactor. The reactor was charged with 8534 g iron
(99.98%
purity), 182 g vanadium (99.5% purity), 182 g chromium (99.999% purity) and
182 g
manganese (99.99% purity) through its charging port. The reactor was fitted
with a
graphite cap and a ceramic liner (i.e., the crucible, from Engineering
Ceramics). During
the entire procedure, a slight positive pressure of 97% argon, 3% hydrogen (-
0.5 psig)
was maintained in the reactor using a continuous backspace purge. Bypass
injection of
gas addition was commenced (i.e., gas flow diverted around the reactor was
initiated) at
a rate of 0.15 L/min of argon. The incoming gas line for the gas addition
lance passed
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through a sealed, light-tight enclosure whereby irradiation of the gas with
precise
radiation sources (e.g., wavelength, intensity, etc) was achieved. When the
entire gas
line had been completely purged (assuming a plug flow model), a neon radiation
source
was activated within the sealed enclosure. A timer was initiated. Bypass flow
was
adjusted to 100% argon at a flow rate of 0.15 L/min with trace neon present
(trace can
be defined as < 0.005% volume to < 5%). At a time of 3 minutes, an argon
radiation
source was activated within the sealed enclosure. After completion of another
gas line
purge (assuming a plug flow model), the gas line was switched from bypass to
direct
injection through the gas addition lance.
The induction furnace power was then initiated. The reactor was heated to
450 F, at a rate no greater than 300 F/hr, as limited by the integrity of the
crucible. The
induction furnace operated in the frequency range of 0 Hz to 3000 Hz, with
frequency
determined by a temperature-controlled feedback loop implementing an Omega
Model
CN3000 temperature controller. Upon reaching 450 F, the gas addition lance was
repositioned to 2 inches from the bottom of the reactor. The timer was
reinitiated. At a
time of 2 minutes, the gas composition was changed to 0.15 L/min of 66%
nitrogen,
34% hydrogen and trace neon. After completion of another gas line purge
(assuming a
plug flow model), a krypton radiation source was initiated in the sealed
enclosure. The
reactor heat up continued at a rate no greater than 300 F/hr, as limited by
the integrity of
the crucible, until Tsolldus minus 30 F was achieved. The gas flow rate was
then
increased to 0.3 L/min with a constant gas composition. At T,011dus a second
argon
radiation source was activated within the sealed enclosure. Approach Ts lidus
plus 8 F
over a 3 to 5 minute time span. From TS lidu, plus 8 F to Ts lidu, plus 15 F,
reduce the gas
flow rate to 0.15 L/min with a constant gas composition. Immediately upon
reaching
TS lldu, plus 15 F, a second neon radiation source was initiated in the sealed
enclosure.
Immediately after the second neon radiation source was initiated, the gas
composition
was adjusted to 75% hydrogen, 22% nitrogen, 3% argon, and trace neon. The
molten
bath was held at this condition for 5 minute for stabilization.
After the 5-minute hold, the gas composition was adjusted to 20% helium, 63%
nitrogen, 17% argon, and trace neon. The bath was held under these conditions
for an
additional 15 minutes. Again, following the hold, the gas composition and flow
rate
were adjusted to 100% argon with trace neon at a rate of 0.3 L/min. The
reactor was
held at this condition for 3 minutes. The timer was reinitiated. At a time of
65 minutes,
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graphite saturation assemblies (3/8 inches OD, 36 inches long high purity (<5
ppm
impurities) graphite rods) were inserted to the bottom of the iron alloy
charge through
ports located in the top plate. The iron was cooled to 2243 F over a two-hour
period.
The bath was cooled due to the t-solidus temperature of an iron bath with no
carbon
versus the temperature requirement of a carbon-containing bath. The bath was
then
held at this condition for 2 hours. Every 30 minutes during the hold period,
an attempt
was made to lower the graphite saturation assemblies as dissolution occurred.
As the
iron alloy became saturated with carbon, the graphite saturation assemblies
were
consumed. After the 2-hour hold period was complete, the graphite saturation
assemblies were removed. An additional 90 grams of graphite powder was charged
into
the reactor through the charging port. The bath was then heated to 3525 F over
three
hours. Upon achieving 3525 F, the gas composition and flow rate were adjusted
to
100% nitrogen with trace neon at a rate of 0.3 L/min and held for 5 minutes.
Reduce
the gas flow rate to 0.15 L/min with constant composition. Immediately
following this
reduction in gas flow, the krypton radiation source in the sealed enclosure
was turned
off. The timer was reinitiated. At a time of 3 minutes, the gas flow rate was
reduced to
37.5 ml/min with constant composition. One of the argon radiation sources
inside the
sealed enclosure was turned off. At a time of 5 minutes, the nitrogen
component of the
gas flow was discontinued while maintaining the flow of the trace neon. At a
time of 10
minutes, one of the neon radiation sources within the sealed enclosure was
remotely
rotated. The reactor temperature was lowered to 3360 F over 7 minutes.
The temperature was then varied between 2993 F and 3360 F for 16 cycles.
Each cycle consisted of raising the temperature continuously over 7 minutes
and
lowering the temperature continuously over 7 minutes. After completion of the
14.5
cycles, argon was reintroduced at a flow rate of 0.15 L/min with trace neon.
Five
minutes into the 15th cycle, a xenon radiation source was activated within the
sealed
enclosure. At 6 minutes into the 15th cycle, a long wave ultraviolet radiation
source was
activated in the sealed enclosure. At sweep count 15.5, a short wave
ultraviolet
radiation source was initiated in the sealed enclosure. At sweep count 16, the
xenon
radiation source within the sealed enclosure was remotely rotated. The
temperature of
the iron alloy was varied over another 5 cycles between 2993 F and 3360 F.
After the
fifth cycle, the reactor temperature was then lowered to 2850 F over a 60-
minute
period. Upon achieving the target temperature of 2850, the graphite saturation
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assemblies were reinstalled in the iron alloy and remained there for 1 hour.
The
graphite saturation assemblies were then removed.
Two voltage probes (source and ground probe) were then installed in the
headspace of the reactor and allowed to equilibrate for 5 minutes. Upon
completion of
the five-minute hold the voltage probes were lowered into the bath. The source
probe
was positioned 2 inches below the axial center and 1 inch from the radial
center. The
ground probe was positioned 0.75 inches above the axial position of the source
probe
and 1 inch from the radial center (180 from the source probe). Once the
probes were
installed a five-minute hold at this condition was done to allow the bath to
electronically
equilibrate with the probes. Voltage was then applied to the probes and varied
between
multiple voltage set points. This voltage was in a continuous up/down sweep
between
two predetermined voltages. The first voltage cycle was varied between 17 and
18 volts
for 24 cycles. Each cycle consisted of raising the voltage continuously over
45 seconds
and lowering the voltage continuously over 45 seconds. The second voltage
cycle was
varied between 13.25 and 14.75 volts for 20 cycles. Each cycle consisted of
raising the
voltage continuously over 45 seconds and lowering the voltage continuously
over 45
seconds. The third voltage cycle was varied between 8.75 and 10.25 volts for
17 cycles.
Each cycle consisted of raising the voltage continuously over 45 seconds and
lowering
the voltage continuously over 45 seconds. The fourth voltage cycle was varied
between
4.00 and 7.00 volts for 14 cycles. Each cycle consisted of raising the voltage
continuously over 45 seconds and lowering the voltage continuously over 45
seconds.
The fifth voltage cycle was varied between 1.50 and 5.00 volts for 10 cycles.
Each
cycle consisted of raising the voltage continuously over 45 seconds and
lowering the
voltage continuously over 45 seconds. The sixth voltage cycle was varied
between 0.50
and 2.00 volts for 3 cycles. Each cycle consisted of raising the voltage
continuously
over 45 seconds and lowering the voltage continuously over 45 seconds. When
the final
cycle was completed the voltage was set onto a constant 1-volt setting. This
voltage
remains constant until a later step when the leads are removed.
The reactor temperature was lowered to 2819 F over 5 minutes. The reactor
was held at this temperature for 5 minutes with continued gas addition. The
temperature was then varied between 2757 F and 2819 F over 20 cycles. Each
cycle
consisted of lowering the temperature continuously over 9 minutes and raising
the
temperature continuously over 9 minutes. After the 20th cycle, turning off the
argon
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component of the gas leaving only trace neon gas flow changed third body gas
addition.
The bath was then cooled to 2724 F over 5 minutes. Upon reaching 2724 F, one
of the
neon radiation sources within the sealed enclosure was remotely rotated.
The temperature was then varied between 2622 F and 2724 F over 4.5 cycles.
Each cycle consisted of lowering the temperature continuously over 5 minutes
and
raising the temperature continuously over 3 minutes. In addition, while
raising the
temperature, a 0.15 L/min flow of 60% argon, 40% helium, and trace neon was
added,
and while lowering the temperature, a 0.3 L/min flow of 100% helium, trace
neon, and
trace krypton was added. At sweep count 0.5, a krypton radiation source was
initiated
in the sealed enclosure. At sweep count 1.0, an argon radiation source was
initiated in
the sealed enclosure. At sweep count 4.5, a short wave ultraviolet radiation
source was
terminated in the sealed enclosure. The reactor temperature was lowered to
2586 F
over 5 minutes. The temperature was varied between 2133 F and 2586 F for 15.5
cycles. Each cycle consisted of lowering the temperature continuously over 15
minutes
and raising the temperature continuously over 15 minutes. In addition, while
raising the
temperature, a 0.15 L/min flow of 60% argon, 40% helium, and trace neon was
added,
and while lowering the temperature, a 0.3 L/min flow of 100% helium, trace
neon, and
trace krypton was added. After the 15.5th cycle, turning off all gas
components except
the trace neon gas flow changed third body gas addition.
After the 15.5th cycle, a timer was initiated. At a time of 3 minutes,
remotely
rotate the xenon radiation source within the sealed enclosure. The timer was
then
reinitiated. At 60 minutes, flow rates were adjusted to 0.3 L/min of 100%
argon and
trace neon. At 65 minutes, flow rates were adjusted to 30 ml/min of 60% argon,
40%
helium, and trace neon. Immediately after the flow was adjusted, one of the
neon
radiation sources within the sealed enclosure was remotely rotated. At 68
minutes, flow
rates were adjusted to 0.15 L/min of 100% helium, trace neon and trace
krypton. At 68
minutes 20 seconds, the 1-volt power was brought to zero output and the
voltage power
leads removed from the voltage probes. At 68 minutes 30 seconds, the long wave
ultraviolet radiation source was turned off in the sealed enclosure. At 71
minutes 15
seconds, the voltage probes were repositioned to three inches above the bath
surface.
At 75 minutes, the source and ground probe were removed completely from the
reactor.
After the voltage probes had been removed from the reactor, flow rates were
adjusted to 0.15 L/min of 77% argon, 18% nitrogen, 5% helium, and trace neon.
The
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reactor was then held at temperature and flow rate for 15 minutes. After the
15-minute
hold, an argon radiation source was turned off in the sealed enclosure. The
flow rates
were immediately readjusted to the flow rate 0.15 L/min of 77% argon, 12%
nitrogen,
11 % helium, and trace neon. The reactor was then held at temperature and flow
rate for
25 minutes. After the 25-minute hold, the krypton radiation source was turned
off in
the sealed enclosure. The flow rates were immediately readjusted to a flow
rate of 0.30
L/min of 10% argon, 90% helium and trace neon. The reactor was then held at
temperature and flow rate for 3 minutes. After the 3-minute hold, flow rates
were
adjusted to 0.15 L/min of 10% argon, 90% helium and trace neon and held for 2
minutes. After the 2-minute hold, flow rates were adjusted to 0.30 L/min of 7%
hydrogen, 93% nitrogen and trace neon and held for 10 minutes. After the 10-
minute
hold, flow rates were adjusted to 0.15 L/min of 7% hydrogen, 93% nitrogen and
trace
neon and held for 3 minutes. After the 3-minute hold, flow rates were adjusted
to 30
ml/min of 7% hydrogen, 93% nitrogen and trace neon and held for 2 minutes.
After the
2-minute hold, flow rates were adjusted to 0.15 L/min of 87% argon, 10%
nitrogen, 3%
helium, and trace neon and held for 5 minutes. After the 5-minute hold, flow
rates were
adjusted to 0.6 L/min of 90% argon, 10% nitrogen and trace neon and held for 7
minutes. After the 7-minute hold, flow rates were adjusted to 30 ml/min of 90%
argon,
10% nitrogen and trace neon and held for 2 minutes. After the 2-minute hold,
flow
rates were adjusted to 0.60 L/min of 95% argon, 5% nitrogen and trace neon and
held
for 15 minutes. After the 15-minute hold, flow rates were adjusted to 0.30
L/min of
95% argon, 5% nitrogen and trace neon and held for 5 minutes.
The reactor temperature was raised to 2340 F over 21 minutes. The temperature
was then varied between 2133 F and 2340 F for three cycles. The cycle
consisted of
raising the temperature continuously over 27 minutes and lowering the
temperature
continuously over 27 minutes. After the third cycle, the bath was held at 2340
F for 5
minutes. The reactor temperature was then lowered to 2133 F over 2 minutes 30
seconds. The temperature was then varied between 2340 F and 2133 F for two
cycles.
The cycle consisted of raising the temperature continuously over 11 minutes
and
lowering the temperature continuously over 7 minutes.
After completion of the 2nd cycle, the induction power supply was placed into
manual control. The power was then instantaneously increased 5 kW above the
steady
state power level and immediately upon hitting the 5 kW increased the power
was
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instantaneously decreased back to the steady state power level. The power
level was
then varied up 3.7 kW and down 3.7 kW over 6 cycles. The cycles consisted of
raising
power 3.7 kW above the steady state power level over 25 seconds. Once raised,
the
power level was held at the additional 3.7 kW setting for 45 seconds.
Following the 45
second hold, the power was lowered back to the steady state power level over a
15
second time frame.
After completion of the 6`i' power cycle, the gas flows were adjusted to 0.60
L/min of 100% argon and trace neon and held for 7 minutes. Following the seven-
minute hold, the argon flow was secured leaving only the trace neon flow. Once
the
argon flow was secured, a second lance was positioned inside the reactor. This
lance
was placed at a distance 2/3 from the radial center and 1.5 inches from the
bottom of the
bath. The centerline lance was then repositioned to 1/4 inch from the bottom.
Once the
centerline lance was repositioned, flow was started in the off-centerline
lance at a rate of
30 ml/min of 100% argon and trace neon. A timer was initiated. At a time of 2
minutes, the trace neon flow in the centerline lance was secured. At a time of
2 minutes
30 seconds, flow was initiated in the centerline lance at a flow rate of 30
ml/min of
100% carbon monoxide and held for 3 minutes. After the 3-minute hold, flow
rates
were adjusted in the off-centerline lance to 0.15 L/min of 100% argon and
trace neon
and held for 15 minutes. After the 15-minute hold, flow rates were adjusted in
the off-
centerline lance to trace neon only. Furthermore, the flow rate was adjusted
in the
centerline lance to 0.60 L/min of 100% carbon monoxide and held for 10
minutes.
After the 10-minute hold, the carbon monoxide in the centerline lance was
secured. The
reactor temperature was then lowered to T1 iidu, plus 18 F over 30 minutes.
Upon
reaching the Tsolidu, plus 18 F, flow was adjusted in the centerline lance to
0.30 L/min of
100% carbon monoxide and held for 20 minutes. After the 20-minute hold, all
flow
was secured in the centerline lance and the lance was removed.
After the centerline lance was removed, adjust flow rates in the off-
centerline
lance to 30 ml/min of 88% argon, 12% nitrogen and trace neon and held for 3
minutes.
After the 3-minute hold, flow rates were adjusted to 0.30 L/min of 25% helium,
75%
argon and trace neon and held for 10 minutes. After the 10-minute hold, flow
rates
were adjusted to 0.30 L/min of 88% argon, 12% nitrogen and trace neon and held
for 10
minutes. After the 10-minute hold, flow rates were adjusted to 0.15 L/min of
88%
argon, 12% nitrogen and trace neon and held for 5 minutes. After the 5-minute
hold,
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flow rates were adjusted to 30 cc/min of 88% argon, 12% nitrogen and trace
neon and
held for 2 minutes. After the 2-minute hold, flow rates were adjusted to 0.15
L/min of
88% argon, 12% nitrogen and trace neon. Once the flow rate was adjusted, the
reactor
temperature was lowered to Tsolidus plus 15 F over 45 minutes. Upon reaching
the Tsolidus
plus 15 F, flow was adjusted in the off-centerline lance to 0.30 L/min of 100%
argon
and trace neon and held for 5 minutes.
At the completion of five minute hold, the reactor temperature was lowered to
Tsolidus plus 11 F while maintaining a temperature lowering rate of no more
than 3 F/hr.
Upon reaching Tsolidus plus 11 F, flow rate in the off-centerline lance was
adjusted to
0.30 L/min of 100% hydrogen and trace neon. At the completion of the flow
adjustment, the reactor temperature was then lowered to Tsolidus plus 10 F
while
maintaining a temperature lowering rate of no more than 3 F/hr. Upon reaching
Tsolidus
plus 10 F, flow rate in the off-centerline lance was adjusted to 30 ml/min of
100%
hydrogen and trace neon. At the completion of the flow adjustment, the reactor
temperature was lowered to Tsolidus plus 9 F while maintaining a temperature-
lowering
rate of no more than 3 F/hr. Upon reaching Tsolidus plus 9 F, the gas addition
lance was
relocated into the headspace of the reactor, such that a quarter inch (1/4
inches) dimple
could be observed on the bath surface. The bath was held at Tsolidus plus 9 F
for an
additional 5 minutes for conditioning and equilibration. The reactor was then
cooled to
Tsolidus plus 8 F while maintaining a temperature lowering rate of no more
than 3 F/hr.
Upon reaching Tsolidus plus 8 F a manual power pulse of 2 kW was introduced
with a
single continuous up/down sweep from normal holding power. The reactor was
then
cooled to Tsolidus plus 2 F while maintaining a temperature lowering rate of
no more than
3 F/hr. Upon reaching Tsolidus plus 2 F a manual power pulse of 1.5 kW was
introduced
with a single continuous up/down sweep from normal holding power. Immediately
after the 1.5 kW power pulse, flow was adjusted in the off-centerline lance to
0.15
L/min of 50% hydrogen, 50% helium and trace neon. The reactor was then cooled
to
Tsolidus again maintaining a temperature-lowering rate of no more than 3 F/hr.
Upon
reaching Tsolidus, the induction furnace power supply was lowered to 1 kW and
the
reactor was allowed to cool from Tsolidus to Tsolidus minus 75 F. Upon
reaching Tsolidus
minus 75 F, flow rate in the off-centerline lance was adjusted to 30 ml/min of
60%
helium, 40% hydrogen and trace neon. Following the flow adjustment, the
induction
furnace power supply was lowered to 0.75 kW and the reactor was allowed to
cool to
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1000 F. Upon reaching 1000 F, flow rate in the off-centerline lance was
adjusted to 30
ml/min of 100% helium and trace neon. Following the flow adjustment, the
induction
furnace power supply was lowered to 0.50 kW and the reactor was allowed to
cool to
350 F. Upon reaching 350 F, the induction furnace power supply was shut down
and
the timer reinitiated. At a time of 5 minutes, flow rate in the off-centerline
lance was
adjusted to 0.60 L/min of 100% helium and trace neon. At a time of 9 minutes,
a neon
radiation source within the sealed enclosure was remotely rotated. Upon
completion of
the rotation, flow in the off-centerline lance was adjusted to 0.30 L/min of
88% argon,
12% nitrogen and trace neon.
Following the flow adjustment, the timer was reinitiated. At a time of 25
seconds, a neon radiation source within the sealed enclosure was remotely
rotated. At a
time of 1 minute 30 seconds, a neon radiation source within the sealed
enclosure was
terminated. At a time of 5 minutes an argon radiation source within the sealed
enclosure was terminated. At a time of 6 minute 30 seconds, flow rate was
adjusted to
0.30 L/min of 100% helium and trace neon. At a time of 7 minute, the second
neon
radiation source within the sealed enclosure was terminated.
The timer was reinitiated. At a time of 15 minutes, the trace neon gas flow in
the off-centerline lance was terminated. At a time of 17 minutes 25 seconds,
the xenon
radiation source within the sealed enclosure was remotely rotated. At a time
of '30
minutes, the trace helium gas flow in the off-centerline lance was terminated.
The timer
was reinitiated. At a time of 15 minutes, the xenon radiation source inside
the sealed
enclosure was terminated. Thirty minutes were allowed to pass. The ingot and
crucible
were removed from the reactor in the presence of radiation sources (metal
halide light
sources) utilizing titanium metal tongs.
Upon removal, the crucible was stripped from the metal ingot via a gentle
wedging action. Immediately following removal, the ingot was transferred into
a
quench chamber containing deionized water, ensuring that the top of the ingot
surface
was covered by at least 6 inches of DI water. Upon entrance into the quench
chamber, a
timer was initiated. At a time of 2 hours 15 minutes, a long wave ultraviolet
radiation
source located above the quench vessel was initiated. At a time of 4 hours 7
minutes, a
short wave ultraviolet radiation source located above the quench vessel was
initiated.
At a time of 5 hours 59 minutes 30 seconds, the short wave ultraviolet
radiation source
located above the quench vessel was rotated to the vertical position.
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At a time of 6 hours, the ingot was removed from the quench system using the
titanium metal tongs and transferred to a clean radiation surface countertop.
Exposure
to external radiation sources included the metal halide light and placement
directly
under a skylight (which added filtered sunlight to the irradiation sources).
The ingot
was pat dried. Upon completion of the drying, the long wave ultraviolet
radiation
source located above the quench vessel was rotated vertically and moved up 1
inch.
The timer was then reinitiated. The ingot was irradiated for 10 minutes at
which point
an additional radiation source (krypton lamp) was initiated. At 12 minutes 30
seconds,
the long wave ultraviolet radiation source located above the quench vessel was
rotated
horizontal and moved down to its original position. At 13 minutes, a xenon
radiation
source located above the quench vessel was initiated. At 18 minutes, two
orthogonal
fluorescent lamp racks located next to the countertop were turned on. At 30
minutes,
two angled metal halide lights located next to the countertop were
simultaneously
turned on. At this point the timer was again reinitiated. At 13 minutes 15
seconds, a
'15 neon radiation source located next to the countertop was turned on. At 15
minutes 30
seconds, an argon radiation source located next to the countertop was turned
on. At 23
minutes 45 seconds, the argon radiation source located next to the countertop
was
rotated to an angle of 35 . At 37 minutes 30 seconds, the short wave
ultraviolet
radiation source located above the quench vessel was rotated to 35 . At 47
minutes 30
seconds, the xenon radiation source located above the quench vessel was
rotated to
horizontal. At 52 minutes 45 seconds, the long wave ultraviolet radiation
source
located above the quench vessel was rotated to 35 . At 58 minutes 30 seconds,
the short
wave ultraviolet radiation source located above the quench vessel was rotated
to 55 . At
77 minutes, the krypton radiation source located next to the countertop was
rotated to
vertical. At 89 minutes, the krypton radiation source located next to the
countertop was
rotated to 78 . At 97 minutes, the krypton radiation source located next to
the
countertop was rotated to 88 .
The timer was reinitiated. At a time of 6 hours, the krypton lamp, short wave
ultraviolet, long wave ultraviolet, argon (located over quench vessel), xenon,
argon
(located next to countertop), neon, two orthogonal fluorescent lamp racks, and
the two
angled metal halide lights were sequentially terminated in the given order.
The timer
was again reinitiated. At a time of 6 hours, 30 minutes, normal lab lighting
(metal
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halides) was turned off. The timer was reinitiated. For 48 hours, the ingot
was allowed
to stabilize with no manual intervention (i.e., no handling).
EXAMPLE 7:
EXPERIMENTAL PROCEDURE FOR COPPER, GOLD, SILVER, RHENIUM
ALLOY Method "HD" RUN 14-04-03
A cylindrical alumina-based crucible (99.68% A1203, 0.07% Si02, 0.08% Fe2O3,
0.04% CaO, 0.12% Na203; 4.5 inches O.D. X 3.75 inches I.D. X 14.5 inches
depth) of a
100 pound induction furnace reactor (Inductotherm) fitted with a 73-30R
Powertrak
power supply. A gas addition lance was installed to a position approximately
1/4 inches
from the bottom of the reactor. The reactor was charged with 9080 g copper
(99.98%
purity), 7 g rhenium, 5 g silver and 2 g gold through its charging port. The
reactor was
fitted with a graphite cap and a ceramic liner (i.e., the crucible, from
Engineering
Ceramics). During the entire procedure, a slight positive pressure of 97%
argon, 3%
hydrogen (-0.5 psig) was maintained in the reactor using a continuous
backspace purge.
Bypass injection of gas addition was commenced (i.e., gas flow diverted around
the
reactor was initiated) at a rate of 0.15 L/min of argon. The incoming gas line
for the gas
addition lance passes through a sealed, light-tight enclosure whereby
irradiation of the
gas with precise radiation sources (e.g., wavelength, intensity, etc) can be
achieved.
When the entire gas line had been completely purged (assuming a plug flow
model), a
neon radiation source was activated within the sealed enclosure. A timer was
set to
zero. Bypass flow was adjusted to 100% argon at a flow rate of 0.15 L/min with
trace
neon present (< 0.005% vol. to < 5%). At a time of 3 minutes, an argon
radiation
source was activated within the sealed enclosure. After completion of another
gas line
purge (assuming a plug flow model), the gas line was switched from bypass to
direct
injection through the gas addition lance.
The induction furnace power was then initiated. The reactor was heated to
450 F, at a rate no greater than 300 F/hr, as limited by the integrity of the
crucible. The
induction furnace operated in the frequency range of 0 Hz to 3000 Hz, with
frequency
determined by a temperature-controlled feedback loop implementing an Omega
Model
CN3000 temperature controller. Upon reaching 450 F, the gas addition lance was
repositioned to within 2 inches of the bottom of the reactor. The timer was
again set to
zero. At a time of 2 minutes, the gas composition was changed to 0.15 L/min of
66%
nitrogen, 34% hydrogen with trace neon present. After completion of another
gas line
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purge (assuming a plug flow model), a krypton radiation source is initiated in
the sealed
enclosure. The reactor heat up continued at a rate no greater than 300 F/hr,
as limited
by the integrity of the crucible, until TS >>dus minus 30 F was achieved. The
gas flow rate
was then increased to 0.3 L/min with a constant gas composition. At Ts Iidus a
second
argon radiation source was activated within the sealed enclosure. Tsolidus
plus 8 F was
approached over a 3 to 5 minute time span. From Ts lidus plus 8 F to TS 1;dus
plus 15 F,
the gas flow rate was reduced to 0.15 L/min with a constant gas composition.
Immediately upon reaching Ts lidus plus 15 F, a second neon radiation source
was
initiated in the sealed enclosure. Immediately after the second neon radiation
source is
initiated, the gas composition is adjusted to 75% hydrogen, 22% nitrogen, and
3% argon
with trace neon. The molten bath was held at this condition for 5 minutes for
stabilization.
After the 5 minute hold, the gas composition was adjusted to 20% helium, 63%
nitrogen, 17% argon, and trace neon. The bath was held under these conditions
for an
additional 15 minutes. Again, following the hold, the gas composition and flow
rate
were adjusted to 100% argon with trace neon at a rate of 0.3 L/min. The
reactor was
held at this condition for 3 minutes. The timer was reset to zero. At a time
of 65
minutes, graphite saturation assemblies (3/8 inches OD, 36 inches long high
purity (<5
ppm impurities) graphite rods) were inserted to the bottom of the copper alloy
charge
through ports located in the top plate. The copper alloy was heated to 2359 F
over a 1
hour period. The bath was then held at this condition for 2 hours. Every 30
minutes
during the hold period, an attempt was made to lower the graphite saturation
assemblies
as dissolution occurred. As the copper became saturated with carbon, the
graphite
saturation assemblies were consumed. After the 2 hour hold period was
complete, the
graphite saturation assemblies were removed. An additional 2.06 grams of
graphite
powder was charged into the reactor through the charging port. The bath was
then
heated to 2474 F over one hour. Upon achieving 2474 F, the gas composition and
flow
rate were adjusted to 100% nitrogen with trace neon at a rate of 0.3 L/min.
Hold reactor
conditions for 5 minutes. The gas flow rate was reduced to 0.15 L/min with
constant
composition. Immediately following this reduction in gas flow, the krypton
radiation
source in the sealed enclosure was turned off. The timer was reset to zero. At
a time of
3 minutes, the gas flow rate was reduced to 37.5 ml/min with constant
composition.
One of the argon radiation sources inside the sealed enclosure was turned off.
At a time
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of 5 minutes, the nitrogen component of the gas flow was discontinued, while
maintaining the flow of trace neon. At a time of 10 minutes, one of the neon
radiation
sources within the sealed enclosure was rotated. The reactor temperature is
lowered to
2451 F over 7 minutes.
The temperature was then varied between 2413 F and 2451 F for 16 cycles.
Each cycle consisted of raising the temperature continuously over 7 minutes
and
lowering the temperature continuously over 7 minutes. After completion of the
14.5
cycles, argon was reintroduced at a flow rate of 0.15 L/min with trace neon.
Five
minutes into the 15th cycle, a xenon radiation source was activated within the
sealed
enclosure. At 6 minutes into the 15th cycle, a long wave ultraviolet radiation
source was
activated in the sealed enclosure. At sweep count 15.5, a short wave
ultraviolet
radiation source was initiated in the sealed enclosure. At sweep count 16, the
xenon
radiation source was remotely rotated within the sealed enclosure. The
temperature of
the copper was varied over another 5 cycles between 2413 F and 2451 F. After
the
fifth cycle, the reactor temperature was lowered to 2400 F over a 10 minute
period.
Upon achieving the target temperature of 2400, the graphite saturation
assemblies were
reinstalled in the copper and remained there for 1 hour. The graphite
saturation
assemblies were then removed.
Two voltage probes (source and ground probe) were then installed in the
headspace of the reactor and allowed to equilibrate for 5 minutes. Upon
completion of
the five minute hold the voltage probes were lowered into the bath. The source
probe
was positioned 2 inches below the axial center and 1 inch from the radial
center. The
ground probe was positioned 0.75 inches above the axial position of the source
probe
and 1 inch from the radial center (180 from the source probe). Once the
probes were
installed, a five minute hold at this condition was done to allow the bath to
electronically equilibrate with the probes. Voltage was then applied to the
probes and
varied between multiple voltage set points. This voltage application was in a
continuous up/down sweep between two predetermined voltages. The first voltage
cycle was varied between 17 and 18 volts for 24 cycles. Each cycle consisted
of raising
the voltage continuously over 45 seconds and lowering the voltage continuously
over 45
seconds. The second voltage cycle was varied between 13.25 and 14.75 volts for
20
cycles. Each cycle consisted of raising the voltage continuously over 45
seconds and
lowering the voltage continuously over 45 seconds. The third voltage cycle was
varied
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between 8.75 and 10.25 volts for 17 cycles. Each cycle consisted of raising
the voltage
continuously over 45 seconds and lowering the voltage continuously over 45
seconds.
The fourth voltage cycle was varied between 4.00 and 7.00 volts for 14 cycles.
Each
cycle consisted of raising the voltage continuously over 45 seconds and
lowering the
voltage continuously over 45 seconds. The fifth voltage cycle was varied
between 1.50
and 5.00 volts for 10 cycles. Each cycle consisted of raising the voltage
continuously
over 45 seconds and lowering the voltage continuously over 45 seconds. The
sixth
voltage cycle was varied between 0.50 and 2.00 volts for 3 cycles. Each cycle
consisted
of raising the voltage continuously over 45 seconds and lowering the voltage
continuously over 45 seconds. When the final cycle was completed the voltage
was set
onto a constant 1 volt setting. This voltage setting remained constant until a
later step
during which the leads are removed.
The reactor temperature was then lowered to 2397 F over 5 minutes. The
reactor was held at this temperature for 5 minutes with continued gas
addition. The
temperature was then varied between 2391 F and 2397 F over 20 cycles. Each
cycle
consisted of lowering the temperature continuously over 9 minutes and raising
the
temperature continuously over 9 minutes. After the 20th cycle, third body gas
addition
was changed by turning off the argon component of the gas leaving only trace
neon gas
flow. The bath was then cooled to 2388 F over 5 minutes. Upon reaching 2388 F,
one
of the neon radiation sources was remotely rotated within the sealed
enclosure.
The temperature was then varied between 2380 F and 2388 F over 4.5 cycles.
Each cycle consisted of lowering the temperature continuously over 5 minutes
and
raising the temperature continuously over 3 minutes. In addition, while
raising the
temperature, a 0.15 L/min flow of 60% argon, 40% helium, and trace neon was
added,
and while lowering the temperature, a 0.3 L/min flow of 100% helium, trace
neon, and
trace krypton was added. At sweep count 0.5, a krypton radiation source was
initiated
in the sealed enclosure. At sweep count 1.0, an argon radiation source was
initiated in
the sealed enclosure. At sweep count 4.5, the short wave ultraviolet radiation
source
was terminated in the sealed enclosure. The reactor temperature was then
lowered to
2377 F over 5 minutes. The temperature was varied between 2346 F and 2377 F
for
15.5 cycles. Each cycle consisted of lowering the temperature continuously
over 15
minutes and raising the temperature continuously over 15 minutes. In addition,
while
raising the temperature, a 0.15 L/min flow of 60% argon, 40% helium, and trace
neon
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was added, and while lowering the temperature, a 0.3 L/min flow of 100%
helium, trace
neon, and trace krypton was added. After the 15.5th cycle, third body gas
addition was
changed by turning off all gas components except the trace neon gas flow.
After the 15.5t" cycle, a timer was started. At a time of 3 minutes, the xenon
radiation source was remotely rotated within the sealed enclosure. The timer
was then
reset to zero. At 60 minutes, flow rates were adjusted to 0.3 L/min of 100%
argon and
trace neon. At 65 minutes, flow rates were adjusted to 30 ml/min of 60% argon,
40%
helium, and trace neon. Immediately after the flow was adjusted, one of the
neon
radiation sources was remotely rotated within the sealed enclosure. At 68
minutes, flow
rates were adjusted to 0.15 L/min of 100% helium, trace neon, and trace
krypton. At 68
minutes 20 seconds, the 1 volt power was brought to zero output and the
voltage power
leads removed from the voltage probes. At 68 minutes 30 seconds, the long wave
ultraviolet radiation source was turned off in the sealed enclosure. At 71
minutes 15
seconds, the voltage probes were repositioned to three inches above the bath
surface.
At 75 minutes, the source and ground probes are removed completely from the
reactor.
After the voltage probes have been removed from the reactor, flow rates were
adjusted to 0.15 L/min of 77% argon, 18% nitrogen, 5% helium and trace neon.
The
reactor was then held at temperature and flow rate for 15 minutes. After the
15 minute
hold, one of the argon radiation sources was turned off in the sealed
enclosure. The
flow rates were immediately readjusted to 0.15 L/min of 77% argon, 12%
nitrogen, l I%
helium and trace neon. The reactor was then held at temperature and flow rate
for 25
minutes. After the 25 minute hold, the krypton radiation source was turned off
in the
sealed enclosure. The flow rates were immediately readjusted to 0.30 L/min of
10%
argon, 90% helium and trace neon. The reactor was then held at temperature and
flow
rate for 3 minutes. After the 3 minute hold, flow rates were adjusted to the
flow rate
0.15 L/min of 10% argon, 90% helium and trace neon and held for 2 minutes.
After the
2 minute hold, flow rates were adjusted to 0.30 L/min of 7% hydrogen, 93%
nitrogen
and trace neon and held for 10 minutes. After the 10 minute hold, flow rates
were
adjusted to 0.15 L/min of 7% hydrogen, 93% nitrogen and trace neon and held
for 3
minutes. After the 3 minute hold, flow rates were adjusted to 30 ml/min of 7%
hydrogen, 93% nitrogen and trace neon and held for 2 minutes. After the 2
minute hold,
flow rates were adjusted to 0.15 L/min of 87% argon, 10% nitrogen, 3% helium
and
trace neon and held for 5 minutes. After the 5 minute hold, flow rates were
adjusted to
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0.6 L/min of 90% argon, 10% nitrogen and trace neon and held for 7 minutes.
After the
7 minute hold, flow rates were adjusted to 30 ml/min of 90% argon, 10%
nitrogen and
trace neon and held for 2 minutes. After the 2 minute hold, flow rates were
adjusted to
0.60 L/min of 95% argon, 5% nitrogen and trace neon and held for 15 minutes.
After
the 15 minute hold, flow rates were adjusted to 0.30 Lhnin of 95% argon, 5%
nitrogen
and trace neon and held for 5 minutes.
The reactor temperature was then lowered to 2359 F over 21 minutes. The
temperature was then varied between 2346 F and 2359 F for three cycles. The
cycles
consisted of raising the temperature continuously over 27 minutes and lowering
the
temperature continuously over 27 minutes. After the third cycle, the bath was
held at
2359 F for 5 minutes. The reactor temperature was then lowered to 2346 F over
2
minutes 30 seconds. The temperature was then varied between 2359 F and 2346 F
for
two cycles. The cycles consisted of raising the temperature continuously over
11
minutes and lowering the temperature continuously over 7 minutes.
After completion of the 2 d cycle, the induction power supply was placed into
manual control. The power was then instantaneously increased 5 kW above the
steady
state power level and immediately upon hitting the 5 kW, the power was
instantaneously decreased back to the steady state power level. The power
level was
then varied up 3.7 kW and down 3.7 kW over 6 cycles. The cycles consisted of
raising
power 3.7 kW above the steady state power level over 25 seconds. Once raised,
the
power level was held at the additional 3.7 kW setting for 45 seconds.
Following the 45
second hold, the power was lowered back to the steady state power level over a
15
second time frame.
After the 6th power cycle, the gas flows were adjusted to 0.60 L/min of 100%
argon and trace neon and held for 7 minutes. Following the seven minute hold,
the
argon flow was secured leaving only the trace neon flow. Once the argon flow
was
secured, a second lance was positioned inside the reactor. This lance was
placed at a
distance 2/3 from the radial center and 1.5 inches from the bottom of the
bath. The
centerline lance was then repositioned to 1/4 inch off the bottom. Once the
centerline
lance was repositioned, flow was started in the off-centerline lance at a rate
of 30
ml/min of 100% argon and trace neon. A timer was then initiated. At a time of
2
minutes, the trace neon flow in the centerline lance was discontinued. At a
time of 2
minutes 30 seconds, flow was initiated in the centerline lance at a flow rate
of 30
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ml/min of 100% carbon monoxide and held for 3 minutes. After the 3 minute
hold,
flow rates were adjusted in the off-centerline lance to 0.15 L/min of 100%
argon and
trace neon and held for 15 minutes. After the 15 minute hold, flow rates were
adjusted
in the off-centerline lance to trace neon only. Furthermore, the flow rate was
adjusted
in the centerline lance to 0.60 L/min of 100% carbon monoxide and held for 10
minutes. After the 10 minute hold, the carbon monoxide in the centerline lance
was
turned off. The reactor temperature was then lowered to Ts Iidus plus 18 F
over 30
minutes. Upon reaching the Ts Iidu, plus 18 F, flow was adjusted in the
centerline lance
to 0.30 L/min of 100% carbon monoxide and held for 20 minutes. After the 20
minute
hold, all flow was secured in the centerline lance and the lance was removed.
After the centerline lance was removed, flow rates in the off-centerline lance
were adjusted to 30 ml/min of 88% argon, 12% nitrogen and trace neon and held
for 3
minutes. After the 3 minute hold, flow rates were adjusted to 0.30 L/min of
25%
helium, 75% argon and trace neon and held for 10 minutes. After the 10 minute
hold,
flow rates were adjusted to 0.30 L/min of 88% argon, 12% nitrogen and trace
neon and
held for 10 minutes. After the 10 minute hold, flow rates were adjusted to
0.15 L/min
of 88% argon, 12% nitrogen and trace neon and held for 5 minutes. After the 5
minute
hold, flow rates were adjusted to 30 ml/min of 88% argon, 12% nitrogen and
trace neon
and held for 2 minutes. After the 2 minute hold, flow rates were adjusted to
0.15 L/min
of 88% argon, 12% nitrogen and trace neon. Once the flow rate was adjusted,
the
reactor temperature was lowered to Ts Iidu, plus 15 F over 45 minutes. Upon
reaching
the Ts 11du, plus 15 F, flow was adjusted in the off-centerline lance to 0.30
L/min of
100% argon and trace neon and held for 5 minutes.
At the completion of five minute hold, the reactor temperature was lowered to
Ts 11dus plus 11 F while maintaining a temperature lowering rate of no more
than 3 F/hr.
Upon reaching TS Iidus plus 11 F, flow rate in the off-centerline lance was
adjusted to
0.30 L/min of 100% hydrogen and trace neon. At the completion of the flow
adjustment, the reactor temperature was lowered to TS Iidus plus 10 F while
maintaining
a temperature lowering rate of no more than 3 F/hr. Upon reaching T,.Iidus
plus 10 F,
flow rate in the off-centerline lance was adjusted to 30 ml/min of 100%
hydrogen and
trace neon. At the completion of the flow adjustment, the reactor temperature
was
lowered to TS Iidu, plus 9 F while maintaining a temperature lowering rate of
no more
than 3 F/hr. Upon reaching T,01Idus plus 9 F, the gas addition lance was
relocated into
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the headspace of the reactor, such that a quarter inch (1/4 inches) dimple
could be
observed on the bath surface. The bath was held at TS udus plus 9 F for an
additional 5
minutes for conditioning and equilibration. The reactor was then cooled to Ts
lidus plus
8 F while maintaining a temperature lowering rate of no more than 3 F/hr. Upon
reaching TS 1[dus plus 8 F a manual power pulse of 2 kW was introduced with a
single
continuous up/down sweep from normal holding power. The reactor was then
cooled to
Ts lidus plus 2 F while maintaining a temperature lowering rate of no more
than 3 F/hr.
Upon reaching T,ofidus plus 2 F, a manual power pulse of 1.5 kW was introduced
with a
single continuous up/down sweep from normal holding power. Immediately after
the
1.5 kW power pulse, flow was adjusted in the off-centerline lance to 0.15
L/min of 50%
hydrogen, 50% helium, and trace neon. The reactor was then cooled to TS I;dus
again
maintaining a temperature-lowering rate of no more than 3 F/hr. Upon reaching
Tsolidus,
the induction furnace power supply was lowered to 1 kW and the reactor was
allowed to
cool from Tsolidus to Ts tidus minus 75 F. Upon reaching Tsolidus minus 75 F,
flow rate in
the off-centerline lance was adjusted to 30 ml/min of 60% helium, 40% hydrogen
and
trace neon. Following the flow adjustment, the induction furnace power supply
was
lowered to 0.75 kW and the reactor was allowed to cool to 1000 F. Upon
reaching
1000 F, flow rate in the off-centerline lance was adjusted to 30 ml/min of
100% helium
and trace neon. Following the flow adjustment, the induction furnace power
supply was
lowered to 0.50 kW and the reactor was allowed to cool to 350 F. Upon reaching
350 F, the induction furnace power supply was shut down and a timer initiated
as time
zero (e.g., Timer = To). At a time of 5 minutes, flow rate in the off-
centerline lance was
adjusted to 0.60 L/min of 100% helium and trace neon. At a time of 9 minutes,
a neon
radiation source was remotely rotated within the sealed enclosure. Upon
completion of
the 90 rotation, flow in the off-centerline lance was adjusted to 0.30 L/min
of 88%
argon, 12% nitrogen and trace neon.
Following the flow adjustment, the timer was reinitiated to time zero. At a
time
of 25 seconds, a neon radiation source within the sealed enclosure was
remotely rotated.
At a time of 1 minute 30 seconds, a neon radiation source within the sealed
enclosure
was turned off. At a time of 5 minutes, an argon radiation source within the
sealed
enclosure was turned off. At a time of 6 minute 30 seconds, flow rate was
adjusted to
0.30 L/min of 100% helium and trace neon. At a time of 7 minute, the second
neon
radiation source within the sealed enclosure was turned off.
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The timer was reinitiated to time zero (e.g., Timer = To). At a time of 15
minutes, the trace neon gas flow in the off-centerline lance was stopped. At a
time of
17 minutes 25 seconds, the xenon radiation source was remotely rotated 90
within the
sealed enclosure. At a time of 30 minutes, the trace helium gas flow in the
off-
centerline lance was turned off. The timer was reinitiated to time zero (e.g.,
Timer =
To). At a time of 15 minutes, the xenon radiation source inside the sealed
enclosure was
turned off. Thirty minutes were allowed to pass. The ingot and crucible were
removed
from the reactor using titanium metal tongs in the presence of light from
metal halide
lamps.
Upon removal from the reactor assembly, the crucible was stripped from the
metal ingot via a gentle wedging action. Immediately following removal, the
ingot was
transferred into a quench chamber containing deionized water, ensuring that
the top of
the ingot surface was covered by at least 6 inches of deionized (DI) water.
Upon
immersion into the quench chamber, a timer was established. At a time of 2
hours 15
minutes, a long wave ultraviolet radiation source located above the quench
vessel was
initiated. At a time of 4 hours 7 minutes, a short wave ultraviolet radiation
source
located above the quench vessel was initiated. At a time of 5 hours 59 minutes
30
seconds, the short wave ultraviolet radiation source located above the quench
vessel
was rotated to a vertical position.
At a time of 6 hours, the ingot was removed from the quench system using the
titanium metal tongs and transferred to a clean radiation surface countertop.
Exposure
to external radiation sources included the metal halide light and placement
directly
under a skylight (which added filtered sunlight to the irradiation sources).
The ingot
was pat dried. Upon completion of the drying, the long wave ultraviolet
radiation
source located above the quench vessel was rotated to a vertical position and
moved up
1 inch. The timer was then reset to zero. The ingot was irradiated for 10
minutes at
which point an additional radiation source (krypton lamp) was initiated. At 12
minutes
seconds, the long wave ultraviolet radiation source located above the quench
vessel
was rotated and moved down to its original position. At 13 minutes, a xenon
radiation
30 source located above the quench vessel was initiated. At 18 minutes, two
orthogonal
fluorescent lamp racks located next to the countertop were turned on. At 30
minutes,
two angled metal halide lights located next to the countertop were
simultaneously
turned on. At this point the timer was again reset. At 13 minutes 15 seconds,
a neon
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radiation source located next to the countertop was turned on. At 15 minutes
30
seconds, an argon radiation source located next to the countertop was turned
on. At 23
minutes 45 seconds, the argon radiation source located next to the countertop
was
rotated to an angle of 35 . At 37 minutes 30 seconds, the short wave
ultraviolet
radiation source located above the quench vessel was rotated to 35 . At 47
minutes 30
seconds, the xenon radiation source located above the quench vessel was
rotated to
horizontal. At 52 minutes 45 seconds, the long wave ultraviolet radiation
source
located above the quench vessel was rotated to 35 . At 58 minutes 30 seconds,
the short
wave ultraviolet radiation source located above the quench vessel was rotated
to 55 . At
77 minutes, the krypton radiation source located next to the countertop was
rotated to
vertical. At 89 minutes, the krypton radiation source located next to the
countertop was
rotated to 78 . At 93 minutes, the ingot was lifted using composite black
rubber gloves
and a tailored material that acts an energy filter was placed under the ingot.
The
tailored material used as an energy filter has an XRF as depicted in Appendix
1. The
ingot was then lowered onto the tailored energy filter. During the
installation no direct
skin contact with the ingot was allowed. At 97 minutes, the krypton radiation
source
located next to the countertop was rotated to 88 .
At this point the timer was again reset. At a time of 6 hours, the krypton
lamp,
short wave ultraviolet, long wave ultraviolet, argon (located over quench
vessel), xenon,
argon (located next to countertop), neon, two orthogonal fluorescent lamp
racks, and the
two angled metal halide lights were sequentially terminated in the given
order. The
timer was again reset. At a time of 6 hours, 30 minutes, normal lab lighting
(metal
halides) was turned off. The timer was reset. For 48 hours, the ingot was
allowed to
stabilize with no manual intervention (i.e., no handling).
EXAMPLE 8:
EXPERIMENTAL PROCEDURE FOR COPPER Method "HD" RUN 14-04-05
A cylindrical alumina-based crucible (99.68% A1203, 0.07% SiO2, 0.08% Fe203,
0.04% CaO, 0.12% Na203i 4.5 inches O.D. X 3.75 inches I.D. X 14.5 inches
depth) of a
100 pound induction furnace reactor (Inductotherm) fitted with a 73-30R
Powertrak
power supply. A gas addition lance was installed to a position approximately
I/4 inches
from the bottom of the reactor. The reactor was charged with 9080 g copper
(99.98%
purity) through its charging port. The reactor was fitted with a graphite cap
and a
ceramic liner (i.e., the crucible, from Engineering Ceramics). During the
entire
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procedure, a slight positive pressure of 97% argon, 3% hydrogen (-0.5 psig)
was
maintained in the reactor using a continuous backspace purge. Bypass injection
of gas
addition was commenced (i.e., gas flow diverted around the reactor was
initiated) at a
rate of 0.15 L/min of argon. The incoming gas line for the gas addition lance
passed
through a sealed, light-tight enclosure whereby irradiation of the gas with
precise
radiation sources (e.g., wavelength, intensity, etc) was achieved. When the
entire gas
line was completely purged (assuming a plug flow model), a neon radiation
source was
activated within the sealed enclosure. A timer was set to zero. Bypass flow
was
adjusted to 100% argon at a flow rate of 0.15 L/min with trace neon present.
(trace can
be defined as < 0.005% vol. to < 5%). At a time of 3 minutes, an argon
radiation source
was activated within the sealed enclosure. After completion of another gas
line purge
(assuming a plug flow model), the gas line was switched from bypass to direct
injection
through the gas addition lance.
The induction furnace power was then initiated. The reactor was heated to
450 F, at a rate no greater than 300 F/hr, as limited by the integrity of the
crucible. The
induction furnace operated in the frequency range of 0 Hz to 3000 Hz, with
frequency
determined by a temperature-controlled feedback loop implementing an Omega
Model
CN3000 temperature controller. Upon reaching 450 F, the gas addition lance was
repositioned to 2 inches from the bottom of the reactor. The timer was again
set to zero.
At a time of 2 minutes, the gas composition was changed to 0.15 L/min of 66%
nitrogen, 34% hydrogen with trace neon present. After completion of another
gas line
purge (assuming a plug flow model), a krypton radiation source was initiated
in the
sealed enclosure. The reactor heat up was continued at a rate no greater than
300 F/hr,
as limited by the integrity of the crucible, until T,01idu, minus 30 F was
achieved. The
gas flow rate was then increased to 0.3 L/min with a constant gas composition.
At
Ts lidus a second argon radiation source was activated within the sealed
enclosure. Tsolidus
plus 8 F was approached over a 3 to 5 minute time span. From Ts0I;dus plus 8 F
to T,01idus
plus 15 F, the gas flow rate was reduced to 0.15 L/min with a constant gas
composition.
Immediately upon reaching TS lidus plus 15 F, a second neon radiation source
was
initiated in the sealed enclosure. Immediately after the second neon radiation
source
was initiated, the gas composition was adjusted to 75% hydrogen, 22% nitrogen,
3%
argon and trace neon. The molten bath was held at this condition for 5 minute
for
stabilization.
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After the 5 minute hold, the gas composition was adjusted to 20% helium, 63%
nitrogen, 17% argon, and trace neon. The bath was held under these conditions
for an
additional 15 minutes. Again, following the hold, the gas composition and flow
rate
were adjusted to 100% argon with trace neon at a rate of 0.3 L/min. The
reactor was
held at this condition for 3 minutes. The timer was reset to zero. At a time
of 65
minutes, graphite saturation assemblies (3/8 inches OD, 36 inches long high
purity (<5
ppm impurities) graphite rods) were inserted to the bottom of the copper
charge through
ports located in the top plate. The copper was heated to 2359 F over a one
hour period.
The bath was then held at this condition for 2 hours. Every 30 minutes during
the hold
period, an attempt was made to lower the graphite saturation assemblies as
dissolution
occurred. As the copper became saturated with carbon, the graphite saturation
assemblies were consumed. After the 2 hour hold period was complete, the
graphite
saturation assemblies were removed. An additional 2.06 grams of graphite
powder was
charged into the reactor through the charging port. The bath was then heated
to 2474 F
over one hour. Upon achieving 2474 F, the gas composition and now rate were
adjusted to 100% nitrogen with trace neon at a rate of 0.3 L/min. The reactor
conditions
were held for 5 minutes. The gas flow rate was reduced to 0.15 L/min with
constant
composition. Immediately following this reduction in gas flow, the krypton
radiation
source in the sealed enclosure was turned off. The timer was reset to zero. At
a time of
3 minutes, the gas flow rate was reduced to 37.5 ml/min with constant
composition.
One of the argon radiation sources inside the sealed enclosure was turned off.
At a time
of 5 minutes, the nitrogen component of the gas flow was discontinued, while
maintaining the flow of the trace neon. At a time of 10 minutes, one of the
neon
radiation sources was remotely rotated (90 ) within the sealed enclosure. The
reactor
temperature was lowered to 2451 IT over 7 minutes.
The temperature was then varied between 2413 F and 2451 F for 16 cycles.
Each cycle consisted of raising the temperature continuously over 7 minutes
and
lowering the temperature continuously over 7 minutes. After completion of the
14.5
cycles, argon was reintroduced at a flow rate of 0.15 L/min with trace neon.
Five
minutes into the 15th cycle, a xenon radiation source was activated within the
sealed
enclosure. At 6 minutes into the 15th cycle, a long wave ultraviolet radiation
source was
activated in the sealed enclosure. At sweep count 15.5, a short wave
ultraviolet
radiation source was initiated in the sealed enclosure. At sweep count 16,
remotely
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rotate the xenon radiation source within the sealed enclosure. The temperature
of the
copper was varied over another 5 cycles between 2413 F and 2451 F. After the
fifth
cycle, the reactor temperature was lowered to 2400 F over a 10 minute period.
Upon
achieving the target temperature of 2400, the graphite saturation assemblies
were
reinstalled in the copper and remained there for 1 hour. The graphite
saturation
assemblies were then removed.
Two voltage probes (source and ground probe) were then installed in the
headspace of the reactor and allowed to equilibrate for 5 minutes. Upon
completion of
the five minute hold the voltage probes were lowered into the bath. The source
probe
should be positioned 2 inches below the axial center and 1 inch from the
radial center.
The ground probe was positioned 0.75 inches above the axial position of the
source
probe and 1 inch from the radial center (180 from the source probe). Once the
probes
were installed a five minute hold at this condition was done to allow the bath
to
electronically equilibrate with the probes. Voltage was then applied to the
probes and
varied between multiple voltage set points. This voltage application was in a
continuous up/down sweep between two predetermined voltages. The first voltage
cycle was varied between 17 and 18 volts for 24 cycles. Each cycle consisted
of raising
the voltage continuously over 45 seconds and lowering the voltage continuously
over 45
seconds. The second voltage cycle was varied between 13.25 and 14.75 volts for
20
cycles. Each cycle consisted of raising the voltage continuously over 45
seconds and
lowering the voltage continuously over 45 seconds. The third voltage cycle was
varied
between 8.75 and 10.25 volts for 17 cycles. Each cycle consisted of raising
the voltage
continuously over 45 seconds and lowering the voltage continuously over 45
seconds.
The fourth voltage cycle was varied between 4.00 and 7.00 volts for 14 cycles.
Each
cycle consisted of raising the voltage continuously over 45 seconds and
lowering the
voltage continuously over 45 seconds. The fifth voltage cycle was varied
between 1.50
and 5.00 volts for 10 cycles. Each cycle consisted of raising the voltage
continuously
over 45 seconds and lowering the voltage continuously over 45 seconds. The
sixth
voltage cycle was varied between 0.50 and 2.00 volts for 3 cycles. Each cycle
consisted
of raising the voltage continuously over 45 seconds and lowering the voltage
continuously over 45 seconds. When the final cycle was completed the voltage
was set
onto a constant 1 volt setting. This voltage setting remains constant until a
later step
during which the leads are removed.
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The reactor temperature was lowered to 2397 F over 5 minutes. The reactor
was held at this temperature for 5 minutes with continued gas addition. The
temperature was then varied between 2391 F and 2397 F over 20 cycles. Each
cycle
consisted of lowering the temperature continuously over 9 minutes and raising
the
temperature continuously over 9 minutes. After the 20th cycle, third body gas
addition
was changed by turning off the argon component of the gas leaving only trace
neon gas
flow. The bath was then cooled to 2388 F over 5 minutes. Upon reaching 2388 F,
remotely rotate one of the neon radiation sources within the sealed enclosure.
The temperature was then varied between 2380 F and 2388 F over 4.5 cycles.
Each cycle consisted of lowering the temperature continuously over 5 minutes
and
raising the temperature continuously over 3 minutes. In addition, while
raising the
temperature, a 0.15 L/min flow of 60% argon, 40% helium, and trace neon was
added,
and while lowering the temperature, a 0.3 L/min flow of 100% helium, trace
neon, and
trace krypton was added. At sweep count 0.5, a krypton radiation source was
initiated
in the sealed enclosure. At sweep count 1.0, an argon radiation source was
initiated in
the sealed enclosure. At sweep count 4.5, the short wave ultraviolet radiation
source
was terminated in the sealed enclosure. The reactor temperature was lowered to
2377 F
over 5 minute. The temperature was varied between 2346 F and 2377 F for 15.5
cycles. Each cycle consisted of lowering the temperature continuously over 15
minutes
and raising the temperature continuously over 15 minutes. In addition, while
raising the
temperature, a 0.15 L/min flow of 60% argon, 40% helium, and trace neon was
added,
and while lowering the temperature, a 0.3 L/min flow of 100% helium, trace
neon, and
trace krypton was added. After the 15.5th cycle, third body gas addition was
changed by
turning off all gas components except the trace neon gas flow.
After the 15.5th cycle, a timer was established. At a time of 3 minutes, the
xenon
radiation source was rotated 90 within the sealed enclosure. The timer was
then reset
to zero. At 60 minutes, flow rates were adjusted to 0.3 L/min of 100% argon
and trace
neon. At 65 minutes, flow rates were adjusted to 30 ml/min of 60% argon, 40%
helium,
and trace neon. Immediately after the flow was adjusted, one of the neon
radiation
sources was remotely rotated 90 within the sealed enclosure. At 68 minutes,
flow rates
were adjusted to 0.15 L/min of 100% helium, trace neon and trace krypton. At
68
minutes 20 seconds, the 1 volt power was brought to zero output and the
voltage power
leads removed from the voltage probes. At 68 minutes 30 seconds, the long wave
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ultraviolet radiation source was turned off in the sealed enclosure. At 71
minutes 15
seconds, the voltage probes were repositioned to three inches above the bath
surface.
At 75 minutes, the source and ground probes were removed completely from the
reactor.
After the voltage probes had been removed from the reactor, flow rates were
adjusted to 0.15 L/min of 77% argon, 18% nitrogen, 5% helium and trace neon.
The
reactor was then held at temperature and flow rate for 15 minutes. After the
15 minute
hold, an argon radiation source was turned off in the sealed enclosure. The
flow rates
were immediately readjusted to 0.15 L/min of 77% argon, 12% nitrogen, 11%
helium
and trace neon. The reactor was then held at temperature and flow rate for 25
minutes.
After the 25 minute hold, the krypton radiation source was turned off in the
sealed
enclosure. The flow rates were immediately readjusted to 0.30 L/min of 10%
argon,
90% helium and trace neon. The reactor was then held at temperature and flow
rate for
3 minutes. After this 3 minute hold, flow rates were adjusted to 0.15 L/min of
10%
argon, 90% helium and trace neon and held for 2 minutes. After this 2 minute
hold,
flow rates were adjusted to 0.30 L/min of 7% hydrogen, 93% nitrogen and trace
neon
and held for 10 minutes. After this 10 minute hold, flow rates were adjusted
to 0.15
L/min of 7% hydrogen, 93% nitrogen and trace neon and held for 3 minutes.
After this
3 minute hold, flow rates were adjusted to 30 ml/min of 7% hydrogen, 93%
nitrogen
and trace neon and held for 2 minutes. After this 2 minute hold, flow rates
were
adjusted to 0.15 L/min of 87% argon, 10% nitrogen, 3% helium and trace neon
and held
for 5 minutes. After this 5 minute hold, flow rates were adjusted to 0.6 L/min
of 90%
argon, 10% nitrogen and trace neon and held for 7 minutes. After this 7 minute
hold,
flow rates were adjusted to 30 ml/min of 90% argon, 10% nitrogen and trace
neon and
held for 2 minutes. After this 2 minute hold, flow rates were adjusted to 0.60
L/min of
95% argon, 5% nitrogen and trace neon and held for 15 minutes. After this 15
minute
hold, flow rates were adjusted to 0.30 L/min of 95% argon, 5% nitrogen and
trace neon
and held for 5 minutes.
The reactor temperature was then lowered to 2359 F over 21 minutes. The
temperature was then varied between 2346 F and 2359 F for three cycles. The
cycles
consisted of raising the temperature continuously over 27 minutes and lowering
the
temperature continuously over 27 minutes. After the third cycle, the bath was
held at
2359 F for 5 minutes. The reactor temperature was then lowered to 2346 F over
2
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minutes 30 seconds. The temperature was then varied between 2359 F and 2346 F
for
two cycles. The cycles consisted of raising the temperature continuously over
11
minutes and lowering the temperature continuously over 7 minutes.
After the completion of the 2d cycle, the induction power supply was placed
into manual control. The power was then instantaneously increased 5 kW above
the
steady state power level and immediately upon hitting the 5kW increase the
power was
instantaneously decreased back to the steady state power level. The power
level was
then varied up 3.7 kW and down 3.7 kW over 6 cycles. The cycles consisted of
raising
power 3.7 kW above the steady state power level over 25 seconds. Once raised,
the
power level was held at the additional 3.7 kW setting for 45 seconds.
Following the 45
second hold, the power was lowered back to the steady state power level over a
15
second time frame.
After the 6th power cycle, the gas flows were adjusted to 0.60 L/min of 100%
argon and trace neon and held for 7 minutes. Following the seven minute hold,
the
argon flow was turned off leaving only the trace neon flow. Once the argon
flow was
turned off, a second lance was positioned inside the reactor. This lance
should be
placed at a position 2/3 of the distance from the radial center and 1.5 inches
from the
bottom of the bath. The centerline lance was then repositioned to t/4 inch
from the
bottom. Once the centerline lance was repositioned, flow was started in the
off-
centerline lance at a rate of 30 ml/min of 100% argon and trace neon. A timer
was then
initiated at zero (e.g., Timer = To). At a time of 2 minutes, the trace neon
flow in the
centerline lance was stopped. At a time of 2 minutes 30 seconds, flow was
initiated in
the centerline lance at a flow rate of 30 ml/min of 100% carbon monoxide and
held for
3 minutes. After the 3 minute hold, flow rates were adjusted in the off-
centerline lance
to 0.15 L/min of 100% argon and trace neon and held for 15 minutes. After the
15
minute hold, flow rates were adjusted in the off-centerline lance to trace
neon only.
Furthermore, the flow rate was adjusted in the centerline lance to 0.60 L/min
of 100%
carbon monoxide and held for 10 minutes. After the 10 minute hold, the carbon
monoxide in the centerline lance was turned off. The reactor temperature was
then
lowered to T,Widu, plus 18 F over 30 minutes. Upon reaching the TS tid, , plus
18 F, flow
was adjusted in the centerline lance to 0.30 L/min of 100% carbon monoxide and
held
for 20 minutes. After the 20 minute hold, all flow was discontinued in the
centerline
lance and the lance was removed.
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After the centerline lance was removed, flow rates are adjusted in the off-
centerline lance to 30 ml/min of 88% argon, 12% nitrogen and trace neon and
held for 3
minutes. After the 3 minute hold, flow rates were adjusted to 0.30 L/min of
25%
helium, 75% argon and trace neon and held for 10 minutes. After the 10 minute
hold,
flow rates were adjusted to 0.30 L/min of 88% argon, 12% nitrogen and trace
neon and
held for 10 minutes. After the 10 minute hold, flow rates were adjusted to
0.15 L/min
of 88% argon, 12% nitrogen and trace neon and held for 5 minutes. After the 5
minute
hold, flow rates were adjusted to 30 ml/min of 88% argon, 12% nitrogen and
trace neon
and held for 2 minutes. After the 2 minute hold, flow rates were adjusted to
0.15 L/min
of 88% argon, 12% nitrogen and trace neon. Once the flow rate was adjusted,
the
reactor temperature was then lowered to TS udõS plus 15 F over 45 minutes.
Upon
reaching the TS udus plus 15 F, flow was adjusted in the off-centerline lance
to 0.30
L/min of 100% argon and trace neon and held for 5 minutes.
At the completion of the 5 minute hold, the reactor temperature was then
lowered to TS 1idu, plus 11 F while maintaining a temperature lowering rate of
no more
than 3 F/hr. Upon reaching Ts lidu, plus 11 F, the flow rate in the off-
centerline lance
was adjusted to 0.30 L/min of 100% hydrogen and trace neon. At the completion
of the
flow adjustment, the reactor temperature was then lowered to TS vdu, plus 10 F
while
maintaining a temperature lowering rate of no more than 3 F/hr. Upon reaching
TS iidus
plus 10 F, the flow rate in the off-centerline lance was adjusted to 30 ml/min
of 100%
hydrogen and trace neon. At the completion of the flow adjustment, the reactor
temperature was lowered to TS tidu, plus 9 F while maintaining a temperature
lowering
rate of no more than 3 F/hr. Upon reaching T iidu, plus 9 F, the gas addition
lance was
relocated into the headspace of the reactor, such that a quarter inch (1/4
inches) dimple
could be observed on the bath surface. The bath was held at TS iidu, plus 9 F
for an
additional 5 minutes for conditioning and equilibration. The reactor was then
cooled to
Ts iidus plus 8 F while maintaining a temperature lowering rate of no more
than 3 F/hr.
Upon reaching TS tidus plus 8 F a manual power pulse of 2 kW was introduced
with a
single continuous up/down sweep from normal holding power. The reactor was
then
cooled to TS sdus plus 2 F while maintaining a temperature lowering rate of no
more than
3 F/hr. Upon reaching Ts0lidus plus 2 F a manual power pulse of 1.5 kW was
introduced
with a single continuous up/down sweep from normal holding power. Immediately
after the 1.5 kW power pulse, flow was adjusted in the off-centerline lance to
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L/min of 50% hydrogen, 50% helium and trace neon. The reactor was then cooled
to
Ts tidus again maintaining a temperature-lowering rate of no more than 3 F/hr.
Upon
reaching TS lidus, the induction furnace power supply was lowered to 1 kW and
the
reactor was allowed to cool from Ts jidus to Ts lidus minus 75 F. Upon
reaching Ts lidus
minus 75 F, flow rate in the off-centerline lance was adjusted to 30 ml/min of
60%
helium, 40% hydrogen and trace neon. Following the flow adjustment, the
induction
furnace power supply was lowered to 0.75 kW and the reactor was allowed to
cool to
1000 F. Upon reaching 1000 F, flow rate in the off-centerline lance was
adjusted to 30
ml/min of 100% helium and trace neon. Following the flow adjustment, the
induction
furnace power supply was lowered to 0.50 kW and the reactor was allowed to
cool to
350 F. Upon reaching 350 F, the induction furnace power supply was shut down
and a
timer initiated at time zero. At a time of 5 minutes, flow rate in the off-
centerline lance
was adjusted to 0.60 L/min of 100% helium and trace neon. At a time of 9
minutes, a
neon radiation source within the sealed enclosure was remotely rotated 90 .
Upon
completion of the rotation, flow in the off-centerline lance was adjusted to
0.30 L/min
of 88% argon, 12% nitrogen and trace neon.
Following the flow adjustment, reinitiate the timer to zero. At a time of 25
seconds, remotely rotate a neon radiation source within the sealed enclosure
(90 ). At a
time of 1 minute 30 seconds, a neon radiation source within the sealed
enclosure was
turned off. At a time of 5 minutes, a argon radiation source within the sealed
enclosure
was turned off. At a time of 6 minute 30 seconds, flow rate was adjusted to
0.30 L/min
of 100% helium and trace neon. At a time of 7 minute, the second neon
radiation
source within the sealed enclosure was turned off.
The timer was reinitiated to time zero. At a time of 15 minutes, the trace
neon
gas flow in the off-centerline lance was turned off. At a time of 17 minutes
25 seconds,
the xenon radiation source within the sealed enclosure was remotely rotated 90
. At a
time of 30 minutes, the trace helium gas flow in the off-centerline lance was
turned off.
The timer was reinitiated to time zero. At a time of 15 minutes, the xenon
radiation
source inside the sealed enclosure was turned off. Thirty minutes were allowed
to pass.
The ingot and crucible were removed from the reactor in the presence of
radiation
sources (metal halide light sources) utilizing titanium metal tongs.
Upon removal, the crucible was stripped from the metal ingot via a gentle
wedging action. Immediately following removal, the ingot was transferred into
a
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quench chamber containing deionized water, ensuring that the top of the ingot
surface
was covered by at least 6 inches of DI water. Upon entrance into the quench
chamber, a
timer was established at time zero. At a time of 2 hours 15 minutes, a long
wave
ultraviolet radiation source located above the quench vessel was initiated. At
a time of
4 hours 7 minutes, a short wave ultraviolet radiation source located above the
quench
vessel was initiated. At a time of 5 hours 59 minutes 30 seconds, the short
wave
ultraviolet radiation source located above the quench vessel was rotated (90 )
to a tip up
position.
At a time of 6 hours, the ingot was removed from the quench system using the
titanium metal tongs and transferred to a clean radiation surface countertop.
Exposure
to external radiation sources included the metal halide light and placement
directly
under a skylight (which added filtered sunlight to the irradiation sources).
The ingot
was pat dried. Upon completion of the drying, the long wave ultraviolet
radiation
source located above the quench vessel was rotated to a vertical orientation
and moved
up 1 inch. The timer was then reset to zero. The ingot was irradiated for 10
minutes at
which point an additional radiation source (krypton lamp) was initiated. At 12
minutes
30 seconds, the long wave ultraviolet radiation source located above the
quench vessel
was rotated (90 ) and moved down to its original position. At 13 minutes, a
xenon
radiation source located above the quench vessel was initiated. At 18 minutes,
two
orthogonal fluorescent lamp racks located next to the countertop were turned
on. At 30
minutes, two angled metal halide lights located next to the countertop were
simultaneously turned on. At this point the timer was again reset to zero. At
13
minutes 15 seconds, a neon radiation source located next to the countertop was
turned
on. At 15 minutes 30 seconds, an argon radiation source located next to the
countertop
was turned on. At 23 minutes 45 seconds, the argon radiation source located
next to the
countertop was rotated to an angle of 35 . At 37 minutes 30 seconds, rotate
the short
wave ultraviolet radiation source located above the quench vessel to 35 . At
47 minutes
seconds, the xenon radiation source located above the quench vessel was
rotated to a
horizontal orientation. At 52 minutes 45 seconds, the long wave ultraviolet
radiation
30 source located above the quench vessel was rotated to 35 . At 58 minutes 30
seconds,
the short wave ultraviolet radiation source located above the quench vessel
was rotated
to 55 . At 77 minutes, the krypton radiation source located next to the
countertop was
rotated to a vertical orientation. At 89 minutes, the krypton radiation source
located
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next to the countertop was rotated to 78 . At 93 minutes, the ingot was lifted
using
composite black rubber gloves and a tailored material that acts as an energy
filter was
placed under the ingot. The tailored material used as an energy filter has an
XRF as
depicted in Appendix 1. The ingot was then lowered onto the tailored energy
filter. At
97 minutes, the krypton radiation source located next to the countertop was
rotated to
88
At this point the timer was again reset to zero. At a time of 6 hours, the
krypton
lamp, short wave ultraviolet, long wave ultraviolet, argon (located over
quench vessel),
xenon, argon (located next to countertop), neon, two orthogonal fluorescent
lamp racks,
and the two angled metal halide lights were sequentially turned off in the
given
(aforementioned) order. The timer was again reset to zero. At a time of 6
hours, 30
minutes, normal lab lighting (metal halides) was turned off. The timer was
reset to
zero. For 48 hours, the ingot was allowed to stabilize with no manual
intervention (i.e.,
no handling).
Analytical Protocols:
X-ray Fluorescence
An ARL 8410 XRF was used to analyze each of the sample ingots. An ARL
8410 is a sequential wavelength dispersive spectrometer (WDS). Specific
emission
lines are used to determine the presence or absence, and the concentrations of
various elements. Each characteristic x-ray line is measured in sequence by
the
instrument by controlling the instrument geometry.
The ARL 8410 (WDS) spectrometer relies on the fundamentals of x-ray
diffraction. X-ray fluorescence occurs when matter is bombarded by a stream of
high-energy incident x-ray photons. When the incident X-radiation strikes the
sample, the incident x-rays may be absorbed, scattered, or transmitted for the
measurement of the fluorescent yield.
The ARL 8410 utilizes an end-window rhodium (Rh) x-ray tube. The end-
window is composed of beryllium, and holds the tube at high vacuum. The
filaments are heated giving off electrons by thermoionic emission. This beam
of
electrons then bombards the target Rh anode across a 10-70 keV voltage
potential.
Thus, primary x-rays are produced during the collision. The emitted x-ray
spectrum
consists of (1) "Continuum" or "Bremstrahlung" radiation, (2) Characteristic x-
ray
lines of the target material (e.g., K and L series), and (3) Characteristic
lines from
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any contaminants. Thus, the primary spectrum appears as a series of sharp
intense
peaks arrayed over a broad hump of continuum radiation. The ARL is equipped
with and uses two types of photon detectors, the Flow Proportional Counter
(FPC)
and the Scintillation Counter (SC).
The manufactured metal samples, unless otherwise specified, are prepared by
cutting a sample with an approximate cross-section of 1.1875" from the cooled
ingot. The axial edge and radial edge are then denoted. For non-brittle
samples, a
cube-shaped sample is used. When possible, a smooth surface is prepared for
analysis; the axial and radial faces are sequentially polished. The sample
faces are
sanded to 400 grit and then a polishing wheel is employed with 600 grit paper.
Finally, a 1 m polishing compound completes the smoothing process.
Prior to analysis, the sample is cleaned with isopropyl alcohol (IPA) and
placed in a sample cassette/holder. The sample holder is then loaded into the
XRF.
The orientation of the detector crystal with respect to the sample and the
photon detector is controlled synchronously such that characteristic x-ray
lines can
be accurately measured. A sequential measurement consists of positioning the
diffraction crystal at a given theta (diffraction angle) and the detector at
two-theta
and counting for a given period of time. The crystal and detector are then
rotated to
a different angle for the next characteristic x-ray line.
XRF 386 Software by Fisons Instruments is used to control the crystal and
detector placement. Uniquant Version 2 software, developed by Omega Data
Systems provides the data reduction algorithms for each analytical protocol.
The
sample results include an elemental composition list along with the associated
concentrations for each sample.
Measurement of Magnetism and Material Attraction
The magnetic and material attraction properties of the manufactured ingots
were tested via four methods:
Magnetic Attraction: An 1/8 inch diameter (0.0625 inch thick) neodymium iron
boron magnet (NdFeB) was scanned consistently and uniformly across the surface
of
the ingot to detect areas of attraction. Areas of attraction were then noted
at specific
sites on the surface in both a vertical and horizontally inverted (i.e.,
upside down)
orientation.
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iF atu=. IL a lu.l u.=}a Lrr. luu .. u=u -u uu.a uu.. .=.u..
Attraction to Iron: The attraction of iron chips (99%,,,t purity; between 10
and 25
mesh), iron powder (94%,,,t Fe, 3%Wt C, 3%Wt S), and spherical sponge iron
(99.8%,,t
purity, -50 to +100 mesh) to specific areas on the tailored ingots was
observed and
recorded. The retention of the iron media (chips, sponge balls, or powder) on
the
ingot surface was observed in a vertical and horizontally inverted (i.e.,
upside-down)
orientation.
Gauss Measurement: An F. W. Bell 4048 Gauss meter was used to perform precise
measurements of the magnetic fields observable across the surfaces of the
ingots. A
scan of each face was performed to create grids of the magnetic force. These
scans
provide an indication of the magnetic flux density, the property of magnetic
fields
that determines the force that is exerted upon a current or moving charge.
Hence, a
large magnetic field measurement should be indicative of strong attraction and
conversely no magnetic field measurement should be indicative of no
attraction.
The magnetic behavior of various points on the ingot were specifically
quantified to
note that even though they exhibited clear magnetic attraction, an
insignificant
Gauss reading was observed (e.g., comparable to the background magnetic field
measured at the earth's surface).
Non-magnetic Attraction: Many of the manufactured materials were found to
exhibit unique attraction to non-magnetic, non-ferromagnetic materials. For
example, sulfur powder was shown to exhibit an attraction to the surface of
the
tailored ingots. The sulfur powder (99.9% purity, 20 mesh) was spread evenly
over
the surface of the clean, polished, dry manufactured ingot. The ingot was then
rotated to a vertical position (90 to the ground). The retention of powder
was
documented via photography and manual mapping in a lab notebook. The sample
was inverted completely (180 rotation from its resting position on the
surface).
Again, powder retention was documented. This procedure was repeated on both
the
top and bottom surfaces of the manufactured ingot.
Hardness
Hardness testing was performed via multiple techniques, including Moh's
hardness testing and Rockwell hardness testing (both standard techniques). In
Moh's hardness testing the test angle approaches 0 , while in Rockwell testing
the
test angle approaches 90 . By testing at multiple angles, changes to different
contributing aspects of changing the composition of matter could be tested.
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The Rockwell method (ASTM 18-84 Standard Test Methods for Rockwell
Hardness and Rockwell Superficial Hardness of Metallic Materials) employs
either a
ball or a diamond cone in a precision-testing instrument that is designed to
measure
depth of penetration accurately. Two superimposed impressions are made, one
with
a load of 10 kg and the second with a load of 100 kg. The depth to which the
major
load drives the ball or cone below that depth to which the minor load has
previously
driven it is taken as a measure of the hardness. For hardened steels, greater
accuracy
is obtained by using a diamond cone (120 with slightly rounded tip) applied
under a
major load of 150 kg. The Rockwell hardness test B uses the 1/16" diameter
steel
ball with a 100 kg load. Scale B is appropriate for copper alloys, soft
steels,
aluminum alloys, malleable iron, etc.; Scale C is appropriate for steel, hard
cast
irons, pearlitic malleable iron, titanium, deep case hardened steel and other
materials
harder than B 100. The method using the cone is designated Rockwell C test.
Based
on the depth of the indentation, the hardness scale can be read directly from
the
scale, the higher the number, the harder the material. The dial-like scale is
really a
depth gauge, graduated in special units specific to the test being performed,
e.g.,
Rockwell Hardness C.
The Rockwell results are a useful measure of relative resistance to
indentation; however, the Rockwell test does not serve well as a predictor of
other
properties such as strength or resistance to scratches, abrasion, or wear.
Hence, the
Rockwell hardness test cannot be used alone for product specifications.
The Moh's Scales, in use since 1822, is used to rank the relative hardness of
minerals via the ability of materials to resist scratching by another
material. Moh's
scale consists of 10 minerals arranged in order from 1 to 10. Diamond is rated
as the
hardest and is indexed as 10. Talc is indexed as 1 and is the softest. Each
mineral in
the scale will scratch those below it:
Mineral Index
Diamond 10
Corundum 9
Topaz 8
Quartz 7
Orthoclase (Feldspar) 6
A atite 5
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iS""" +6a0 `6.ds .õdf No,p 11 It .. si.,AS :is` w~wL{ 4..,P s1,0
Fluorite 4
Calcite 3
Gypsum 2
Talc 1
The steps are not of equal value (i.e., nonlinear) and the difference in
hardness
between 9 and 10 is much greater than between 1 and 2 (i.e., step size
approaches an
exponential function). The hardness is determined by finding which of the
standard
minerals the test material will scratch or not scratch; the hardness will lie
between
two points on the scale-the first point being the mineral which is scratched
and the
next point being the mineral which is not scratched. In the determination
procedure,
it is necessary to be certain that a scratch is actually made and not just a
"chalk"
mark that will rub off. Natural copper is between 2 and 3 and tool steel is
between 6
and 7.
Appearance/Color
The color of each sample is noted via visual evaluation. In addition, unique
surface configurations are documented (for example, the expulsion of material
from
the bath upon cooling). Digital photography is used to document the physical
appearance.
Results:
The following is a list of manufactured materials prepared by the techniques
described herein and the ingot compositions.
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it 1' -11 t{,,.tt
Table 1: Manufactured Ingots Prepared via Specified Technique
Experimental Experimental Metal Quantity Purity
Protocol/Method Run Number rams wt
"AB" 14-03-02 Copper 9080 99.98
(Example 1)
"AB" without 14-03-03 Copper 9080 99.98
EM radiation
"AB" 14-01-10 Aluminum 3454 99.9
"AB" 14-01-11 Aluminum 3454 99.9
"HA" 14-02-06 Copper 9080 99.98
(Example 2
"HA" 14-04-02 Aluminum 4540 99.99
(Example 3)
44111)" 14-01-20 Cobalt 8899 99.5
(Example 4) Vanadium 182 99.5
Rhenium 7 99.997
"HD" 14-01-21 Nickel 9080 99.97
(Example 5) Rhenium 5 99.997
"HD" 14-01-13 Iron 8534 99.98
(Example 6) Vanadium 182 99.5
Chromium 182 99.999
Manganese 182 99.99
"HD" 14-04-03 Copper 9080 99.98
(Example 7) Rhenium 7 99.997
Silver 5 99.99
Gold 2 99.99
"HD" 14-04-05 Copper 9080 99.98
(Example 8)
"H1)" with 14-01-15 Iron 8534 99.98
modulated cool Vanadium 182 99.5
down Chromium 182 99.999
Manganese 182 99.99
"HD" with 14-02-03 Iron 9973.4 99.98
modulated EM Vanadium 212.2 99.5
radiation Chromium 212.2 99.999
Manganese 212.2 99.99
"HD" with 14-04-06 Copper 9080 99.98
modulated (EM
radiation) angle
of incidence
XRF Results:
Appendix 2 shows tables of XRF data results for the manufactured materials.
Note in each table the apparent detection of materials not present in the
initial
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u 'h.a: li 1, ,...II It 11, fl .1'= n..dstarting materials. Such detections
are indicative of a shift in the energy of the
manufactured materials, manifesting itself in "false positives" for the
detection of
elements not present.
In addition, despite the fact that the manufactured ingots were prepared in a
very well-mixed reactor, where composition should be homogeneous, significant
"apparent" compositional differences exist in the axial and radial directions.
Note
XRF data for each ingot is presented in back-to-back tables in Appendix 2.
This
anisotropic behavior is again indicative of changes in the energy patterning
of the
manufactured materials.
Such shifts in energy are demonstrated best in identical experiments that
were performed manufacturing copper (Runs 14-03-02 and 14-03-03). The primary
difference in these two experimental runs was to perform electromagnetic (EM)
energy addition to the third-body gases prior to injection into the reactor.
The XRF
results for these experiments are summarized below in Table 2:
Table 2: XRF Results Summary for 14-03-02 and 14-03-03
Element '14-03-02 14-03-03;
(wt %) (EM radiation addition
through third-bod gases)
Axial. Radial Axial Radial
Cu 97.95 99.03 99.55 99.23
Al 1.79 0.79 0.23 0.29
Si 0.111 - 0.038 0.27
La 0.012 - 0.02 -
Pr 0.005 - - 0.006
Gd - - 0.003 0.003
Er - 0.008 0.013 0.017
EConc. 99.8 99.5 99.0 99.3
Note the differences in axial and radial concentrations; the detection of
elements not
present in any of the initial feed materials or reactor materials; and the
differences in
experimental results for identical experimental programs except for the
addition of
EM radiation through third-body gases.
Physical Appearance and Color
Visual inspection of the manufactured materials indicates that the physical
characteristics of the material have been dramatically altered. Major physical
changes can include color, texture, the appearance of void spaces in the ingot
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internals, the expulsion of metal during the cooling process, and apparent
volumetric
changes.
Comparison of ingots of similar composition, but manufactured via alternate
techniques, can exemplify the physical manifestations of changes to the
composition
of matter. The exterior volume of ingot 14-04-01 (Example 1 of USSN
10/123,028,
substituting Al for Cu) is significantly greater (-30%) than 14-04-02 with an
internal
void in the ingot that runs approximately 80% down the length of the ingot.
Interestingly, the ingot 14-04-01 was subjected to lower volumetric gas flow
rates
than ingot 14-04-02; hence gas expansion is not a plausible explanation for
the
physical differences. Additionally, the ingot prepared via the subject method
exhibits a definite charcoal appearance, as opposed to the silvery appearance
of 14-
04-01. The exteriors are also different: smooth versus foil-like. Note that
the
magnetic behavior of ingot 14-04-01 was stronger than that of 14-04-02; yet
both
exhibited magnetic behavior not seen in natural aluminum. See magnetic
attraction
section for a discussion of magnetic attraction in tailored materials.
Similar differences in physical appearance were observed in manufactured
copper ingots as well. The observed physical differences between the two
ingots
were:
- 14-01-01 (Example 1 of USSN 10/123,028) had a void running
approximately 1/3-1/2 the depth of the ingot; while 14-02-06 actually had
major expulsion of material from the bath.
- 14-01-01 had the traditional copper color with some iridescence while the
ingot 14-02-06 exhibited a strong red color, also with some iridescence and
apparent band gap shift.
Interesting physical characteristics were also observable in copper ingots
prepared by one of the alternate techniques described herein. Based on
alterations to
the experimental plan, for example changes to the third body addition and/or
electromagnetic radiation sources, the material outcome were significantly
different.
Two copper ingots developed via an identical experimental plan except for
the addition of electromagnetic radiation through third-body addition. The
surface
of ingot 14-03-02 was smooth and exhibits what could be described as a "wood
grain" finish. Ingot 14-03-03 exhibited a "dimpled" rough finish, with what
appeared to be mosaic patterning. Material expulsion to form a "crown" was
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more significant in run 14-03-03. The color in ingot 14-03-02 followed the
traditional copper coloring more closely than 14-03-03 that exhibited a
broader
spectrum of colors including red and brown tones. As Table 2 shows, the
induced
elements were different for the two runs despite being prepared in the same
containment system, with identical operating conditions except for the
addition of
EM radiation to third body gases. Hence, the composition of matter has clearly
been
altered in both of these manufactured ingots.
Hardness Testing
Hardness testing was performed on material standards, natural copper,
manufactured copper prepared via the technique outlined in U.S. Patent
6,572,792
131, and manufactured copper prepared by the technique delineated herein. Two
primary hardness techniques were used: Rockwell Hardness and Moh's Hardness.
The Metals Handbook defines hardness as "Resistance of metal to plastic
deformation, usually by indentation." However, the term may also refer to
stiffness
or temper, to resistance to scratching, abrasion, or cutting. Hardness testing
does
not give a direct measurement of an engineering performance property; it
correlates
well with strength, wear resistance, and other properties.
Rockwell Hardness testing is an indentation testing method in which an
indenter is impressed into the test sample at a prescribed load to measure the
material's resistance to deformation. A Rockwell hardness number is then
calculated from the depth of permanent deformation of the sample after
application
and removal of the test load. Various indenter shapes and sizes combined with
a
range of test loads form a matrix of Rockwell hardness scales.
Moh's Hardness testing is a scratch test in which known standards are used
to scratch materials to specify surface hardness through resistance to
scratching.
Interesting test results were obtained in the testing of many of the
manufactured
ingots. For example, a sample could exhibit an exceptionally high Moh's
hardness
(i.e., resistance to scratching indicative of strong interfacial energy
enhancement) yet
shatter under the Rockwell Hardness Test (i.e., highly brittle material).
A Moh's scratch test was performed on a manufactured Fe/V/Cr/Mn ingot.
The surface was impervious to scratching by the Moh's Standard for a hardness
of
10, diamond. In fact, the diamond tip was actually damaged by the manufactured
alloy, indicating that the tailored material had an apparent Moh's Hardness
>10.
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Tool steel, a man-made material of natural elements with a similar composition
to
this tailored ingot, typically has a Moh's hardness between 6 and 7. This
tailored
material exhibited a hardness far exceeding that which would be expected from
natural materials and greater than that which had been seen in any previous
manufactured material (i.e., materials prepared via the method presented in
U.S.
Patent 6,572,792). Quite clearly, this process for tailoring material can
significantly
raise the hardness, with an abundance of beneficial, commercially-relevant
implications (e.g., drilling, mining, etc.).
Similar results on another tailored copper ingot compared with some
standards provided by the testing manufacturer. Note that the tailored
material
exhibited a very high Moh's hardness factor and exhibited greater hardness in
the
radial direction than in the axial direction. This anisotropic hardness
behavior is
generated through material tailoring. Despite this Moh's hardness factor, the
same
tailored ingot exhibited brittle failure during the Rockwell testing.
Magnetic and Material Attraction
Three different copper ingots were tailored via the techniques described
herein. Each of these ingots was subjected to a slightly different
experimental
protocol. For example, the experimental program may have varied by the time,
type,
or method of EM radiation addition. The resultant magnetic and physical
attraction
properties of each ingot are significantly different from natural copper and
significantly different from each other. The attraction behavior of these
three ingots
is summarized in below:
Table 3: Attraction Behavior of Tailored Copper Ingots (9080 g, 99.98%
purity)
Experimental Experimental NdFeB Sulfur
Run Number Protocol/Method Magnet` Attraction
Attraction
14-02-06 "HA" Observed Observed
14-04-05 "HD" Observed Observed
14-03-02 "AB" Observed Observed
Natural Copper None None
Each ingot exemplified magnetic attraction induced by the tailoring process:
behavior not present in natural copper. In addition to magnetic attraction,
these
ingots exhibited attraction to other non-magnetic materials, such as sulfur.
In each
92
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WO 2007/106094 PCT/US2006/009560
case, the testing for the attraction behavior of the sulfur powder was
performed on a
clean, polished, dry surface of the ingot to prohibit any effects of surface
tension or
adhesion. Additionally, the areas of magnetic attraction and sulfur attraction
were at
significantly different locations on the ingot, removing the possibility of
induced
attraction or other extraneous surface effects.
Three important points to note:
1. The sulfur attraction was at different locations than the magnetic
attraction, eliminating induction, surface irregularities, surface
adhesion, etc. as possible explanations for the attraction.
2. The intensity of the sulfur attraction and the magnetic attraction
mimicked each other. That is, ingots that exhibit multiple points of
magnetic attraction (widespread) tend to have extensive regions of
sulfur attraction.
3. The surfaces were polished, cleaned, and dried thoroughly before the
testing was performed. Analysis was performed in a fully vertical
position.
Each of these points supports the supposition of a change in the composition
of matter affecting the electromagnetic behavior of the tailored material.
Natural
copper exhibits no attraction to either magnets or sulfur. Yet, the
manufactured
copper, tailored via three different protocols, all exhibited unique
attraction
behavior.
In addition to pure copper, various alloys were subjected to the experimental
protocol outlined herein and similar results were obtained: non-ferromagnetic
material attraction, ferromagnetic material attraction, and magnetic
attraction.
The first example of such behavior is a Nickel/Rhenium ingot, Ingot 14-01-
21. This ingot, composed predominantly of Ni, will attract a magnet in its
natural
state. Hence, no magnetic testing was performed. However the attraction of
sulfur
powder and various ferromagnetic materials (Fe chips (99%w,t purity; 10-25
mesh),
spherical sponge Fe (ranging from "50 to +100 mesh, 99.8%w,t pure), and Fe
powder
94%w,t Fe, 3%w,t S, and 3%w,t C, none of which are attracted to natural nickel
or
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rhenium in the absence of an induced magnetic field caused by the presence of
a
magnet) were tested.
The Nickel/Rhenium tailored ingot exhibited unique material attraction
throughout the entire ingot (i.e., a volumetric property vs. a surface
property) as
exemplified on multiple faces of the cut ingot. To further demonstrate that
surface
irregularities are not the source of the unique attraction, an ingot was cut
and the
surface polished. The clean, dry, polished surface was then used for
evaluating the
attraction behavior of tailored materials.
In a similar emulation of the behavior observed in the tailored copper ingots,
the tailored Nickel/Rhenium ingot also exhibited significant attraction to
sulfur
powder.
To further demonstrate that the attraction behavior is caused by a change in
the composition of matter that in turn alters the electromagnetic behavior of
the
tailored material, a polished surface of the Ni/Re tailored ingot was tested
for sulfur
attraction (i.e., eliminate the effects of surface irregularities).
Additionally, the ingot
was rotated 180 . The same attraction patterning was observed independent of
vertical orientation, eliminating a surface lip or defect as a possible
explanation for
the attraction.
To demonstrate that the attraction behavior observed was not unique to
nickel alloys (e.g., due to their ferromagnetic behavior), a similar set of
attraction
experiments was performed on a tailored copper ingot containing Cu, Re, Ag,
and
Au. Sulfur attraction was achieved on multiple surfaces, in this instance, the
top and
the bottom.
This tailored copper alloy ingot exhibited multiple points of attraction to a
Nd/Fe/B magnet.
In yet another set of experiments to investigate the behavior of tailored
ingots
that are ferromagnetic in their natural state (i.e., can be induced to have a
magnetic
field, through the alignment of magnetic moments using a natural magnet), a
tailored
cobalt alloy ingot (Co/V/Re Ingot 14-01-20) was tested for material attraction
immediately following the end of the tailoring process. The manufactured
Co/V/Re
ingot did attract iron immediately following the tailoring process in limited
regions.
Given these positive attraction-testing results, further tests were performed
on the tailored copper and copper alloy (non-ferromagnetic) ingots. These non-
94
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ferromagnetic materials should not attract either a magnet or iron in their
natural
state. Yet, each of the manufactured copper ingots attracted spherical sponge
iron
(99.8%,,,t pure, -50 to +100 mesh). Ingots 14-04-05, 14-04-03, 14-02-06, all
exhibited a fairly random patterning ("sprinkling") of attraction, while ingot
14-03-
02 appears to have definite "lines" of attraction.
Magnetic Field Testing: Gauss Measurements
In a natural material, the attraction of a magnet or ferromagnet is
accompanied by the appearance of a magnetic field (caused by the alignment of
magnetic moments in the magnetic or ferromagnetic material creating a
measurable
field strength, magnetic density or magnetic flux). Since each of these
tailored
materials exhibited an attraction to a Nd/Fe/B magnet (and many attracted
ferromagnetic iron), Gauss readings were taken at designated intervals across
the
ingot surface to observe any potential magnetic fields (using an F.W. Bell
4048
Gauss Meter). The detailed magnetic grids obtained from such testing may be
found
in Appendix 3. The results are summarized in Table 4 below.
Table 4: Gauss Meter Readings Showing No Significant Measurable Magnetic
Fields on Tailored Ingots
'Expt'l Run Tailored Material 'Significant Maximum
Number and Experimental Magnetic Absolute
"Method"/Protocol Fieldt Gauss
Readin ,''r
14-04-05 Cu "HD" None 0.0 0.2
14-02-06 Cu "HA" None 0.0 0.2
14-03-02 Cu "AB" None 0.0 0.2
14-01-21 Ni/Re "HD" None 0.0 0.5
14-04-03 Cu/Re/Au/Ag "HD" None 0.0 0.2
tThe average magnetic field observed at the earth's surface is between
0.1-0.5 gauss.
The maximum absolute gauss reading for natural, high purity
(99.9%,,,,t) copper was 0.0 0.2.
The maximum absolute gauss reading for natural, high purity
(99.99%,,,t) nickel was 0.0 0.6.
Note, no significant detectable magnetic field was observed on any of these
tailored
ingots despite their ability to attract and hold a magnet at 90 (i.e.,
vertical
orientation). The measured gauss strengths are comparable to the background
levels
measured at the earth's surface. The average magnetic field observed at the
earth's
CA 02643749 2008-08-26
WO 2007/106094 PCT/US2006/009560
surface is between 0.1-0.5 gauss. Commercially available magnets exhibit gauss
strengths measured in the 1000's: Nd/Fe/B magnets 10,500-14,000 gauss, SmCo
8,000-12,000 gauss, AlNiCo 6,000-13,500 gauss and Ferrite 2,000-4,000 gauss.
In
addition, the areas exhibiting the greatest apparent magnetic force (0.5
gauss) were
tested for attraction to iron filings. No iron filings held on these
particular locations.
The conclusions that can be drawn from this series of documented
attractions:
= Tailored materials exhibit unique attraction to magnetic, ferromagnetic,
and non-magnetic materials that are not observed in natural materials.
= Unlike natural materials, tailored materials exhibit no correlation
between observable magnetic field strength (as measured by a gauss
meter) and material attraction (magnetic, ferromagnetic, or non-
magnetic).
= The unique attraction properties of tailored materials are attributable to a
change in the electromagnetic behavior, indicative of a change in the
composition of matter.
= These surface attractions are not attributable to surface irregularities or
induced magnetic fields as the tailored materials:
1. Have exhibited unique attraction in the "raw" and polished state,
in multiple positions, and on multiple surfaces (both internal and
external).
2. Have attracted fine particles (sulfur and spherical iron sponge)
and large particles (1/8" diameter magnetic, iron chips).
3. Have exhibited multiple areas of attraction and those areas
attracting sulfur are not necessarily the same areas that attract
ferromagnetic or magnetic materials. Similarly, areas that attract
magnets are not necessarily the areas that attract ferromagnets or
non-magnets.
Exhibit negligible magnetic field strengths as measured by an F.W. Bell 4048
gauss
meter.
1 Zee, A. Quantum Field Theory in a Nutshell. Princeton: Princeton U P, 2003
2 Wen, Xiao-Gang. Quantum Field Theory of Many-Body Systems. New York:
Oxford U P, 2004
96
CA 02643749 2008-08-26
WO 2007/106094 PCT/US2006/009560
3 Stormer, Horst, L., Daniel C. Tsui, Arthur C. Gossard. "The Fractional
Quantum
Hall Effect." Reviews of Modern Physics 71.2 (1999): S298-S305
4 Thurston, William, P. Three-Dimensional Geometry and Topology. Vol. 1.
Princeton: Princeton U P, 1997
5 Thurston, William, P. The Geometry and Topology of Three-Manifolds. March
2002. Princeton U P <http://www.msri.org/publications/books/gt3m>
6 Nakahara, Mikio. Geometry, Topology and Physics. Second Edition. London:
Institute of Physics Publishing, 2003
7 Nash, Charles. Differential Topology and Quantum Field Theory. London:
Academic P, 1991
8 Maskit, Bernard. "Moduli of Marked Reimann Surfaces." Bulletin of the
American Mathematical Society 80.4 (1974): 773-777
9 Kra, Irwin. "Horocyclic Coordinates for Riemann Surfaces and Moduli Spaces.
1:
Teichmuller and Riemann Spaces of Kleinian Groups." Journal of the American
Mathematical Society 3.3 (1990): 499-578
10 Keen, Linda, Bernard Maskit, and Caroline Series. Geometric Finiteness and
Uniqueness for Kleinian Groups with Circle Packing Limit Sets. December 1991.
<www.arxiv.org/ abs/math/9201299>
1 Keen, Linda and Caroline Series. "Pleating Coordinates for the Maskit
Embedding
of the Teichmuller Space of Punctured Tori." Topology 32.4 (1993): 719-749
While this invention has been particularly shown and described with
references to preferred embodiments thereof, it will be understood by those
skilled in
the art that various changes in form and details may be made therein without
departing from the scope of the invention encompassed by the appended claims.
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APPENDIX 1
ANALYSIS REPORT by Uniquant
-------------------------------------------------------------------------------
-
OLD.183
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = ENERGY FILTER: Tailored Material (RADIAL, INNER SURFACE)
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+E1 means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.042 29+Cu 97.54 0.08 51 Sb <
ll+Na 0.50 0.03 30+Zn < 52 Te <
12+Mg 0.046 0.005 31+Ga 0.007 0.003 53 I <
13+A1 0.91 0.04 32 Ge < 55 Cs <
14+Si 0.51 0.03 33 As < 56 Ba <2e 0.003
15+P 0.009 0.001 34 Se < SumLa..Lu 0.015 0.070
16+S 0.118 0.009 35 Br < 72+Hf <2e 0.022
16 So 37 Rb < 73+Ta <
17+C1 0.23 0.02 38 Sr < 74 W <
18 Ar < 39 Y < 75 Re <
19+K 0.031 0.003 40 Zr < 76 Os <
20+Ca 0.033 0.003 41 Nb < 77+1r 0.026 0.008
21 Sc < 42+Mo 0.007 0.002 78 Pt <
22+Ti 0.004 0.001 44 Ru < 79 Au <2e 0.007
23 V < 45 Rh < 80 Hg <2e 0.006
24+Cr < 46 Pd < 81 T1 <
25 Mn < 47 Ag <2e 0.002 82 Pb <2e 0.003
26+Fe 0.012 0.001 48 Cd <2e 0.002 83 Bi <
27+Co < 49 In < 90+Th 0.009 0.003
28 Ni < 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag <2e 0.002 60 Nd <
8 0 75 Re < 62 Sm <2e 0.002
9 F < 76 Os < 63 Eu <2e 0.001
77+Ir 0.026 0.008 64 Gd <2e 0.001
78 Pt < 65 Tb <
79 Au <2e 0.007 66 Dy <
67 Ho <
68+Er 0.008 0.003
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100%: 98.35
98
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ANALYSIS REPORT by Uniquant
-------------------------------------------------------------------------------
-
OLD.184
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = ENERGY FILTER: Tailored Material (RADIAL, OUTER SURFACE)
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.045 29+Cu 98.84 0.05 51 Sb <
11+Na 0.37 0.02 30+Zn < 52 Te <
12+Mg 0.041 0.005 31 Ga <2e 0.003 53 I <
13+Al 0.26 0.02 32 Ge < 55 Cs <
14+Si 0.083 0.007 33 As < 56+Ba 0.009 0.003
15+P 0.006 0.001 34 Se < SumLa..Lu 0.007 0.071
16+S 0.099 0.008 35 Br < 72+Hf <
16 So 37 Rb < 73+Ta <
17+C1 0.22 0.02 38 Sr < 74 W <
18 Ar < 39 Y < 75 Re <
19+K 0.025 0.002 40 Zr < 76 Os <
20+Ca 0.027 0.002 41 Nb < 77 Ir <2e 0.008
21+Sc 0.0023 0.0008 42 Mo < 78 Pt <
22 Ti < 44 Ru < 79 Au <
23 V < 45 Rh < 80 Hg <
24+Cr 0.0023 0.0006 46 Pd < 81 Tl <
25 Mn < 47 Ag < 82 Pb <
26+Fe 0.004 0.001 48 Cd < 83 Bi <2e 0.005
27 Co < 49 In < 90 Th <
28 Ni < 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59+Pr 0.006 0.002
7 N 47 Ag < 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76 Os < 63 Eu <
77 Ir <2e 0.008 64 Gd <
78 Pt < 65 Tb <
79 Au < 66 Dy <
67 Ho <
68 Er <
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 97.7 %
99
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Appendix 2
ANALYSIS REPORT by Uniquant
-------------------------------------------------------------------------------
-
OLD.180
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-01-15 AXIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon (7/94)
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100'
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.045 29+Cu 0.024 0.002 51 Sb <
11 Na < 30 Zn < 52 Te <
12+Mg 0.010 0.005 31+Ga 0.003 0.001 53 I <2e 0.002
13+Al 2.05 0.07 32 Ge < 55 Cs <2e 0.002
14+Si 0.41 0.02 33 As < 56 Ba <
15+P 0.0046 0.0004 34 Se < SumLa..Lu 0.02 0.21
16+S 0.022 0.002 35 Br < 72+Hf 0.017 0.005
16 So 37 Rb < 73 Ta <
17+Cl 0.0060 0.0007 38 Sr < 74+W 0.033 0.004
18 Ar < 39 Y < 75 Re <2e 0.004
19+K < 40 Zr < 76 Os <
20+Ca 0.020 0.002 41 Nb < 77+Ir <2e 0.004
21+Sc < 42 Mo <2e 0.002 78 Pt <
22 Ti < 44 Ru < 79 Au <2e 0.003
23+V 2.03 0.07 45 Rh < 80 Hg <
24+Cr 2.13 0.07 46 Pd < 81 Tl <
25+Mn 2.07 0.07 47 Ag < 82 Pb <2e 0.002
26+Fe 91.2 0.1 48 Cd < 83 Bi <
27 Co < 49 In < 90+Th 0.009 0.002
28 Ni <2e 0.003 50 Sn <2e 0.001 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59+Pr <2e 0.009
7 N 47 Ag < 60 Nd <
8 0 75 Re <2e 0.004 62+Sm <
9 F < 76 Os < 63+Eu <
77+Ir <2e 0.004 64 Gd <
78 Pt < 65+Tb <
79 Au <2e 0.003 66 Dy <
67 Ho <2e 0.007
68+Er <
69+Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% 94.4 %
100
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ANALYSIS REPORT by Uniquant
-------------------------------------------------------------------------------
-
OLD.181
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-01-15 RADIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon (7/94)
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100¾
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.046 29+Cu 0.010 0.002 51 Sb <
ll+Na 0.057 0.010 30 Zn < 52 Te <
12 Mg < 31 Ga < 53+1 0.005 0.002
13+A1 1.46 0.05 32 Ge < 55 Cs <
14+Si 0.069 0.007 33 As < 56 Ba <2e 0.003
15+P 0.0034 0.0003 34 Se < SumLa..Lu 0.01 0.21
16+S 0.012 0.001 35 Br < 72+Hf 0.011 0.005
16 So 37 Rb < 73 Ta <
17+Cl 0.0020 0.0005 38 Sr < 74+W 0.031 0.004
18 Ar < 39 Y < 75 Re <
19+K < 40 Zr < 76 Os <
20+Ca 0.014 0.001 41+Nb < 77 Ir <2e 0.004
21+Sc 0.0045 0.0006 42 Mo <2e 0.002 78 Pt <
22+Ti 0.0027 0.0006 44 Ru < 79 Au <
23+V 2.00 0.07 45 Rh < 80 Hg <2e 0.003
24+Cr 2.09 0.07 46 Pd < 81 Tl <
25+Mn 2.07 0.07 47 Ag < 82 Pb <2e 0.002
26+Fe 92.1 0.1 48 Cd <2e 0.002 83 Bi <
27 Co < 49 In < 90+Th 0.006 0.002
28 Ni < 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59+Pr <2e 0.009
7 N 47 Ag < 60 Nd <
8 0 75 Re < 62+Sm <
9 F < 76 Os < 63+Eu <
77 Ir <2e 0.004 64 Gd <
78 Pt < 65+Tb <
79 Au < 66 Dy <
67 Ho <
68+Er <
69+Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 98.1 %
101
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ANALYSIS REPORT by Uniquant
-------------------------------------------------------------------------------
OLD.113
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-03-02 AXIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wtd < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.042 29+Cu 97.95 0.07 51 Sb <
ll+Na 0.064 0.011 30+Zn < 52 Te <
12 Mg < 31 Ga <2e 0.003 53 I <
13+A1 1.79 0.06 32 Ge <2e 0.002 55 Cs <
14+Si 0.111 0.009 33 As < 56 Ba <2e 0.003
15+P < 34 Se < SumLa..Lu 0.023 0.069
16+S 0.0042 0.0004 35 Br < 72+Hf <
16 So 37 Rb < 73+Ta <
17+C1 0.017 0.001 38 Sr < 74 W <
18 Ar < 39 Y < 75 Re <
19 K < 40 Zr < 76 Os <
20+Ca 0.0056 0.0008 41 Nb < 77+Ir 0.032 0.008
21 Sc < 42+Mo 0.006 0.002 78 Pt <
22+Ti 0.0062 0.0008 44 Ru < 79 Au 0.014 0.007
23 V < 45 Rh <2e 0.002 80 Hg <2e 0.006
24+Cr < 46 Pd < 81 Tl <
25 Mn < 47 Ag < 82 Pb <2e 0.003
26 Fe < 48 Cd < 83 Bi <
27 Co < 49 In < 90 Th <
28 Ni < 50 Sn < 92 U <
Light Elements Noble Elements Lanthanides
4 Be 44 Ru < 57+La 0.012 0.003
B 45 Rh <2e 0.002 58 Ce <
6 C 46 Pd < 59 Pr 0.005 0.002
7 N 47 Ag < 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76 Os < 63 Eu <2e 0.002
77+Ir 0.032 0.008 64 Gd <
78 Pt < 65 Tb <2e 0.002
79 Au 0.014 0.007 66 Dy <
67 Ho <
68 Er <
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 99.8 %
102
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ANALYSIS REPORT by Uniquant
----------------------------------------------------------------------------
OLD.114
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-03-02 RADIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100 %
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.044 29+Cu 99.03 0.05 51 Sb <
ll+Na 0.089 0.012 30+Zn < 52 Te <
12 Mg < 31+Ga 0.011 0.003 53 I <
13+Al 0.79 0.04 32 Ge < 55 Cs <
14 Si < 33 As < 56 Ba <
15+P < 34 Se < SumLa..Lu 0.011 0.070
16+S 0.0061 0.0006 35 Br < 72+Hf <2e 0.022
16 So 37 Rb < 73+Ta <
17+C1 0.016 0.001 38+Sr 0.003 0.001 74 W <
18 Ar < 39 Y < 75 Re <2e 0.008
19 K < 40 Zr < 76 Os <
20+Ca 0.0062 0.0008 41 Nb < 77+1r 0.025 0.008
21+Sc 0.0027 0.0010 42 Mo < 78 Pt <
22 Ti < 44 Ru < 79 Au <2e 0.007
23 V < 45 Rh < 80 Hg <2e 0.006
24 Cr < 46 Pd < 81 Tl <
25 Mn < 47+Ag 0.004 0.002 82 Pb <
26 Fe < 48 Cd <2e 0.002 83 Bi <
27+Co < 49 In < 90+Th 0.006 0.003
28 Ni < 50 Sn < 92 U <
==== Light Elements.===== ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47+Ag 0.004 0.002 60 Nd <
8 0 75 Re <2e 0.008 62 Sm <
9 F < 76 Os < 63 Eu <
77+Ir 0.025 0.008 64 Gd <
78 Pt < 65 Tb <
79 Au <2e 0.007 66 Dy <
67 Ho <
68+Er 0.008 0.004
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 99.5 %
103
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ANALYSIS REPORT by Uniquant
-----------------------------------------------------------------------------
OLD.180
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-04-06 AXIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+E1 means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.045 29+Cu 97.48 0.08 51 Sb <
ll+Na 0.11 0.01 30+Zn < 52 Te <
12 Mg < 31 Ga <2e 0.003 53 I <
13+Al 0.20 0.01 32 Ge <2e 0.003 55 Cs <
14+Si 2.10 0.07 33 As < 56 Ba <2e 0.003
15+P < 34 Se < SumLa..Lu 0.012 0.062
16 S 35 Br < 72+Hf <2e 0.022
16+So 0.0077 0.0007 37 Rb < 73+Ta <
17+Cl 0.012 0.001 38 Sr <2e 0.001 74 W <
18 Ar < 39 Y < 75 Re <
19 K < 40 Zr < 76 Os <
20+Ca 0.0048 0.0008 41 Nb < 77+Ir 0.031 0.009
21+Sc 0.0076 0.0008 42 Mo < 78 Pt <
22 Ti < 44 Ru < 79 Au <2e 0.007
23 V < 45 Rh < 80 Hg <2e 0.006
24 Cr < 46 Pd < 81 T1 <
25 Mn < 47 Ag < 82 Pb <2e 0.003
26 Fe < 48 Cd < 83 Bi <
27+Co 0.0024 0.0007 49 In < 90 Th <2e 0.003
28 Ni < 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag < 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76 Os < 63 Eu <
77+Ir 0.031 0.009 64 Gd <
78 Pt < 65 Tb <
79 Au <2e 0.007 66 Dy <
67 Ho <
68+Er 0.012 0.003
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 94.5 %
104
CA 02643749 2008-08-26
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ANALYSIS REPORT by Uniquant
---------------------------------------------------------------------------
OLD. 181
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-04-06 RADIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.044 29+Cu 98.00 0.07 51 Sb <
ll+Na 0.10 0.01 30+Zn < 52 Te <
12 Mg < 31 Ga <2e 0.003 53 I <
13+Al 0.19 0.01 32 Ge < 55 Cs <2e 0.003
14+Si 1.66 0.06 33 As < 56 Ba <2e 0.003
15+P < 34 Se < SumLa..Lu 0.008 0.062
16+S 0.0066 0.0006 35 Br < 72+Hf <2e 0.023
16 So 37 Rb < 73+Ta <
17+Cl 0.0075 0.0009 38 Sr < 74 W <
18 Ar < 39 Y < 75 Re <
19+K 0.0024 0.0007 40 Zr < 76 Os <
20+Ca 0.0033 0.0008 41 Nb < 77+Ir 0.027 0.008
21 Sc < 42+Mo 0.007 0.002 78 Pt <
22 Ti < 44 Ru < 79 Au <2e 0.007
23 V < 45 Rh < 80 Hg <
24 Cr < 46 Pd < 81 Tl <2e 0.005
25 Mn < 47 Ag < 82 Pb <
26 Fe < 48 Cd < 83 Bi <
27+Co 0.0022 0.0006 49 In < 90 Th <
28 Ni < 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag < 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76 Os < 63 Eu 0.003 0.001
77+Ir 0.027 0.008 64 Gd <
78 Pt < 65 Tb <
79 Au <2e 0.007 66 Dy <
67 Ho <
68+Er <2e 0.003
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 96.7 %
105
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ANALYSIS REPORT by Uniquant
-----------------------------------------------------------------------------
OLD.363
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelil T1AP
Sample ident = 14-01-10 AXIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.015 29+Cu 0.0098 0.0009 51 Sb <
ll+Na 0.008 0.002 30+Zn 0.0037 0.0004 52 Te <
12+Mg < 31+Ga 0.0090 0.0008 53 I <
13+Al 83.8 0.2 32 Ge < 55 Cs <
14+Si 15.9 0.2 33 As < 56 Ba <2e 0.003
15+P 0.011 0.001 34 Se < SumLa..Lu 0.004 0.016
16 S 35 Br < 72 Hf <
16+So 0.045 0.004 37 Rb < 73 Ta <
17+Cl 0.034 0.003 38 Sr < 74+W 0.013 0.001
18 Ar < 39 Y < 75 Re <
19+K 0.007 0.001 40+Zr < 76 Os <
20+Ca 0.017 0.001 41 Nb < 77 Ir <
21 Sc < 42 Mo < 78 Pt <
22+Ti < 44 Ru < 79 Au <
23+V < 45 Rh < 80 Hg <
24+Cr < 46 Pd < 81 T1 <
25+Mn 0.0021 0.0004 47 Ag < 82+Pb <
26+Fe 0.16 0.01 48 Cd < 83 Bi <
27 Co < 49 In < 90 Th <
28+Ni 0.014 0.001 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La .<
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag < 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76 Os < 63 Eu <
77 Ir < 64+Gd 0.0021 0.0010
78 Pt < 65 Tb <
79 Au < 66 Dy <
67 Ho <
68 Er <
69 Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 85.8 %
106
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ANALYSIS REPORT by Uniquant
----------------------------------------------------------------------------
OLD.364
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-01-10 RADIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+E1 means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.016 29+Cu 0.013 0.001 51 Sb <
11 Na <2e 0.002 30+Zn 0.0031 0.0004 52 Te <
12+Mg < 31+Ga 0.0107 0.0010 53 I <
13+A1 75.1 0.2 32 Ge < 55 Cs <
14+Si 24.5 0.2 33 As < 56+Ba <2e 0.003
15+P 0.013 0.001 34 Se < SumLa..Lu 0.002 0.015
16 S 35 Br < 72 Hf <
16+So 0.030 0.003 37 Rb < 73 Ta <
17+Cl 0.049 0.004 38 Sr < 74+W 0.009 0.001
18 Ar < 39 Y < 75 Re <
19+K 0.0061 0.0010 40+Zr < 76 Os <
20+Ca 0.0092 0.0008 41 Nb < 77 Ir <
21 Sc < 42 Mo < 78 Pt <
22+Ti < 44 Ru < 79 Au <
23+V < 45+Rh < 80 Hg <
24+Cr < 46 Pd < 81 Tl <
25+Mn 0.0021 0.0004 47 Ag < 82+Pb 0.0026 0.0005
26+Fe 0.18 0.01 48 Cd < 83 Bi <
27 Co < 49 In < 90 Th <
28+Ni 0.014 0.001 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45+Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag < 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76 Os < 63 Eu <
77 Ir < 64 Gd <
78 Pt < 65 Tb <
79 Au < 66 Dy <
67 Ho <
68 Er <
69 Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 89.9 %
107
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ANALYSIS REPORT by Uniquant
-----------------------------------------------------------------------------
OLD.412
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-01-11 LOWER SECTION AXIAL (UNPOLISHED)
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
SumBe..F 0 0.020 29+Cu 0.24 0.02 51 Sb <
ll+Na 0.095 0.008 30+Zn 0.0060 0.0006 52 Te <
12+Mg <2e 0.004 31+Ga 0.015 0.001 53 I <
13+A1 98.35 0.06 32 Ge < 55+Cs <2e 0.003
14+Si 0.89 0.04 33 As < 56+Ba 0.012 0.004
15+P 0.017 0.002 34 Se < SumLa..Lu 0.006 0.020
16 S 35 Br < 72+Hf <2e 0.001
16+So 0.038 0.003 37 Rb < 73 Ta <
17+Cl 0.109 0.009 38 Sr < 74+W 0.013 0.002
18 Ar < 39 Y < 75 Re <
19+K 0.029 0.002 40+Zr < 76+Os 0.0028 0.0010
20+Ca 0.038 0.003 41 Nb < 77+Ir <
21 Sc < 42 Mo < 78 Pt <
22+Ti 0.0046 0.0008 44 Ru < 79 Au <
23+V 0.0022 0.0005 45 Rh < 80 Hg <
24+Cr 0.0031 0.0005 46 Pd < 81 Tl <
25+Mn 0.0035 0.0005 47 Ag < 82+Pb <
26+Fe 0.098 0.008 48 Cd < 83 Bi <
27+Co 0.0045 0.0005 49 In < 90 Th <
28+Ni 0.0055 0.0006 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag < 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76+Os 0.0028 0.0010 63 Eu <2e 0.001
77+Ir < 64 Gd <2e 0.001
78 Pt < 65 Tb <
79 Au < 66 Dy <
67 Ho <
68 Er <
69 Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0,
Sum Conc's before normalisation to 100% : 65.2 %
108
CA 02643749 2008-08-26
WO 2007/106094 PCT/US2006/009560
n v..a s: =b,a` .,..IS sl...lf sL.ds , sl..,ts :;ii' ...,.P sG,s ILdG
ANALYSIS REPORT by Uniquant
----------------------------------------------------------------------------
OLD.414
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-01-11 LOWER SECTION RADIAL (UNPOLISHED)
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 o
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0.032 0.019 29+Cu 0.13 0.01 51 Sb <
ll+Na 0.032 0.003 30+Zn 0.0058 0.0005 52 Te <
12+Mg <2e 0.004 31+Ga 0.016 0.001 53 I <
13+Al 96.85 0.09 32 Ge < 55+Cs <2e 0.003
14+Si 2.37 0.07 33 As < 56+Ba <2e 0.004
15+P 0.015 0.001 34 Se < SumLa..Lu 0.005 0.018
16 S 35 Br < 72+Hf 0.0027 0.0010
16+So 0.23 0.02 37 Rb < 73 Ta <
17+C1 0.056 0.005 38 Sr < 74+W 0.013 0.001
18 Ar < 39 Y < 75 Re <
19+K 0.024 0.002 40+Zr 0.0020 0.0003 76 Os <
20+Ca 0.15 0.01 41 Nb < 77+Ir <
21 Sc < 42 Mo < 78 Pt <
22+Ti 0.015 0.001 44 Ru < 79 Au <
23+V 0.0024 0.0004 45 Rh < 80 Hg <
24+Cr < 46 Pd < 81 Ti =<
25+Mn 0.0031 0.0005 47 Ag < 82 Pb <
26+Fe 0.054 0.005 48 Cd < 83 Bi <
27 Co < 49 In < 90 Th <
28+Ni 0.0048 0.0006 50 Sn < 92 U <
Light Elements Noble Elements Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag < 60 Nd <2e 0.001
8 0 75 Re < 62 Sm <
9 F <2e 0.019 76 Os < 63 Eu <2e 0.001
77+Ir < 64 Gd <
78 Pt < 65 Tb <
79 Au < 66 Dy <
67 Ho <
68 Er <
69 Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 69.7 %
109
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WO 2007/106094 PCT/US2006/009560
rr .rve . a I.at rrti Vrvv1 rturli . llrvrll ;:I`a rrvvll Ili+dk il.rll
ANALYSIS REPORT by Uniquant
----------------------------------------------------------------------------
OLD.417
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-01-11 UPPER SECTION AXIAL (UNPOLISHED)
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 s
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
SumBe..F 0.054 0.019 29+Cu 0.16 0.01 51 Sb <
ll+Na 0.066 0.005 30+Zn 0.0062 0.0006 52 Te <
12+Mg 0.014 0.004 31+Ga 0.024 0.002 53 I <
13+A1 97.80 0.07 32 Ge < 55 Cs <2e 0.003
14+Si 1.56 0.06 33 As < 56+Ba 0.009 0.004
15+P 0.035 0.003 34 Se < SumLa..Lu 0.010 0.018
16 S 35 Br < 72+Hf <2e 0.001
16+So 0.027 0.002 37 Rb < 73 Ta <
17+C1 0.058 0.005 38 Sr < 74+W 0.010 0.001
18 Ar < 39 Y < 75 Re <
19+K 0.021 0.002 40+Zr < 76 Os <
20+Ca 0.017 0.002 41 Nb < 77 Ir <
21 Sc < 42 Mo < 78 Pt <
22+Ti < 44+Ru < 79 Au <
23+V < 45 Rh < 80 Hg <
24+Cr < 46 Pd < 81 Tl <
25+Mn 0.0029 0.0005 47+Ag < 82 Pb <
26+Fe 0.111 0.009 48 Cd < 83 Bi <
27+Co < 49 In < 90 Th <
28+Ni 0.0055 0.0006 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44+Ru < 57 La <
B 45 Rh < 58+Ce 0.004 0.002
6 C 46 Pd < 59 Pr <
7 N 47+Ag < 60+Nd 0.003 0.001
8 0 75 Re < 62 Sm <
9+F 0.054 0.019 76 Os < 63+Eu 0.003 0.001
77 Ir < 64 Gd <
78 Pt < 65 Tb <
79 Au < 66 Dy <
67 Ho <
68 Er <
69 Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 68.1 %
110
CA 02643749 2008-08-26
WO 2007/106094 PCT/US2006/009560
ANALYSIS REPORT by Uniquant
----------------------------------------------------------------------------
OLD.423
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-01-11 UPPER SECTION RADIAL (UNPOLISHED)
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+E1 means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
SumBe..F 0.035 0.019 29+Cu 0.16 0.01 51 Sb <
11+Na 0.054 0.004 30+Zn 0.0064 0.0006 52 Te <
12+Mg 0.013 0.004 31+Ga 0.025 0.002 53 I <
13+A1 93.7 0.1 32 Ge < 55+Cs <2e 0.003
14+Si 4.7 0.1 33 As < 56+Ba 0.010 0.004
15+P 0.019 0.002 34 Se < SumLa..Lu 0.014 0.019
16 S 35 Br < 72+Hf <2e 0.001
16+So 0.63 0.03 37 Rb < 73 Ta <
17+C1 0.063 0.005 38 Sr < 74+W 0.007 0.001
18 Ar < 39 Y < 75 Re <
19+K 0.039 0.003 40+Zr < 76 Os <
20+Ca 0.44 0.03 41 Nb < 77+Ir <
21 Sc < 42 Mo < 78 Pt <
22+Ti 0.029 0.003 44 Ru < 79 Au <
23+V < 45 Rh < 80 Hg <
24+Cr < 46 Pd < 81 Ti <
25+Mn 0.0030 0.0005 47 Ag < 82 Pb <
26+Fe 0.097 0.008 48 Cd < 83 Bi <
27+Co < 49 In < 90+Th <2e 0.001
28+Ni 0.0066 0.0006 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58+Ce 0.004 0.002
6 C 46 Pd < 59 Pr <
7 N 47 Ag < 60 Nd <2e 0.001
8 0 75 Re < 62 Sm <
9 F <2e 0.019 76 Os < 63+Eu 0.003 0.001
77+Ir < 64 Gd <
78 Pt < 65 Tb <
79 Au < 66 Dy <
67 Ho <
68 Er <
69 Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 68.9 %
111
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WO 2007/106094 PCT/US2006/009560
t4 i.il II . 'hail' b..ilti..le 11õit .. II..+Ie .~i l' en.i{5 1{u,Jt Ilia{t
ANALYSIS REPORT by Uniquant
-----------------------------------------------------------------------------
OLD.446
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-01-13 AXIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.037 29+Cu 0.114 0.009 51 Sb <
ll+Na 0.050 0.010 30 Zn 0.005 0.002 52 Te <
12+Mg 0.023 0.004 31 Ga <2e 0.002 53 I <
13+A1 1.73 0.06 32 Ge < 55 Cs <2e 0.004
14+Si 1.05 0.05 33 As < 56+Ba 0.009 0.004
15+P 0.0067 0.0006 34 Se < SumLa..Lu 0 0.19
16 S 35 Br < 72+Hf 0.043 0.008
16+So 0.45 0.03 37 Rb < 73 Ta <
17+Cl 0.011 0.001 38+Sr 0.046 0.004 74+W 0.014 0.006
18 Ar < 39 Y < 75 Re <
19+K 0.019 0.002 40+Zr 1.55 0.06 76 Os <
20+Ca 0.82 0.04 41 Nb < 77 Ir <2e 0.005
21 Sc < 42 Mo < 78 Pt <
22+Ti 0.035 0.003 44 Ru < 79 Au <2e 0.005
23+V 1.75 0.06 45 Rh <2e 0.003 80 Hg <
24+Cr 1.99 0.07 46 Pd < 81 Tl <
25+Mn 1.72 0.06 47+Ag 0.005 0.002 82 Pb <2e 0.002
26+Fe 88.6 0.2 48 Cd < 83 Bi <
27 Co < 49 In < 90 Th <
28 Ni < 50 Sn <2e 0.002 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh <2e 0.003 58 Ce <
6 C 46 Pd < 59+Pr <
7 N 47+Ag 0.005 0.002 60 Nd <
8 O 75 Re < 62+Sm <
9 F < 76 Os < 63+Eu <
77 Ir <2e 0.005 64 Gd <
78 Pt < 65+Tb <
79 Au <2e 0.005 66 Dy <
67 Ho <
68+Er <
69 Tm <
70 Yb- <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 60.3 %
112
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,. rw,t[ =Iurr wwtt v.õ1' 'Yw,t: , [LõIS .;i' ., ,1~'tul' [tw1~
ANALYSIS REPORT by Uniquant
---------------------------------------------------------------------------
OLD.447
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Geill T1AP
Sample ident = 14-01-13 RADIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+E1 means involved in Sum=100%
Z wt% StdErr z wto StdErr z wt% StdErr
SumBe..F 0 0.032 29+Cu 0.096 0.008 51 Sb <
11+Na 0.094 0.009 30+Zn 0.010 0.002 52 Te <
12+Mg 0.030 0.003 31 Ga < 53 I <
13+Al 0.59 0.03 32 Ge < 55 Cs <
14+Si 0.14 0.01 33 As < 56 Ba <
15+P 0.0047 0.0004 34 Se < SumLa..Lu 0.01 0.19
16+S 0.044 0.004 35 Br < 72+Hf 0.015 0.005
16 So 37 Rb < 73 Ta <
17+C1 0.017 0.002 38 Sr < 74+w 0.012 0.005
18 Ar < 39 Y < 75 Re <
19+K 0.012 0.001 40+Zr 0.20 0.01 76 Os <2e 0.004
20+Ca 0.023 0.002 41 Nb < 77 Ir <2e 0.004
21+Sc < 42+Mo 0.004 0.002 78 Pt <
22+Ti 0.0076 0.0007 44 Ru < 79 Au <2e 0.004
23+V 1.95 0.06 45 Rh < 80 Hg <2e 0.003
24+Cr 2.33 0.07 46 Pd < 81 Tl .<
25+Mn 1.74 0.06 47 Ag < 82 Pb 0.004 0.002
26+Fe 92.7 0.1 48 Cd < 83 Bi <
27 Co < 49 In < 90 Th <
28 Ni < 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57+La 0.010 0.002
B 45 Rh < 58+Ce <
6 C 46 Pd < 59+Pr <
7 N 47 Ag < 60 Nd <
8 0 75 Re < 62+Sm <
9 F < 76 Os <2e 0.004 63+Eu <
77 Ir <2e 0.004 64 Gd <
78 Pt < 65+Tb <
79 Au <2e 0.004 66 Dy <
67 Ho <2e 0.009
68+Er <
69+Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 84.4 %
113
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ANALYSIS REPORT by Uniquant
----------------------------------------------------------------------------
OLD.488
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-01-20 AXIAL (THIN SECTION)
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.87 29+Cu 0.37 0.02 51 Sb <
ll+Na 0.28 0.02 30+Zn 0.013 0.003 52 Te <
12+Mg 0.035 0.004 31 Ga < 53 I <
13+A1 2.49 0.07 32 Ge < 55 Cs <2e 0.003
14+Si 0.32 0.02 33 As < 56 Ba <
15+P 0.0081 0.0007 34 Se < SumLa..Lu 0.01 10.00
16 S 35 Br < 72 Hf <2e 0.006
16+So < 37 Rb < 73 Ta <
17+C1 0.078 0.006 38 Sr < 74 W <
18 Ar < 39 Y < 75+Re 0.046 0.006
19+K 0.0086 0.0008 40+Zr < 76 Os <
20+Ca 0.054 0.005 41 Nb < 77 Ir <
21+Sc < 42 Mo <2e 0.002 78 Pt <
22+Ti < 44 Ru < 79 Au <
23+V 1.79 0.06 45 Rh < 80 Hg <
24+Cr 0.022 0.007 46 Pd < 81 Tl <2e 0.003
25+Mn 0.0082 0.0007 47 Ag <2e 0.002 82 Pb <2e 0.002
26+Fe 0.53 0.03 48 Cd <2e 0.002 83 Bi <
27+Co 93.8 0.1 49 in < 90 Th 0.005 0.002
28+Ni 0.18 0.01 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59+Pr <
7 N 47 Ag <2e 0.002 60 Nd <
8 0 75+Re 0.046 0.006 62 Sm <
9+F < 76 Os < 63+Eu 0.006 0.002
77 Ir < 64 Gd <2e 0.002
78 Pt < 65 Tb <
79 Au < 66 Dy <
67+Ho <
68+Er <
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 93.4 %
114
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ANALYSIS REPORT by Uniquant
-----------------------------------------------------------------------------
OLD.792
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-02-06 AXIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wto- StdErr z wt% StdErr
SumBe..F 0 0.043 29+Cu 98.80 0.05 51 Sb <
11+Na 0.065 0.012 30+Zn < 52 Te <
12 Mg < 31 Ga <2e 0.003 53 I <
13+Al 0.47 0.03 32 Ge < 55 Cs <
14+Si 0.59 0.03 33 As < 56 Ba <
15+P < 34 Se < SumLa..Lu 0.015 0.073
16+S 0.0031 0.0003 35 Br < 72+Hf <
16 So 37 Rb < 73+Ta <
17+C1 0.0103 0.0009 38 Sr < 74 W <
18+Ar 0.016 0.001 39 Y < 75 Re <
19 K < 40 Zr < 76 Os <2e 0.007
20+Ca 0.0036 0.0008 41 Nb < 77+Ir 0.024 0.008
21 Sc < 42 Mo < 78 Pt <
22 Ti < 44 Ru < 79 Au <2e 0.007
23 V < 45 Rh <2e 0.002 80 Hg <2e 0.006
24 Cr < 46 Pd < 81 T1 <
25 Mn < 47+Ag 0.004 0.002 82 Pb <
26 Fe < 48 Cd < 83 Bi <
27+Co < 49 In < 90 Th <2e 0.003
28 Ni < 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh <2e 0.002 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47+Ag 0.004 0.002 60 Nd <2e 0.002
8 0 75 Re < 62 Sm <
9 F < 76 Os <2e 0.007 63 Eu <
77+Ir 0.024 0.008 64 Gd <2e 0.002
78 Pt < 65 Tb <
79 Au <2e 0.007 66 Dy <
67 Ho <
68+Er 0.009 0.004
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 98.6 %
115
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ANALYSIS REPORT by Uniquant
-----------------------------------------------------------------------------
OLD.791 of 8-May-02 Today 8-May-02
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelil T1AP
Sample ident = 14-02-06 RADIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.042 29+Cu 98.23 0.07 51 Sb <
ll+Na 0.089 0.012 30+Zn < 52 Te <
12 Mg < 31+Ga 0.008 0.003 53 I <
13+A1 0.88 0.04 32 Ge < 55 Cs <
14+Si 0.69 0.03 33 As < 56+Ba 0.007 0.003
15+P < 34 Se < SumLa..Lu 0.014 0.074
16+S 0.0061 0.0006 35 Br < 72+Hf <
16 So 37 Rb < 73+Ta <
17+C1 0.027 0.002 38 Sr <2e 0.001 74 W <
18+Ar 0.015 0.001 39 Y < 75 Re <
19+K 0.0075 0.0008 40 Zr < 76 Os <
20 Ca < 41 Nb < 77+Ir 0.020 0.008
21 Sc < 42 Mo < 78 Pt <2e 0.007
22+Ti 0.004 0.001 44 Ru < 79 Au <
23 V < 45 Rh < 80 Hg <2e 0.006
24 Cr < 46 Pd < 81 Tl <
25 Mn < 47+Ag 0.004 0.002 82 Pb <
26 Fe < 48 Cd < 83 Bi <
27 Co < 49 In < 90 Th <
28 Ni < 50 Sn < 92 U <2e 0.003
==== Light Elements ==== Noble Elements ===== Lanthanides =======
4 Be 44 Ru < 57+La <2e 0.005
B 45 Rh < 58 Ce ..<
6 C 46 Pd < 59 Pr <
7 N 47+Ag 0.004 0.002 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76 Os < 63+Eu 0.005 0.002
77+Ir 0.020 0.008 64 Gd <
78 Pt <2e 0.007 65 Tb :'<
79 Au < 66 Dy <
67 Ho <
68 Er <
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 98.3 %
116
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-----------------------------------------------------------------------------
OLD.582
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelil T1AP
Sample ident = 14-02-03 AXIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+E1 means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
SumBe..F 0 0.043 29+Cu 0.048 0.004 51 Sb <
ll+Na 0.13 0.01 30 Zn < 52 Te <
12+Mg 0.044 0.005 31 Ga < 53 I <2e 0.002
13+Al 0.080 0.007 32 Ge < 55 Cs <
14+Si 0.019 0.008 33 As < 56 Ba <
15+P 0.0042 0.0004 34 Se < SumLa..Lu 0 0.21
16+S 0.023 0.002 35 Br < 72 Hf <2e 0.005
16 So 37 Rb < 73+Ta 0.46 0.03
17+C1 0.026 0.002 38 Sr < 74+W 0.015 0.004
18+Ar 0.0055 0.0010 39 Y < 75 Re <2e 0.004
19+K 0.0022 0.0006 40 Zr < 76 Os <
20+Ca 0.014 0.001 41+Nb < 77 Ir <
21+Sc 0.0030 0.0006 42 Mo < 78 Pt <
22 Ti < 44 Ru < 79 Au <
23+V 2.14 0.07 45 Rh < 80 Hg <
24+Cr 2.54 0.07 46 Pd < 81 T1 <
25+Mn 2.34 0.07 47 Ag < 82+Pb 0.005 0.002
26+Fe 92.1 0.1 48 Cd < 83 Bi <
27 Co < 49 In < 90+Th 0.011 0.002
28 Ni <2e 0.003 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59+Pr <2e 0.010
7 N 47 Ag < 60 Nd <
8 0 75 Re <2e 0.004 62+Sm <
9 F < 76 Os < 63+Eu <
77 Ir < 64 Gd <
78 Pt < 65+Tb <
79 Au < 66 Dy <
67 Ho <
68+Er <
69+Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 96.6 %
117
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ANALYSIS REPORT by Uniquant
-----------------------------------------------------------------------------
OLD.583
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-02-03 RADIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
- --------- -------------------------
SumBe..F 0 0.041 29+Cu 0.031 0.003 51 Sb <
ll+Na 0.074 0.011 30+Zn 0.004 0.002 52 Te <
12+Mg 0.066 0.005 31 Ga < 53 I <
13+A1 0.083 0.007 32 Ge < 55 Cs <2e 0.002
14+Si 0.027 0.008 33 As < 56 Ba <2e 0.003
15+P 0.0044 0.0004 34+Se < SumLa..Lu 0 0.21
16+S 0.022 0.002 35 Br < 72 Hf <2e 0.005
16 So 37 Rb < 73+Ta 0.51 0.03
17+C1 0.040 0.003 38 Sr < 74+W 0.013 0.004
18+Ar 0.0093 0.0009 39 Y < 75 Re <
19+K < 40 Zr < 76 Os <
20+Ca 0.043 0.004 41 Nb < 77 Ir <
21+Sc 0.0031 0.0006 42+Mo 0.005 0.002 78 Pt <
22 Ti < 44 Ru < 79 Au <
23+V 2.17 0.07 45 Rh < 80 Hg <
24+Cr 2.57 0.07 46 Pd < 81 Tl <2e 0.002
25+Mn 2.37 0.07 47 Ag < 82+Pb 0.004 0.002
26+Fe 91.9 0.1 48 Cd < 83 Bi <
27 Co < 49 In < 90+Th <2e 0.002
28 Ni <2e 0.002 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59+Pr ..<
7 N 47 Ag < 60 Nd <
8 0 75 Re < 62+Sm <
9 F < 76 Os < 63+Eu <
77 Ir < 64 Gd <
78 Pt < 65+Tb <
79 Au < 66 Dy <
67 Ho <
68+Er <
69+Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 98.5 %
118
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ANALYSIS REPORT by Uniquant
------------------------------------------------------------------------------
OLD.177
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-04-05 AXIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+E1 means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
---------------------- -- -- -- -
SumBe..F 0 0.047 29+Cu 96.98 0.09 51 Sb <
11+Na 0.081 0.012 30+Zn < 52 Te <
12 Mg < 31 Ga 0.006 0.003 53 I <
13+Al 0.36 0.02 32 Ge <2e 0.003 55 Cs <
14+Si 2.48 0.07 33 As < 56 Ba <2e 0.003
15+P < 34 Se < SumLa..Lu 0.027 0.070
16+5 0.0084 0.0008 35 Br < 72+Hf
16 So 37 Rb < 73+Ta <
17+C1 0.019 0.002 38 Sr < 74 W <
18 Ar < 39 Y < 75 Re <
19+K < 40 Zr < 76 Os <
20+Ca 0.0094 0.0009 41 Nb < 77+Ir 0.033 0.008
21+Sc 0.0025 0.0008 42 Mo <2e 0.002 78 Pt <
22+Ti <2e 0.001 44 Ru < 79 Au <
23 V < 45 Rh < 80 Hg <2e 0.006
24 Cr < 46 Pd < 81 T1 <
25 Mn < 47 Ag <2e 0.002 82 Pb <
26 Fe < 48 Cd <2e 0.002 83 Bi <
27+Co 0.0020 0.0008 49 In < 90 Th <2e 0.003
28 Ni < 50 Sn < 92 U <
Light Elements Noble Elements Lanthanides
4 Be 44 Ru < 57+La 0.012 0.004
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag <2e 0.002 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76 Os < 63 Eu <
77+Ir 0.033 0.008 64 Gd <
78 Pt < 65 Tb <
79 Au < 66 Dy <
67 Ho <
68+Er 0.013 0.004
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 97.4 %
119
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ANALYSIS REPORT by Uniquant
-----------------------------------------------------------------------------
OLD.178
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gell1 T1AP
Sample ident = 14-04-05 RADIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+E1 means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
-------- -------------------------
SumBe..F 0 0.049 29+Cu 97.84 0.07 51 Sb <
11+Na 0.082 0.013 30+Zn < 52 Te <
12 Mg < 31 Ga <2e 0.003 53 I <
13+Al 0.63 0.03 32 Ge < 55 Cs <
14+Si 1.34 0.05 33 As < 56 Ba <2e 0.003
15+P < 34 Se < SumLa..Lu 0.032 0.071
16+S 0.0066 0.0006 35 Br < 72+Hf <
16 So 37 Rb < 73+Ta <
17+Cl 0.018 0.002 38 Sr < 74 W <
18 Ar < 39 Y < 75 Re <2e 0.008
19+K 0.0021 0.0008 40 Zr < 76 Os <
20+Ca 0.0058 0.0008 41 Nb < 77+Ir 0.032 0.009
21+Sc 0.0042 0.0009 42 Mo <2e 0.002 78 Pt <
22+Ti 0.004 0.001 44 Ru < 79 Au <2e 0.007
23+V < 45 Rh < 80 Hg <
24 Cr < 46 Pd < 81 Tl <
25 Mn < 47 Ag <2e 0.002 82 Pb <
26 Fe < 48+Cd 0.004 0.002 83 Bi <
27 Co < 49+1n 0.004 0.002 90 Th <2e 0.003
28 Ni < 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57+La 0.022 0.005
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag <2e 0.002 60 Nd <
8 0 75 Re <2e 0.008 62 Sm <
9 F < 76 Os < 63 Eu 0.003 0.002
77+Ir 0.032 0.009 64 Gd <
78 Pt < 65 Tb <
79 Au <2e 0.007 66 Dy <
67 Ho <
68+Er <2e 0.004
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 97.7 %
120
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------------------------------------------------------------------------------
OLD.115
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Geill T1AP
Sample ident = 14-03-03 AXIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
- --------------------- -------------------------
SumBe..F 0 0.046 29+Cu 99.55 0.03 51 Sb <
ll+Na 0.079 0.012 30+Zn < 52 Te <
12 Mg < 31 Ga <2e 0.003 53 I <
13+A1 0.23 0.02 32 Ge <2e 0.003 55 Cs <
14+Si 0.038 0.006 33 As < 56 Ba <2e 0.003
15+P < 34 Se < SumLa..Lu 0.038 0.069
16+S 0.0030 0.0003 35 Br < 72+Hf <
16 So 37 Rb < 73+Ta <
17+Cl 0.0102 0.0009 38 Sr < 74 W <
18 Ar < 39 Y < 75 Re <
19+K 0.013 0.001 40 Zr < 76 Os <
20+Ca 0.0031 0.0008 41 Nb < 77+Ir 0.030 0.008
21 Sc < 42 Mo < 78 Pt <
22+Ti 0.0026 0.0007 44 Ru < 79 Au <
23 V < 45 Rh <2e 0.002 80 Hg <2e 0.006
24 Cr < 46 Pd < 81 Tl <
25 Mn < 47 Ag <2e 0.002 82 Pb <
26 Fe < 48 Cd <2e 0.002 83 Bi <
27+Co < 49 In < 90+Th 0.007 0.003
28 Ni < 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57+La 0.020 0.003
B 45 Rh <2e 0.002 58 Ce <2e 0.002
6 C 46 Pd < 59 Pr <
7 N 47 Ag <2e 0.002 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76 Os < 63 Eu <
77+Ir 0.030 0.008 64 Gd 0.003 0.002
78 Pt < 65 Tb <
79 Au < 66 Dy <
67 Ho <
68+Er 0.013 0.004
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 99.0 %
121
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------------------------------------------------------------------------------
OLD.116
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 014-03-03 RADIALk
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+E1 means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.045 29+Cu 99.23 0.04 51 Sb <
ll+Na 0.086 0.011 30+Zn < 52 Te <
12 Mg < 31 Ga 0.006 0.003 53 I <2e 0.002
13+A1 0.29 0.02 32 Ge < 55 Cs <
14+Si 0.27 0.02 33 As 0.009 0.004 56+Ba 0.007 0.003
15+P < 34 Se < SumLa..Lu 0.027 0.069
16+S 0.0034 0.0003 35 Br < 72+Hf <
16 So 37 Rb < 73+Ta <
17+Cl 0.0100 0.0009 38+Sr 0.003 0.001 74 w <
18 Ar < 39 Y < 75 Re <
19 K < 40 Zr < 76 Os <2e 0.007
20+Ca 0.0109 0.0010 41 Nb < 77+Ir 0.022 0.008
21 Sc < 42 Mo < 78 Pt <
22 Ti < 44 Ru < 79 Au <2e 0.007
23 V < 45 Rh <2e 0.002 80 Hg <
24+Cr 0.0026 0.0006 46 Pd < 81+T1 0.019 0.005
25 Mn < 47 Ag <2e 0.002 82 Pb <2e 0.003
26 Fe < 48 Cd < 83 Bi <
27+Co < 49 In < 90+Th 0.011 0.003
28 Ni < 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh <2e 0.002 58 Ce <
6 C 46 Pd < 59+Pr 0.006 0.002
7 N 47 Ag <2e 0.002 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76 Os <2e 0,007 63 Eu <
77+Ir 0.022 0.008 64+Gd 0.003 0.002
78 Pt < 65 Tb <
79 Au <2e 0.007 66 Dy <
67 Ho <
68+Er 0.017 0.004
69 Tm <
70 Yb <
71+Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 99.3 %
122
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n r..a n u 'b..d' yudt iSnA, ,L.d, , ,f,.=U .u ,...dt U it +1u.,4
ANALYSIS REPORT by Uniquant
-----------------------------------------------------------------------------
OLD.185
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-01-21 AXIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
---------- -------------------------
SumBe..F 0 0.043 29 Cu < 51 Sb <
it+Na 0.046 0.010 30+Zn 0.008 0.003 52 Te <
12 Mg < 31 Ga < 53 1 <
13+A1 3.73 0.09 32 Ge < 55 Cs <
14+Si 0.63 0.03 33 As < 56 Ba <
15+P 0.0051 0.0005 34+Se 0.006 0.002 SumLa..Lu' 0.10 1.19
16+S 0.0086 0.0008 35 Br < 72+Hf =0.036 0.008
16 So 37 Rb < 73+Ta <
17+C1 0.0050 0.0009 38 Sr < 74+W <
18 Ar < 39 Y < 75+Re 0.054 0.007
19 K < 40+Zr 2.05 0.07 76 Os <
20+Ca 0.0038 0.0008 41 Nb < 77 Ir <2e 0.006
21 Sc < 42+Mo < 78 Pt <
22 Ti <2e 0.001 44 Ru < 79 Au <2e 0.005
23+V < 45+Rh 0.004 0.002 80+Hg <2e 0.005
24 Cr < 46 Pd < 81 Ti
<
25 Mn < 47 Ag <2e 0.002 82 Pb <
26+Fe <2e 0.002 48 Cd < 83 Bi <
27+Co 0.044 0.004 49 In < 90 Th <
28+Ni 93.3 0.1 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45+Rh 0.004 0.002 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag <2e 0.002 60 Nd <
8 0 75+Re 0.054 0.007 62 Sm <
9 F < 76 Os < 63 Eu <
77 Ir <2e 0.006 64 Gd <
78 Pt < 65 Tb <
79 Au <2e 0.005 66+Dy <
67+Ho <
68 Er <
69 Tm <
70+Yb <2e 0.26
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 98.3 %
123
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WO 2007/106094 PCT/US2006/009560
It +i.r.d= I5 r 'N ~+r .}i It..,i 11..,1= r 4,.d+ .rt .uuls +I .1? +I ait
ANALYSIS REPORT by Uniquant
-------------------------------------------------------------------------------
OLD.186
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll T1AP
Sample ident = 14-01-21 RADIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.043 29 Cu < 51 Sb <
ll+Na 0.060 0.010 30+Zn 0.006 0.003 52 Te <
12 Mg < 31 Ga <2e 0.002 53 I <2e 0.002
13+A1 3.12 0.08 32 Ge < 55 Cs <
14+Si 0.72 0.04 33 As < 56 Ba <
15+P 0.0072 0.0006 34+Se 0.007 0.002 SumLa..Lu 0.13 1.18
16+S < 35 Br < 72+Hf 0.067 0.008
16 So 37 Rb < 73+Ta <
17+Cl 0.0025 0.0008 38 Sr < 74+W <
18 Ar < 39 Y < 75+Re 0.041 0.007
19 K < 40+Zr 3.09 0.08 76 Os <
20+Ca 0.0024 0.0007 41 Nb < 77 Ir <2e 0.005
21 Sc < 42+Mo < 78 Pt <2e 0.006
22+Ti 0.0071 0.0010 44 Ru < 79 Au <
23+V < 45 Rh < 80+Hg <2e 0.005
24 Cr < 46 Pd < 81 Tl <
25 Mn < 47 Ag <2e 0.002 82 Pb 0.005 0.002
26 Fe < 48 Cd < 83 Bi <
27+Co 0.043 0.004 49 In < 90+Th <2e 0.004
28+Ni 92.7 0.1 50 Sn < 92 U <2e 0.003
Light Elements Noble Elements Lanthanides
4 Be 44 Ru < 57+La Ø008 0.004
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag <2e 0.002 60 Nd <
8 0 75+Re 0.041 0.007 62 Sm <
9 F < 76 Os < 63 Eu <2e 0.001
77 Ir <2e 0.005 64 Gd <
78 Pt <2e 0.006 65 Tb <
79 Au < 66+Dy <
67+Ho <
68 Er <
69 Tm <
70+Yb <2e 0.26
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 98.4 %
124
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it 11-t, it .).,I, -R It II f ItIi .d ..,...lt 4.,I, ^.=Il
ANALYSIS REPORT by Uniquant
-------------------------------------------------------------------------------
OLD.187
Spectrometers configuration: ARL 8410 Rh 60kV L1F220 LiF420 Gelll T1AP
Sample ident = 14-04-02 AXIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0 0.021 29+Cu 0.025 0.002 51 Sb <
ll+Na 0.019 0.002 30+Zn < 52 Te <
12+Mg 0.011 0.004 31 Ga < 53 I <
13+A1 93.3 0.1 32 Ge < 55 Cs <
14+Si 6.4 0.1 33 As < 56+Ba <2e 0.004
15+P 0.016 0.001 34 Se < SumLa..Lu.'0.006 0.017
16+S 0.045 0.004 35 Br < 72+Hf 0.0042 0.0010
16 So 37 Rb < 73 Ta <
17+Cl 0.029 0.003 38 Sr < 74+W 0.014 0.001
18 Ar < 39 Y < 75 Re <
19+K 0.0042 0.0010 40 Zr < 76 Os ;.<
20+Ca 0.039 0.003 41 Nb < 77 Ir <
21 Sc < 42 Mo < 78 Pt <
22+Ti 0.082 0.007 44 Ru < 79 Au <
23+V < 45 Rh < 80 Hg <
24+Cr < 46 Pd < 81 Tl <
25+Mn < 47+Ag 0.0021 0.0007 82 Pb <
26+Fe 0.028 0.002 48 Cd < 83 Bi <
27+Co < 49 In < 90 Th <
28+Ni 0.0044 0.0005 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47+Ag 0.0021 0.0007 60 Nd <
8 0 75 Re < 62 Sm <
9 F < 76 Os < 63 Eu <2e 0.001
77 Ir < 64+Gd <2e 0.001
78 Pt < 65 Tb <
79 Au < 66 Dy <
67 Ho <
68 Er <
69 Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 80.0 %
125
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R 'I-'. It 1 1- ".& 11.,51 4 II I1-II ':;iI1 '.'. i It lk ii-il
ANALYSIS REPORT by Uniquant
-------------------------------------------------------------------------------
OLD.188
Spectrometers configuration: ARL 8410 Rh 60kV LiF220 LiF420 Gelll TlAP
Sample ident = 14-04-02 RADIAL
Kappa list = 15-Nov-94
Calculated as : Elements Spectral impurity data : CAL.909 Teflon
X-ray path = Vacuum Film type = No supporting film
Case number = 0 Known Area, %Rest, Diluent/Sample and Mass/Area
Eff.Diam. = 25.00 mm Eff.Area = 490.6 mm2
KnownConc = 0 %
Rest = 0 %
Dil/Sample = 0
Viewed Mass = 18000.00 mg
Sample Height = 5 mm
< means that the concentration is < 20 ppm
<2e means wt% < 2 StdErr. The + in Z+El means involved in Sum=100%
Z wt% StdErr z wt% StdErr z wt% StdErr
------------------------- ------------------------- -------------------------
------------------------- ------------------------- -------------------------
SumBe..F 0.048 0.020 29+Cu 0.027 0.002 51 Sb <
11+Na 0.016 0.002 30+Zn < 52 Te .<
12+Mg 0.012 0.004 31 Ga < 53 I <
13+Al 96.13 0.10 32 Ge < 55+Cs <2e 0.003
14+Si 3.16 0.08 33 As < 56+Ba 0.009 0.003
15+P 0.015 0.001 34 Se < SumLa..Lu 0.002 0.017
16+S 0.029 0.003 35 Br < 72+Hf 0.0027 0.0009
16 So 37 Rb < 73 Ta <
17+Cl 0.035 0.003 38 Sr < 74+W 0.014 0.001
18 Ar < 39 Y < 75 Re <
19+K 0.009 0.001 40 Zr < 76 Os <
<
20+Ca 0.37 0.02 41 Nb < 77 It
21 Sc < 42 Mo < 78 Pt <
22+Ti 0.074 0.006 44 Ru < 79 Au <
23 V < 45 Rh < 80 Hg
24+Cr 0.0023 0.0005 46 Pd < 81 Tl <
25 Mn < 47 Ag < 82 Pb '<
26+Fe 0.027 0.002 48 Cd < 83 Bi <
27+Co < 49 In < 90 Th = <
28+Ni 0.0046 0.0005 50 Sn < 92 U <
==== Light Elements ==== Noble Elements ===== Lanthanides
4 Be 44 Ru < 57 La <
B 45 Rh < 58 Ce <
6 C 46 Pd < 59 Pr <
7 N 47 Ag < 60 Nd <
8 0 75 Re < 62 Sm <
9+F 0.048 0.020 76 Os < 63 Eu <
77 Ir < 64 Gd <
78 Pt < 65 Tb <
79 Au < 66 Dy <
67 Ho <
68 Er <
69 Tm <
70 Yb <
71 Lu <
KnownConc= 0 REST= 0 D/S= 0
Sum Conc's before normalisation to 100% : 79.1 %
126
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u. rru.. rl .~ 'iu.)." u.ll 4Fr.ri1 1{writ .r Iirr~i .iifr ,.u.ln,..l. rlr+.tr
Appendix 3
Tailored Copper Ingot 14-04-05 "HD" Run:
F. W. Bell 4048 Gauss meter readings on the top
surface of the bottom section (i.e., internal surface
that exhibited attraction).
A B C D E F G H I J K L M
1 0 ,0.1 0 0
2 -0.1 0 0 0 0 0 0
3 1 0.2 0 0 0.1 0 0 0 0 701
4 11 0 0 0 -0.1 0 -0.1 -0.1 0 0= 0
0 0 0 0 0 0 0 0 0 X0.1 0
6 0 0.1 0 0 0 0 0 0 -0.1 0 0 -0.1 0
7 0 0 0 0 0 0 0 0 0 0 0 0 0
8 0 0 0.1 0 0 -0.1 -0.1 0 0 0.1 0 0 0
9 0.1 -0.1 0 0 0 0 0 0 0 0 0 0
0 0 0 0.1 0.1 0 0 0 0 0 0
11 0 -0.1 0 0 0 0 0.1 0 0
12 0 0.1 0 0 0 0
13 0 0 0 0 0.
Average 0.019424
Maximum 0.2
Minimum 0
of Absolute Values
Measurements in Gauss
127
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u ,.uV 11 1 1, -p '1 .il It-It = Bmll '::iP . it li-ll Iln.l,
Tailored Copper Ingot 14-02-06 "HA" Run:
F. W. Bell 4048 Gauss meter readings on the top
surface of the bottom section (i.e., internal surface
that exhibited attraction).
A B C D E F G H I J K L M
1 0 0 0 C
2 .2 -0.1 -0.2 0 -0.1 0 0 0
3 -0.1' -0.2:; -0.2 0 0 -0.1 0 0
4 0 0 0 0 0 -0:2 -0.1 -0.1 0 0
0 1 -0.2 -0.1 -0.2 -0.2 -012 0 0 -0.1 0 -0.2 -0.1
6 0 0 0 0 0 0.1 -0.11 0 0 0 -01 0 1 0
7 0 -0.1 0 0 -0.1 0 0 -0.1 0 0 0 -0.1 0
8 0.1 0 -0.1 0 -0.1 0 -0.2 0 0 0.1 0 -0.2 0
9 0.1 0 -0.1 0 -0.1 -0.1 -0.1 0 -0.1 0 -0.1 -0.1
0 -0.1 -0.1 0 0 0 0 -0.1 -0.1 -0.2 -0.1
11 -0.2 -0.1 -0.1 -0.1 0 0 -0.1 0 -0.1 -0
12 -0.1 -0.2 0 0 0 -0.1 -0.1
13 0 0 0
Average 0.061151
Maximum 0.2
Minimum 0
of Absolute Values
Measurements in Gauss
128
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rt IWO, n `1 1' ...,.1: %" el...l, ,,
Tailored Copper Ingot 14-03-02 "AB" Run:
F. W. Bell 4048 Gauss meter readings on the top
surface of the bottom section (i.e., internal surface
that exhibited attraction).
A B C D E F G H I J K L M
1 0 0.1 0 0 T 0
2 .1 -0.1 0.1 0 0 0.1 0.1 0.1
3 0 0 0.1 0 0.1 0.1 0 0 0
4 0 0 0 0 0 0 0 0 0 0 0.1
0 0 0 0 0 0 0 0,1 0 0 0 0
6 0 0 0 0 0 0 0 0 0 0 0 0 0
7 0 -0.1 0 0 0.1 0 0 0 -0.1 -0.1 0 0.1 0
8 0:1 0 0 0 0 0 0 0 0 0.1 0 0 0.1
9 0 0 0.1 0 0 0.1 0.1 0 0 0 0 0.
0.1 0.1 0 0 0 0 0.1 0 0 0 0
11 -0.2 0 -0.1 0 0 0 0 0 0 -0
12 0 0 0 -0.1 -0.1 0 0
13 0 0 0 0 0
Average 0.023741
Maximum 0.2
Minimum 0
of Absolute Values
Measurements in Gauss
129
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u w,n n. . 1..v u,. LI 4-11 11 11 . p,,,v ig' . -li 11.111 16141
Tailored Alloy Ingot 14-01-21 Ni/Re Alloy "HD"
Run:
F. W. Bell 4048 Gauss meter readings on the top
surface of the bottom section (i.e., internal surface
that exhibited attraction).1
A B C D E F G H I J K L M
1 0 -0.2 -0.3 -0.
2 .0 0 -0.2 -0,2 -0.2 -0.3 -0.2 - .
3 1 0 -0.1 -0.3 -0.2 -0.1 -0.1 -0.2 -0.2 0
4 0.1 0.1 0 0 -0.1 -0.3 0 -0.1 -0.2 0
0 0 0 0.2 -0.1 -0.1 -0.3 -0.2 0 -0.1 0 -0.2 0
6 0 0 0 0 -0.2 -0.2 0.3 -0.1 -0.2 0 -0.1 0 0
01
7 -0.1 0 -0.2 -0.2 0 0 -0.2 -0.2 -0.2 0 0 0.4 0
E -0.1 0 0 -0.1 0 0 -0.2 0 0 0 -0.2 -0.5 -0.5
9 -0.1 -0.1 0 0 -0.2 0 0 0 -0.2 -0.2 -0.3 -0.
1 0 0 -0.1 -0.1 -0.2 -01 0 0 -0.1 -0.2 -0.4 -0.2
11 .2 -0.1 -0.2 0 -0.2 0 0.1 0 -0.2 -0.3 -0
12 -0.1 -0.1 0 0 -0.1 -0.2 -0.4
1 3 0.4 0.4 -0.4 -0
Average 0.133094
Maximum 0.5
Minimum 0
of Absolute Values
Measurements in Gauss
1 The higher absolute values of the magnetic fields observable on this
tailored ingot (i.e., 0.5 gauss
vs. 0.2 gauss) may be due to the ferromagnetic nature of nickel (i.e., a
slight, but measurable
alignment of magnetic moments). However, even at an absolute value of 0.5
Gauss, these magnetic
field strengths are negligible and comparable to the background levels
measured at the earth's surface
(0.1-0.5 gauss). The areas exhibiting the highest measurable magnetic fields
on these tailored ingots
(0.5 Gauss) were specifically measured for material attraction and none was
observed (i.e., would not
hold Fe filings). The areas with gauss readings of +0.5 were not the areas
that exhibited the greatest
attraction.
130
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r Ira.t it . =1.3' arialr I.rrlt ri.i.i. n i.i.i ..t ..se.i Irrri .f ,
Tailored Alloy Ingot 14-04-03 Cu/Re/Au/Ag Alloy
"HD" Run:
F. W. Bell 4048 Gauss meter readings on the top
surface of the bottom section (i.e., internal surface
that exhibited attraction).
A B C D E F G H I J K L M
1 0 -0.1 0 -0.1
2 ,2 0 0 0 -0.1' 0 0 0
3 .1 0 0 0 -0.1 0 -0.1 0 0. 0
-0.2
4 0 0 0 0 0.1 -0.1 0 0 0 -0.1
:'4T'--++ 0 0 -0.2 -0.2 0,2 0 0 0 0 1
7 -0.2 -0.1 0 0 -0.1 -0.2 -0.1 -0.2 0 -0.1. -0.1 -0.2 -0.1
8 0 0 -0.1 -0.2 -0.2 0 -0.2' -0.2 -0.1 0 -0.1 -0.2
9 0.1 0.1 0.1 0 0 0 0 0 0 0 -0.2 0
0 0 -0.2 -0.2 0 -0.2 0 0 0 -0.1 0
11 -0.1 0 0 -0.1 -0.1 -0.1 0 -0.2 -0.2
12 0 0 0 0 0 0 0 -
13 F-O-~-O 0 0
Average 0.054676
Maximum 0.2
Minimum 0
of Absolute Values
Measurements in Gauss
131
