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HIGH STRENGTH LOW DENSITY SYNTHETIC PROPPANTS FOR
HYDRAULICALLY FRACTURING AND RECOVERING HYDROCARBONS
[0001] This application: (i) claims under 35 U.S.C. 119(e)(1) the
benefit of
the filing date of July 4, 2013 of US provisional application serial number
61/843,014; (ii)
claims under 35 U.S.C. 119(e)(1) the benefit of the filing date of February
28, 2014 of
US provisional application serial number 61/946,598; (iii) is a continuation-
in-part of US
patent application serial number 14/268,150 filed May 2, 2014; and, (iv) is a
continuation-in-part of US patent application serial number 14/212,896 filed
March 14,
2014, the entire disclosures of each of which are incorporated herein by
reference.
BACKGROUND OF THE INVENTION
Field of the Invention
[0002] The present inventions relate to synthetic proppants, ceramic
proppants and polymeric derived ceramic proppants; methods for making these
proppants; fracing fluids utilizing these proppants; and hydraulic fracturing
methods with
these proppants. In particular, the present inventions relate to proppants and
hydraulic
fracturing activities that utilize polymeric derived siloxane based ceramics.
Thus, the
present inventions further relate to treating wells, e.g., hydrocarbon
producing wells,
water wells and geothermal wells, to increase and enhance the production from
these
wells by siloxane based polymeric derived ceramic proppant hydraulic
fracturing. Still
more particularly, methods are provided for increasing the fluid conductivity
between a
subterranean formation containing a desired natural resource, e.g., natural
gas, crude
oil, water, and geothermal heat source, and a well or borehole to transport
the natural
resource to the surface or a desired location or collection point for that
natural resource.
[0003] In the production of natural resources from formations
within the earth
a well or borehole is drilled into the earth to the location where the natural
resource is
believed to be located. These natural resources may be a hydrocarbon
reservoir,
containing natural gas, crude oil and combinations of these; the natural
resource may
be fresh water; it may be a heat source for geothermal energy; or it may be
some other
natural resource that is located within the ground.
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[0004] These resource-containing formations may be a few hundred
feet, a
few thousand feet, or tens of thousands of feet below the surface of the
earth, including
under the floor of a body of water, e.g., below the sea floor. In addition to
being at
various depths within the earth, these formations may cover areas of differing
sizes,
shapes and volumes.
[0005] Unfortunately, and generally, when a well is drilled into
these
formations the natural resources rarely flow into the well at rates, durations
and
amounts that are economically viable. This problem occurs for several reasons,
some
of which are well understood, others of which are not as well understood, and
some of
which may not yet be known. These problems can relate to the viscosity of the
natural
resource, the porosity of the formation, the geology of the formation, the
formation
pressures, and the perforations that place the production tubing in the well
in fluid
communication with the formation, to name a few.
[0006] Typically, and by way of general illustration, in drilling
a well an initial
borehole is made into the earth, e.g., the surface of land or seabed, and then
subsequent and smaller diameter boreholes are drilled to extend the overall
depth of the
borehole. In this manner as the overall borehole gets deeper its diameter
becomes
smaller; resulting in what can be envisioned as a telescoping assembly of
holes with the
largest diameter hole being at the top of the borehole closest to the surface
of the earth.
[0007] Thus, by way of example, the starting phases of a subsea drill
process
may be explained in general as follows. Once the drilling rig is positioned on
the
surface of the water over the area where drilling is to take place, an initial
borehole is
made by drilling a 36" hole in the earth to a depth of about 200 - 300 ft.
below the
seafloor. A 30" casing is inserted into this initial borehole. This 30" casing
may also be
called a conductor. The 30" conductor may or may not be cemented into place.
During
this drilling operation a riser is generally not used and the cuttings from
the borehole,
e.g., the earth and other material removed from the borehole by the drilling
activity are
returned to the seafloor. Next, a 26" diameter borehole is drilled within the
30" casing,
extending the depth of the borehole to about 1,000 - 1,500 ft. This drilling
operation
may also be conducted without using a riser. A 20" casing is then inserted
into the 30"
conductor and 26" borehole. This 20" casing is cemented into place. The 20"
casing
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has a wellhead secured to it. (In other operations an additional smaller
diameter
borehole may be drilled, and a smaller diameter casing inserted into that
borehole with
the wellhead being secured to that smaller diameter casing.) A BOP (blow out
preventer) is then secured to a riser and lowered by the riser to the sea
floor; where the
BOP is secured to the wellhead. From this point forward all drilling activity
in the
borehole takes place through the riser and the BOP.
[0008] For a land based drill process, the steps are similar,
although the large
diameter tubulars, 30" ¨ 20" are typically not used. Thus, and generally,
there is a
surface casing that is typically about 13 3/8" diameter. This may extend from
the
surface, e.g., wellhead and BOP, to depths of tens of feet to hundreds of
feet. One of
the purposes of the surface casing is to meet environmental concerns in
protecting
ground water. The surface casing should have sufficiently large diameter to
allow the
drill string, product equipment such as ESPs and circulation mud to pass
through.
Below the casing one or more different diameter intermediate casings may be
used. (It
is understood that sections of a borehole may not be cased, which sections are
referred
to as open hole.) These can have diameters in the range of about 9" to about
7",
although larger and smaller sizes may be used, and can extend to depths of
thousands
and tens of thousands of feet. Inside of the casing and extending from a pay
zone, or
production zone of the borehole up to and through the wellhead on the surface
is the
production tubing. There may be a single production tubing or multiple
production
tubings in a single borehole, with each of the production tubing endings being
at
different depths.
[0009] Typically, when completing a well, it is necessary to
perform a
perforation operation, and perform a hydraulic fracturing, or fracing
operation. In
general, when a well has been drilled and casing, e.g., a metal pipe, is run
to the
prescribed depth, the casing is typically cemented in place by pumping cement
down
and into the annular space between the casing and the earth. (It is understood
that
many different down hole casing, open hole, and completion approaches may be
used.)
The casing, among other things, prevents the hole from collapsing and fluids
from
flowing between permeable zones in the annulus. Thus, this casing forms a
structural
support for the well and a barrier to the earth.
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[0010] While important for the structural integrity of the well,
the casing and
cement present a problem when they are in the production zone. Thus, in
addition to
holding back the earth, they also prevent the hydrocarbons from flowing into
the well
and from being recovered. Additionally, the formation itself may have been
damaged by
the drilling process, e.g., by the pressure from the drilling mud, and this
damaged area
of the formation may form an additional barrier to the flow of hydrocarbons
into the well.
Similarly, in most situations where casing is not needed in the production
area, e.g.,
open hole, the formation itself is generally tight, and more typically can be
very tight,
and thus, will not permit the hydrocarbons to flow into the well. In some
situations the
formation pressure is large enough that the hydrocarbons readily flow into the
well in an
uncased, or open hole. Nevertheless, as formation pressure lessens a point
will be
reached where the formation itself shuts-off, or significantly reduces, the
flow of
hydrocarbons into the well. Also such low formation pressure could have
insufficient
force to flow fluid from the bottom of the borehole to the surface, requiring
the use of
artificial lift.
[0011] To address, in part, this problem of the flow of
hydrocarbons (as well
as other resources, e.g., geothermal) into the well being blocked by the
casing, cement
and the formation itself, openings, e.g., perforations, are made in the well
in the area of
the pay zone. Generally, a perforation is a small, about 1/4 "to about 1" or
2" in
diameter hole that extends through the casing, cement and damaged formation
and
goes into the formation. This hole creates a passage for the hydrocarbons to
flow from
the formation into the well. In a typical well, a large number of these holes
are made
through the casing and into the formation in the pay zone.
[0012] Generally, in a perforating operation a perforating tool or
gun is
lowered into the borehole to the location where the production zone or pay
zone is
located. The perforating gun is a long, typically round tool, that has a small
enough
diameter to fit into the casing or tubular and reach the area within the
borehole where
the production zone is believed to be. Once positioned in the production zone
a series
of explosive charges, e.g., shaped charges, are ignited. The hot gases and
molten
metal from the explosion cut a hole, i.e., the perf or perforation, through
the casing and
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into the formation. These explosive-made perforations extend a few inches,
e.g., 6" to
18" into the formation.
[0013] The ability of, or ease with which, the natural resource
can flow out of
the formation and into the well or production tubing (into and out of, for
example, in the
case of engineered geothermal wells, and some advanced recovery methods for
hydrocarbon wells) can generally be understood as the fluid communication
between
the well and the formation. As this fluid communication is increased several
enhancements or benefits may be obtained: the volume or rate of flow (e.g.,
gallons per
minute) can increase; the distance within the formation out from the well
where the
natural resources will flow into the well can be increase (e.g., the volume
and area of
the formation that can be drained by a single well is increased, and it will
thus take less
total wells to recover the resources from an entire field); the time period
when the well is
producing resources can be lengthened; the flow rate can be maintained at a
higher
rate for a longer period of time; and combinations of these and other
efficiencies and
benefits.
[0014] Fluid communication between the formation and the well can
be
greatly increased by the use of hydraulic fracturing techniques. The first
uses of
hydraulic fracturing date back to the late 1940s and early 1950s. In general
hydraulic
fracturing treatments involve forcing fluids down the well and into the
formation, where
the fluids enter the formation and crack, e.g., force the layers of rock to
break apart or
fracture. These fractures create channels or flow paths that may have cross
sections of
a few micron's, to a few millimeters, to several millimeters in size, and
potentially larger.
The fractures may also extend out from the well in all directions for a few
feet, several
feet and tens of feet or further. It should be remembered that the
longitudinal axis of the
well in the reservoir may not be vertical: it may be on an angle (either
slopping up or
down) or it may be horizontal. For example, in the recovery of shale gas and
oil the
wells are typically essentially horizontal in the reservoir. The section of
the well located
within the reservoir, i.e., the section of the formation containing the
natural resources,
can be called the pay zone.
[0015] Typical fluid volumes in a propped fracturing treatment of a
formation
in general can range from a few thousand to a few million gallons. Proppant
volumes
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can approach several thousand cubic feet. In general the objective of a
proppant
fracturing is to create and enhance fluid communication between the wellbore
and the
hydrocarbons in the formation, e.g., the reservoir. Thus, proppant fracturing
techniques
are used to create and enhance conductive pathways for the hydrocarbons to get
from
the reservoir to the wellbore. Further, a desirable way of enhancing the
efficacy of
proppant fracturing techniques is to have uniform proppant distribution. In
this manner
a uniformly conductive fracture along the wellbore height and fracture half-
length can be
provided. However, the complicated nature of proppant settling, and in
particular in non-
Newtonian fluids often causes a higher concentration of proppant to settle
down in the
lower part of the fracture. This in turn can create a lack of adequate
proppant coverage
on the upper portion of the fracture and the wellbore. Clustering of proppant,
encapsulation, bridging, crushing and embedment are a few negative occurrences
or
phenomena that can lower the potential conductivity of the proppant pack, and
efficacy
of hydraulic fracture and the well.
[0016] The fluids used to perform hydraulic fracture can range from very
simple, e.g., water, to very complex. Additionally, these fluids, e.g.,
fracing fluids or
fracturing fluids, typically carry with them proppants; but not in all cases,
e.g., when
acids are used to fracture carbonate formations. Proppants are small
particles, e.g.,
grains of sand, aluminum shot, sintered bauxite, ceramic beads, resin coated
sand or
ceramics, that are flowed into the fractures and hold, e.g., "prop" or hold
open the
fractures when the pressure of the fracturing fluid is reduced and the fluid
is removed to
allow the resource, e.g., hydrocarbons, to flow into the well.
[0017] In this manner the proppants hold open the fractures,
keeping the
channels open so that the hydrocarbons can more readily flow into the well.
Additionally, the fractures greatly increase the surface area from which the
hydrocarbons can flow into the well. Proppants may not be needed, or generally
may
not be used when acids are used to create a frac and subsequent channel in a
carbonate rich reservoir, where the acids dissolve part or all of the rock
leaving an
opening for the formation fluids to flow to the wellbore.
[0018] Typically fracturing fluids consist primarily of water but also have
other
materials in them. The number of other materials, e.g., chemical additives
used in a
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typical fracture treatment varies depending on the conditions of the specific
well being
fractured. Generally, a typical fracture treatment will use from about 2 to
about 25
additives.
[0019] Generally the predominant fluids being used for fracture
treatments in
the shale formations are water-based fracturing fluids mixed with friction-
reducing
additives, e.g., slick water, or slick water fracs. Overall the concentration
of additives in
most slick water fracturing fluids is generally about 0.5% to 2% with water
and sand
making up 98% to 99.5% by weight. The addition of friction reducers allows
fracturing
fluids and proppant to be pumped to the target zone at a higher rate and
reduced
pressure than if water alone were used.
[0020] In addition to friction reducers, other such additives may
be, for
example, biocides to prevent microorganism growth and to reduce biofouling of
the
fractures; oxygen scavengers and other stabilizers to prevent corrosion of
metal pipes;
and acids that are used to remove drilling mud damage within the near-
wellbore.
[0021] Further these chemicals and additives could be one or more of the
following, and may have the following uses or address the following needs:
diluted acid
(15%), e.g., hydrochloric acid or muriatic acid, which may help dissolve
minerals and
initiate cracks in the rock; a biocide, e.g., glutaraldehyde, which eliminates
bacteria in
the water that produce corrosive byproducts; a breaker, e.g., ammonium
persulfate,
which allows a delayed break down of the gel polymer chains; a corrosion
inhibitor, e.g.,
N,N-dimethyl formamide, which prevents the corrosion of pipes and equipment; a
cross-
linker, e.g., borate salts, which maintains fluid viscosity as temperature
increases; a
friction reducer; e.g., polyacrylamide or mineral oil, which minimizes
friction between the
fluid and the pipe; guar gum or hydroxyethyl cellulose, which thickens the
water in order
to help suspend the proppant; an iron control agent, e.g., citric acid, which
prevents
precipitation of metal oxides; potassium chloride, which creates a brine
carrier fluid; an
oxygen scavenger, e.g., ammonium bisulfite, which removes oxygen from the
water to
reduce corrosion; a pH adjuster or buffering agent, e.g., sodium or potassium
carbonate, which helps to maintain the effectiveness of other additives, such
as, e.g.,
the cross-linker; scale inhibitor, e.g., ethylene glycol, which prevents scale
deposits in
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pipes and equipment; and a surfactant, e.g., isopropanol, which is used to
increase the
viscosity of the fracture fluid.
[0022] The composition of the fluid, the characteristics of the
proppant, the
amount of proppant, the pressures and volumes of fluids used, the number of
times,
e.g., stages, when the fluid is forced into the formation, and combinations
and variations
of these and other factors may be preselected and predetermined for specific
fracturing
jobs, based upon the formation, geology, perforation type, nature and
characteristics of
the natural resource, and formation pressure, among other things.
[0023] Generally, proppant transport inside a hydraulic fracture
has two
components when the fracture is being generated. The horizontal component is
generally dictated by the fluid velocity and associated streamlines which help
carry
proppant to the tip of the fracture. The vertical component is generally
dictated by the
terminal particle settling velocity of the proppant particle in the fluid and
is a function of
proppant diameter and density as well as fluid viscosity and density. The
terminal
settling velocity, the fluid velocity, and thus the proppant transportation
and deposit into
the fractures can be further effected and complicated by the various phenomena
and
conditions present during the fracturing operation.
[0024] Proppant characteristics can play an important, if not
critical role, in the
success of the hydraulic fracturing operation. The proppants' ability to
remain dispersed
in the fluid and flow to the desired locations in the fractures, and to do so
in a
predictable manner to form packs, or assemblies of proppant in manners that
enhance,
rather than restrict, the flow of the natural resource being recovered is
based upon its
characteristics. The proppants must also be cost effective and preferably
inexpensive
to make and use, because of the large amounts of proppant material that is
required for
a fracturing job. Yet they must be strong enough to withstand the pressures of
the
formation and keep the fractures open. They must also be compatible with the
various
other components of the fracturing fluid, which for example, may include
acids, such as
HCI. Thus, for these and other reasons, the art has searched for, but prior to
the
present inventions has failed to find, a low density, highly uniform,
inexpensive, and
strong proppant.
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[0025] Materials made of, or derived from, carbosilane or
polycarbosilane (Si-
C), silane or polysilane (Si-Si), silazane or polysilazane (Si-N-Si), silicon
carbide (SiC),
carbosilazane or polycarbosilazane (Si-N-Si-C-Si), siloxane or polysiloxanes
(Si-0) are
known. These general types of materials have great, but unrealized promise;
and have
failed to find large-scale applications or market acceptance. Instead, their
use has been
relegated to very narrow, limited, low volume, high priced and highly specific
applications, such as a ceramic component in a rocket nozzle, or a patch for
the space
shuttle. Thus, they have failed to obtain wide spread use as ceramics, and it
is believed
they have obtained even less acceptance and use, if any, as a plastic
material, e.g.,
cured but not pyrolized.
[0026] To a greater or lesser extent all of these materials and
the process
used to make them suffer from one or more failings, including for example:
they are
exceptionally expensive and difficult to make, having costs in the thousands
and tens-
of-thousands of dollars per pound; they require high and very high purity
starting
materials; the process requires hazardous organic solvents such as toluene,
tetrahydrofuran (THF), and hexane; the materials are incapable of making non-
reinforced structures having any usable strength; the process produces
undesirable and
hazardous byproducts, such as hydrochloric acid and sludge, which may contain
magnesium; the process requires multiple solvent and reagent based reaction
steps
coupled with curing and pyrolizing steps; the materials are incapable of
forming a useful
prepreg; and their overall physical properties are mixed, e.g., good
temperature
properties but highly brittle.
[0027] As a result, although believed to have great promise, these
types of
materials have failed to find large-scale applications or market acceptance
and have
remained essentially scientific curiosities.
Related Art and Terminology
[0028] As used herein, unless specified otherwise, the terms
"hydrocarbon
exploration and production", "exploration and production activities", "E&P",
and "E&P
activities", and similar such terms are to be given their broadest possible
meaning, and
include surveying, geological analysis, well planning, reservoir planning,
reservoir
management, drilling a well, workover and completion activities, hydrocarbon
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production, flowing of hydrocarbons from a well, collection of hydrocarbons,
secondary
and tertiary recovery from a well, the management of flowing hydrocarbons from
a well,
and any other upstream activities.
[0029] As used herein, unless specified otherwise, the term
"earth" should be
given its broadest possible meaning, and includes, the ground, all natural
materials,
such as rocks, and artificial materials, such as concrete, that are or may be
found in the
ground.
[0030] As used herein, unless specified otherwise "offshore" and
"offshore
drilling activities" and similar such terms are used in their broadest sense
and would
include drilling activities on, or in, any body of water, whether fresh or
salt water,
whether manmade or naturally occurring, such as for example rivers, lakes,
canals,
inland seas, oceans, seas, such as the North Sea, bays and gulfs, such as the
Gulf of
Mexico. As used herein, unless specified otherwise the term "offshore drilling
rig" is to
be given its broadest possible meaning and would include fixed towers,
tenders,
platforms, barges, jack-ups, floating platforms, drill ships, dynamically
positioned drill
ships, semi-submersibles and dynamically positioned semi-submersibles. As used
herein, unless specified otherwise the term "seafloor" is to be given its
broadest
possible meaning and would include any surface of the earth that lies under,
or is at the
bottom of, any body of water, whether fresh or salt water, whether manmade or
naturally occurring.
[0031] As used herein, unless specified otherwise, the term
"borehole" should
be given it broadest possible meaning and includes any opening that is created
in the
earth that is substantially longer than it is wide, such as a well, a well
bore, a well hole,
a micro hole, a slimhole and other terms commonly used or known in the arts to
define
these types of narrow long passages. Wells would further include exploratory,
production, abandoned, reentered, reworked, and injection wells. They would
include
both cased and uncased wells, and sections of those wells. Uncased wells, or
section
of wells, also are called open holes, or open hole sections. Boreholes may
further have
segments or sections that have different orientations, they may have straight
sections
and arcuate sections and combinations thereof. Thus, as used herein unless
expressly
provided otherwise, the "bottom" of a borehole, the "bottom surface" of the
borehole and
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similar terms refer to the end of the borehole, i.e., that portion of the
borehole furthest
along the path of the borehole from the borehole's opening, the surface of the
earth, or
the borehole's beginning. The terms "side" and "wall" of a borehole should to
be given
their broadest possible meaning and include the longitudinal surfaces of the
borehole,
whether or not casing or a liner is present, as such, these terms would
include the sides
of an open borehole or the sides of the casing that has been positioned within
a
borehole. Boreholes may be made up of a single passage, multiple passages,
connected passages, (e.g., branched configuration, fishboned configuration, or
comb
configuration), and combinations and variations thereof.
[0032] As used herein, unless specified otherwise, the term "advancing a
borehole", "drilling a well", and similar such terms should be given their
broadest
possible meaning and include increasing the length of the borehole. Thus, by
advancing a borehole, provided the orientation is not horizontal and is
downward, e.g.,
less than 90 , the depth of the borehole may also be increased.
[0033] Boreholes are generally formed and advanced by using mechanical
drilling equipment having a rotating drilling tool, e.g., a bit. For example,
and in general,
when creating a borehole in the earth, a drilling bit is extending to and into
the earth and
rotated to create a hole in the earth. To perform the drilling operation the
bit must be
forced against the material to be removed with a sufficient force to exceed
the shear
strength, compressive strength or combinations thereof, of that material. The
material
that is cut from the earth is generally known as cuttings, e.g., waste, which
may be
chips of rock, dust, rock fibers and other types of materials and structures
that may be
created by the bit's interactions with the earth. These cuttings are typically
removed
from the borehole by the use of fluids, which fluids can be liquids, foams or
gases, or
other materials know to the art.
[0034] The true vertical depth ("TVD") of a borehole is the
distance from the
top or surface of the borehole to the depth at which the bottom of the
borehole is
located, measured along a straight vertical line. The measured depth ("MD") of
a
borehole is the distance as measured along the actual path of the borehole
from the top
or surface to the bottom. As used herein unless specified otherwise the term
depth of a
borehole will refer to MD. In general, a point of reference may be used for
the top of
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the borehole, such as the rotary table, drill floor, well head or initial
opening or surface
of the structure in which the borehole is placed.
[0035] As used herein, unless specified otherwise, the term "drill
pipe" is to be
given its broadest possible meaning and includes all forms of pipe used for
drilling
activities; and refers to a single section or piece of pipe. As used herein
the terms
"stand of drill pipe," "drill pipe stand," "stand of pipe," "stand" and
similar type terms
should be given their broadest possible meaning and include two, three or four
sections
of drill pipe that have been connected, e.g., joined together, typically by
joints having
threaded connections. As used herein the terms "drill string," "string,"
"string of drill
pipe," string of pipe" and similar type terms should be given their broadest
definition and
would include a stand or stands joined together for the purpose of being
employed in a
borehole. Thus, a drill string could include many stands and many hundreds of
sections
of drill pipe.
[0036] As used herein, unless specified otherwise, the terms
"workover,"
"completion" and "workover and completion" and similar such terms should be
given
their broadest possible meanings and would include activities that take place
at or near
the completion of drilling a well, activities that take place at or the near
the
commencement of production from the well, activities that take place on the
well when
the well is a producing or operating well, activities that take place to
reopen or reenter
an abandoned or plugged well or branch of a well, and would also include for
example,
perforating, cementing, acidizing, fracturing, pressure testing, the removal
of well debris,
removal of plugs, insertion or replacement of production tubing, forming
windows in
casing to drill or complete lateral or branch wellbores, cutting and milling
operations in
general, insertion of screens, stimulating, cleaning, testing, analyzing and
other such
activities.
[0037] As used herein, unless specified otherwise, the terms
"formation,"
"reservoir," "pay zone," and similar terms, are to be given their broadest
possible
meanings and would include all locations, areas, and geological features
within the
earth that contain, may contain, or are believed to contain, hydrocarbons.
[0038] As used herein, unless specified otherwise, the terms "field," "oil
field"
and similar terms, are to be given their broadest possible meanings, and would
include
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any area of land, sea floor, or water that is loosely or directly associated
with a
formation, and more particularly with a resource containing formation, thus, a
field may
have one or more exploratory and producing wells associated with it, a field
may have
one or more governmental body or private resource leases associated with it,
and one
or more field(s) may be directly associated with a resource containing
formation.
[0039] As used herein, unless specified otherwise, the terms
"conventional
gas", "conventional oil", "conventional", "conventional production" and
similar such terms
are to be given their broadest possible meaning and include hydrocarbons,
e.g., gas
and oil, that are trapped in structures in the earth. Generally, in these
conventional
formations the hydrocarbons have migrated in permeable, or semi-permeable
formations to a trap, or area where they are accumulated. Typically, in
conventional
formations a non-porous layer is above, or encompassing the area of
accumulated
hydrocarbons, in essence trapping the hydrocarbon accumulation. Conventional
reservoirs have been historically the sources of the vast majority of
hydrocarbons
produced. As used herein, unless specified otherwise, the terms
"unconventional gas",
"unconventional oil", "unconventional", "unconventional production" and
similar such
terms are to be given their broadest possible meaning and includes
hydrocarbons that
are held in impermeable rock, and which have not migrated to traps or areas of
accumulation.
[0040] As used herein, unless stated otherwise, room temperature is 25 C.
And, standard temperature and pressure is 25 C and 1 atmosphere. As used
herein,
unless stated otherwise, generally, the term "about" is meant to encompass a
variance
or range of 10%, the experimental or instrument error associated with
obtaining the
stated value, and preferably the larger of these.
SUMMARY
[0041] There has been a long-standing, expanding and unmeet need,
for
improved ways to obtain resources, and in particular, hydrocarbon resources
from the
earth. Hydraulic fracturing technology, and in particular proppants and
fracturing fluids,
have not advanced at a sufficient rate and pace, to keep up with the evolution
and
advances in hydrocarbon exploration and production. Thus, there exists a long
felt,
increasing and unfulfilled need for, among other things, a proppant material
having
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predetermined characteristics to enhance hydraulic fracturing operations and
the
recovery of natural resources, such as oil and natural gas, from wells. The
present
inventions, among other things, solve these needs by providing the articles of
manufacture, devices and processes taught, and disclosed herein.
[0042] Thus, there is provided a polysiloxane derived ceramic proppant for
use in hydraulic fracturing operations for the recovery of hydrocarbons from a
subterranean formation, the proppant having: a plurality of spherical type
structures; at
least about 95% of each of the plurality of spherical type structures having a
predetermined diameter, and having an apparent specific gravity of less than
about 2.5;
the structures comprising a ceramic comprising silicon, oxygen and carbon;
and, the
structures having a crushed fines mass percent of less than about 10 at 4
lbs/ft2 @
4,000 psi; and a short term conductivity of at least about 8,000 MD-FT at
10,000 psi
closure.
[0043] Still further the proppants and methods may have one or
more of the
following features: wherein wherein the proppant is made from a polysilocarb
batch
comprising a molar ratio of hydride groups to vinyl groups is about 1.12 to 1
to about
2.36 to 1; wherein wherein the proppant is made from a polysilocarb batch
comprising a
molar ratio of hydride groups to vinyl groups is about 1.50 to 1; wherein
wherein the
proppant is made from a polysilocarb batch comprising a molar ratio of hydride
groups
to vinyl groups is about 3.93 to 1; and wherein wherein the proppant is made
from a
polysilocarb batch comprising a molar ratio of hydride groups to vinyl groups
is about
5.93 to 1.
[0044] There is further provided a polysiloxane derived ceramic
proppant for
use in hydraulic fracturing operations for the recovery of hydrocarbons from a
subterranean formation, the proppant having: a plurality of spherical type
structures; at
least about 95% of each of the plurality having a specific gravity of less
than about 2;
and, the structures comprising a pyrolized material derived from a precursor
comprising
a matrix having a backbone of the formula ¨R1-Si-C-C-Si-O-Si-C-C-Si-R2-; where
R1
and R2 comprise materials selected from the group consisting of methyl,
hydroxyl, vinyl
and allyl.
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[0045] Moreover, the proppants and methods may have one of more of
the
following features: wherein the plurality comprises at least about 100,000
spherical type
structures; 500,000 spherical type structures; wherein the plurality comprises
at least
about 1,000,000 spherical type structures; wherein the plurality comprises at
least about
10,000,000 spherical type structures; wherein the plurality comprises at least
about
100,000 volumetric structures; 500,000 volumetric structures; wherein the
plurality
comprises at least about 1,000,000 volumetric structures; and wherein the
plurality
comprises at least about 10,000,000 volumetric structures
[0046] Still further the proppants and methods may have one or
more of the
following features: wherein the predetermined diameter is from about 10 mesh;
wherein
the predetermined diameter is from about 20 mesh; wherein the predetermined
diameter is from about 30 mesh; wherein the predetermined diameter is from
about 40
mesh; wherein the predetermined diameter is from about 70 mesh; wherein the
predetermined diameter has a smaller diameter than about 100 mesh; wherein the
predetermined diameter has a smaller diameter than about 200 mesh; wherein the
proppants have a specific gravity of less about 1.8; wherein the proppants
have a
specific gravity of less about 2.0; and wherein the proppants have a bulk
density of
about 1.5 g/cc or less; wherein the predetermined diameter is smaller than
about 10
mesh and the proppants have an apparent specific gravity of less than about
2.5;
wherein the predetermined diameter is smaller than about 30 mesh and the
proppants
have an apparent specific gravity of less than about 2.5; and wherein the
predetermined
diameter is smaller than about 30 mesh and the proppants have an apparent
specific
gravity of less than about 2; wherein the predetermined diameter is smaller
than about
100 mesh and the proppants have an apparent specific gravity of less than
about 2; and
wherein the predetermined diameter is smaller than about 200 mesh and the
proppants
have an apparent specific gravity of less than about 2.
[0047] Additionally, there is provided a polysiloxane derived
ceramic proppant
for use in hydraulic fracturing operations for the recovery of hydrocarbons
from a
subterranean formation, the proppant having: a plurality of spherical type
structures,
the structures comprising silicon, oxygen and carbon; the plurality having a
medium
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particle size distribution and a mean particle size distribution; and, wherein
the medium
and the mean are essentially the same.
[0048] Yet additionally, the proppants and methods may have one or
more of
the following features: wherein the medium and the mean particle size
distribution have
a difference of no greater than 0.010; wherein the medium and the mean
particle size
distribution have a difference of no greater than 0.005; and wherein the
medium and the
mean particle size distribution have a difference of no greater than 0.002.
[0049] Still further there is provided a a hydraulic fracturing
fluid for
hydraulically fracturing a well, the fluid having: at least about 100,000
gallons of a water,
and a synthetic proppant; and, the proppant having an apparent specific
gravity of less
than about 2.5 and and a crush test of less than about 1 /0 fines generated at
15,000
psi.
[0050] Additionally, there is provided a hydraulic fracturing
fluid for
hydraulically fracturing a well, the fluid having: at least about 100,000
gallons of a water,
and a synthetic proppant; and, the proppant having an apparent specific
gravity of less
than about 2.0 and and a crush test of less than about 1 /0 fines generated at
10,000
psi.
[0051] Moreover, there is provided a synthetic proppant for use in
hydraulic
fracturing operations for the recovery of hydrocarbons from a subterranean
formation,
the proppant having: a plurality of volumetric structures; having an apparent
specific
gravity of less than about 2.5; the structures comprising silicon, oxygen and
carbon; the
structures having a crushed fines mass percent of less than about 10 at 4
lbs/ft2 @
4,000 psi; and a short term conductivity of at least about 8,000 MD-FT at
10,000 psi
closure; and, wherein the structure comprises a material resulting from the
pyrolysis of a
polymeric precursor comprising a backbone having the formula¨R1-Si-C-C-Si-O-Si-
C-C-
Si-R2-, where R1 and R2 comprise materials selected from the group consisting
of
methyl, hydroxyl, vinyl and allyl.
[0052] Still further there is provided a synthetic proppant for
use in hydraulic
fracturing operations for the recovery of hydrocarbons from a subterranean
formation,
the proppant having: a plurality of volumetric structures; having an apparent
specific
gravity of less than about 2.5; the structures comprising silicon, oxygen and
carbon; the
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structures having a crushed fines mass percent of less than about 10 at 4
lbs/ft2 @
4,000 psi; and a short term conductivity of at least about 8,000 MD-FT at
10,000 psi
closure; and, wherein the structure comprises a material resulting from the
pyrolysis of a
polymeric precursor comprising a polysilocarb batch comprising a molar ratio
of hydride
groups to vinyl groups is about 3.93 to 1.
[0053] Yet moreover, there is provided a synthetic proppant for
use in
hydraulic fracturing operations for the recovery of hydrocarbons from a
subterranean
formation, the proppant having: a plurality of volumetric structures; having
an apparent
specific gravity of less than about 2.5; the structures comprising silicon,
oxygen and
carbon; the structures having a crushed fines mass percent of less than about
10 at 4
lbs/ft2 @ 4,000 psi; and a short term conductivity of at least about 8,000 MD-
FT at
10,000 psi closure; and, wherein the structures have an actual density and an
apparent
density; and the actual density and apparent density are within 5% of each
other.
[0054] Yet further, there is provided a synthetic proppant for use
in hydraulic
fracturing operations for the recovery of hydrocarbons from a subterranean
formation,
the proppant having: a plurality of volumetric structures; having an apparent
specific
gravity of less than about 2.5; the structures comprising silicon, oxygen and
carbon; the
structures having a crushed fines mass percent of less than about 10 at 4
lbs/ft2 @
4,000 psi; and a short term conductivity of at least about 8,000 MD-FT at
10,000 psi
closure; and, wherein the structures have an actual density and an apparent
density;
and the actual density and apparent density are essentially the same.
[0055] There is further provided a method of enhancing
conductivity of a well
to increase the recovery of hydrocarbons from a subterranean hydrocarbon
reservoir
associated with the well, the method including: positioning a polysiloxane
derived
ceramic proppant in a fluid channel in a subterranean reservoir comprising
hydrocarbons, whereby the proppant is in fluid association with the
hydrocarbons; and,
flowing the hydrocarbons over the polysiloxane derived ceramic proppant; and,
recovering the hydrocarbons that have flowed over the proppant.
[0056] Further there are provided methods and proppants that may
have one
or more of the following features: the proppant is a material resulting from
the pyrolysis
of a polymeric precursor comprising a backbone having the formula¨R1-Si-C-C-Si-
O-Si-
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C-C-Si-R2-, where R1 and R2 comprise materials selected from the group
consisting of
methyl, hydroxyl, vinyl and allyl; the proppant is a filled proppant; the
proppant is a
polysilocarb derived ceramic proppant; the proppant is made up of silicon,
carbon and
oxygen; wherein the proppant is made from a polysilocarb batch comprising a
precursor
selected from the group consisting of methyl hydrogen, siloxane backbone
additive,
vinyl substituted and vinyl terminated polydimethyl siloxane, vinyl
substituted and
hydrogen terminated polydimethyl siloxane, allyl terminated polydimethyl
siloxane,
silanol terminated polydimethyl siloxane, hydrogen terminated polydimethyl
siloxane,
vinyl terminated diphenyl dimethyl polysiloxane, hydroxyl terminated diphenyl
dimethyl
polysiloxane, hydride terminated diphenyl dimethyl polysiloxane, styrene vinyl
benzene
dimethyl polysiloxane, and tetramethyltetravinylcyclotetrasiloxane; wherein
the proppant
is made from a polysilocarb batch comprising a precursor comprising methyl
hydrogen
and a siloxane backbone additive; ; wherein the proppant is made from a
polysilocarb
batch comprising a precursor comprising styrene vinyl benzene dimethyl
polysiloxane;
wherein the proppant is made from a polysilocarb batch comprising a precursor
comprising methyl hydrogen, vinyl terminated polydimethyl siloxane, and
tetramethyltetravinylcyclotetrasiloxane; wherein the proppant is made from a
polysilocarb batch comprising a precursor comprising methyl hydrogen, vinyl
terminated
polydimethyl siloxane, tetramethyltetravinylcyclotetrasiloxane and a catalyst;
wherein
the proppant is made from a polysilocarb batch comprising a precursor
comprising a
methyl terminated hydride substituted polysiloxane; wherein the proppant is
made from
a polysilocarb batch comprising a precursor selected from the group consisting
of a
methyl terminated vinyl polysiloxane, a vinyl terminated vinyl polysiloxane, a
hydride
terminated vinyl polysiloxane, and an allyl terminated dimethyl polysiloxane;
wherein the
proppant is made from a polysilocarb batch comprising a precursor selected
from the
group consisting of a vinyl terminated dimethyl polysiloxane, a hydroxy
terminated
dimethyl polysiloxane, a hydride terminated dimethyl polysiloxane, and a
hydroxy
terminated vinyl polysiloxane; and, wherein the proppant is made from a
polysilocarb
batch comprising a precursor selected from the group consisting of a phenyl
terminated
dimethyl polysiloxane, a phenyl and methyl terminated dimethyl polysiloxane, a
methyl
terminated dimethyl diphenyl polysiloxane, a vinyl terminated dimethyl
diphenyl
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polysiloxane, a hydroxy terminated dimethyl diphenyl polysiloxane, and a
hydride
terminated dimethyl diphenyl polysiloxane.
[0057] Yet further there are provided proppants that can consists
essentially
of silicon, carbon and oxygen, e.g., its main and primary materials are,
silicon, carbon
and oxygen, while other minor, non-functional components may be present.
Additionally, there provided proppants that can consist of silicon, carbon and
oxygen,
e.g., they are made up solely of silicon, carbon, and oxygen.
[0058] In addition there are provided methods and proppants that
may have
one or more of the following features: wherein the proppant is made from a
polysilocarb
batch comprising a molar ratio of hydride groups to vinyl groups is about 1.12
to 1 to
about 2.36 to 1; wherein the proppant is made from a polysilocarb batch
comprising a
molar ratio of hydride groups to vinyl groups is about 1.50 to 1; wherein the
proppant is
made from a polysilocarb batch comprising a molar ratio of hydride groups to
vinyl
groups is about 3.93 to 1; wherein the proppant is made from a polysilocarb
batch
comprising a molar ratio of hydride groups to vinyl groups is about 5.93 to 1;
wherein
the proppant is a spherical proppant; wherein the proppant is an essentially
perfectly
spherical proppant; and, wherein the proppant a substantially perfectly
spherical
proppant.
[0059] Further there are provided methods and proppants that may
have one
or more of the following features: wherein the hydrocarbon is natural gas and
the
formation is a shale formation; wherein the hydrocarbon is crude oil and the
formation is
a shale formation; wherein the shale formation is Barnett shale; wherein the
shale
formation is Bakken shale; wherein the shale formation is Utica shale; and
wherein the
shale formation is Eagleford shale; and wherein the shale formation is another
shale
formation known or later discovered.
[0060] Moreover, there is provided a method of enhancing
conductivity of a
well to increase the recovery of hydrocarbons from a subterranean hydrocarbon
reservoir associated with the well, the method including: positioning a
synthetic
proppant in a fluid channel in a subterranean reservoir comprising
hydrocarbons,
whereby the proppant is in fluid association with the hydrocarbons; the
proppant having
an apparent specific gravity of less than about 2 and a crush test of less
than about 1 /0
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fines generated at 10,000 psi., flowing the hydrocarbons over the polysiloxane
derived
ceramic proppant; and, recovering the hydrocarbons that have flowed over the
proppant.
[0061] Yet still further there are provided methods and proppants
that may
have one or more of the following features: wherein the proppant has an actual
density
and an apparent density; and the actual density and apparent density are
within 5% of
each other; wherein the proppant has an actual density and an apparent
density; and
the actual density and apparent density are the same; wherein the proppant has
a
specific gravity of less than, a crush test of less than about 1 /0 fines
generated at
15,000 psi; wherein the plurality of proppants has at least about 100,000
spherical type
proppants; and wherein the plurality of proppants has at least about 1,000,000
spherical
type proppants.
[0062] Further there is provided a method of enhancing
conductivity of a well
to increase the recovery of hydrocarbons from a subterranean hydrocarbon
reservoir
associated with the well, the method including: positioning a synthetic
proppant in a fluid
channel in a subterranean reservoir comprising hydrocarbons, whereby the
proppant is
in fluid association with the hydrocarbons; the proppant having an apparent
specific
gravity of less than about 2.5 and a crush test of less than about 1 /0 fines
generated at
15,000 psi., flowing the hydrocarbons over the polysiloxane derived ceramic
proppant;
and, recovering the hydrocarbons that have flowed over the proppant.
[0063] Furthermore, there is provided a method of enhancing
conductivity of a
well to increase the recovery of hydrocarbons from a subterranean hydrocarbon
reservoir associated with the well, including: positioning a ceramic proppant
in a fluid
channel in a subterranean reservoir comprising hydrocarbons, whereby the
proppant is
in fluid association with the hydrocarbons; the proppant comprises silicon,
oxygen and
carbon; and, flowing the hydrocarbons over the proppant; and, recovering the
hydrocarbons that have flowed over the proppant.
[0064] Yet still further there are provided methods and proppants
that may
have one or more of the following features: wherein the proppant has a
specific gravity
of less than 2; wherein the proppant has a crush test of less than about 1%
fines
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generated at 15,000 psi; and, wherein the proppant has a specific gravity of
less than 2,
a crush test of less than about 1 /0 fines generated at 15,000 psi.
[0065] In addition there is provided a method of hydraulically
fracturing a well,
including: preparing at least about 100,000 gallons of a hydraulic fracturing
fluid, the
hydraulic fracturing fluid comprising a polysiloxane derived ceramic proppant;
pumping
at least about 100,000 gallons of hydraulic fracturing fluid into a borehole
in a formation,
and out of the borehole into the formation; whereby fractures are created in
the
formation; and, leaving at least some of the proppant in the fractures.
[0066] Yet still further there are provided methods and proppants
that may
have one or more of the following features: wherein the fracturing fluid has
at least
about llb per gallon of proppant; wherein the fracturing fluid has at least
about 2 lbs per
gallon of proppant; the fracturing fluid has at least 3 lbs per gallon of
proppant; wherein
the fracturing fluid has at least 4 lbs per gallon of proppant; the fracturing
fluid has at
least 5 lbs per gallon of proppant, at least about 8 lbs/gal; at least about
10 lbs/gal; and
about 12Ibs/gal or more.
[0067] Still further there is provided a method of hydraulically
fracturing a well,
the method including: preparing at least about 100,000 gallons of a hydraulic
fracturing
fluid, the hydraulic fracturing fluid comprising a synthetic proppant; the
proppant having
an apparent specific gravity of less than about 2 and a crush test of less
than about 1 /0
fines generated at 10,000 psi., pumping at least about 100,000 gallons of
hydraulic
fracturing fluid into a borehole in a formation, and out of the borehole into
the formation;
whereby fractures are created in the formation; and, leaving at least some of
the
proppant in the fractures.
[0068] Moreover, there is provided a method of hydraulically
fracturing a well,
including: preparing at least about 100,000 gallons of a hydraulic fracturing
fluid, the
hydraulic fracturing fluid comprising a synthetic proppant; the proppant
having an
apparent specific gravity of less than about 2.5 and and a crush test of less
than about
1 /0 fines generated at 15,000 psi., pumping at least about 100,000 gallons of
hydraulic
fracturing fluid into a borehole in a formation, and out of the borehole into
the formation;
whereby fractures are created in the formation; and, leaving at least some of
the
proppant in the fractures.
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[0069] Still additionally there is provide a method of enhancing
conductivity of
a well to increase the recovery of hydrocarbons from a subterranean
hydrocarbon
reservoir associated with the well, the method including: locating a plurality
of
polysiloxane derived ceramic proppants in flow channels in a subterranean
formation
comprising a reservoir of hydrocarbons, whereby the proppants are in contact
with the
formation and the hydrocarbons; and, a well connecting a surface of the earth
to the
formation; moving the hydrocarbons from the formation through the proppant
containing
flow channels and into the well; and moving the hydrocarbons to the surface.
[0070] Yet still further there are provided methods and proppants
that may
have one or more of the following features: wherein the proppants have a
particle size
disruption of at least about 95% of the proppants being within about a 10 mesh
range;
wherein the proppants have a specific gravity of less 1.9; wherein the
proppants have a
bulk density of less about 1.3 g/cc; wherein the proppants have a bulk density
of less
about 1.3 g/cc.
BRIEF DESCRIPTION OF THE DRAWINGS
[0071] FIG. 1 is a Scanning Electron Photomicrograph (SEM) of an
embodiment of a spherical polysiloxane derived ceramic ("PsDC") proppant in
accordance with the present invention (440x, 300pm reference bar).
[0072] FIG. 2 is an SEM of an embodiment of a PsDC in accordance
with the
present invention after being subjected to a load, and exposing internal
surfaces in
accordance with the present inventions (370x, 360pm reference bar) .
[0073] FIG. 3 is a Krumbein and Sloss Sphericity and Roundness
chart.
[0074] FIG. 4 is a chart comparing the conductivity data for an
embodiment of
proppants in accordance with the present invention with published conductivity
data for
prior art proppants.
[0075] FIG. 5 is a table and chart showing increased propped area
for an
embodiment of a PsDC hydraulic fracture treatment in accordance with the
present
invention.
[0076] FIG. 6 is a perspective view of a formation showing
increased propped
area and geometry for an embodiment of a PsDC hydraulic fracture in accordance
with
the present invention.
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[0077] FIG. 7 is a chart showing the increase in initial
production ("IP) and an
increase in decline curve reduction ("DCR") for an embodiment of a PsDC
hydraulic
fracture treatment in accordance with the present invention.
[0078] FIG. 8 is a perspective view of a hydraulic fracturing site
in accordance
with the present invetnions.
[0079] FIG. 9 is a schematic diagram and flow chart for an
embodiment of a
process for making embodiments of PsDC proppants in accordance with the
present
inventions.
[0080] FIG. 10 is a chemical formula for an embodiment of a methyl
terminated hydride substituted polysiloxane precursor material in accordance
with the
present inventions.
[0081] FIG. 11 is a chemical formula for an embodiment of a methyl
terminated vinyl polysiloxane precursor material in accordance with the
present
inventions.
[0082] FIG. 12 is a chemical formula for an embodiment of a vinyl
terminated
vinyl polysiloxane precursor material in accordance with the present
inventions.
[0083] FIG. 13 is a chemical formula for an embodiment of a
hydride
terminated vinyl polysiloxane precursor material in accordance with the
present
inventions.
[0084] FIG. 14 is a chemical formula for an embodiment of an allyl
terminated
dimethyl polysiloxane precursor material in accordance with the present
inventions.
[0085] FIG. 15 is a chemical formula for an embodiment of a vinyl
terminated
dimethyl polysiloxane precursor material in accordance with the present
inventions.
[0086] FIG. 16 is a chemical formula for an embodiment of a
hydroxy
terminated dimethyl polysiloxane precursor material in accordance with the
present
inventions.
[0087] FIG. 17 is a chemical formula for an embodiment of a
hydride
terminated dimethyl polysiloxane precursor material in accordance with the
present
inventions.
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[0088] FIG. 18 is a chemical formula for an embodiment of a
hydroxy
terminated vinyl polysiloxane precursor material in accordance with the
present
inventions.
[0089] FIG. 19 is a chemical formula for an embodiment of a phenyl
terminated dimethyl polysiloxane precursor material in accordance with the
present
inventions.
[0090] FIG. 20 is a chemical formula for an embodiment of a phenyl
and
methyl terminated dimethyl polysiloxane precursor material in accordance with
the
present inventions.
[0091] FIG. 21 is a chemical formula for an embodiment of a methyl
terminated dimethyl diphenyl polysiloxane precursor material in accordance
with the
present inventions.
[0092] FIG. 22 is a chemical formula for an embodiment of a vinyl
terminated
dimethyl diphenyl polysiloxane precursor material in accordance with the
present
inventions.
[0093] FIG. 23 is a chemical formula for an embodiment of a
hydroxy
terminated dimethyl diphenyl polysiloxane precursor material in accordance
with the
present inventions.
[0094] FIG. 24 is a chemical formula for an embodiment of a
hydride
terminated dimethyl diphenyl polysiloxane precursor material in accordance
with the
present inventions.
[0095] FIG. 25 is a chemical formula for an embodiment of a methyl
terminated phenylethyl polysiloxane precursor material in accordance with the
present
inventions.
[0096] FIG. 26 is a chemical formula for an embodiment of a tetravinyl
cyclosiloxane in accordance with the present inventions.
[0097] FIG. 27 is chemical formula for an embodiment of a trivinyl
cyclosiloxane in accordance with the present inventions.
[0098] FIG. 28 is a chemical formula for an embodiment of a
divinyl
cyclosiloxane in accordance with the present inventions.
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[0099] FIG. 29 is a chemical formula for an embodiment of a
trivinyl hydride
cyclosiloxane in accordance with the present inventions.
[00100] FIG. 30 is a chemical formula for an embodiment of a divinyl dihydride
cyclosiloxane in accordance with the present inventions.
[00101] FIG. 31 is a chemical formula for an embodiment of a dihydride
cyclosiloxane in accordance with the present inventions.
[00102] FIG. 32 is a chemical formula for an embodiment of a dihydride
cyclosiloxane in accordance with the present inventions.
[00103] FIG. 33 is a chemical formula for an embodiment of a silane in
accordance with the present inventions.
[00104] FIG. 34 is a chemical formula for an embodiment of a silane in
accordance with the present inventions.
[00105] FIG. 35 is a chemical formula for an embodiment of a silane in
accordance with the present inventions.
[00106] FIG. 36 is a chemical formula for an embodiment of a silane in
accordance with the present inventions.
[00107] FIG. 37 is a chemical formula for an embodiment of a methyl
terminated dimethyl ethyl methyl phenyl silyl silane polysiloxane precursor
material in
accordance with the present inventions.
[00108] FIG. 38 is chemical formulas for an embodiment of a polysiloxane
precursor material in accordance with the present inventions.
[00109] FIG. 39 is chemical formulas for an embodiment of a polysiloxane
precursor material in accordance with the present inventions.
[00110] FIG. 40 is chemical formulas for an embodiment of a polysiloxane
precursor material in accordance with the present inventions.
[00111] FIG. 41 is a chemical formula for an embodiment of an ethyl methyl
phenyl silyl- cyclosiloxane in accordance with the present inventions.
[00112] FIG. 42 is a chemical formula for an embodiment of a cyclosiloxane in
accordance with the present inventions.
[00113] FIG. 43 is a chemical formula for an embodiment of a siloxane
precursor in accordance with the present inventions.
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[00114] FIGS. 43A to 43D are chemical formula for embodiments of the E1 and
E2 groups in the formula of FIG. 43.
[00115] FIG. 44 is a chemical formula for an embodiment of an orthosilicate in
accordance with the present inventions.
[00116] FIG. 45 is a chemical formula for an embodiment of a polysiloxane in
accordance with the present inventions.
[00117] FIG. 46 is a chemical formula for an embodiment of a triethoxy methyl
silane in accordance with the present inventions.
[00118] FIG. 47 is a chemical formula for an embodiment of a diethoxy methyl
phenyl silane in accordance with the present inventions.
[00119] FIG. 48 is a chemical formula for an embodiment of a diethoxy methyl
hydride silane in accordance with the present inventions.
[00120] FIG. 49 is a chemical formula for an embodiment of a diethoxy methyl
vinyl silane in accordance with the present inventions.
[00121] FIG. 50 is a chemical formula for an embodiment of a dimethyl ethoxy
vinyl silane in accordance with the present inventions.
[00122] FIG. 51 is a chemical formula for an embodiment of a diethoxy
dimethyl silane in accordance with the present inventions.
[00123] FIG. 52 is a chemical formula for an embodiment of an ethoxy dimethyl
phenyl silane in accordance with the present inventions.
[00124] FIG. 53 is a chemical formula for an embodiment of a diethoxy
dihydride silane in accordance with the present inventions.
[00125] FIG. 54 is a chemical formula for an embodiment of a triethoxy phenyl
silane in accordance with the present inventions.
[00126] FIG. 55 is a chemical formula for an embodiment of a diethoxy hydride
trimethyl siloxane in accordance with the present inventions.
[00127] FIG. 56 is a chemical formula for an embodiment of a diethoxy methyl
trimethyl siloxane in accordance with the present inventions.
[00128] FIG. 57 is a chemical formula for an embodiment of a trimethyl ethoxy
silane in accordance with the present inventions.
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[00129] FIG. 58 is a chemical formula for an embodiment of a diphenyl
diethoxy silane in accordance with the present inventions.
[00130] FIG. 59 is a chemical formula for an embodiment of a dimethyl ethoxy
hydride siloxane in accordance with the present invention.
[00131] FIGS. 60A to 60F are chemical formulas for starting materials in
accordance with the present inventions.
[00132] FIG. 61 is an embodiment of a proppant preform forming and curing
system in accordance with the present invention.
[00133] FIG. 62 is a perspective view of a formation showing increased
propped area and geometry for an embodiment of a PsDC in accordance with the
present invention.
[00134] FIG. 63 is a chart showing the increase in natural gas production for
an
embodiment of a PsDC hydraulic fracture treatment in accordance with the
present
invention as compared to a conventional proppant.
[00135] FIG. 64 is a photograph of the fines created at 4k API (ISO) crush
test
of an embodiment of proppants in accordance with the present invention.
[00136] FIG. 65 is a photograph of the fines created at 5k API (ISO) crush
test
of an embodiment of proppants in accordance with the present invention.
[00137] FIG. 66 is a chart comparing the specific gravity and strength of an
embodiment of a PsDC proppants in accordance with the present invention with
conventional proppants (having specific gravities greater than 2.5).
[00138] FIG. 67 is a chart comparing the settling rate of an embodiment of a
PsDC proppants in accordance with the present invention with conventional
proppants.
[00139] FIG. 68 is a chart comparing the particle size distribution for a
batch of
an embodiment of a PsDC proppant in accordance with the present invention with
a
batch of a conventional proppant.
[00140] FIG. 69 is a 400x magnification of an embodiment of a PsDC proppant
in accordance with the present inventions
[00141] FIG. 70 is a perspective view of an off shore well.
[00142] FIG. 71 is a cross sectional view of an off shore well.
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DESCRIPTION OF THE PREFERRED EMBODIMENTS
[00143] In general, the present inventions relate to synthetic proppants;
methods for making these proppants; fracing fluids utilizing the proppants;
and hydraulic
fracturing methods.
[00144] In general, embodiments of the present inventions relate to polymeric
derived ceramic proppants; methods for making these proppants; fracing fluids
utilizing
these proppants; and hydraulic fracturing methods. In particular, the present
inventions
relate to proppants and hydraulic fracturing activities that utilize polymeric
derived
siloxane based ceramics, e.g., polysilocarb derived materials.
[00145] In general, embodiments of the present inventions further relate to
treating wells, e.g., hydrocarbon producing wells, water wells and geothermal
wells, to
increase and enhance the production from these wells; and thus, for example,
these
embodiments relate to new hydraulic fracturing treatments and methods. Still
more
particularly, embodiments of methods are provided for increasing the fluid
conductivity
between a subterranean formation containing a desired natural resource, e.g.,
natural
gas, crude oil, water, and geothermal heat source, and a well or borehole to
transport
the natural resource to the surface or a desired location or collection point
for that
natural resource. For example, embodiments of the present inventions further
relate to
treating wells, e.g., hydrocarbon producing wells, water wells and geothermal
wells, to
increase and enhance the production from these wells by synthetic proppant
hydraulic
fracturing treatments, including siloxane based polymeric derived ceramic
proppant
hydraulic fracturing, and including polysilocarb based polymer derived ceramic
proppant
hydraulic fracturing.
[00146] As used herein, unless specified otherwise, the terms " /0",
"percent",
"weight /0" and "mass /0" and similar such terms are used interchangeably
and refer to
the weight of a first component as a percentage of the weight of the total,
e.g., batch,
mixture or proppant. As used herein, unless specified otherwise "volume /0"
and " /0
volume" and similar such terms refer to the volume of a first component as a
percentage
of the volume of the total, e.g., batch, mixture or proppant. As used herein,
unless
specified otherwise, mesh size and mesh can be corresponded to the relative
diameters
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as set forth in Table 1. As used herein, unless specified otherwise: if
particles are
described as having a mesh size of "A" it means that the particles will pass
through that
mess, but will be stopped by a smaller mesh size; if particles are described
as having a
mesh size of + (plus) mesh "A" it means that the particles will sit upon
(e.g., be stopped
by) the mesh "A" screen or sieve; and, if particles are described as being ¨
(minus)
mesh "A" it means that the particles will pass through (e.g., not be stopped
by) the mesh
"A" screen or sieve. When particle sizes, for a sample of proppants (a few 100
proppants, to thousands of proppants, to millions of proppants, to tons of
proppants) are
described as "A"/"B", "A" denotes the largest size of the distribution of
sizes, and "B"
denotes the smallest size of the distribution of sizes. Thus, a sample of
proppants
being characterized as mesh 20/40 would have proppants that will pass through
a 20
mesh sieve, but will not pass through (i.e., are caught by, sit a top) a 40
mesh sieve.
[00147] Table 1
: U.S. Mesh . Inches .... Microns
Millimeters
:
i (i.e., mesh) i
, ....................................... ,
+. (pm) (mm)
i
3 0.2650 6730 6.730
: 4 : .. 0.1870 4760 4.760
=.. ,
5 0.1570 4000 ..... 4.000
..- ........................ +
6 0.1320 3360 3.360
--i
: 7 0.1110 2830 2.830 õ 4 õ
8 0.0937 .. 2380 2.380
..- +.-
10 0.0787 2000 2.000
! +. i
12 0.0661 1680 1.680
: 14 : .. 0.0555 1410 1.410
.,, ,
, 16 0.0469 1190 1.190
+. i
18 0.0394 1000 1.000
: 20 .
: 0.0331 841 0.841
,
25 0.0280 707 0.707
: .
30 .
0.0232 595 , 0.595
350 00165
0.0197 500 0.500
4. :
: : 400 0.400
: .
45 .
+. 0.0138 354 0.354
! ................................................... i
50 0.0117 297 0.297
: 60 .
. 0.0098 250 0.250
,
................................. 70 0.0083 ' 210
0.210
..- + . ..
80 0.0070 177 0.177
,
100 0.0059 149, 0.149
120 0.0049 125 0.125
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140 , 0.0041 105 0.105
170 0.0035 88
0.088
-
200 0.0029 74 0.074
230 , 0.0024 63 0.063
270 ; 0.0021 53 0.053
325 0.0017 44 0.044
400 0.0015 37 0.037
[00148] Generally, the synthetic proppants and, any preforms, may be any
predetermined volumetric shape. The preform proppants may be the same shape or
a
different shape from the final synthetic proppants. Thus, the preforms, the
proppants
and both, may be shaped into balls, spheres, squares, prolate spheroids,
ellipsoids,
spheroids, eggs, cones, rods, boxes, multifaceted structures, and polyhedrons
(e.g.,
dodecahedron, icosidodecahedron, rhombic triacontahedron, and prism), as well
as,
other structures or shapes. The synthetic proppants may be made into the shape
of
any proppant that has been used, has been suggested, is being used, or may be
developed in the future for use in hydraulic fracing, or in other similar
types of
operations. There shapes may also be random, such obtained from breaking up a
block
of material.
[00149] Spherical type structures are examples of a presently preferred shape
for proppants. Sphere and spherical shall mean, and include unless expressly
stated
otherwise, any structure that has at least about 90% of its total volume
within a "perfect
sphere," i.e., all points along the surface of the structure have radii of
equal distance. A
spherical type structure shall mean, and include all spheres, and any other
structure
having at least about 70% of its total volume within a perfect sphere.
[00150] Although this specification focuses on proppants, and in particular
proppants for hydraulic fracturing, it is to be understood that the small
volumetric
shapes (preferably predetermined volumetric shapes) of the present materials,
e.g.,
beads, etc., may have many other uses, in addition to hydraulic fracturing,
and that the
scope of protection to be afford such materials is not limited to proppants,
and hydraulic
fracturing. These shapes can be many different sizes (for proppant, as well as
other
uses), including any of the sizes on Table 1, and can be larger and smaller.
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[00151] The batch formulations and processes of making synthetic proppants
provides the ability to make proppants that are, among other shapes, spheres,
perfect
spheres, essentially perfect spheres (any other structure having at least
about 98% of
its total volume within a perfect sphere), and substantially perfect spheres
(any other
structure having at least about 95% of its total volume within a perfect
sphere).
[00152] Turning to FIG. 1 there is shown a scanning electron photo micrograph
(SEPM) of an embodiment of a synthetic proppant of the present invention. The
proppant is spherical, and has no porosity. The outer surface is smooth,
uniform and
solid. FIG. 2 shows a proppant of the same type as FIG. 1 that has been
subject to a
load, of at least about 12,000 psi or greater. The proppant has fractured and
pieces of
the proppant have fallen away, revealing the inner sections of the proppant,
and
showing that the proppant has no porosity, e.g., there are no voids or pores
(open or
closed). The proppants of FIGS. 1 and 2 are polymer derived ceramic (PDC), and
in
particular, are polysilocarb derived ceramics (PsDC).
[00153] Embodiments of the synthetic proppant preferably have an apparent
density that is close to, i.e., within 90% of the actual density of the
material making up
the proppant; more preferably the apparent density of the proppant is
essentially the
same as the actual density, i.e., within 95% of the actual density, and still
more
preferably the apparent density of the proppant is the same as the actual
density, i.e.,
within 98% of the actual density. Thus, it is understood that apparent density
takes into
consideration (would include in the calculation) the voids in a structure if
any; while
actual density would not. For example, a common sponge would have an apparent
density that is significantly lower than its actual density. The absence of
pores, or voids,
from the structure of the volumetric shapes is preferred, both absent from the
surface
and from the interior.
[00154] The volumetric shapes of the synthetic proppants may also be
characterized by using a Krumbein and Sloss chart (FIG. 3) and analysis, which
is a
well known methodology by those of skill in the art, and which is also set
forth in Section
7, "Proppant sphericity and roundness" of ANSI/API Recommended Practice 19C,
May
2008 (also ISO 13503-2:2006). Under this characterization, the synthetic
proppants
may have average sphericity of at least about 0.5, at least about 0.7, at
least about 0.9,
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and greater. The synthetic proppants may have an average roundness of at least
about
0.5, at least about 0.7, at least about 0.9 and greater. The siloxane derived
ceramic
proppants, e.g., polysilocarb derived ceramic proppants, may have average
sphericity of
at least about 0.5, at least about 0.7, at least about 0.9, and greater. The
siloxane
derived ceramic proppants, e.g., polysilocarb derived ceramic proppants, may
have an
average roundness of at least about 0.5, at least about 0.7, at least about
0.9 and
greater. The polysiloxane derived ceramic proppants, e.g., polysilocarb
derived ceramic
proppants, may have average sphericity/roundness values of about 0.9/ 0.9,
0.7/
0.9, 0.9/ 0.7 and 0.7/ 0.7.
[00155] Synthetic proppants, e.g., polysilocarb derived ceramic proppants
("PsDC proppant"), may, for example, also have some, or all of, the
characteristics set
forth in Table 2, which characteristics are based upon testing and
methodologies that
are well know in the art, and which are also set forth in ANSI/API Recommended
Practice 19C, May 2008 (also ISO 13503-2:2006) as well as, API RP 56/58/60
(the
entire disclosure of each of which is incorporated herein by reference).
Generally,
testing that may be used in categorizing proppants can be found in, and is
known to
those of skill in the art, in ANSI, API, and ISO, publications, reports,
standards, etc.,
which collectively will be referred to herein as "API (ISO)." Other additional
testing and
categorizations may be used, which generally known to those of skill in the
art, or that
are set forth in this specification. Embodiments of the present inventions can
exceed,
out perform and both, one or more of the characteristics set forth in Table 2.
[00156] Table 2
Example Example Example PsDC PsDC
31 1 2 proppant proppant
Characteristic/Phy Preferred More
sical Property Range
Preferred
Range
Turbidity (NTU) 57 19 26 15 13 250 20
Krumbein Shape
Factors
Roundness >0.9 >0.9 >0.9 0.7 0.7 0.8 0.95
Sphericity >0.9 >0.9 >0.9 .07 0.8 0.8 0.95
Clusters ( /0) 0 0 0 1 0
Bulk Density (g/cc) 1.25 1.27 1.27 1.4 1.20
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Bulk Density lbs/ft2 78.12 79.25 79.44 87.40 74.91
Specific Gravity 2.1 2.09 2.12 1.90 1.70 2.1-1.0
1.8-1.3
Particle size ==
==
.. = =
= =
.. = =
= =
.. ..
:: ..
.... .... .... .... ....
.... .... .... .... ....
..
== ..
= = ..
= = ..
= = :::
==
. ..
= = i
.... .... .... .... ....
...
==
..
== = =
..
= = = =
..
= = = =
..
= = ==
=
. = =
..
= = ....
distribution ..
..
....
==
==
.. ..
..
....
= =
= =
.. ..
..
....
= =
= =
.. ..
..
....
= =
= =
.. ..
...
==
..
= ..
..
....
= =
= =
..
.. .. .. .. . ..
.. .. .. .. .. ..
.. .. .. .. . ..
.. .. .. .. .. ..
Sieve iiii
16 = 0.0 0.0 0.0 0.0 0.0
18 0.0 0.0 0.0 0.0 0.0
:::.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:..:.:.:.:.:.:.:.
:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.
20 0.0 0.2 0.0 0.0 0.0
25 3.5 13.3 1.4 0.0 0.0
30 96.5 73.1 96.9 1 0.0
35 0.1 9.5 1.6 8 0.0
:::.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:..:.:.:.:.:.:.:.
:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.
40 0.0 2.2 0.0 89 0.0
50 0.0 0.4 0.0 2 0.0
60 0.0 0.0 0.0 0.0 0.0
70 0.0 0.0 0.0 0.0 0.0
:::.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:..:.:.:.:.:.:.:.
:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.
80 0.0 0.0 0.0 0.0 0.0
90 0.0 0.0 0.0 0.0 0.0
100 0.0 0.0 0.0 0.0 0.0
110 0.0 0.0 0.0 0.0 1
:::.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:..:.:.:.:.:.:.:.
:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.
120 0.0 0.0 0.0 0.0 97
130 0.0 0.0 0.0 0.0 2
140 0.0 0.0 0.0 0.0 0.0
150 0.0 0.0 0.0 0.0 0.0
:::.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:..:.:.:.:.:.:.:.
:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.:.
160 0.0 0.0 0.0 0.0 0.0
Pan 0.0 0.0 0.0 0.0 0.4 1.0 =0.5
kin size 100 98.1 99.9 99 93 95*
97**
Mean Particle 0.659 0.653 0.655 0.400 0.149 1.680-
0.841-
Diameter mm 0.053
0.074
Median Particle 0.657 0.645 0.652 0.395 0.140 1.680-
0.841-
Diameter (MPD) 0.053
0.074
mm
Solubility in 12/3 3.5 3.1 2.4 3.5 3.8 7.0 <4
HCL/HF for 0.5 HR
@ 150 F(%
weight loss)
Solubility in 15% 0.2 1.8 0.3 0.4 7.0 <4
HCL for 0.5 HR @
150 F (% weight
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loss)
Settling Rate 51.26 49.24 51.74 15.00 10.00 30
12
(ft/min)
ISO crush Analysis 9.6 7.5 7.5 0
8.0
( /0 Fines) 4 lbs/ft2
@ 4,000 psi ..
= ..
=
ISO crush Analysis 13.2 9.7 9.1 6.7 0
8.0
( /0 Fines) 4 lbs/ft2
@ 5,000 psi
ISO crush Analysis 11.3 9.9 8.4 0
8.0
( /0 Fines) 4 lbs/ft2 .
:
@ 6,000 psi :=.:=
...
.............................::
ISO crush Analysis 8.6 10 8.9 0
8.0
( /0 Fines) 4 lbs/ft2 =
@ 7,000 psi :=.:=
... .:.:
= =
= = ..
=
ISO crush Analysis 10.4 ::: :: 12 9.9 0
8.0
( /0 Fines) 4 lbs/ft2 ..
@ 8,000 psi ...
=
==
.:.:
...= ..
=
:
Wettability (pH of Fair Fair Good Fair Wettable
Fair or
Water Extract)
better
pH of Water
Extract
Initial pH 7.99 8.56 8.4 8.2 x x
mL NaOH 0.70 0.55 0.6 0.75 0.6 0.2
0.6 0.05
to pH 9
mL NaOH 3.00 2.30 3.10 2.10 2.5 1.5
2.5 0.5
to pH 10
mL NaOH 6.20 6.10 6.25 6.0 6.0 1
6.0 0.5
to pH 11
* ** for a particular targeted diameter sphere size within the targeted
range
[00157] The characteristics and physical properties identified in Table 2 are
further explained as follows.
[00158] Turbidity -- A measure to determine the levels of dust, silt,
suspended
clay, or finely divided inorganic matter levels in fracturing proppants. High
turbidity
reflects improper proppant manufacturing and/or handling practices. The more
often
and more aggressively a proppant is handled, the higher the turbidity.
Offloading
pressures exceeding characteristics or guidelines can have a detrimental
effect on the
proppant performance. Produced dust can consume oxidative breakers, alter
fracturing
fluid pH, and/or interfere with crosslinker mechanisms. As a result, higher
chemical
loadings may be required to control fracturing fluid rheological properties
and
performance. If fluid rheology is altered, then designed or modeled fracture
geometry
and conductivity will be altered. A change in conductivity directly correlates
to reservoir
flow rate.
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[00159] Krumbein Shape Factors ¨ Determines proppant roundness and
sphericity. Grain roundness is a measure of the relative sharpness of grain
corners, or
of grain curvature. Particle sphericity is a measure of how closely a proppant
particle
approaches the shape of a sphere. Charts developed by Krumbein and Sloss in
1963
are the most widely used method of determining shape factors.
[00160] Clusters ¨ Proppant grains should consist of single, well-rounded
particles. During the mining and manufacturing process of proppants, grains
can attach
to one another causing a cluster. It is recommended by ISO 13503-2 that
clusters be
limited to less than 1% to be considered suitable for fracturing proppants.
[00161] Bulk Density ¨ A dry test to gain an estimation of the weight of
proppant that will fill a unit volume, and includes both proppant and porosity
void
volume. This is used to determine the weight of a proppant needed to fill a
fracture or a
storage tank.
[00162] Specific Gravity ¨ Also called Apparent Density, it includes internal
porosity of a particle as part of its volume. It is measured with a low
viscosity fluid that
wets the particle surface.
[00163] Sieve Analysis: Particle Size Distribution & Median Particle Diameter¨
Also called a sieve analysis, this test determines the particle size
distribution of a
proppant sample. Calibrated sieves are stacked according to ISO 13503-2
recommended practices and loaded with a pre-measured amount of proppant. The
stack is placed in a Ro-Tap sieve shaker for 10 minutes and then the amount on
each
sieve is measured and a percent by weight is calculated on each sieve. A
minimum of
90 % of the tested proppant sample should fall between the designated sieve
sizes. Not
over 0.1 /o of the total tested sample should be larger than the first sieve
size and not
over 1.0% should fall on the pan. The in-size percent, mean particle diameter,
and
median particle diameter are calculated, which relates directly to propped
fracture flow
capacity and reservoir productivity.
[00164] API / ISO Crush Test ¨ The API test is useful for comparing proppant
crush resistance and overall strength under varying stresses. A proppant is
exposed to
varying stress levels and the amount of fines is calculated and compared to
manufacturer specifications. A PT Crush Profile -- can show graphically how
median
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particle diameter (MPD) can vary with changes in closure stress. Unlike the
ISO crush
test, the PT Crush Profile uses the entire proppant sample for crushing at
each stress,
the sample is then sieved to determine particle distribution, and MPD is then
calculated.
A change in MPD directly correlates to flow capacity and reservoir
productivity.
[00165] Acid Solubility ¨ The solubility of a proppant in 12-3 hydrochloric-
hydrofluoric acid (HCI- HF) is an indication of the amount of undesirable
contaminates.
Exposing a proppant (specifically gravel pack/frac pack materials) may result
in
dissolution of part of the proppant, deterioration in propping capabilities,
and a reduction
in fracture conductivity in the zone contacted by such acid. The loss of
fracture
conductivity near the wellbore may cause a dramatic reduction in well
productivity.
[00166] pH of Water Extract ¨ This test reflects the potential chemical impact
of
a proppant on fracturing fluid pH. Processing or manufacturing of prior art
proppants
can leave residues, or 'free phenol' in the case of resin coated proppants,
which can
interfere with polymer hydration rates, crosslinking mechanisms, etc. These
effects if
detected can usually be remedied by increasing buffering capacity, but if
undetected
can alter fracturing fluid rheology, change fracture geometry, and impact
propped
fracture conductivity. A change in conductivity directly correlates to
reservoir production
rate.
[00167] Preferably the synthetic proppant has, minimal, little, to no affect
on the
chemistry of the fracturing fluid, regardless of the different additives that
can be in a
fracturing fluid. In particular, it is highly preferable that the synthetic
proppant does not
effect or change the chemistry of the fracturing fluid. The synthetic proppant
many, in
embodiments, provide enhancements or benefits, either chemical, physical or
both, to
the fracturing fluid, e.g., reduced abrasion, increased lubricity, buffering
and specialty
properties, e.g., by having a specialty surface treatment, such as a biocide.
[00168] In general PsDC proppants essential have little to no affect on the pH
of the fracturing fluid. Thus, they can be used with most, in not all,
fracturing fluids and
will not adversely affect or impact pH, buffering, or pH control, or
intentional or planned
pH variations, of the wellbore fluids during the fracturing procedures.
Further, the PsDC
proppants may be coated with, or otherwise contain pH control or solution
buffering
materials, or sites, and in this manner help to control or maintain a
predetermined pH for
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the fracturing fluids in the down hole environment during fracturing
procedures or during
production of hydrocarbons.
[00169] Regardless of the failure mechanism, fluid flow, or hydraulic
mechanisms taking place, the synthetic proppants, e.g., PDC proppants, e.g.,
PsDC
proppants exhibit surprising and exceptional performance features, including
among
other things improved strength to weight ratios, and improved conductivities
over prior
art proppants.
[00170] For example, turning to FIG. 4, which is a chart comparing the short-
term conductivity data (line 450) for the proppant of Example 1 with published
long-term
conductivity data for prior art proppants, Ottawa 451 (high grade sand), RCS
452 (resin
coated sand), 453 LW Ceramic (lightweight ceramic proppant), 454 ISP Ceramic
(intermediate strength proppant), and 455 HS Ceramic (high strength ceramic
proppant). From the data present in FIG. 4 it can be seen that the proppant of
Example
1, 450, even though it had an API (ISO) crush test value of 4,000 psi,
exhibited superior
conductivity to all prior art proppants evaluated from closure of 5,000 psi to
15,000 psi.
[00171] Further, embodiments of synthetic proppants, e.g., PDC proppants,
e.g., PsDC proppants can exhibit conductivity data, at pressures about 5,000
psi over
its API (ISO) crush test rating: that are at least about 70 % of its
conductivity data at its
rated pressure; that are at least about 80% of its conductivity data at its
rated pressure;
that are at least about 90% of its conductivity data at its rated pressure;
and greater.
Embodiments of PsDC proppants can exhibit conductivity data, at pressures
about
10,000 psi over its API (ISO) crush test rating: that are at least about 60%
of its
conductivity data at its rated pressure; that are at least about 70% of its
conductivity
data at its rated pressure; that are at least about 80% of its conductivity
data at its rated
pressure; and greater.
[00172] The enhanced conductivity data alone or in combination with other
enhanced features of embodiments of synthetic proppants, e.g., PDC proppants,
e.g.,
PsDC proppants, such as sphericity, roundness, uniform size distribution, and
density
provide for the potential for significant improvements in both long-term and
short-term in
reservoir recovery, e.g., for enhanced initial production, short term and long
term
production of hydrocarbons from a well.
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[00173] Thus, for example, performing a synthetic, e.g., PDC, e.g., PsDC
hydraulic fracture treatment, and thus having these proppants in the
hydrocarbon
reservoir, may for example provide benefits such as increases in initial flow
of the
hydrocarbons, increases in the ability to maintain those increased initial
flows for extend
or longer periods of time over the life of the well, increase time when the
well remains
producing, increases in the ability to drain larger areas of a reservoir with
or from a
single well, and combinations and variations of these and other benefits that
may be
realized through the use of synthetic proppants, e.g., PDC proppants, e.g.,
PsDC
proppants in hydrocarbon, water and geothermal resources exploration and
production.
[00174] Thus, for example, turning to FIG. 5 there is a table, and charted
data
500 showing the increase in propped area this is obtainable with embodiments
of
synthetic proppants, e.g., PDC proppants, e.g., PsDC proppants. The propped
area
can be increased by increasing the propped fracture half-length (PFHL), shown
by
double-arrow 503, and by increasing the propped height (PH), shown by double-
arrow
502, and preferably both. The increase in the propped area is shown by line
501. In
the table and chart of FIG. 5, the expected performance of the proppant of
Example 2 is
compared against the performance of a conventional proppant. The proppant of
Example 2 can have a 20% increase in PFHL and PH, which results in a 73%
increase
in total propped area. More preferably, the proppant of Example 2 can have a
50%
increase in PFHL and PH, which results in a 237% increase in total propped
area. It is
theorized that, among other reasons, because of the reduced density (both
apparent
and actual) of the synthetic proppants, e.g., PDC proppants, e.g., PsDC
proppants, and
their considerable increase in strength, for these reduced densities, the
synthetic
proppants are capable of obtaining these significantly larger propped fracture
areas,
and thus significantly greater hydrocarbon production from a PsDC
hydraulically
fractured well than can be obtained from prior proppants and fracturing
treatments.
[00175] Turning to FIG. 6, the increase in both PFHL, as well as PH that can
be achieved from using the PsDC proppant of Example 2 is illustrated. A well
601 in a
formation 600 has a lateral section 605. The lateral section 605 has three
zones that
are perforated and subjected to a PsDC hydraulic fracturing treatment. The
propped
area for the PsDC hydraulic fracturing treatments, 602a, 603a, 604a, is
substantially
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larger than the maximum propped area, 602b, 603b, 604b that could be obtained
with
conventional proppants.
[00176] Thus, the PsDC hydraulic fracturing treatments provide the ability to
increase the Initial Product (IP) from the well (e.g., the amount of
production that the
well produces during an initial time period typically, about 90 days, about
180 days, and
generally less than 1 year), to increase the Decline Curve Reduction (DCR) for
the well
(e.g., generally over time the amount of production from a well declines over
time,
slowing this decline in production is viewed as an increase in the DCR), and
both.
Turning to FIG. 7 there is shown a chart 700 showing the effect on total
production that
can be obtained from PsDC hydraulic fracturing treatments. In FIG. 7 there is
shown a
chart 700 showing potential increases in DCR 701 and IP & DCR 702, and the
effect
these increases have on total production from the well over a 10 year period.
Thus,
embodiments of the PsDC hydraulic fracturing treatments have the ability to
increase
the 10 year production of a well by at least about 20%, at least about 30% at
least about
60%, at least about 100% and more.
[00177] In general, unless specifically stated otherwise, the percentage
increases, improved performance, and other comparisons that are made in this
specification to current and prior art proppants, fracturing technologies, and
treatments,
are based upon modeling, predictions, data and calculations known to those of
skill in
the art for providing the production and performance features for a well that
is treated
with such current or prior art technologies.
[00178] The processes and the formulations used to make the synthetic
proppants, e.g., PDC proppants, e.g., PsDC proppants, provide the ability to
make
proppants having a very narrow particle size distribution. Thus, embodiments
of these
processes produce proppants that are within at least 90% of the targeted size,
at least
95% of the targeted size, and at least 99% of the targeted size. For example,
the
process can produce spherical proppant, spherical type proppants, essentially
perfect
spherical proppant, and substantially perfect spherical proppant, each of
which can
have at least about 90% of their size within a 10 mesh range, at least about
95% of their
size within a 10 mesh range, at least about 98% of their size within a 10 mesh
range,
and at least about 99% of their size within a 10 mesh range. Further, and for
example,
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the process can produce spherical proppant, spherical type proppants,
essentially
perfect spherical proppant, and substantially perfect spherical proppant, each
of which
can have at least about 90% of their size within a 5 mesh range, at least
about 95% of
their size within a 5 mesh range, at least about 98% of their size within a 5
mesh range,
and at least about 99% of their size within a 5 mesh range. Preferably, these
levels of
uniformity in the production of the synthetic proppants, e.g., PDC proppants,
e.g., PsDC
proppants, is obtained without the need for filtering, sorting or screening
the cured
proppants, and without the need for filtering, sorting or screening the
pyrolized
proppants. In addition to having the ability to tightly control size
distribution,
embodiments of the present processes and formulations provide the ability to
make a
large number of highly uniform predetermined shapes, e.g., at least about 90%,
at least
about 95% and at least about 99% of the proppants have a predetermined
sphericity
and/or roundness. For example, at least about 98% of the proppants made from a
batch can be essentially spherical.
[00179] In FIG. 8 there is shown a perspective view of a synthetic, e.g., PDC,
e.g., PsDC hydraulic fracturing site 800. Thus, positioned near the well head
814 there
are, pumping trucks 806, proppant, e.g., PsDc proppant, storage containers
810, 811, a
proppant feeder assembly 809, a mixing truck 808, and fracturing fluid holding
units
812. It is understood that FIG. 8 is an illustration and simplification of a
fracturing site.
Such sites may have more, different, and other pieces of equipment such as
pumps,
holding tanks, mixers, and chemical holding units, mixing and addition
equipment, lines,
valves and transferring equipment, as well as control and monitoring
equipment.
[00180] A high-pressure line 805 that transfers high pressure fracturing fluid
from the pump trucks 806 into the well. The wellhead 804 may also have further
well
control devices associated with it, such as a BOP. Fracturing fluid from
holding units
812 is transferred through lines 813 to mixing truck 808, where proppant from
storage
containers 810, 811 is feed, (metered in a controlled fashion) by assembly 809
and
mixed with the fracturing fluid. The fracturing fluid and proppant mixture is
then
transferred to the pump trucks 806, by line 803, where the pump trucks 806
pump the
fracturing fluid into the well by way of high pressure line 805.
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[00181] In embodiments, the PsDCs are mixed with fracing fluids for down hole
hydraulic fracturing operations to, for example, recover hydrocarbons, such as
crude oil
and natural gas. Typically, between about 0.1 and about 12 lbs/gal, between
about 3
and about 10 lbs/gal, between about 0.1 and about 1 lbs/gal, between about 1.1
and
about 2 lbs/gal, between about 2.1 and about 4 lbs/gal, and between about 3.1
and
about 8 lbs/gal of PsDC are mixed into fracing fluid, greater and lesser
amounts than
about 12 lbs/gal and about 1 lbs/gal are also contemplated. Typically, at
least about
10,000 gals, at least about 100,000 gals, at least about 1,000,000 gals and
more of
fracing fluid are used in a fracing operation. Thus, in general hundreds of
thousands, if
not millions of pounds of proppant, e.g., PsDC proppant, could be used in a
single
hydraulic fracturing operation.
[00182] The highly uniform nature of embodiments of the present proppants
provides for many new and previously unavailable advantageous ways to meter
and
add in a controlled manner, the proppant to fracturing fluid, for a fracturing
treatment.
The proppant can be added using volumetric measurements, or metering systems,
instead of weight based metering system of the prior art. Volumetric systems
using
embodiments of the present proppants provides the same or greater level of
control
because, among other things, the proppants of the present invention are highly
uniform
and thus volume of these proppants equates linearly, and with high
predictability, to the
weight of the proppants. This ability to meter, in a controlled manner, by
volume, the
proppants of the present inventions provides the ability to add these
proppants in a
controlled manner to the well head, to the high pressure line, and generally,
after the
high pressure, high volume pumps. Such addition will greatly reduce the wear
on the
pumps and increase their lives.
[00183] Because such large volumes of proppants are used in these
operations, and because of the importance in understanding and knowing the
characteristics of the proppant, both on a micro level (e.g., a single
spherical type
structure) and on the macro level (e.g., how the proppant pack behaves in the
down
hole environment) sampling methods have been developed and are well know in
the art
to obtain representative samples for testing and characterization of a larger
volume of
proppant, e.g., a lot, a load, a rail car, etc. These sampling methods are set
forth in API
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RP 56, ISO 13503-2:2006, and in ANSI/API Recommended Practice 19C, First
Edition,
May 2008. Unless expressly stated otherwise, or contrary to the context, as
used
herein, when PsDC characteristics, properties, or both are used they will
refer to a
representative sample of the proppant.
[00184] Generally, in the manufacture of PsDCs a polysilocarb batch is formed
into a preform proppant. Depending upon the viscosity and other
characteristics of the
polysilocarb batch, and the intended shape of the proppant, the preform may be
made
by techniques such as extruding, molding, drawing, spinning, dripping,
spraying,
vibrating, polymer emulsion (emulsion polymerization, including micro-emulsion
polymerization, capable of making a substantial range of sizes, e.g., from
about 10
mesh to about 400 mesh, from about 20 mesh to about 200 mesh, from about 500
microns and less, from about 50 microns and less, from about 10 microns and
less) and
other techniques known to the arts to create small structures of a
predetermined shape,
and preferably in large volumes, preferably that are highly uniform and more
preferably
both. Further it is understood, that although it is presently preferred that
the preform
and the proppant be their approximate size and shape upon cure, or prior to
pyrolysis,
the polysilocarb batch can be cured into a puck like structure, e.g., roughly
the size and
shape of a hockey puck, a brick like structure or other larger volumetric
shape. This
larger shape can be cured, hard cured, and pyrolized, and broken down into
smaller
sizes (preferably after pyrolysis). This process of later breaking down,
typically,
although not necessarily, results in a proppant that is not of uniform or
consistent shape,
size and both.
[00185] The curing process may take place upon initial forming, if the preform
is unrestrained, to make certain that the predetermined shape is locked, e.g.,
fixed or
set, so that later handing of the preform will not change the shape. The
curing process
may be continuous, e.g., initial cure to hard cure occurs in one time period
and process,
or may take place in several stages, e.g., an initial cure for a set time
period and
temperature, a cure of a set time period and temperature, and a hard cure for
a set time
period and temperature. These cure stages may take place back-to-back with no
intervening time periods or they may be staggered in time, with intervening
time periods
where the preform is maintained at ambient temperature, or where the preform
is
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subjected to some other process. For example, an initial cure may be
performed, a
cure may then be performed, in which case the preform has the appearance of
haying a
hard skin with gelatinous center, at which point the preform could be
subjected to a
shaping operation to get it into is final form, at which point the hard cure
would be
performed.
[00186] In general, and for example, for the purposes of making beads, or ball
shaped proppants one or more of the process parameters and equipment set forth
in
table 3 can be used.
[00187] Table 3
Nozzle Thermal Heat Exchanger Curing Process
Production of proppant beads Temperature range 0 to 1600 C Temperature
range 0 to 1600 C
thru the use of internal and multi zone / range controlled multi zone /
range controlled
external orifices, atomization (manually or
automated ¨ local or
mechanically, pressure, and gas remote)
to produce tight mesh distribution
(within 1 to 5 mesh sizes of
target size) beads ranging from
2000 micron to 75 micron.
Produced thru the use of a Air, Steam, Electrical, Gas, Phased curing
process in part or
temperature compensated Waste Heat, or Solar source of whole
(liquid, air, gas, radiant, or heat
mechanical) controllable one or
more active orifices or filament,
(vibration, heat, pressure,
pulsation, 20Hz to 20,000Hz
frequency)
Orifices or filament material; Material of Construction ¨ Air or inert
gas controlled
made from metal, composite, metallic, composite, fire brick, or
atmosphere
plastic, precious metal, jewel, or ceramic
ceramic,
Gravity or pressure compensated Radiant, convection, direct heat, Air,
Steam, Electrical, Gas,
orifices or filament Waste Heat, or Solar
source of
heat
Continuous operation and flow; Vertical to horizontal orientations Heat
transferring media of air,
or batch process inert gas, radiant,
convection,
condensing, vapor, or direct heat
Viscosity range 1 to 1000 Up to and including Adiabatic Multi Chambered
or portioned
enabled
Static and dynamic particle 1' to 500' Structure Height Continuous and
batch
processing
Multi Chambered or portioned Static and dynamic
particle
processin
...............................................................................
...............................................................................
.......
,..............................................................................
...,
...............................................................................
...
Heat transferring media of air,
inert gas, radiant, convective,
condensing: vapor: or direct heat
Staticand dynamic particle
...............................................................................
....
processing
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[00188] Turning to FIG. 9 there is provided a schematic flow diagram of an
embodiment of a proppant preform forming and curing system 900. The system 900
has a precursor batch preparation system 901, which is used to blend, mix,
catalyze, or
other preparation steps that may be performed to prepare the precursor batch
for
forming and curing. These preparation steps and systems are taught and
disclosed in
US patent application serial number 14/268,150, the entire disclosure of which
is
incorporated herein by reference. A transfer line 902 transfers the precursor
batch to a
formation device 903, which forms the precursor batch into a shape of the
proppant.
The shaped precursor is then cured in curing device 904 to a preform, or
preform
proppant. (It should be noted that preparation steps may occur along the
transfer line
902, and at the formation device 903.) The cured preformed proppants are then
transferred by transfer device 905 (which may not be present, could be a
continuous
system such as a conveyor system, or air pressure transfer system, a batch
system,
including hand pushed bins) to the pyrolysis device 906. In the pyrolysis
device 906 the
preform proppants are pyrolized to from a ceramic, e.g. the PsDC proppants.
The
pyrolysis may be continuous, semi-continuous, or batch. It may take place in
an inert
atmosphere, an inert reduced pressure atmosphere, a vacuum, air, a flowing
inert
atmosphere, a flowing reduced pressure atmosphere, and combinations and
variations
of these. Post cure processing station 910a and post pyrolysis processing
station 910b
my be used to perform steps such as sorting, filtering, sieving, inspecting,
washing,
drying, treating, coating, and combinations of these and other post processing
steps.
Transfer device 907 transfers the finished proppants to a storage and delivery
station
908, where the finished proppant can be transferred into shipping devices 909,
e.g. a
truck, container, barge or rail car.
[00189] In general, preferred embodiments of the synthetic proppants of the
present inventions are made from unique and novel silicon (Si) based materials
that are
easy to manufacture, handle and have surprising and unexpected properties and
applications. These silicon based materials go against the general trends of
the art of
silicon chemistry and uses. Generally, the art of silicon chemistry, and in
particular
organosilicon chemistry, has moved toward greater and greater complexity in
the
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functional groups that are appended to, and a part of, a silicon based
polymeric
backbone. Similarly, in general, the processes that are utilized to make these
polymers
have moved toward greater and greater complexity. Embodiments of the present
new
material systems for use as proppants move away from this trend, by preferably
functionalizing a silicon based polymeric backbone with simpler structures,
such as
phenyl, phenylethyl and smaller groups, and do so with processes that are
simplified,
e.g., solvent free, reduced solvent, lower cost starting materials, fewer
steps, and
reduction of reaction intermediates.
[00190] Further, and generally, the art views silicones as tacky, soft or
liquid
materials that are used with, on, or in conjunction with, other materials to
enhance or
provide a performance feature to those other materials. Silicon based
materials
generally are not viewed as stand alone products, primary products, or
structural
elements. The preferred silicon based materials for use as proppants, however,
move
away from this trend and understanding in the art. These silicon based
materials
provide materials that are exceptionally strong, and can function as stand
alone
products and composites, among other things.
[00191] Generally, preferred embodiments of the synthetic proppants of the
present inventions are directed to polymer derived ceramics (PDC), and more
preferably toward "polysilocarb" materials, e.g., material containing silicon
(Si), oxygen
(0) and carbon (C), and materials that have been pyrolized from such
materials.
Polysilocarb materials may also contain other elements. Polysilocarb materials
are
made from one or more polysilocarb precursor formulation or precursor
formulation.
The polysilocarb precursor formulation contains one or more functionalized
silicon
polymers, or monomers, as well as, potentially other ingredients, such as for
example,
inhibitors, catalysts, pore formers, fillers, reinforcers, fibers, particles,
colorants,
pigments, dies, polymer derived ceramics ("PDC"), ceramics, metals, metal
complexes,
and combinations and variations of these and other materials and additives.
[00192] The precursor batch may also contain non-silicon based cross linking
agents, that are intended to, provide, the capability to cross-link during
curing. For
example, cross linking agents that can be used include DCPD ¨
dicylcopentadiene, 1,4
butadiene, divnylbenzene, Isoprene, norbornadiene, propadiene, 4-
vinylcyclohexene,
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2-3 heptadiene 1, 3 butadiene and cyclooctadiene. Generally, any hydrocarbon
that
contains two (or more) unsaturated, C=C bonds that can react with a Si-H, Si-
OH, or
other Si bond in a precursor, can be used as a cross linking agent. Some
organic
materials containing oxygen, nitrogen, and sulphur may also function as cross
linking
moieties.
[00193] The polysilocarb precursor formulation is then cured to form a solid
or
semi-sold material, e.g., a plastic. The polysilocarb precursor formulation
may be
processed through an initial cure, to provide a partially cured material,
which may also
be referred to, for example, as a preform, green material, or green cure (not
implying
anything about the material's color). The green material may then be further
cured.
Thus, one or more curing steps may be used. The material may be "end cured,"
i.e.,
being cured to that point at which the material has the necessary physical
strength and
other properties for its intended purpose. The amount of curing may be to a
final cure
(or "hard cure"), i.e., that point at which all, or essentially all, of the
chemical reaction
has stopped (as measured, for example, by the absence of reactive groups in
the
material, or the leveling off of the decrease in reactive groups over time).
Thus, the
material may be cured to varying degrees, depending upon its intended use and
purpose. For example, in some situations the end cure and the hard cure may be
the
same.
[00194] The curing may be done at standard ambient temperature and
pressure ("SATP", 1 atmosphere, 25 C), at temperatures above or below that
temperature, at pressures above or below that pressure, and over varying time
periods
(both continuous and cycled, e.g., heating followed by cooling and reheating),
from less
than a minute, to minutes, to hours, to days (or potentially longer), and in
air, in liquid, or
in a preselected atmosphere, e.g., Argon (Ar) or nitrogen (N2).
[00195] The polysilocarb precursor formulations can be made into non-
reinforced, non-filled, composite, reinforced, and filled structures,
intermediates and end
products, and combinations and variations of these and other types of
materials.
Further, these structures, intermediates and end products can be cured (e.g.,
green
cured, end cured, or hard cured), uncured, pyrolized to a ceramic, and
combinations
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and variations of these (e.g., a cured material may be filled with pyrolized
beads derived
from the same polysilocarb as the cured material).
[00196] The precursor formulations may be used to form "neat" materials, (by
"neat" material it is meant that all, and essentially all of the structure is
made from the
precursor material or unfilled formulation; and thus, there are no fillers or
reinforcements). They may be used to form composite materials, e.g.,
reinforced
products. They may be used to form non-reinforced materials, which are
materials that
are made of primarily, essentially, and preferably only from the precursor
materials.
[00197] In making the polysilocarb precursor formulation into a volumetric
shape or structure, the polysilocarb formulation can be, for example, sprayed,
spray
dried, emulsified, polymer emulsification, polymer micro-emulsification,
thermally
sprayed, molded, flowed, formed, extruded, spun, dropped, injected or
otherwise
manipulated into essentially any volumetric shape, including the shapes for
the
proppant, and combinations and variations of these. These volumetric shapes
would
include, for example, spheres, pellets, rings, lenses, disks, panels, cones,
frustoconical
shapes, squares, rectangles, trusses, angles, channels, hollow sealed
chambers,
hollow spheres, blocks, sheets, coatings, films, skins, particulates, beams,
rods, angles,
columns, fibers, staple fibers, tubes, cups, pipes, and combinations and
various of these
and other more complex shapes, both engineering and architectural.
Additionally, they
may be shaped into preforms, or preliminary shapes that correspond to, or
with, a final
product, such as for example use in or with, a break pad, a clutch plate, a
break shoe, a
motor, high temperature parts of a motor, a diesel motor, rocket components,
turbine
components, air plane components, space vehicle components, building
materials,
shipping container components, and other structures or components.
[00198] The polysilocarb precursor formulations may be used with reinforcing
materials to form a composite material. Thus, for example, the formulation may
be
flowed into, impregnated into, absorbed by or otherwise combined with a
reinforcing
material, such as carbon fibers, glass fiber, woven fabric, non-woven fabric,
copped
fibers, fibers, rope, braided structures, ceramic powders, glass powders,
carbon
powders, graphite powders, ceramic fibers, metal powders, carbide pellets or
components, staple fibers, tow, nanostructures of the above, PDCs, any other
material
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that meets the temperature requirements of the process and end product, and
combinations and variations of these. Thus, for example, the reinforcing
materials may
be any of the high temperature resistant reinforcing materials currently used,
or capable
of being used with, existing plastics and ceramic composite materials.
Additionally,
because the polysilocarb precursor formulation may be formulated for a lower
temperature cure (e.g., SATP) or a cure temperature of for example about 100
F to
about 400 F, the reinforcing material may be polymers, organic polymers, such
as
nylons, polypropylene, and polyethylene, as well as aramid fibers, such as
NOMEX or
KEVLAR.
[00199] The reinforcing material may also be made from, or derived from the
same material as the formulation that has been formed into a fiber and
pyrolized into a
ceramic, or it may be made from a different precursor formulation material,
which has
been formed into a fiber and pyrolized into a ceramic. In addition to ceramic
fibers
derived from the precursor formulation materials that may be used as
reinforcing
material, other porous, substantially porous, and non-porous ceramic
structures derived
from a precursor formulation material may be used.
[00200] The polysilocarb precursor formulation may be used to form a filled
material. A filled material would be any material having other solid, or semi-
solid,
materials added to the polysilocarb precursor formulation. The filler material
may be
selected to provide certain features to the cured product, the ceramic product
or both.
These features may relate to or be aesthetic, tactile, thermal, density,
radiation,
chemical, magnetic, electric, and combinations and variations of these and
other
features. These features may be in addition to strength. Thus, the filler
material may
not affect the strength of the cured or ceramic material, it may add strength,
or could
even reduce strength in some situations. The filler material could impart
color, magnetic
capabilities, fire resistances, flame retardance, heat resistance, electrical
conductivity,
anti-static, optical properties (e.g., reflectivity, refractivity and
iridescence), aesthetic
properties (such as stone like appearance in building products), chemical
resistivity,
corrosion resistance, wear resistance, abrasions resistance, thermal
insulation, UV
stability, UV protective, and other features that may be desirable, necessary,
and both,
in the end product or material. Thus, filler materials could include copper
lead wires,
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thermal conductive fillers, electrically conductive fillers, lead, optical
fibers, ceramic
colorants, pigments, oxides, dyes, powders, ceramic fines, PDC particles, pore-
formers,
carbosilanes, silanes, silazanes, silicon carbide, carbosilazanes, siloxane,
powders,
ceramic powders, metals, metal complexes, carbon, tow, fibers, staple fibers,
boron
containing materials, milled fibers, glass, glass fiber, fiber glass, and
nanostructures
(including nanostructures of the forgoing) to name a few.
[00201] The fill material may also be made from, or derived from the same
material as the formulation that has been formed into a cured or pyrolized
solid, or it
may be made from a different precursor formulation material, which has been
formed
into a cured solid or semi-solid, or pyrolized solid.
[00202] The polysilocarb formulation and products derived or made from that
formulation may have metals and metal complexes. Thus, metals as oxides,
carbides
or silicides can be introduced into precursor formulations, and thus into a
silica matrix in
a controlled fashion. Thus, using organometallic, metal halide (chloride,
bromide,
iodide), metal alkoxide and metal amide compounds of transition metals and
then
copolymerizing in the silica matrix, through incorporation into a precursor
formulation is
contemplated.
[00203] For example, Cyclopentadienyl compounds of the transition metals can
be utilized. Cyclopentadienyl compounds of the transition metals can be
organized into
two classes: Bis-cyclopentadienyl complexes; and Mono-cyclopentadienyl
complexes.
Cyclopentadienyl complexes can include C5H5, C5Me5, C5H4Me, CH5R5 (where R =
Me,
Et, Propyl, i-Propyl, butyl, lsobutyl, Sec-butyl). In either of these cases Si
can be
directly bonded to the Cyclopentadienyl ligand or the Si center can be
attached to an
alkyl chain, which in turn is attached to the Cyclopentadienyl ligand.
[00204] Cyclopentadienyl complexes, that can be utilized with precursor
formulations and in products, can include: bis-cyclopentadienyl metal
complexes of first
row transition metals (Titanium, Vanadium, Chromium, Iron, Cobalt, Nickel);
second row
transition metals (Zirconium, Molybdenum, Ruthenium, Rhodium, Palladium);
third row
transition metals (Hafnium, Tantalum, Tungsten, Iridium, Osmium, Platinum);
Lanthanide series (La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho); Actinide
series (Ac,
Th, Pa, U, Np).
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[00205] Monocyclopentadienyl complexes may also be utilized to provide metal
functionality to precursor formulations and would include monocyclopentadienyl
complexes of: first row transition metals (Titanium, Vanadium, Chromium, Iron,
Cobalt,
Nickel); second row transition metals (Zirconium, Molybdenum, Ruthenium,
Rhodium,
Palladium); third row transition metals (Hafnium, Tantalum, Tungsten, Iridium,
Osmium,
Platinum) when preferably stabilized with proper ligands, (for instance
Chloride or
Carbonyl).
[00206] Alky complexes of metals may also be used to provide metal
functionality to precursor formulations and products. In these alkyl complexes
the Si
center has an alkyl group (ethyl, propyl, butyl, vinyl, propenyl, butenyl)
which can bond
to transition metal direct through a sigma bond. Further, this would be more
common
with later transition metals such as Pd, Rh, Pt, Ir.
[00207] Coordination complexes of metals may also be used to provide metal
functionality to precursor formulations and products. In these coordination
complexes
the Si center has an unsaturated alkyl group (vinyl, propenyl, butenyl,
acetylene,
butadienyl) which can bond to carbonyl complexes or ene complexes of Cr, Mo,
W, Mn,
Re, Fe, Ru, Os, Co, Rh, Ir, Ni. The Si center may also be attached to a
phenyl,
substituted phenyl or other aryl compound (pyridine, pyrimidine) and the
phenyl or aryl
group can displace carbonyls on the metal centers.
[00208] Metal alkoxides may also be used to provide metal functionality to
precursor formulations and products. Metal alkoxide compounds can be mixed
with the
Silicon precursor compounds and then treated with water to form the oxides at
the same
time as the polymer, copolymerize. This can also be done with metal halides
and metal
amides. Preferably, this may be done using early transition metals along with
Aluminum, Gallium and Indium, later transition metals: Fe, Mn, Cu, and
alkaline earth
metals: Ca, Sr, Ba, Mg.
[00209] Compounds where Si is directly bonded to a metal center which is
stabilized by halide or organic groups may also be utilized to provide metal
functionality
to precursor formulations and products.
[00210] Additionally, it should be understood that the metal and metal
complexes may be the continuous phase after pyrolysis, or subsequent heat
treatment.
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Formulations can be specifically designed to react with selected metals to in
situ form
metal carbides, oxides and other metal compounds, generally known as cermets
(e.g.,
ceramic metallic compounds). The formulations can be reacted with selected
metals to
form in situ compounds such as mullite, alumino silicate, and others. The
amount of
metal relative to the amount of silica in the formulation or end product can
be from about
0.1 mole % to 99.9 mole %, about 1 mole % or greater, about 10 mole % or
greater,
about 20 mole percent or greater % and greater. The forgoing use of metals
with the
present precursor formulas can be used to control and provide predetermined
stoichiometries.
[00211] Filled materials would include reinforced materials. In many cases,
cured, as well as pyrolized polysilocarb filled materials can be viewed as
composite
materials. Generally, under this view, the polysilocarb would constitute the
bulk or
matrix phase, (e.g., a continuous, or substantially continuous phase), and the
filler
would constitute the dispersed (e.g., non-continuous), phase.
[00212] It should be noted, however, that by referring to a material as
"filled" or
"reinforced" it does not imply that the majority (either by weight, volume, or
both) of that
material is the polysilcocarb. Thus, generally, the ratio (either weight or
volume) of
polysilocarb to filler material could be from about 0.1:99.9 to 99.9:0.1.
Smaller amounts
of filler material or polysilocarb could also be present or utilized, but
would more
typically be viewed as an additive or referred to in other manners. Thus, the
terms
composite, filled material, polysilocarb filled materials, reinforced
materials, polysilocarb
reinforced materials, polysilocarb filled materials, polysilocarb reinforced
materials and
similar such terms should be viewed as non-limiting as to amounts and ratios
of the
material's constitutes, and thus in this context, be given their broadest
possible
meaning.
[00213] The polysilocarb precursor formulation may be specifically formulated
to cure under conditions (e.g., temperature, and perhaps time) that match,
e.g., are
predetermined to match, the properties of the reinforcing material, filler
material or
substrate. These materials may also be made from, or derived from, the same
material
as the polysilocarb precursor formulation that is used as the matrix, or it
may be made
from a different polysilocarb precursor formulation. In addition to ceramic
fibers derived
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from the polysilocarb precursor formulation materials, porous, substantially
porous, and
non-porous ceramic structures derived from a polysilocarb precursor
formulation
material may be used as filler or reinforcing material.
[00214] The polysilocarb precursor formulations may be used to coat or
impregnate a woven or non-woven fabric, made from for example carbon fiber,
glass
fibers or fibers made from a polysilocarb precursor formulation (the same or
different
formulation), to from a prepreg material. Further, a polysilocarb precursor
formulation
may be used as an interface coating on the reinforcing material, for use
either with a
polysilocarb precursor formulation as the matrix material. Further, carbon
fiber may be
heat treated to about 1,400 to about 1,800 or higher, which creates a surface
feature
that eliminates the need for a separate interface coating, for use with
polysilocarb
precursor formulations.
[00215] Fillers can reduce the amount of shrinkage that occurs during the
processing of the formulation into a ceramic, they can be used to provide a
predetermined density of the product, either reducing or increasing density,
and can be
used to provide other customized and predetermined product and processing
features.
Fillers, at larger amounts, e.g., greater than 10%, can have the effect of
reducing
shrinkage during cure.
[00216] Depending upon the particular application, product or end use, the
filler
can be evenly distributed in the precursor formulation, unevenly distributed,
a
predetermined rate of settling, and can have different amounts in different
formulations,
which can then be formed into a product having a predetermined amounts of
filler in
predetermined areas, e.g., striated layers having different filler
concentration.
[00217] Preferably, for a typical filled product, the filler is substantially
evenly
distributed and more preferably evenly distributed within the end product. In
this
manner localize stresses or weak points can be avoided. Generally, for a non-
reinforced material each filler particle may have a volume that is less than
about 0.3%,
less than about 0.2%, less than about 0.1%, and less than about 0.05% of the
volume
of a product, intermediate or proppant. For example, if the product is
spherical in shape
and the filler is spherical in shape the diameter of the filler should
preferable be about
1/10 to about 1/20 of the diameter of the proppant particle, and more
preferably the filler
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diameter should be less than about 1/20 of the diameter of the proppant
particle.
Generally, the relative amount of filler used in a material should preferable
be about
30% to about 65% of the volume of the sphere, e.g., volume /0.
[00218] Generally, when a small particulate filler, e.g., fines, beads,
pellets, is
used for the purposes of increasing strength, without the presence of fibers,
fabric, etc.,
generally at least about 2% to at least about 5 volume /0, can show an
increase in the
strength, although this may be greater or smaller depending upon other
factors, such as
the shape and volume of the product, later processing conditions, e.g., cure
time,
temperature, number of pyrolysis reinfiltrations. Generally, as the filler
level increases
from about above 5 volume % no further strength benefits may be realized. Such
small
particulate filled products, in which appreciable strength benefits are
obtained from the
filler, and in particular an increase in strength of at least about 5%, at
last about 10%
and preferably at least about 20% would be considered to be reinforced
products and
materials.
[00219] At various points during the manufacturing process, the polysilocarb
structures, intermediates and end products, and combinations and variations of
these,
may be machined, milled, molded, shaped, broken, drilled or otherwise
mechanically
processed and shaped.
[00220] The precursor formulations are preferably clear or are essentially
colorless and generally transmissive to light in the visible wavelengths. They
may,
depending upon the formulation have a turbid, milky or clouding appearance.
They may
also have color bodies, pigments or colorants, as well as color filler (which
can survive
pyrolysis, for ceramic end products, such as those used in ceramic pottery
glazes). The
precursor may also have a yellow or amber color or tint, without the need of
the addition
of a colorant.
[00221] The precursor formulations may be packaged, shipped and stored for
later use in forming products, e.g., proppants, or they may be used directly
in these
processes, e.g., continuous process to make a prpppant. Thus, a precursor
formulation
may be stored in 55 gallon drums, tank trucks, rail tack cars, onsite storage
tanks
having the capable of holding hundreds of gals, and shipping totes holding
1,000 liters,
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by way of example. Additionally, in manufacturing process the formulations may
be
made and used in a continuous, and semi-continuous processes.
[00222] The present inventions, among other things, provide substantial
flexibility in designing processes, systems, ceramics, having processing
properties and
end product performance features to meet predetermined and specific
performance
criteria. Thus, for example the viscosity of the precursor formulation may me
predetermined by the formulation to match a particular morphology of the
reinforcing
material, the cure temperature of the precursor formulation may be
predetermined by
the formulation to enable a prepreg to have an extended shelf life. The
viscosity of the
of the precursor formulation may be established so that the precursor readily
flows into
the processing head, e.g., a sonic nozzle. The formulation of the precursor
formulation
may also, for example, be such that the strength of a cured preform is
sufficient to allow
rough or initial processing of the preform, prior to pyrolysis, e.g., breaking
up of a puck
to provide small, e.g., about 10 mm diameters to about 10 micron diameters,
and
potentially smaller to the micron and submicron diameter size.
[00223] Custom and predetermined control of when chemical reactions occur
in the various stages of the process from raw material to final end product
can provide
for reduced costs, increased process control, increased reliability, increased
efficiency,
enhanced product features, and combinations and variation of these and other
benefits.
The sequencing of when chemical reactions take place can be based primarily
upon the
processing or making of precursors, and the processing or making of precursor
formulations; and may also be based upon cure and pyrolysis conditions.
Further, the
custom and predetermined selection of these steps, formulations and
conditions, can
provide enhanced product and processing features through chemical reactions,
molecular arrangements and rearrangements, and microstructure arrangements and
rearrangements, that preferably have been predetermined and controlled.
[00224] It should be understood that the use of headings in this specification
is
for the purpose of clarity, and are not limiting in any way. Thus, the
processes and
disclosures described under a heading should be read in context with the
entirely of this
specification, including the various examples. The use of headings in this
specification
should not limit the scope of protection afford the present inventions.
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[00225] Generally, the process form making the present polysilocarb materials
involves one or more steps. The starting materials are obtained, made or
derived.
Precursors are obtained or can be made from starting materials. The precursors
are
combined to form a precursor formulation. The precursor formulation is then
shaped,
dropped, extruded, sprayed, formed, molded, etc. into a desired form, which
form is
then cured, which among other things transforms the precursor formulation into
a plastic
like material. This cured plastic like material can then be pyrolyzed into a
ceramic. It
being understood, that these steps may not all be used, that some of these
steps may
be repeated, once, twice or several times, and that combinations and
variations of these
general steps may be utilized to obtain a desired product or result.
Processes for Obtaining a Polysilocarb Precursor Formulation
[00226] Polysilocarb precursor formulations can generally be made using two
types of processes, although other processes and variations of these types of
processes may be utilized. These processes generally involve combining
precursors to
form a polysilocarb precursor formulation. One type of process generally
involves the
mixing together of precursor materials in preferably a solvent free process
with
essentially no chemical reactions taking place, e.g., "the mixing process."
The other
type of process generally involves chemical reactions to form specific, e.g.,
custom,
polysilocarb precursor formulations, which could be monomers, dimers, trimers
and
polymers. Generally, in the mixing process essentially all, and preferably
all, of the
chemical reactions take place during subsequent processing, such as during
curing,
pyrolysis and both. It should be understood that these terms - reaction type
process
and the mixing type process - are used for convenience, e.g., a short hand
reference,
and should not be viewed as limiting. Further, it should be understood that
combinations and variations of these two processes may be used in reaching a
precursor formulation, and in reaching intermediate, end and final products.
Depending
upon the specific process and desired features of the product the precursors
and
starting materials for one process type can be used in the other. These
processes
provide great flexibility to create custom features for intermediate, end and
final
products, and thus, typically, either process type, and combinations of them,
can
provide a specific predetermined product. In selecting which type of process
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preferable factors such as cost, controllability, shelf life, scale up,
manufacturing ease,
etc., can be considered.
[00227] The two process types are described in this specification, among other
places, under their respective headings. It should be understood that the
teachings for
one process, under one heading, and the teachings for the other process, under
the
other heading, can be applicable to each other, as well as, being applicable
to other
sections and teachings in this specification, and vice versa. The starting or
precursor
materials for one type of process may be used in the other type of process.
Further, it
should be understood that the processes described under these headings should
be
read in context with the entirely of this specification, including the various
examples.
Thus, the use of headings in this specification should not limit the scope of
protection
afford the present inventions.
[00228] Additionally, the formulations from the mixing type process may be
used as a precursor, or component in the reaction type process. Similarly, a
formulation
from the reaction type process may be used in the mixing type process. Thus,
and
preferably, the optimum performance and features from either process can be
combined
and utilized to provide a cost effective and efficient process and end
product.
[00229] In addition to being commercially available the precursors may be
made by way of an alkoxylation type, e.g., ethoxylation process. In this
process
chlorosilanes are reacted with ethanol in the presences of a catalysis, e.g.,
HCI, to
provide the precursor materials, which materials may further be reacted to
provide
longer chain precursors. Other alcohols, e.g., Methanol may also be used.
Thus, the
compounds the formulas of FIGS. 60A to 60F are reacted with ethanol (C-C-OH)
to
form the precursors of FIGS. 46-59. In some of these reactions phenols may be
the
source of the phenyl group, which is substitute for a hydride group that has
been placed
on the silicon. One, two or more step reaction may need to take place.
The Mixing Type Process
[00230] Precursor materials may be methyl hydrogen, and substituted and
modified methyl hydrogens, siloxane backbone additives, reactive monomers,
reaction
products of a siloxane backbone additive with a silane modifier or an organic
modifier,
and other similar types of materials, such as silane based materials, silazane
based
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materials, carbosilane based materials, phenol/formaldehyde based materials,
and
combinations and variations of these. The precursors are preferably liquids at
room
temperature, although they may be solids that are melted, or that are soluble
in one of
the other precursors. (In this situation, however, it should be understood
that when one
precursor dissolves another, it is nevertheless not considered to be a
"solvent" as that
term is used with respect to the prior art processes that employ non-
constituent
solvents, e.g., solvents that do not form a part or component of the end
product, are
treated as waste products, and both.)
[00231] The precursors are mixed together in a vessel, preferably at room
temperature. Preferably, little, and more preferably no solvents, e.g., water,
organic
solvents, polar solvents, non-polar solvents, hexane, THF, toluene, are added
to this
mixture of precursor materials. Preferably, each precursor material is
miscible with the
others, e.g., they can be mixed at any relative amounts, or in any
proportions, and will
not separate or precipitate. At this point the "precursor mixture" or
"polysilocarb
precursor formulation" is compete (noting that if only a single precursor is
used the
material would simply be a "polysilocarb precursor" or a "polysilocarb
precursor
formulation"). Although complete, fillers and reinforcers may be added to the
formulation. In preferred embodiments of the formulation, essentially no, and
more
preferably no chemical reactions, e.g., crosslinking or polymerization, takes
place within
the formulation, when the formulation is mixed, or when the formulation is
being held in
a vessel, on a prepreg, or other time period, prior to being cured.
[00232] Additionally, inhibitors such as cyclohexane, 1-Ethyny1-1-cyclohexanol
(which may be obtained from ALDRICH), Octamethylcyclotetrasiloxane,
tetramethyltetravinylcyclotetrasiloxane (which may act, depending upon amount
and
temperature as a reactant or a reactant retardant (i.e., slows down a reaction
to
increase pot life), e.g., at room temperature it is a retardant and at
elevated
temperatures it is a reactant), may be added to the polysilocarb precursor
formulation,
e.g., an inhibited polysilocarb precursor formulation. Other materials, as
well, may be
added to the polysilocarb precursor formulation, e.g., a filled polysilocarb
precursor
formulation, at this point in processing, including fillers such as SiC
powder, PDC
particles, pigments, particles, nano-tubes, whiskers, or other materials,
discussed in this
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specification or otherwise known to the arts. Further, a formulation with both
inhibitors
and fillers would be considered an inhibited, filled polysilocarb precursor
formulation.
[00233] Depending upon the particular precursors and their relative amounts in
the polysilocarb precursor formulation, polysilocarb precursor formulations
may have
shelf lives at room temperature of greater than 12 hours, greater than 1 day,
greater
than 1 week, greater than 1 month, and for years or more. These precursor
formulations may have shelf lives at high temperatures, for example, at about
90 F, of
greater than 12 hours, greater than 1 day, greater than 1 week, greater than 1
month,
and for years or more. The use of inhibitors may further extend the shelf life
in time, for
higher temperatures, and combinations and variations of these. As used herein
the
term "shelf life" should be given its broadest possible meaning unless
specified
otherwise, and would include the formulation being capable of being used for
its
intended purpose, or performing, e.g., functioning, for its intended use, at
100% percent
as well as a freshly made formulation, at least about 90% as well as a freshly
made
formulation, at least about 80% as well as a freshly made formulation, and at
about 70%
as well as a freshly made formulation.
[00234] Precursors and precursor formulations are preferably non-hazardous
materials. They have flash points that are preferably above about 70 C, above
about
80 C, above about 100 C and above about 300 C, and above. They may be
noncorrosive. They may have as low vapor pressure, may have low or no odor,
and
may be non- or mildly irritating to the skin.
[00235] A catalyst may be used, and can be added at the time of, prior to,
shortly before, or at an earlier time before the precursor formulation is
formed or made
into a structure, prior to curing. The catalysis assists in, advances,
promotes the curing
of the precursor formulation to form a preform.
[00236] The time period where the precursor formulation remains useful for
curing after the catalysis is added is referred to as "pot life", e.g., how
long can the
catalyzed formulation remain in its holding vessel before it should be used.
Depending
upon the particular formulation, whether an inhibitor is being used, and if so
the amount
being used, storage conditions, e.g., temperature, and potentially other
factors,
precursor formulations can have pot lives, for example of from about 5 minutes
to about
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days, about 1 day to about 6 days, about 4 to 5 days, about 1 hour to about 24
hours, and about 12 hours to about 24 hours.
[00237] The catalysis can be any platinum (Pt) based catalyst, which can for
example be diluted to a range from: 1 part per million Pt to 200 parts per
million (ppm)
5 and preferably in the 5 ppm to 50 ppm range. It can be a peroxide based
catalyst with a
10 hour half life above 90 C at a concentration of between 0.5% and 2%. It can
be an
organic based peroxide. It can be any organometallic catalyst capable of
reacting with
Si-H bond, Si-OH bonds, or unsaturated carbon bonds, these catalyst may
include:
dibutyltin dilaurate, zinc octoate, and titanium organometallic compounds.
10 Combinations and variations of these and other catalysts may be used.
Such catalysts
may be obtained from ARKEMA under the trade name LUPEROX, e.g., LUPEROX 231.
[00238] Further, custom and specific combinations of these and other catalysts
may be used, such that they are matched to specific formulation formulations,
and in
this way selectively and specifically catalyze the reaction of specific
constituents.
Custom and specific combinations of catalysts may be used, such that they are
matched to specific formulation formulations, and in this way selectively and
specifically
catalyze the reaction of specific constituents at specific temperatures.
Moreover, the
use of these types of matched catalyst¨formulations systems may be used to
provide
predetermined product features, such as for example, pore structures,
porosity,
densities, density profiles, and other morphologies of cured structures and
ceramics.
[00239] In this mixing type process for making a precursor formulation,
preferably chemical reactions or molecular rearrangements only take place
during the
making of the precursors, the curing process of the preform, and in the
pyrolizing
process. Thus, chemical reactions, e.g., polymerizations, reductions,
condensations,
substitutions, take place or are utilized in the making of a precursor. In
making a
polysilocarb precursor formulation preferably no and essentially no, chemical
reactions
and molecular rearrangements take place. These embodiments of the present
mixing
type process, which avoid the need to, and do not, utilize a polymerization or
other
reaction during the making of a precursor formulation, provides significant
advantages
over prior methods of making polymer derived ceramics. Preferably, in the
embodiments of these mixing type of formulations and processes,
polymerization,
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crosslinking or other chemical reactions take place primarily, preferably
essentially, and
more preferably solely in the preform during the curing process.
[00240] The precursor may be methyl hydrogen (MH), which formula is shown
in FIG. 10. The MH may have a molecular weight (mw) may be from about 400 mw
to
about 10,000 mw, from about 600 mw to about 1,000 mw, and may have a viscosity
preferably from about 20 cps to about 40 cps. The percentage of methylsiloxane
units
"X" may be from 1 /0 to 100%. The percentage of the dimethylsiloxane units "Y"
may be
from 0% to 99%. This precursor may be used to provide the backbone of the
cross-
linked structures, as well as, other features and characteristics to the cured
preform and
ceramic material. Typically, methyl hydrogen fluid (MHF) has minimal amounts
of "Y",
and more preferably "Y" is for all practical purposes zero.
[00241] The precursor may be a siloxane backbone additive, such as vinyl
substituted polydimethyl siloxane, which formula is shown in FIG. 11. This
precursor
may have a molecular weight (mw) may be from about 400 mw to about 10,000 mw,
and may have a viscosity preferably from about 50 cps to about 2,000 cps. The
percentage of methylvinylsiloxane units "X" may be from 1 /0 to 100%. The
percentage
of the dimethylsiloxane units "Y" may be from 0% to 99%. Preferably, X is
100%. This
precursor may be used to decrease cross-link density and improve toughness, as
well
as, other features and characteristics to the cured preform and ceramic
material.
[00242] The precursor may be a siloxane backbone additive, such as vinyl
substituted and vinyl terminated polydimethyl siloxane, which formula is shown
in FIG.
12. This precursor may have a molecular weight (mw) may be from about 500 mw
to
about 15,000 mw, and may preferably have a molecular weight from about 500 mw
to
1,000 mw, and may have a viscosity preferably from about 10 cps to about 200
cps.
The percentage of methylvinylsiloxane units "X" may be from 1% to 100%. The
percentage of the dimethylsiloxane units "Y" may be from 0% to 99%. This
precursor
may be used to provide branching and decrease the cure temperature, as well
as, other
features and characteristics to the cured preform and ceramic material.
[00243] The precursor may be a siloxane backbone additive, such as vinyl
substituted and hydrogen terminated polydimethyl siloxane, which formula is
shown in
FIG. 13. This precursor may have a molecular weight (mw) may be from about 300
mw
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to about 10,000 mw, and may preferably have a molecular weight from about 400
mw to
800 mw, and may have a viscosity preferably from about 20 cps to about 300
cps. The
percentage of methylvinylsiloxane units "X" may be from 1 /0 to 100%. The
percentage
of the dimethylsiloxane units "Y" may be from 0% to 99%. This precursor may be
used
to provide branching and decrease the cure temperature, as well as, other
features and
characteristics to the cured preform and ceramic material.
[00244] The precursor may be a siloxane backbone additive, such as allyl
terminated polydimethyl siloxane, which formula is shown in FIG. 14. This
precursor
may have a molecular weight (mw) may be from about 400 mw to about 10,000 mw,
and may have a viscosity preferably from about 40 cps to about 400 cps. The
repeating
units are the same. This precursor may be used to provide UV curability and to
extend
the polymeric chain, as well as, other features and characteristics to the
cured preform
and ceramic material.
[00245] The precursor may be a siloxane backbone additive, such as vinyl
terminated polydimethyl siloxane, which formula is shown in FIG. 15. This
precursor
may have a molecular weight (mw) may be from about 200 mw to about 5,000 mw,
and
may preferably have a molecular weight from about 400 mw to 1,500 mw, and may
have a viscosity preferably from about 10 cps to about 400 cps. The repeating
units are
the same. This precursor may be used to provide a polymeric chain extender,
improve
toughness and to lower cure temperature down to for example room temperature
curing, as well as, other features and characteristics to the cured preform
and ceramic
material.
[00246] The precursor may be a siloxane backbone additive, such as silanol
(hydroxy) terminated polydimethyl siloxane, which formula is shown in FIG. 16.
This
precursor may have a molecular weight (mw) may be from about 400 mw to about
10,000 mw, and may preferably have a molecular weight from about 600 mw to
1,000
mw, and may have a viscosity preferably from about 30 cps to about 400 cps.
The
repeating units are the same. This precursor may be used to provide a
polymeric chain
extender, a toughening mechanism, can generate nano- and micro- scale
porosity, and
allows curing at room temperature, as well as other features and
characteristics to the
cured preform and ceramic material.
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[00247] The precursor may be a siloxane backbone additive, such as silanol
(hydroxy) terminated vinyl substituted dimethyl siloxane, which formula is
shown in FIG.
18. This precursor may have a molecular weight (mw) may be from about 400 mw
to
about 10,000 mw, and may preferably have a molecular weight from about 600 mw
to
1,000 mw, and may have a viscosity preferably from about 30 cps to about 400
cps.
The percentage of methylvinylsiloxane units "X" may be from 1% to 100%. The
percentage of the dimethylsiloxane units "Y" may be from 0% to 99%.
[00248] The precursor may be a siloxane backbone additive, such as hydrogen
(hydride) terminated polydimethyl siloxane, which formula is shown in FIG. 17.
This
precursor may have a molecular weight (mw) may be from about 200 mw to about
10,000 mw, and may preferably have a molecular weight from about 500 mw to
1,500
mw, and may have a viscosity preferably from about 20 cps to about 400 cps.
The
repeating units are the same. This precursor may be used to provide a
polymeric chain
extender, as a toughening agent, and it allows lower temperature curing, e.g.,
room
temperature, as well as, other features and characteristics to the cured
preform and
ceramic material.
[00249] The precursor may be a siloxane backbone additive, such as phenyl
terminated polydimethyl siloxane, which formula is shown in FIG. 19. This
precursor
may have a molecular weight (mw) may be from about 500 mw to about 2,000 mw,
and
may have a viscosity preferably from about 80 cps to about 300 cps. The
repeating
units are the same. This precursor may be used to provide a toughening agent,
and to
adjust the refractive index of the polymer to match the refractive index of
various types
of glass, to provide for example transparent fiberglass, as well as, other
features and
characteristics to the cured preform and ceramic material.
[00250] The precursor may be a siloxane backbone additive, such as methyl-
phenyl terminated polydimethyl siloxane, which formula is shown in 20. This
precursor
may have a molecular weight (mw) may be from about 500 mw to about 2,000 mw,
and
may have a viscosity preferably from about 80 cps to about 300 cps. The
repeating
units are the same. This precursor may be used to provide a toughening agent
and to
adjust the refractive index of the polymer to match the refractive index of
various types
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of glass, to provide for example transparent fiberglass, as well as, other
features and
characteristics to the cured preform and ceramic material.
[00251] The precursor may be a siloxane backbone additive, such as diphenyl
dimethyl polysiloxane, which formula is shown in FIG. 21. This precursor may
have a
molecular weight (mw) may be from about 500 mw to about 20,000 mw, and may
have
a molecular weight from about 800 to about 4,000, and may have a viscosity
preferably
from about 100 cps to about 800 cps. The percentage of dimethylsiloxane units
"X"
may be from 25% to 95%. The percentage of the diphenyl siloxane units "Y" may
be
from 5% to 75%. This precursor may be used to provide similar characteristics
to the
precursor of FIG. 20, as well as, other features and characteristics to the
cured preform
and ceramic material.
[00252] The precursor may be a siloxane backbone additive, such as vinyl
terminated diphenyl dimethyl polysiloxane, which formula is shown in FIG. 22.
This
precursor may have a molecular weight (mw) may be from about 400 mw to about
20,000 mw, and may have a molecular weight from about 800 to about 2,000, and
may
have a viscosity preferably from about 80 cps to about 600 cps. The percentage
of
dimethylsiloxane units "X" may be from 25% to 95%. The percentage of the
diphenyl
siloxane units "Y" may be from 5% to 75%. This precursor may be used to
provide
chain extension, toughening agent, changed or altered refractive index, and
improvements to high temperature thermal stability of the cured material, as
well as,
other features and characteristics to the cured preform and ceramic material.
[00253] The precursor may be a siloxane backbone additive, such as hydroxy
terminated diphenyl dimethyl polysiloxane, which formula is shown in FIG. 23.
This
precursor may have a molecular weight (mw) may be from about 400 mw to about
20,000 mw, and may have a molecular weight from about 800 to about 2,000, and
may
have a viscosity preferably from about 80 cps to about 400 cps. The percentage
of
dimethylsiloxane units "X" may be from 25% to 95%. The percentage of the
diphenyl
siloxane units "Y" may be from 5% to 75%. This precursor may be used to
provide
chain extension, toughening agent, changed or altered refractive index, and
improvements to high temperature thermal stability of the cured material, can
generate
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nano- and micro- scale porosity, as well as other features and characteristics
to the
cured preform and ceramic material.
[00254] The precursor may be a siloxane backbone additive, such as hydride
terminated diphenyl dimethyl polysiloxane, which formula is shown in FIG. 24.
This
precursor may have a molecular weight (mw) may be from about 400 mw to about
20,000 mw, and may have a molecular weight from about 800 to about 2,000, and
may
have a viscosity preferably from about 60 cps to about 300 cps. The percentage
of
dimethylsiloxane units "X" may be from 25% to 95%. The percentage of the
diphenyl
siloxane units "Y" may be from 5% to 75%. This precursor may be used to
provide
chain extension, toughening agent, changed or altered refractive index, and
improvements to high temperature thermal stability of the cured material, as
well as,
other features and characteristics to the cured preform and ceramic material.
[00255] The precursor may be a siloxane backbone additive, such as styrene
vinyl benzene dimethyl polysiloxane, which formula is shown in FIG. 25. This
precursor
may have a molecular weight (mw) may be from about 800 mw to at least about
10,000
mw to at least about 20,000 mw, and may have a viscosity preferably from about
50 cps
to about 350 cps. The percentage of styrene vinyl benzene siloxane units "X"
may be
from 1% to 60%. The percentage of the dimethylsiloxane units "Y" may be from
40% to
99%. This precursor may be used to provide improved toughness, decreases
reaction
cure exotherm, may change or alter the refractive index, adjust the refractive
index of
the polymer to match the refractive index of various types of glass, to
provide for
example transparent fiberglass, as well as, other features and characteristics
to the
cured preform and ceramic material.
[00256] The precursor may be a reactive monomer, such as
tetramethyltetravinylcyclotetrasiloxane ("TV"), which formula is shown in FIG.
26. This
precursor may be used to provide a branching agent, a three-dimensional cross-
linking
agent, (and in certain formulations, e.g., above 2%, and certain temperatures
(e.g.,
about from about room temperature to about 60 C, it acts as an inhibitor to
cross-
linking, e.g., in may inhibit the cross-linking of hydride and vinyl groups),
as well as,
other features and characteristics to the cured preform and ceramic material.
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[00257] The precursor may be a reactive monomer, such as trivinyl
cyclotetrasiloxane, which formula is shown in FIG. 27. The precursor may be a
reactive monomer, such as divinyl cyclotetrasiloxane, which formula is shown
in FIG.
28. The precursor may be a reactive monomer, such as monohydride
cyclotetrasiloxane, which formula is shown in FIG. 29. The precursor may be a
reactive
monomer, such as dihydride cyclotetrasiloxane, which formula is shown in FIG.
30. The
precursor may be a reactive monomer, such as hexamethyl cyclotetrasiloxane,
which
formula is shown in FIG. 31 and FIG. 32.
[00258] The precursor may be a silane modifier, such as vinyl phenyl methyl
silane, which formula is shown in FIG. 33. The precursor may be a silane
modifier,
such as diphenyl silane, which formula is shown in FIG. 34. The precursor may
be a
silane modifier, such as diphenyl methyl silane, which formula is shown in
FIG. 35
(which may be used as an end capper or end termination group). The precursor
may
be a silane modifier, such as phenyl methyl silane, which formula is shown in
FIG. 36
(which may be used as an end capper or end termination group).
[00259] The precursors of FIGS. 33, 34 and 36 can provide chain extenders
and branching agents. They also improve toughness, alter refractive index, and
improve high temperature cure stability of the cured material, as well as
improving the
strength of the cured material, among other things. The precursor of FIG. 35
may
function as an end capping agent, that may also improve toughness, alter
refractive
index, and improve high temperature cure stability of the cured material, as
well as
improving the strength of the cured material, among other things.
[00260] The precursor may be a reaction product of a silane modifier with a
siloxane backbone additive, such as phenyl methyl silane substituted MH, which
formula is shown in FIG. 35.
[00261] The precursor may be a reaction product of a silane modifier (e.g.,
FIGS. 33 to 36) with a vinyl terminated siloxane backbone additive (e.g., FIG.
15), which
formula is shown in FIG. 38, where R may be the silane modifiers having the
structures
of FIGS. 33 to 36.
[00262] The precursor may be a reaction product of a silane modifier (e.g.,
FIGS. 33 to 36) with a hydroxy terminated siloxane backbone additive (e.g.,
FIG. 16),
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which formula is shown in FIG. 39, where R may be the silane modifiers having
the
structures of FIGS. 33 to 36.
[00263] The precursor may be a reaction product of a silane modifier (e.g.,
FIGS. 33 to 36) with a hydride terminated siloxane backbone additive (e.g.,
FIG. 17),
which formula is shown in FIG. 40, where R may be the silane modifiers having
the
structures of FIGS. 33 to 36.
[00264] The precursor may be a reaction product of a silane modifier (e.g.,
FIGS. 33 to 36) with TV (e.g., FIG. 26), which formula is shown in FIG. 39.
[00265] The precursor may be a reaction product of a silane modifier (e.g.,
FIGS. 33 to 36) with a cyclosiloxane, examples of which formulas are shown in
FIG. 26
(TV), FIG. 41, and in FIG. 3342, where R1, R2, R3, and R4 may be a methyl or
the silane
modifiers having the structures of FIGS. 33 to 36, taking into consideration
steric
hindrances.
[00266] The precursor may be a partially hydrolyzed tertraethyl orthosilicate,
which formula is shown in FIG. 44, such as TES 40 or Silbond 40.
[00267] The precursor may also be a methylsesquisiloxane such as SR-350
available from General Electric Company, Wilton, Conn. The precursor may also
be a
phenyl methyl siloxane such as 604 from Wacker Chemie AG. The precursor may
also
be a methylphenylvinylsiloxane, such as H62 C from Wacker Chemie AG.
[00268] The precursors may also be selected from the following:
SiSiB HF2020, TRIMETHYLSILYL TERMINATED METHYL HYDROGEN SILICONE
FLUID 63148-57-2; SiSiB HF2050 TRIMETHYLSILYL TERMINATED
METHYLHYDROSILOXANE DIMETHYLSILOXANE COPOLYMER 68037-59-2; SiSiB
HF2060 HYDRIDE TERMINATED METHYLHYDROSILOXANE DIMETHYLSILOXANE
COPOLYMER 69013-23-6; SiSiB HF2038 HYDROGEN TERMINATED
POLYDIPHENYL SILOXANE; SiSiB HF2068 HYDRIDE TERMINATED
METHYLHYDROSILOXANE DIMETHYLSILOXANE COPOLYMER 115487-49-5;
SiSiB HF2078 HYDRIDE TERMINATED POLY(PHENYLDIMETHYLSILOXY)
SILOXANE PHENYL SILSESQUIOXANE, HYDROGEN-TERMINATED 68952-30-7;
SiSiB VF6060 VINYLDIMETHYL TERMINATED VINYLMETHYL DIMETHYL
POLYSILOXANE COPOLYMERS 68083-18-1; SiSiB VF6862 VINYLDIMETHYL
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TERMINATED DIMETHYL DIPHENYL POLYSILOXANE COPOLYMER 68951-96-2;
SiSiB VF6872 VINYLDIMETHYL TERMINATED DIMETHYL-METHYLVINYL-
DIPHENYL POLYSILOXANE COPOLYMER; SiSiB PC9401 1,1,3,3-TETRAMETHYL-
1,3-DIVINYLDISILOXANE 2627-95-4; SiSiB PF1070 SILANOL TERMINATED
POLYDIMETHYLSILOXANE (0F1070) 70131-67-8; SiSiB OF1070 SILANOL
TERMINATED POLYDIMETHYSILOXANE 70131-67-8; OH-ENDCAPPED
POLYDIMETHYLSILOXANE HYDROXY TERMINATED OLYDIMETHYLSILOXANE
73138-87-1; SiSiB VF6030 VINYL TERMINATED POLYDIMETHYL SILOXANE
68083-19-2; and, SiSiB HF2030 HYDROGEN TERMINATED
POLYDIMETHYLSILOXANE FLUID 70900-21-9.
[00269] Thus, in additional to the forgoing specific precursors, it is
contemplated that a precursor may be compound of the general formula of FIG.
43,
wherein end cappers E1 and E2 are chosen from groups such as trimethyl silicon
(SiC3H9) FIG. 43A, dimethyl silicon hydroxy (SiC20H7) FIG. 43C, dimethyl
silicon
hydride (SiC2H7) FIG. 43B and dimethyl vinyl silicon (SiC4H9) FIG. 43D. The R
groups
R1, R2, R3, and R4 may all be different, or one or more may be the same, thus
R2 is the
same as R3 is the same as R4, R1 and R2 are different with R3 and R4 being the
same,
etc. The R groups are chosen from groups such as phenyl, vinyl, hydride,
methyl, ethyl,
allyl, phenylethyl, methoxy, and alkxoy.
[00270] In general, embodiments of formulations for polysilocarb formulations
may for example have from about 20% to about 99% MH, about 0% to about 30%
siloxane backbone additives, about 1% to about 60% reactive monomers, and,
about
0% to about 90% reaction products of a siloxane backbone additives with a
silane
modifier or an organic modifier reaction products.
[00271] In mixing the formulations a sufficient time to permit the precursors
to
become effectively mixed and dispersed. Generally, mixing of about 15 minutes
to an
hour is sufficient. Typically, the precursor formulations are relatively, and
essentially,
shear insensitive, and thus the type of pumps or mixing are not critical. It
is further
noted that in higher viscosity formulations additional mixing time may be
required. The
temperature of the formulations, during mixing should be kept below about 45
degrees
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C, and preferably about about 10 degrees C. (It is noted that these mixing
conditions
are for the pre-catalyzed formulations)
The Reaction Type Process
[00272] In the reaction type process, in general, a chemical reaction is used
to
combine one, two or more precursors, typically in the presence of a solvent,
to form a
precursor formulation that is essentially made up of a single polymer that can
then be
cured and if need be pyrolized. This process provides the ability to build
custom
precursor formulations that when cured can provide plastics having unique and
desirable features such as high temperature, flame resistance and retardation,
strength
and other features. The cured materials can also be pyrolized to form ceramics
having
unique features. The reaction type process allows for the predetermined
balancing of
different types of functionality in the end product by selecting function
groups for
incorporation into the polymer that makes up the precursor formulation, e.g.,
phenyls
which typically are not used for ceramics but have benefits for providing high
temperature capabilities for plastics, and styrene which typically does not
provide high
temperature features for plastics but provides benefits for ceramics.
[00273] In general a custom polymer for use as a precursor formulation is
made by reacting precursors in a condensation reaction to form the polymer
precursor
formulation. This precursor formulation is then cured into a preform through a
hydrolysis reaction. The condensation reaction forms a polymer of the type
shown in
FIG. 45, where R1 and R2 in the polymeric units can be a H, a Methyl (Me)(-C),
a vinyl (-
C=C), alkyl (-R), a phenyl (Ph)(-C6H5), an ethoxy (-O-C-C), a siloxy, methoxy
(-O-C),
alkoxy, (-O-R), hydroxy, (-0-H), and phenylethyll (¨C-C-C6H5). R1 and R2 may
be the
same or different. The custom precursor polymers can have several different
polymeric
units, e.g., A1, A2, An , and may include as many as 10, 20 or more units, or
it may
contain only a single unit. (For example, if methyl hydrogen fluid is made by
the
reaction process). The end units, Si End 1 and Si End 2, can come from the
precursors
of FIGS. 50, 52, 57, and 49. Additionally, if the polymerization process is
properly
controlled a hydroxy end cap can be obtained from the precursors used to
provide the
repeating units of the polymer.
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[00274] In general, the precursors, e.g., FIGS. 46 to 59 are added to a vessel
with ethanol (or other material to absorb heat, e.g., to provide thermal
mass), an excess
of water, and hydrochloric acid (or other proton source). This mixture is
heated until it
reaches its activation energy, after which the reaction is exothermic. In this
reaction
the water reacts with an ethoxy group of the silicon of the precursor monomer,
forming a
hydroxy (with ethanol as the byproduct). Once formed this hydroxy becomes
subject to
reaction with an ethoxy group on the silicon of another precursor monomer,
resulting in
a polymerization reaction. This polymerization reaction is continued until the
desired
chain length(s) is built.
[00275] Control factors for determining chain length are: the monomers chosen
(generally, the smaller the monomers the more that can be added before they
begin to
coil around and bond to themselves); the amount and point in the reaction
where end
cappers are introduced; and the amount of water and the rate of addition.
Thus, the
chain lengths can be from about 180 mw (viscosity about 5 cps) to about 65,000
mw
(viscosity of about 10,000 cps), greater than about 1000 mw, greater than
about 10,000
mw, greater than about 50,000 mw and greater. Further, the polymerized
precursor
formulation may, and typically does, have polymers of different molecular
weights,
which can be predetermined to provide formulation, cured, and ceramic product
performance features.
[00276] Upon completion of the polymerization reaction the material is
transferred into a separation apparatus, e.g., a separation funnel, which has
an amount
of deionized water that is from about 1.2 x to about 1.5 x the mass of the
material. This
mixture is vigorously stirred for about less than 1 minute and preferably from
about 5 to
sections. Once stirred the material is allowed to settle and separate, which
may take
25 from about 1 to 2 hours. The polymer is the higher density material and
is removed
from the vessel. This removed polymer is then dried by either warming in a
shallow tray
at 90 C for about two hours; or, preferably, is passed through a wiped film
distillation
apparatus, to remove any residual water and ethanol. Alternatively, sodium
bicarbonate
sufficient to buffer the aqueous layer to a pH of about 4 to about 7 is added.
It is further
30 understood that other, and commercial, manners of separating the polymer
from the
material may be employed.
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[00277] Preferably a catalyst is used in the curing process of the polymer
pressure formulations from the reaction type process. The same polymers as
used for
curing the formulation from the mixing type process can be used. It is noted
that unlike
the mixing type formulations, a catalyst is not necessarily required. However,
if not
used, reaction time and rates will be slower. The pyrolysis of the cured
material is
essentially the same as the cured material from the mixing process.
Curing and Pyrolysis
[00278] The preform can be cured in a controlled atmosphere, such as an inert
gas, or it can be cured in the atmosphere. The curing can be conducted in
reduce
pressure, e.g., vacuum, or in reduced pressure flowing gas (e.g., inert)
streams. The
cure conditions, e.g., temperature, time, rate, can be predetermined by the
formulation
to match, for example the size of the preform, the shape of the preform, or
the mold
holding the preform to prevent stress cracking, off gassing, or other problems
associated with the curing process. Further, the curing conditions may be such
as to
take advantage of, in a controlled manner, what may have been previously
perceived as
problems associated with the curing process. Thus, for example, off gassing
may be
used to create a foam material having either open or closed structure.
Further, the
porosity of the material may be predetermined such that, for example, a
particular pore
size may be obtained, and in this manner a filter or ceramic screen having
predetermined pore sizes, flow characteristic may be made.
[00279] The preforms, either unreinforced, neat, or reinforced, may be used as
a stand alone product, an end product, a final product, or a preliminary
product for
which later machining or processing may be performed on. The preforms may also
be
subject to pyrolysis, which converts the preform material into a ceramic.
[00280] During the curing process some formulations may exhibit an exotherm,
i.e., a self heating reaction, that can produce a small amount of heat to
assist or drive
the curing reaction, or they may produce a large amount of heat that may need
to be
managed and removed in order to avoid problems, such as stress fractures.
During the
cure off gassing typically occurs and results in a loss of material, which
loss is defined
generally by the amount of material remaining, e.g., cure yield. The
formulations and
polysilocarb precursor formulations of embodiments of the present inventions
can have
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cure yields of at least about 90%, about 92%, about 100%. In fact, with air
cures the
materials may have cure yields above 100%, e.g., about 101-105%, as a result
of
oxygen being absorbed from the air. Additionally, during curing the material
shrinks,
this shrinkage may be, depending upon the formulation and the nature of the
preform
shape, and whether the preform is reinforce, neat or unreinforced, from about
20%, less
than 20%, less than about 15%, less than about 5%, less than about 1%, less
than
about 0.5%, less than about 0.25% and smaller.
[00281] In pyrolizing the preform, or cured structure or cured material, it is
heated to above about 650 C to about 1,2000C. At these temperatures typically
all
organic structures are either removed or combined with the inorganic
constituents to
form a ceramic. Typically at temperatures in the 650 C to 1,2000C range the
material
is an amorphous glassy ceramic. When heated above 1,2000C the material may
from
nano crystalline structures, or micro crystalline structures, such as SiC,
Si3N4, SiCN, 13
SiC, and above 1,9000C an a SiC structure may form.
[00282] During pyrolysis material is loss through off gassing. The amount of
material remaining at the end of a pyrolysis set is referred to as char yield
(or pyrolysis
yield). The formulations and polysilocarb precursor formulations of
embodiments of the
present inventions can have char yields of at least about 60%, about 70%,
about 80%,
and at least about 90%, at least about 91% and greater. In fact, with air
pyrolysis the
materials may have cure yields well above 91%, which can approach 100%. In
order to
avoid the degradation of the material in an air pyrolysis (noting that
typically pyrolysis is
conducted in an inert atmospheres) specifically tailored formulations must be
used,
such as for example, formulations high in phenyl content (at least about 11%,
and
preferably at least about 20% by weight phenyls), formulations high in allyl
content (at
least about 15% to about 60%). Thus, there is provided formulations and
polysilocarb
precursor formulations that are capable of being air pyrolized to form a
ceramic and to
preferably do so at char yield in excess of at least about 80% and above 88%.
[00283] The initial or first pyrolysis step generally yields a structure that
is not
very dense, and for example, has not reached the density required for its
intended use.
However, in some examples, such as the use of light weight spheres, the first
pyrolysis
may be sufficient. Thus, typically a reinfiltration process may be performed
on the
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pyrolized material, to add in additional polysilocarb precursor formulation
material, to fill
in, or fill the voids and spaces in the structure. This reinfiltrated material
is they
repyrolized. This process of pyrolization, reinfiltration may be repeated,
through one,
two, three, and up to 10 or more times to obtain the desired density of the
final product.
Additionally, with formulations of embodiments of the present inventions, the
viscosity of
the formulation may be tailored to provide more efficient reinfiltrations, and
thus, a
different formulation may be used at later reinfiltration steps, as the voids
or pores
become smaller and more difficult to get the formulation material into it. The
high char
yields, and other features of embodiments of the present invention, enable the
manufacture of completely closed structures, e.g., "helium tight" materials,
with less
than twelve reinfiltration steps, less than about 10 reinfiltrations steps and
less than five
reinfiltrations steps. Thus, by way of example, an initial inert gas pyrolysis
may be
performed with a high char yield formulation followed by four reinfiltration
air pyrolysis
steps.
[00284] Upon curing the polysilocarb precursor formulation a cross linking
reaction takes place that provides a cross linked structure having, among
other things,
an -Ri-Si-C-C-Si-O-Si-C-C-Si-R2- where R1 and R2 vary depending upon, and are
based upon, the precursors used in the formulation.
[00285] Embodiments of the present inventions have the ability to utilize
precursors that have impurities, high-level impurities and significant
impurities. Thus,
the precursors may have more than about 0.1% impurities, more than about 0.5%,
more
than about 1% impurities, more than about 5% impurities, more than about 10%
impurities, and more than about 50% impurities. In using materials with
impurities, the
amounts of these impurities, or at least the relative amounts, so that the
amount of
actual precursor is known, should preferably be determined by for example GPC
(Gel
Permeation Chromatography) or other methods of analysis. In this manner the
formulation of the polysilocarb precursor formulation may be adjusted for the
amount of
impurities present. The ability of embodiments of the present invention to
utilize lower
level impurity materials, and essentially impure materials, and highly impure
materials,
provides significant advantages over other method of making polymer derived
ceramics.
This provides two significant advantages, among other things. First, the
ability to use
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impure, lower purity, materials in embodiments of the present inventions,
provides the
ability to greatly reduce the cost of the formulations and end products, e.g.,
cured
preforms, cured parts, and ceramic parts or structures. Second, the ability to
use
impure, lower purity, materials in embodiments of the present inventions,
provides the
ability to have end products, e.g., cured preforms, cured parts, and ceramic
parts or
structures, that have a substantially greater consistence from part to part,
because
variations in starting materials can be adjusted for during the formulation of
each
polysilocarb precursor formulation.
[00286] Turning to FIG. 61 there is provided an embodiment of a proppant
preform forming and curing system 6100. The system 6100 has a curing tower
6101, a
tank 6119 for holding the polysiloxane precursor batch, a metering device 6118
for
transferring the batch along feed line 6117 to a distribution header 6103.
Mixing,
agitating, commingling, pumping, flow control, reactor, and regulating devices
may also
be utilized in transferring, handling and metering of the precursor batch. The
distribution header 6103 has nozzle assemblies 6104, 6105, 6106, 6107, 6108,
6109
having nozzles 6104a, 6105a, 6106a, 6107a, 6108a,6109a respectively. Heat
shields
6110, 6111, 6112 protect the nozzle assemblies and distribution header from
being
damaged by the heat of the tower 6101, or from overheating or otherwise
adversely
affecting the temperature of the nozzle assemblies and distribution header.
For
example, they prevent the temperature to rise to the point where the batch
would cure in
the distribution header or nozzle assembly thus clogging them. The heat
shields may
utilize air, such as with an air knife, metallic, ceramic, gas, oil, fluid,
chemical, heat
exchangers, reflectors, water, and others.
[00287] The tower 6101 has wall 6102 containing heating units, as well as,
insolation and control devices for the heating units. In the embodiment of
FIG. 61 the
tower is configured to have two zones: a first or forming zone 6113; and a
second or
curing zone 6114. Depending upon the size of the beads, balls or spherical
being
formed the forming zone 6113 should have sufficient height, and a temperature
selected
for that height, that allows the drops of precursor material leaving a nozzle
to form a
predetermined shape, for example, as perfect a sphere as is possible, before
or when
the drop transitions (e.g., falls from zone 6113 to zone 6114) into curing
zone 6114.
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Curing zone 6114 should have sufficient height, and a temperature selected for
that
height, to cure the preform proppants into hard enough structures that their
striking the
diverter 6115 and being collected and held in the pan 6116 does not adversely
affect
their shape. Additional curing, e.g., a hard cure can take place in the pan
6116, in
another furnace, or in a third zone in the tower.
[00288] Although two temperature zones and six nozzles are utilized in the
embodiment of FIG. 61, more or less zones and nozzles may be used. Thus, there
may
be a single zone or nozzle, two zones or nozzles, a dozen zones or nozzles, or
more,
and combinations and variations of these. If is further understood that in
addition to
nozzles these types of devices may be used at the top of the tower to
initially form or
shape the drop of precursor material that becomes the preform proppant. Thus,
filaments, vibrating filaments that drip the precursor at a controlled rate
and under
controlled conditions may be used, as well as, various spraying, dispensing,
and
forming techniques. Other apparatus may also be employed to form the precursor
batch into a spherical type structure and then cure that structure with
minimal or no
adverse consequences to the shape of the preform.
[00289] The following examples are provided to illustrate various embodiments
of oil field treatments, hydraulic fracturing treatments, processes,
precursors, batches,
cured preform proppants, synthetic proppants, PDC proppants, and PsDC
proppants of
the present inventions. These examples are for illustrative purposes, and
should not be
viewed as, and do not otherwise limit the scope of the present inventions. The
percentages used in the examples, unless specified otherwise, are weight
percents of
the total batch, preform or structure.
[00290] Examples
[00291] EXAMPLE 1
[00292] Using a tower forming and cure system, a polysilocarb batch having
75% MH, 15% TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% Luprox 231
peroxide) is formed from a sonic nozzle having an internal diameter of 0.180
inches into
droplets that fall from the nozzle into and through an 8 foot curing tower.
The
temperature at the top of the tower is from 495-505 C the temperature at the
bottom of
the tower is 650 C. There are no discrete temperature zones in the tower.
Airflow up
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the tower is by convection. A collection pan at the bottom of the tower is
maintained at
1100C. The forming and curing are done in air. The preform proppants are
removed
from the pan and post (hard) cured at 200 C in air for 2 hours. The hard cured
preform
proppants are pyrolized at 10000C in an argon atmosphere for 2 hours. The cure
yield
is from 99% to 101%. The char yield is 86%.
[00293] EXAMPLE 2
[00294] Using a tower forming and cure system, a polysilocarb batch having
70% MH, 20% TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% Luprox 231
peroxide) is formed from a sonic nozzle having an internal diameter of 0.180
inches into
droplets that fall from the nozzle into and through an 8 foot curing tower.
The
temperature at the top of the tower is from 495-505 C the temperature at the
bottom of
the tower is 650 C. There are no discrete temperature zones in the tower.
Airflow up
the tower is by convection. A collection pan at the bottom of the tower is
maintained at
110 C. The forming and curing are done in air. The preform proppants are
removed
from the pan and post (hard) cured at 200 C in air for 2 hours. The hard cured
preform
proppants are pyrolized at 1000 C in an argon atmosphere for 2 hours. The cure
yield
is from 99% to 101%. The char yield is 86%.
[00295] EXAMPLE 2a
[00296] Turning to FIG. 66, there is provided a chart comparing the strength
and density of an embodiment of the proppant of Example 2 with prior art
proppants.
[00297] EXAMPLE 2b
[00298] Turning to FIG. 67, there is provided a chart comparing the setting
rate
of an embodiment of the proppant of Example 2 with prior art proppants. The
lower the
settling rate the greater the likelihood that the proppant will remain
suspended in the
fracturing fluid and travel out further away from the borehole, and into the
fracture area,
during the fracture treatment.
[00299] EXAMPLE 2c
[00300] Turning to FIG. 68, there is provided a chart comparing the very
narrow particle size distribution of an embodiment of Example 2 with prior art
proppants;
illustrating the significantly narrower distribution than is found in the
prior art.
[00301] EXAMPLE 3
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[00302] Using a tower forming and cure system, a polysilocarb batch having
70% MH, 20% TV, 10% VT and 1% catalyst (10 ppm platinum and 0.5% Luprox 231
peroxide) is formed from a sonic nozzle having an internal diameter of 0.180
inches into
droplets that fall from the nozzle into and through an 8 foot curing tower.
The
temperature at the top of the tower is from 345 C the temperature at the
bottom of the
tower is 550 C. There are no discrete temperature zones in the tower. Airflow
up the
tower is by convection. The collection pan is maintained at 110 C. The forming
and
curing are done in air. The preform proppants are removed from the pan and
post
(hard) cured at 200 C in air for 3 hours. The hard cured preform proppants are
pyrolized at 1000 C in an argon atmosphere for 2 hours. The cure yield is from
99% to
101%. The char yield is 86%.
[00303] EXAMPLE 4
[00304] PsDC proppants are made using a tower cure system. 50% by volume
fly ash is added to a polysilocarb batch having 70% MH, 20% TV, 10% VT and 1%
catalyst (10 ppm platinum and 0.5% Luprox 231 peroxide). This batch is formed
from a
sonic nozzle having an internal diameter of 0.180 inches into droplets that
fall from the
nozzle into and through an 18 foot curing tower. The temperature at the top of
the
tower is from 200-500 C the temperature at the bottom of the tower is from 200-
600 C.
There are no discrete temperature zones in the tower. Airflow up the tower is
by
convection. The collection pan is maintained at 110 C. The forming and curing
are
done in air. The preform proppants are removed from the pan and post (hard)
cured at
200 C in air for 3 hours. The hard cured preform proppants are pyrolized at
10000C in
an argon atmosphere for 2 hours. The cure yield is from 99% to 101%. The char
yield
is 86%.
[00305] EXAMPLE 5
[00306] 40% by volume AL203 having a diameter of 0.5 pm is added to a
polysilocarb batch having 70% MH, 20% TV, 10% VT and 1% catalyst (10 ppm
platinum
and 0.5% Luprox 231 peroxide). Using a tower cure system, this batch is formed
from a
sonic nozzle having an internal diameter of 0.180 inches into droplets that
fall from the
nozzle into and through an 18 foot curing tower. The temperature at the top of
the
tower is from 200-500 C the temperature at the bottom of the tower is from 200-
600 C.
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There are no discrete temperature zones in the tower. Airflow up the tower is
by
convection. The collection pan is maintained at 1100C. The forming and curing
are
done in air. The preform proppants are removed from the pan and post (hard)
cured at
200 C in air for 3 hours. The hard cured preform proppants are pyrolized at
10000C in
an argon atmosphere for 2 hours. The cure yield is from 99% to 101%. The char
yield
is 86%.
[00307] EXAMPLE 6
[00308] A polysilocarb batch having 70% of the MH precursor (molecular
weight of about 800) and 30% of the TV precursor are mixed together in a
vessel and
put in storage for later use. The polysilocarb batch has good shelf life and
room
temperature and the precursors have not, and do not react with each other. The
polysilocarb batch has a viscosity of about 15 cps. 28 % of an about 80 micron
to about
325 mesh SiC filler is added to the batch to make a filled polysilocarb batch,
which can
be kept for later use. Just prior to forming and curing 10 ppm of a platinum
catalyst is
added to each of the polysilocarb batches and this catalyzed batch is dropped
on a tray
to form droplets which are cured in an air oven at about 125 C for about 30
minutes.
The cured drop structures are spherical type structures with densities of
about 1.1 -1.7
g/cc, diameters of about 200 microns to about 2 mm, and crush strengths of
about 3 - 7
ksi.
[00309] EXAMPLE 7
[00310] A polysilocarb batch having 70% of the MH precursor (molecular
weight of about 800) and 30% of the TV precursor are mixed together in a
vessel and
put in storage for later use. The polysilocarb batch has good shelf life and
room
temperature and the precursors have not, and do not react with each other. The
polysilocarb batch has a viscosity of about 15 cps. 21% of a silica fume
(about 325
mesh) are added to the batch to make a filled polysilocarb batch, which can be
kept for
later use. Just prior to forming into preform proppants, 10 ppm of a platinum
catalyst is
added to the polysilocarb batch and these catalyzed batches are dropped into
the
curing tower and air cured. The cured drop structures are spherical type
structures with
densities of about 1.1 -1.7 g/cc, diameters of about 200 microns, and
(API/ISO) crush
strengths of about 7k psi.
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[00311] EXAMPLE 8
[00312] A polysilocarb batch having 75% of the MH precursor (molecular
weight of about 800) and 25% of the TV precursor are mixed together in a
vessel and
put in storage for later use. The polysilocarb batch has good shelf life and
room
temperature and the precursors have not, and do not react with each other. The
polysilocarb batch has a viscosity of about 18 cps. 40% of a silica fume to
about 325
mesh silica filler is added to the batch to make a filled polysilocarb batch,
which can be
kept for later use. Prior to forming and curing 10 ppm of a platinum catalyst
is added to
each of the polysilocarb batch and this batch is formed into spherical
proppants under
similar forming and curing conditions to those of the forming and curing tower
in
Example 1.
[00313] EXAMPLE 9
[00314] A polysilocarb batch having 10% of the MH precursor (molecular
weight of about 800), 73% of the STY (FIG. 10 and having 10% X, molecular
weight of
about 1,000), and 16% of the TV precursor, and 1% of the OH terminated
precursor of
the formula of FIG. 5, having a molecular weight of about 1,000 are mixed
together in a
vessel and put in storage for later use. The polysilocarb batch has good shelf
life and
room temperature and the precursors have not, and do not react with each
other. The
polysilocarb batch has a viscosity of about 72 cps. 10 ppm of a platinum
catalyst is
added to the polysilocarb batch. Drops of the catalyzed batch are dripped into
a hot air
column having a temperature of about 375 C and fall by gravity for about a
distance of
8 ft in the air column. The cured spheres from the bottom of the air column
are
pyrolized in an inert atmosphere at 1,0000C for about 120 minutes. The
pyrolized
round spheres have a very uniform size (e.g., monosize distribution), density
of about
1.9 ¨ 2.0 g/cc, a diameter of about 400-800 microns, and a (API/ISO) crush
strength of
about 5.5 ¨ 7k psi.
[00315] EXAMPLE 10
[00316] A polysilocarb batch having about 70% MH, 20% TV precursor, 10%
VT (molecular weight of about 6000), and 1% of the OH terminated precursor of
the
formula of FIG. 16, having a molecular weight of about 800 are mixed together
in a
vessel and put in storage for later use. The polysilocarb batch has good shelf
life and
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room temperature and the precursors have not, and do not react with each
other. The
polysilocarb batch has a viscosity of about 55 cps. Prior to forming the
preform
proppants 10 ppm of a platinum and peroxide catalyst mixture is added to the
polysilocarb batch. Drops of the catalyzed batch are dripped into a hot air
column
having a temperature of about 375 C and fall by gravity for about a distance
of 8 ft in
the air column. The cured spheres from the bottom of the air column are
pyrolized in an
inert atmosphere at 1,0000C for about 120 minutes. The pyrolized round spheres
have
a very uniform size (e.g., monosize distribution), density of about 2.0 ¨ 2.1
g/cc, a
diameter of about 400-800 microns, and a crush strength of about (API/ISO) 4 ¨
5.5k
psi.
[00317] EXAMPLE 11
[00318] A polysilocarb batch has 75% MH, 15% TV, 10% VT and a viscosity of
about 65 cps. 10 ppm of a platinum and peroxide catalyst mixture is added to
this batch
and drops of the catalyzed batch are dripped into a hot air column having a
temperature
of about 375 C and fall by gravity for about a distance of 8 ft in the air
column. The
cured spheres from the bottom of the air column are pyrolized in an inert
atmosphere at
1,000 C for about 60 minutes. The pyrolized round spheres have a very uniform
size
(e.g., monosize distribution), density of about 2.0 ¨ 2.1 g/cc, a diameter of
about 400-
800 microns, and a crush strength of about (API/ISO) 4 ¨ 5.5k psi.
[00319] EXAMPLE 12
[00320] A polysilocarb batch having 70% of the MH and 30% of the VT having
a molecular weight of about 500 and about 42% of a submicron and a 325 mesh
silica
are mixed together in a vessel and put in storage for later use. The
polysilocarb batch
has good shelf life and room temperature and the precursors have not, and do
not react
with each other. The polysilocarb batch has a viscosity of about 300 cps.
PsDCs are
are made from this batch following the methods of Example 1.
[00321] EXAMPLE 13
[00322] PsDCs having the following characteristics:
Sizes (mesh) 200, 100, 70, 60, 40,
20, or 10
Specific Gravity (w/in 1.00
.05g/cc)
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Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI for <.3.5
0.5 Hr@ 150 deg F
Solubility in 10% HCI for <.2
0.5 Hr@ 150 deg F
Settling Rate 2.39
ISO Crush Analysis >5000
(>10% fines)
[00323] EXAMPLE 14
[00324] PsDCs having the following characteristics.
Sizes (mesh) 200, 100, 70, 60, 40, 20,
or 10
Specific Gravity (w/in 1.10
.05g/cc)
Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI <.3.5
for 0.5 Hr@ 150 deg F
Solubility in 10% HCI <.2
for 0.5 Hr@ 150 deg F
Settling Rate 2.89
ISO Crush Analysis >5000
(>10% fines)
[00325] EXAMPLE 15
[00326] PsDCs having the following characteristics.
Sizes (mesh) 200, 100, 70, 60, 40, 20,
or 10
Specific Gravity (w/in 1.20
.05g/cc)
Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI <.3.5
for 0.5 Hr@ 150 deg F
Solubility in 10% HCI <.2
for 0.5 Hr@ 150 deg F
Settling Rate 3.47
ISO Crush Analysis >5000
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(>10% fines)
[00327] EXAMPLE 16
[00328] PsDCs having the following characteristics.
Sizes (mesh) 200, 100, 70, 60, 40,
20, or 10
Specific Gravity (w/in 1.30
.05g/cc)
Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI <.3.5
for 0.5 Hr@ 150 deg F
Solubility in 10% HCI <.2
for 0.5 Hr@ 150 deg F
Settling Rate 4.14
ISO Crush Analysis >5000
(>10% fines)
[00329] EXAMPLE 17
[00330] PsDCs having the following characteristics.
Sizes (mesh) 200, 100, 70, 60, 40,
20, or 10
Specific Gravity (w/in 1.40
.05g/cc)
Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI <.3.5
for 0.5 Hr@ 150 deg F
Solubility in 10% HCI <.2
for 0.5 Hr@ 150 deg F
Settling Rate 4.90
ISO Crush Analysis >5000
(>10% fines)
[00331] EXAMPLE 18
[00332] PsDCs having the following characteristics.
Sizes (mesh) 200, 100, 70, 60,
40, 20, or 10
Specific Gravity (w/in 1.50
.05g/cc)
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Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI for <.3.5
0.5 Hr@ 150 deg F
Solubility in 10% HCI for <.2
0.5 Hr@ 150 deg F
Settling Rate 5.78
ISO Crush Analysis (>10% >5000
fines)
[00333] EXAMPLE 19
[00334] PsDCs having the following characteristics.
Sizes (mesh) 200, 100, 70, 60,
40, 20, or 10
Specific Gravity (w/in 1.60
.05g/cc)
Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI for <.3.5
0.5 Hr@ 150 deg F
Solubility in 10% HCI for <.2
0.5 Hr@ 150 deg F
Settling Rate 6.78
ISO Crush Analysis (>10% >5000
fines)
[00335] EXAMPLE 20
[00336] PsDCs having the following characteristics.
Sizes (mesh) 200, 100, 70, 60,
40, 20, or 10
Specific Gravity (w/in 1.70
.05g/cc)
Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI for <.3.5
0.5 Hr@ 150 deg F
Solubility in 10% HCI for <.2
0.5 Hr@ 150 deg F
Settling Rate 7.92
ISO Chush Analysis >10,000
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(>10% fines)
[00337] EXAMPLE 21
[00338] PsDCs having the following characteristics.
Sizes (mesh) 200, 100, 70, 60,
40, 20, or 10
Specific Gravity (w/in 1.80
.05g/cc)
Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI for <.3.5
0.5 Hr@ 150 deg F
Solubility in 10% HCI for <.2
0.5 Hr@ 150 deg F
Settling Rate 9.22
ISO Crush Analysis (>10% >10,000
fines)
[00339] EXAMPLE 22
[00340] PsDCs having the following characteristics.
Sizes (mesh) 200, 100, 70, 60,
40, 20, or 10
Specific Gravity (w/in 1.90
.05g/cc)
Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI for <.3.5
0.5 Hr@ 150 deg F
Solubility in 10% HCI for <.2
0.5 Hr@ 150 deg F
Settling Rate 10.71
ISO Crush Analysis (>10% >10,000
fines)
[00341] EXAMPLE 23
[00342] PsDCs having the following characteristics.
Sizes (mesh) 200, 100, 70, 60,
40, 20, or 10
Specific Gravity (w/in 2.00
.05g/cc)
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Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI for <.3.5
0.5 Hr@ 150 deg F
Solubility in 10% HCI for <.2
0.5 Hr@ 150 deg F
Settling Rate 12.40
ISO Crush Analysis (>10% >10,000
fines)
[00343] EXAMPLE 24
[00344] PsDCs having the following characteristics.
Sizes (mesh) 200, 100, 70, 60,
40, 20, or 10
Specific Gravity (w/in 2.10
.05g/cc)
Sphericity/Roundness greater than .95
Clusters (%) 0
Particle Distribution 95%+ within 5 mesh
Solubility in 12/3 HCI for <.3.5
0.5 Hr@ 150 deg F
Solubility in 10% HCI for <.2
0.5 Hr@ 150 deg F
Settling Rate 14.32
ISO Crush Analysis (>10% >10,000
fines)
[00345] EXAMPLE 25
[00346] The PsDCs of Example 24 are made having a predetermined mesh
size of from about 8 to about 200, with 95% of the particle size distribution
being within
5 mesh of the predetermined value. 4,000,000 pounds of this proppant are mixed
with
1 million gallons of slick water fracturing fluid for a fracturing treatment
of an
unconventional shale formation.
[00347] EXAMPLE 26
[00348] The PsDCs of Example 24 are made having a predetermined mesh
size of from about 8 to about 200, with 95% of the particle size distribution
being within
8 mesh of the predetermined value. 7,000,000 pounds of this proppant are mixed
with
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2 million gallons of slick water fracturing fluid for a fracturing treatment
of an
unconventional shale formation.
[00349] EXAMPLE 27
[00350] The PsDCs or Example 24 are made having a predetermined mesh
size of greater than 200, with 95% of the particle size distribution being
within 8 mesh of
the predetermined value. 4,000,000 pounds of this proppant are mixed with 1
million
gallons of fracturing fluid for a fracturing treatment of a conventional
formation.
[00351] EXAMPLE 28
[00352] The PsDCs or Example 24 are made having a predetermined mesh
size of greater than 200, with 95% of the particle size distribution being
within 5 mesh of
the predetermined value. 7,000,000 pounds of this proppant are mixed with 2
million
gallons of fracturing fluid for a fracturing treatment of an unconventional
shale formation.
[00353] EXAMPLE 29 ¨ Fracturing
[00354] Using embodiments of the PsDC of these examples, e.g., Example 2,
35, 42, 49, 53, 54, and 55 the following fracture plan is carried out on a
formation.
[00355] Interval #1
Fracture Half-Length (ft) 263 Propped Half-Length (ft)
204
Total Fracture Height (ft) 307 Total Propped Height (ft)
238
Depth to Fracture Top (ft) 5449 Depth to Propped Fracture Top
5518
(ft)
Depth to Fracture Bottom (ft)
5756 Depth to Propped Fracture Bottom 5756
(ft)
Equivalent Number of Multiple 1.0 Max. Fracture Width (in)
0.71
Fracs
Fracture Slurry Efficiency** 0.74 Avg. Fracture Width (in)
0.39
Avg. Proppant Concentration
1.51
(lb/ft2)
[00356] Fracture Geometry Summary* - Interval #2
Fracture Half-Length (ft) 244 Propped Half-Length (ft)
193
Total Fracture Height (ft) 308 Total Propped Height (ft)
244
Depth to Fracture Top (ft) 5638 Depth to Propped Fracture Top
5702
(ft)
Depth to Fracture Bottom (ft)
5946 Depth to Propped Fracture Bottom 5946
(ft)
Equivalent Number of Multiple 1.0 Max. Fracture Width (in)
0.68
Fracs
Fracture Slurry Efficiency** 0.74 Avg. Fracture Width (in)
0.41
Avg. Proppant Concentration
1.52
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I ( 1 b/ft2)
[00357] Fracture Geometry Summary* - Interval #3
Fracture Half-Length (ft) 252 Propped Half-Length (ft)
197
Total Fracture Height (ft) 305 Total Propped Height (ft)
238
Depth to Fracture Top (ft) 5882 Depth to Propped Fracture Top
5949
(ft)
Depth to Fracture Bottom (ft) 6187 Depth to Propped Fracture Bottom 6186
(ft)
Equivalent Number of Multiple 1.0 Max. Fracture Width (in)
0.69
Fracs
Fracture Slurry Efficiency** 0.73 Avg. Fracture Width (in)
0.39
Avg. Proppant Concentration
1.52
(lb/ft2)
[00358] Fracture Conductivity Summary* - Interval #1
Avg. Conductivity** (mD=ft)
757.0 Avg. Frac Width (Closed on prop) 0.104
(in)
Dimensionless Conductivity** 37.09 Ref. Formation Permeability (mD) 0.1
Proppant Damage Factor 0.50 Undamaged Prop Perm at Stress 164207
(mD)
Apparent Damage Factor*** 0.00 Prop Perm with Prop Damage
82103
(mD)
Total Damage Factor 0.50 Prop Perm with Total Damage
82103
(mD)
Effective Propped Length (ft) 196 Proppant Embedment (in)
0.008
[00359] Fracture Conductivity Summary* - Interval #2
Avg. Conductivity** (mD=ft)
770.7 Avg. Frac Width (Closed on prop) 0.104
(in)
Dimensionless Conductivity** 39.90 Ref. Formation Permeability (mD) 0.1
Proppant Damage Factor 0.50 Undamaged Prop Perm at Stress 164207
(mD)
Apparent Damage Factor*** 0.00 Prop Perm with Prop Damage
82103
(mD)
Total Damage Factor 0.50 Prop Perm with Total Damage
82103
(mD)
Effective Propped Length (ft) 186 Proppant Embedment (in)
0.008
[00360] Fracture Conductivity Summary* - Interval #3
Avg. Conductivity** (mD=ft)
749.4 Avg. Frac Width (Closed on prop) 0.104
(in)
Dimensionless Conductivity** 38.05 Ref. Formation Permeability (mD) 0.1
Proppant Damage Factor 0.50 Undamaged Prop Perm at Stress 164207
(mD)
Apparent Damage Factor*** 0.00 Prop Perm with Prop Damage
82103
(mD)
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Total Damage Factor 0.50 Prop Perm with Total Damage
82103
(mD)
Effective Propped Length (ft) 189 Proppant Embedment (in)
0.008
[00361] Fracture Pressure Summar * - Interval #1
Model Net Pressure** (psi) 727 BH Fracture Closure Stress (psi)
5050
Observed Net Pressure** (psi) 0 Closure Stress Gradient (psi/ft)
0.898
Hydrostatic Head*** (psi) 2670 Avg. Surface Pressure (psi)
4007
Reservoir Pressure (psi) 2635 Max. Surface Pressure (psi)
4852
[00362] Fracture Pressure Summar * - Interval #2
Model Net Pressure** (psi) 707 BH Fracture Closure Stress (psi)
5050
Observed Net Pressure** (psi) 0 Closure Stress Gradient (psi/ft)
0.867
Hydrostatic Head*** (psi) 2670 Avg. Surface Pressure (psi)
4007
Reservoir Pressure (psi) 2635 Max. Surface Pressure (psi)
4852
[00363] Fracture Pressure Summar * - Interval #3
Model Net Pressure** (psi) 694 BH Fracture Closure Stress (psi)
5050
Observed Net Pressure** (psi) 0 Closure Stress Gradient (psi/ft)
0.834
Hydrostatic Head*** (psi) 2670 Avg. Surface Pressure (psi)
4007
Reservoir Pressure (psi) 2635 Max. Surface Pressure (psi)
4852
[00364] Operations Summary* - Interval #1
Total Clean Fluid Pumped 869.7 Total Proppant Pumped
205,800
(bbls) (klbs)
Total Slurry Pumped (bbls) 994.1 Total Proppant in Fracture
69,500
(klbs)
Pad Volume (bbls) 1190.5 Avg. Hydraulic Horsepower
3923
(hp)
Pad Fraction ( /0 of Slurry 42.9 Max. Hydraulic Horsepower
4751
Vol)** (hp)
Pad Fraction ( /0 of Clean 49.5 Avg Btm Slurry Rate (bpm)
13.6
Vol)**
Primary Fluid Type VIKING D 3 Primary Proppant Type
Example 2
500
Secondary Fluid Type Secondary Proppant Type
[00365] Operations Summary* - Interval #2
Total Clean Fluid Pumped 849.0 Total Proppant Pumped
205,800
(bbls) (klbs)
Total Slurry Pumped (bbls) 971.6 Total Proppant in Fracture
68,300
(klbs)
Pad Volume (bbls) 1190.5 Avg. Hydraulic Horsepower
3923
(hp)
Pad Fraction ( /0 of Slurry 42.9 Max. Hydraulic Horsepower
4751
Vol)** (hp)
Pad Fraction ( /0 of Clean 49.5 Avg Btm Slurry Rate (bpm)
13.3
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Vol)**
Primary Fluid Type VIKING_D_3 Primary Proppant Type Example 2
500
Secondary Fluid Type Secondary Proppant Type
[00366] Operations Summary* - Interval #3
Total Clean Fluid Pumped 833.2 Total
Proppant Pumped 205,800
(bbls) (klbs)
Total Slurry Pumped (bbls) 953.5 Total
Proppant in Fracture 67,000
(klbs)
Pad Volume (bbls) 1190.5 Avg.
Hydraulic Horsepower 3923
(hp)
Pad Fraction ( /0 of Slurry 42.9 Max. Hydraulic Horsepower 4751
Vol)** (hp)
Pad Fraction ( /0 of Clean 49.5 Avg Btm Slurry Rate (bpm) 13.1
Vol)**
Primary Fluid Type VIKING_D_3 Primary Proppant Type Example 2
500
Secondary Fluid Type Secondary Proppant Type
[00367] Model Calibration Summary
Crack Opening Coefficient 8.50e-01
Width Decoupling Coefficient was 1.00e+00
calculated internally
Tip Effects Coefficient 1.00e-04
Tip Radius Fraction 1.00e-02
Tip Effects Scale Volume (bbls) 100.0
Proppant Drag Effect Exponent 8.0
CLE Outside Payzone 1.00
Multiple fractures settings start (V/L/O) 1.0 / 1.0 / 1.0
Multiple fractures settings end (V/L/O) 1.0 / 1.0 / 1.0
[00368] Hydraulic Fracture Growth History* - Interval #1
End of Stage Time Fracture Fracture Fracture
Avg. Model Slurry Equivalent
Stage # Type (mm:ss) Half-Length Height Width
at Fracture Net Efficiency Number of
(ft) (ft) Well Width
Pressure Multifracs
(in) (in) (psi)
1 Main 29:45 223 220 0.498 0.251 645 0.70 1.0
frac
pad
2 Main 31:42 228 228 0.506 0.253 646 0.70 1.0
frac
slurry
3 Main 33:49 234 236 0.513 0.255 646 0.70 1.0
frac
slurry
4 Main 41:23 251 260 0.537 0.267 650 0.71 1.0
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End of Stage Time Fracture Fracture Fracture Avg.
Model Slurry Equivalent
Stage # Type (mm:ss) Half-Length Height Width at
Fracture Net Efficiency Number of
(ft) (ft) Well Width Pressure Multifracs
(in) (in) (psi)
frac
slurry
Main 53:09 257 283 0.593 0.311 678 0.72 1.0
frac
slurry
6 Main 69:22 262 303 0.691 0.379 718 0.74 1.0
frac
slurry
7 Main 72:56 263 307 0.711 0.394 727 0.74 1.0
frac
flush
[00369] Hydraulic Fracture Growth History* - Interval #2
End of Stage Time Fracture Fracture Fracture
Avg. Model Slurry Equivalent
Stage # Type (mm:ss) Half-Length Height Width at Fracture Net
Efficiency Number of
(ft) (ft) Well Width Pressure
Multifracs
(in) (in) (psi)
1 Main 29:45 214 219 0.485 0.254 634 0.69 1.0
frac
pad
2 Main 31:42 218 226 0.492 0.257 635 0.70 1.0
frac
slurry
3 Main 33:49 221 233 0.505 0.265 640 0.70 1.0
frac
slurry
4 Main 41:23 227 255 0.542 0.291 656 0.71 1.0
frac
slurry
5 Main 53:09 234 285 0.595 0.331 676 0.73 1.0
frac
slurry
6 Main 69:22 242 304 0.668 0.400 703 0.74 1.0
frac
slurry
7 Main 72:56 244 308 0.680 0.413 707 0.74 1.0
frac
flush
[00370] Hydraulic Fracture Growth History* - Interval #3
i End of I Stage I Time I Fracture I Fracture I
Fracture I Avg. Model l Slurry l Equivalent I
Stage # Type (mm:ss) Half- Height Width at Fracture
Net Efficiency Number of
Length (ft) Well Width Pressure Multifracs
(ft) (in) (in) (psi)
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End of Stage Time Fracture Fracture Fracture Avg.
Model Slurry Equivalent
Stage # Type (mm:ss) Half- Height Width at Fracture
Net Efficiency Number of
Length (ft) Well Width Pressure Multifracs
(ft) (in) (in) (psi)
1 Main 29:45 211 216 0.474 0.245 613 0.68 1.0
frac
pad
2 Main 31:42 216 224 0.481 0.247 614 0.68 1.0
frac
slurry
3 Main 33:49 221 231 0.489 0.250 614 0.68 1.0
frac
slurry
4 Main 41:23 238 256 0.516 0.263 619 0.69 1.0
frac
slurry
Main 53:09 246 280 0.572 0.306 645 0.71 1.0
frac
slurry
6 Main 69:22 251 301 0.669 0.375 685 0.73 1.0
frac
slurry
7 Main 72:56 252 305 0.689 0.389 694 0.73 1.0
frac
flush
[00371] Propped Fracture Properties by Distance from the Well at Fracture
Center at Depth of 5603ft - Interval #1
Distance Fracture Conductivity Frac System Prop Conc Frac System
from Well System per Frac** Conductivity* per Frac Prop
(ft) Width* (mD=ft) ** (Ib/ft2) Conc****
(in) (mD=ft) (Ib/ft2)
20.4 0.617 1106.6 1106.6 1.55 1.55
40.8 0.611 1573.0 1573.0 2.18 2.18
61.2 0.601 1546.7 1546.7 2.15 2.15
81.6 0.588 1520.1 1520.1 2.11 2.11
102.0 0.570 1480.5 1480.5 2.06 2.06
122.5 0.547 1318.5 1318.5 1.85 1.85
142.9 0.519 1224.8 1224.8 1.73 1.73
163.3 0.485 1039.5 1039.5 1.49 1.49
183.7 0.442 616.9 616.9 0.93 0.93
204.1 0.390 0.0 0.0 0.00 0.00
[00372] Propped Fracture Properties by Distance from the Well at Fracture
Center at Depth of 5792ft - Interval #2
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Distance
Fracture Conductivity Frac System Prop Conc Frac System
from Well System per Frac** Conductivity* per
Frac Prop
(ft) Width* (mD=ft) ** (Ib/ft2) Conc****
(in) (mD=ft) (Ib/ft2)
19.3 0.628 1566.0 1566.0 2.17 2.17
38.6 0.622 1580.7 1580.7 2.19 2.19
58.0 0.612 1553.1 1553.1 2.15 2.15
77.3 0.597 1521.9 1521.9 2.11 2.11
96.6 0.578 1474.4 1474.4 2.05 2.05
115.9 0.554 1304.3 1304.3 1.83 1.83
135.2 0.524 1222.6 1222.6 1.73 1.73
154.5 0.487 1051.9 1051.9 1.50 1.50
173.9 0.441 737.4 737.4 1.09 1.09
193.2 0.384 0.0 0.0 0.00 0.00
[00373] Propped Fracture Properties by Distance from the Well at Fracture
Center at Depth of 6034ft - Interval #3
Distance
Fracture Conductivity Frac System Prop Conc Frac System
from Well System per Frac** Conductivity* per
Frac Prop
(ft) Width* (mD=ft) ** (Ib/ft2) Conc****
(in) (mD=ft) (Ib/ft2)
19.7 0.612 1569.8 1569.8 2.18 2.18
39.4 0.607 1556.2 1556.2 2.16 2.16
59.1 0.597 1529.8 1529.8 2.12 2.12
78.8 0.583 1507.9 1507.9 2.10 2.10
98.5 0.565 1465.3 1465.3 2.04 2.04
118.2 0.543 1302.1 1302.1 1.83 1.83
137.9 0.514 1219.2 1219.2 1.72 1.72
157.5 0.480 1039.7 1039.7 1.49 1.49
177.2 0.437 678.4 678.4 1.01 1.01
196.9 0.384 0.0 0.0 0.00 0.00
[00374] Treatment Schedule
Stage Stage Elapsed Fluid Clean
Prop Stage Slurry Proppant
# Type Time Type Volume Conc Prop. Rate Type
min:sec (gal) (ppg) (klbs) (bpm)
Wellbore Fluid LINEAR 20 6050
GW-32
1 Main 29:45 VIKING_D_3 50000 0.00 0.0 40.00
frac 500
pad
2 Main 31:42 VIKING_D_3 3000 1.2 3.6 40.00 Example
frac 500 2
slurry
3 Main 33:49 VIKING_D_3 3000 2.0 2.2 40.00 Example
frac 500 2
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Stage Stage Elapsed Fluid Clean Prop Stage Slurry Proppant
# Type Time Type Volume Conc Prop. Rate Type
min:sec (gal) (ppg) (klbs)
(bpm)
Slurry
4 Main 41:23 VIKING_D_3 10000 3.6
36.0 40.00 Example
frac 500 2
slurry
Main 53:09 VIKING_D_3 15000 4.2 63.0 40.00
Example
frac 500 2
slurry
6 Main 69:22 VIKING_D_3 20000 4.8 96 40.00 Example
frac 500 2
slurry
7 Main 72:56 LINEAR 20 6000 0.00 0.0
40.00
frac GW-32
flush
[00375] Proppant and Fluid
Material Quantity Units
VIKING_D_3500 2404.8 bbls
LINEAR 20 GW-32 142.9 bbls
Example 2 343.00 klbs
[00376] Leakoff Parameters
Reservoir type User Spec Reservoir fluid compressibility
3.80e-04
(1/psi)
Filtrate to pore fluid perm. 10.00 Reservoir Viscosity (cp) 0.03
ratio, Kp/KI
Reservoir pore pressure 2635 Porosity 0.10
(psi)
Initial fracturing pressure 5563 Gas Leakoff Percentage (%)
100.00
(psi)
[00377] Reservoir Parameters
Reservoir Temperature ( F) 176.00
5 Perforated Interval and Initial Frac Depth are for Interval #1
Depth to center of Perfs (ft) 5624
Perforated interval (ft) 7
Initial frac depth (ft) 5624
[00378] Layer Parameters
Layer # Top of Stress Stress Young's Poisson's Total Ct Pore Fluid
zone (psi) Gradient modulus ratio (ft/min1/2)
Perm.
(ft) (psi/ft) (psi) (mD)
1 0.0 5238 0.932 2.0e+06 0.25
0.000e+00 0.00e+00
2 5620.0 4692 0.832 3.0e+06 0.20
2.208e-03 1.00e-01
3 5660.0 5350 0.932 2.0e+06 0.25
0.000e+00 0.00e+00
4 5820.0 4859 0.832 3.0e+06 0.20
2.208e-03 1.00e-01
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Layer # Top of Stress Stress Young's Poisson's Total Ct Pore Fluid
zone (psi) Gradient modulus ratio
(ft/min1/2) Perm.
(ft) (psi/ft) (psi) (mD)
5860.0 5550 0.932 2.0e+06 0.25 0.000e+00
0.00e+00
6 6050.0 5050 0.832 3.0e+06 0.20 2.208e-03
1.00e-01
7 6090.0 5676 0.932 2.0e+06 0.25 0.000e+00
0.00e+00
[00379] Lithology Parameters
Layer # Top of Lithology Fracture Composite
zone Toughnes Layering
(ft) s Effect
(psi=in1/2)
1 0.0 Shale 2000 1.00
2 5620.0 Sandstone 1000 1.00
3 5660.0 Shale 2000 1.00
4 5820.0 Sandstone 1000 1.00
5 5860.0 Shale 2000 1.00
6 6050.0 Sandstone 1000 1.00
7 6090.0 Shale 2000 1.00
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[00380] Casing Configuration
Length Segment Type Casing ID Casing OD Weight Grade
(ft) (in) (in) (lb/ft)
6500 Cemented 4.950 5.500 15.500 K-55
Casing
[00381] Perforated Intervals
Interval #1 Interval #2 Interval #3
Top of Perfs - TVD (ft) 5620 5820 6052
Bot of Perfs - TVD (ft) 5627 5827 6059
Top of Perfs - MD (ft) 5620 5820 6052
Bot of Perfs - MD (ft) 5627 5827 6059
Perforation Diameter (in) 0.320 0.320 0.320
# of Perforations 7 7 7
[00382] Path Summary
Segment Length MD TVD Dev Ann OD Ann ID Pipe ID
Type (ft) (ft) (ft) (deg) (in) (in) (in)
Casing 6052 6052 6052 0.0 0.000 0.000
4.950
[00383] Model Input Parameters
Fracture Model 3D User-Defined Reservoir Data Lithology-Based
Entry
Run From Job-Design Data Fracture Vertical
Orientation
Proppant Proppant Convection Run Fracture and
Transport Model Wellbore Models
Growth after Allow General Iteration
Shut-in
Backstress Ignore Heat Transfer Ignore
Effects
Acid Fracturing FracproPT (Default) Leakoff Model Lumped-Parameter
Model (Default)
[00384] Fracture Growth Parameters (3D User-Defined)
Parameter Value Default
Crack Opening Coefficient 8.50e-01 8.50e-
01
Tip Effects Coefficient 1.00e-04 1.00e-
04
Channel Flow Coefficient 1.00e+00
1.00e+00
Tip Radius Fraction 1.00e-02 1.00e-
02
Tip Effects Scale Volume (bbls) 100.0 100.0
Fluid Radial Weighting Exponent 0.00e+00
0.00e+00
Width Decoupling Coefficient was calculated 1.00e+00
1.00e+00
internally
[00385] Proppant Model Parameters
I Parameter Value Default I
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Parameter Value Default
Minimum Proppant Concentration (Ib/ft2) 0.20 0.20
Minimum Proppant Diameter (in) 0.0080 0.0080
Minimum Detectable Proppant Concentration (ppg) 0.20 0.20
Proppant Drag Effect Exponent 8.0 8.0
Proppant Radial Weighting Exponent 0.2500 0.2500
Proppant Convection Coefficient 10.00 10.00
Proppant Settling Coefficient 1.00 1.00
Quadratic Backfill Model ON ON
Tip Screen-Out Backfill Coefficient 0.50 0.50
Stop Model on Screenout ON ON
Reset Proppant in Fracture after Closure ON ON
[00386] Low Level Parameters
Parameter Value Default
Perm. Contrast: Distance Effect 3 1.0
Perm. Contrast: Containment Effect 3 Q 1.0
Perm. Contrast: Permeability Level 1.00 1.00
Perm. Contrast Model: FracproPT Default YES
Fluid <gel> Bulk Modulus (psi) 3.000e+10 3.000e+10
Proppant Bulk Modulus (psi) 3.000e+06 3.000e+06
Fluid (gel) Bulk Coefficient of Thermal Expansion 3.000e-04
3.000e-04
(1/deg.F)
Effect of Proppant on Length Growth 1.00 1.00
Fraction of BRACKET FRAC Proppant that is 0.5 0.5
INVERTA-FRAC by Volume
Remember Position of Proppant Banks after closure NO NO
on Proppant
Allow Slippage NO NO
Reset Fluid Leakoff after Frac Closure NO NO
Minimum Volume Limit Value 0.20 0.20
Center Shifting Option:
Fracture Always Stays Connected to Perfs X
Stages can Move from Perfs after Shut-in SIMPXEMER
Fracture can Move from Perfs after Shut-in
Fracture can Move from Perfs at any Time
Stage Splitting Volume Threshold (bbls) 200.0 200.0
Stage Splitting Leakoff Compensation (bbls) 5.0 5.0
[00387] Initial Leakoff and Closure
Parameter Value Default
Initial Leakoff Area Multiplier Coefficient 1.000 1.000
Initial Leakoff Area from Last Simulation (ft2) 4268.528 n/a
Closure Leakoff Area Multiplier Coefficient 0.025 0.025
Default Shut-in Model YES YES
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Parameter Value Default
Shut-in Tip Weighting Coefficient for Leakoff 1.00 1.00
Shut-in Tip Weighting Exponent for Leakoff 1.00 1.00
Minimum Shut-in Volume (bbls) 100.0 100.0
Model Proppant in Flow-back YES YES
Model Wall-building Viscosity Effect NO
[00388] Miscellaneous Growth Parameters
Parameter Value Default
Set Minimum Fracture Height NO NO
Model Very Small Fractures NO NO
Model Head Effects in Fracture NO NO
Model Fracture Center Shifting YES NO
Near-Wellbore Friction Exponent 0.50 0.50
[00389] EXAMPLE 30 ¨ Enhanced Hydrocarbon Recovery using PsDCs
[00390] Turning to FIG. 62, there is shown a schematic perspective view of a
well 6201 in a portion of a formation 6202. The well 6201 has an essentially
horizontal
section 6203 that generally follows a reservoir of hydrocarbons in the
formation. A
perforating operation has been performed on the well 6201, leaving
perforations, 6204a,
6204b, 6204c, 6204d, 6204e, 6204f, 6204g, 6204h, 6204i, 6204j extending from
the
horizontal section 6203 of well 6201 into the formation 6202. There is shown a
fracture
zone or area, e.g., 6210a, 6210b within the reservoir that is typical for
prior proppant
fracturing, using for example a sand as the proppant. And, there is shown a
fracture
zone or area 6220a, 6220b that is obtainable with a PsDC, such as an
embodiment of
the PsDC proppants of these examples, e.g., Example 2, 35, 42, 49, 53, 54, and
55.
The PsDC fracture zone 6220a, 6220b is substantially higher (as shown by
arrows
6221a, 6221b) and longer (as shown by arrows 6222a, 6222b each indicating a
half-
length of the fracture) than the prior art fracture zone 6210a, 6210b.
[00391] EXAMPLE 30A
[00392] Still using FIG. 62 for illustrative purposes, the low density PsDCs
of
Example 2 extend out greater half-lengths 6222a, and 6222b away from the well
6203
and extend up and down greater heights 6221a, 6221b from the center line of
the
perforations, 6204a-6204j, providing for a substantially larger surface area
from which
the hydrocarbons can flow. These enlarged surface areas may be at least about
20%
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larger, at least about 50% larger, at least about 100% larger, at least about
200% larger
and larger still.
[00393] This enlarged surface areas 6220a, 6220b result in increased initial
flows of hydrocarbons by at least about 5%, at least about 10%, at least about
20%, at
least about 40% and more over the smaller areas 6210a, 6210b that are obtained
with
prior proppants.
[00394] The PsDC fracture well may also maintain the increased flow, and
experience less degradation of flow or production over time, when compared to
a
fractured using prior proppant. Thus, the PsDC fractured well may provide
natural gas
production of at least about 200 Mcf/day, at least about 800 Mcf/day, at least
about
1,200 Mcf/day or more for at least about 12 months, at least about 18 months,
at least
about 24 months or more.
[00395] Turning to FIG. 63 there is shown a graph comparing the production
over time of a Marcellus shale gas well using conventional, i.e., prior
proppant fracturing
6301, and using PsDC fracturing 6302.
[00396] EXAMPLE 31
[00397] A proppant is made from the following precursor batch: 70% Methyl
Hydrogen Fluid; 20% Tetravinyltetramethylcyclotetrasiloxane; and 10% Vinyl
Terminated Polydimethylsiloxane (200 cps, - 9400 Mw, SiSiB VF6030 VINYL
TERMINATED POLYDIMETHYL SILOXANE 68083-19-2)
[00398] Using a tower system, this batch is formed from a sonic nozzle having
an internal diameter of 0.180 inches into droplets that fall from the nozzle
into and
through an 18 foot curing tower. The temperature at the top of the tower is
from 200-
500 C the temperature at the bottom of the tower is from 200-600 C. There are
no
discrete temperature zones in the tower. Airflow up the tower is by
convection. The
collection pan is maintained at 110 C. The forming and curing are done in air.
The
preform proppants are removed from the pan and post (hard) cured at 200 C in
air for 3
hours. The hard cured preform proppants are pyrolized at 1000 C in an argon
atmosphere for 2 hours. The cure yield is from 99% to 101%. The char yield is
86%.
[00399] EXAMPLE 32
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[00400] Studies by Coulter & Wells (e.g. SPE JPT, June 1972, pp. 643-650)
have demonstrated that as little as 5% added fines, from prior art proppants,
can reduce
propped fracture conductivity by 50%. The API (ISO) test classifies a proppant
according to the stress at which < 10% fines is generated; for example an API
(ISO) 7k
proppant would produce < 10% fines at 7000 psi. Embodiments of PsDCs, however,
exhibit surprising and exceptionally improved conductivities for materials
having the
same API (ISO) crush strength, when compared to prior art proppants.
[00401] Thus, and surprisingly, these embodiments of PsDCs have a
substantially different behavior from prior art proppants. It is believed and
theorized that
the PsDCs have a different failure mechanism than prior art proppants.
[00402] Thus, it is presently theorized that embodiments of the PsDCs upon
failure exhibit fines that are larger and more jagged than the fines that are
produced
upon the failure of prior art proppants. Additionally, it is presently
theorized that charge,
e.g., the electrostatic charge of the PsDCs, could be potentially providing
the ability to
hold the fines together, and thus may provide one of may explanations for the
enhanced
flow and flow back characteristics of embodiments of the PsDC proppants.
[00403] Thus, for example, turning to FIG. 64 there is shown a photograph of
the fines created at 4k API (ISO) crush test of the proppants of Example 1;
and in FIG.
65 there is shown a photograph of the fines created at 5k API (ISO) crush test
of the
proppants of Example 1. This can be compared against the fines created from
prior art
proppants, which are smaller, finer, and more likely to plug, clog, or create
a filter cake
that adversely affects conductivity. It is theorized that, for this
embodiment, this
different failure mechanism, and different type of fines created, explains the
increased
conductivity values that PsDCs exhibit after failure.
[00404] Regardless of the failure mechanism, fluid flow, or hydraulic
mechanisms taking place, the PsDCs exhibit surprising and exceptional improved
conductivities over prior art proppants.
[00405] EXAMPLE 33
[00406] A polysilocarb formulation has 40% MHF, 40% TV, and 20% VT and
has a hydride to vinyl molar ratio of 1.12:1, and may be used as to form
strong ceramic
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beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00407] EXAMPLE 34
[00408] A polysilocarb formulation has 42% MHF, 38% TV, and 20% VT and
has a hydride to vinyl molar ratio of 1.26:1, and may be used as to form
strong ceramic
beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00409] EXAMPLE 35
[00410] A polysilocarb formulation has 46% MHF, 34% TV, and 20% VT and
has a hydride to vinyl molar ratio of 1.50:1, and may be used as to form
strong ceramic
beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00411] EXAMPLE 36
[00412] A polysilocarb formulation has 49% MHF, 31% TV, and 30% VT and
has a hydride to vinyl molar ratio of 1.75:1, and may be used as to form
strong ceramic
beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00413] EXAMPLE 37
[00414] A polysilocarb formulation has 51 /o MHF, 49% TV, and 0% VT and
has a hydride to vinyl molar ratio of 1.26:1, and may be used as to form
strong ceramic
beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00415] EXAMPLE 38
[00416] A polysilocarb formulation has 55% MHF, 35% TV, and 10% VT and
has a hydride to vinyl molar ratio of 1.82:1, and may be used as to form
strong ceramic
beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00417] EXAMPLE 39
[00418] A polysilocarb formulation has 52% MHF, 28% TV, and 20% VT and
has a hydride to vinyl molar ratio of 2.02:1, and may be used as to form
strong ceramic
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beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00419] EXAMPLE 40
[00420] A polysilocarb formulation has 55% MHF, 25% TV, and 20% VT and
has a hydride to vinyl molar ratio of 2.36:1, and may be used as to form
strong ceramic
beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00421] EXAMPLE 41
[00422] A polysilocarb formulation has 65% MHF, 25% TV, and 10% VT and
has a hydride to vinyl molar ratio of 2.96:1, and may be used as to form
strong ceramic
beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00423] EXAMPLE 42
[00424] A polysilocarb formulation has 70% MHF, 20% TV, and 10% VT and
has a hydride to vinyl molar ratio of 3:93:1, and may be used as to form
strong ceramic
beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00425] EXAMPLE 43
[00426] A polysilocarb formulation has 72% MHF, 18% TV, and 10% VT and
has a hydride to vinyl molar ratio of 4.45:1, and may be used as to form
strong ceramic
beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00427] EXAMPLE 44
[00428] A polysilocarb formulation has 75% MHF, 17% TV, and 8% VT and
has a hydride to vinyl molar ratio of 4.97:1, and may be used as to form
strong ceramic
beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00429] EXAMPLE 45
[00430] A polysilocarb formulation has 95% MHF, 5% TV, and 0% VT and has
a hydride to vinyl molar ratio of 23.02:1, and may be used as to form strong
ceramic
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beads, e.g., proppants for use in hydraulically fracturing hydrocarbon
producing
formations.
[00431] EXAMPLE 46
[00432] Using the reaction type process a precursor formulation was made
using the following formulation. The temperature of the reaction was
maintained at 72
C for 21 hours. This precursor formulation may be used to make a strong
synthetic
pro ppant.
Moles of % of Total
% of Reactant/ Moles of
Moles Moles
Reactant or Solvent Mass Total MW solvent Silane of
Si of Et0H
Methyltriethoxysilane (FIG.
46) 0.00 0.0% 178.30 - 0.00%
- -
Phenylmethyldiethoxysilane
(FIG. 47) 0.00 0.0% 210.35 - 0.00%
- -
Dimethyldiethoxysilane (FIG.
51) 56 7.2% 148.28 0.38
17.71% 0.38 0.76
Methyldiethoxysilane (FIG. 48) 182 23.2% 134.25 1.36
63.57% 1.36 2.71
Vinylmethyldiethoxysilane
(FIG. 49) 64 8.2% 160.29 0.40
18.72% 0.40 0.80
Triethoxysilane (FIG. 53) 0.00 0.0% 164.27 -
0.00% -
Hexane in hydrolyzer 0.00 0.0% 86.18 -
Acetone in hydrolyzer 0.00 0.0% 58.08 -
Ethanol in hydrolyzer 400.00 51.1% 46.07 8.68
Water in hydrolyzer 80.00 10.2% 18.00 4.44
HCI 0.36 0.0% 36.00 0.01
Sodium bicarbonate 0.84 0.1% 84.00 0.01
[00433] EXAMPLE 47
[00434] Using the reaction type process a precursor formulation was made
using the following formulation. The temperature of the reaction was
maintained at 61
C for 21 hours. This precursor formulation may be used to make a strong
synthetic
pro ppant.
Moles of % of Total
% of Reactant/ Moles of
Moles Moles
Reactant or Solvent Mass Total MW solvent Silane of
Si of Et0H
Phenyltriethoxysilane (FIG. 54) 145.00 18.5% 240.37 0.60
34.58% 0.60 1.81
Phenylmethyldiethoxysilane
(FIG. 47) 0.00 0.0% 210.35 - 0.00%
- -
Dimethyldiethoxysilane (FIG.
51) 0.00 0.0% 148.28 0.57
32.88% 0.57 1.55
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Methyldiethoxysilane (FIG. 48) 77.00 9.8% 134.25 -
0.00% - -
Vinylmethyldiethoxysilane
(FIG. 49) 91.00 11.6% 160.29 0.57
32.54% 0.57 1.14
Trimethyethoxysilane (FIG. 57) 0.00 0.0% 118.25 -
0.00% -
Acetone in hydrolyzer 395.00 50.3% 58.08 6.80
Ethanol in hydrolyzer 0.00 0.0% 46.07 -
Water in hydrolyzer 76.00 9.7% 18.00 4.22
HCI 0.36 0.0% 36.00 0.01
Sodium bicarbonate 0.84 0.1% 84.00 0.01
[00435] EXAMPLE 48
[00436] Using the reaction type process a precursor formulation was made
using the following formulation. The temperature of the reaction was
maintained at 61
C for 21 hours. This precursor formulation may be used to make a strong
synthetic
proppant.
Moles of % of Total
% of Reactant/ Moles of Moles Moles
Reactant or Solvent Mass Total MW solvent
Silane of Si of Et0H
Phenyltriethoxysilane (FIG. 54) 0.00 0.00% 240.37 - 0.0%
-
Phenylmethyldiethoxysilane
(FIG. 47) 145.00 18.4% 210.35 0.69 34.47%
0.69 1.38
Dimethyldiethoxysilane (FIG.
51) 0.00 0.00% 148.28 -
0.00% - -
Methyldiethoxysilane (FIG. 48) 88.00 11.2% 134.25 0.66
32.78% 0.66 1.31
Vinylmethyldiethoxysilane
(FIG. 49) 105.00 13.3% 160.29 0.66
32.76% 0.66 1.31
Trimethyethoxysilane (FIG. 57) 0.00 0.0% 118.25 -
0.00% -
Acetone in hydrolyzer 375.00 47.5% 58.08 6.46
Ethanol in hydrolyzer 0.00 0.0% 46.07 -
Water in hydrolyzer 75.00 9.5% 18.00 4.17
HCI 0.36 0.0% 36.00 0.01
Sodium bicarbonate 0.84 0.1% 84.00 0.01
[00437] EXAMPLE 49
[00438] The treatment of pyrolized polysiloxane materials, such as for
example, proppants and other volumetric shapes, with silanes, anti-static
agents and
combinations of these has the ability to increase, and significantly increase
the strength
of the pyrolized materials.
[00439] Thus, treating composition may optionally contain generally used,
e.g.,
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typical, additives such as rheology modifiers, fillers, coalescents such as
glycols and
glycol ethers to aid in proppant storage stability, antifoaming agents such as
Drew L-
139 (commercially available from Drew Industries, a division of Ashland
Chemical),
antistatic agents such as Emerstat 6660A (commercially available from Cognis)
or
Katex 6760 (from Pulcra Chemicals), dust suppression agents, and/or other
generally
used, e.g., typical, additives. Additives may be present in the coatings
composition from
trace amounts (such as <about 0.1% by weight the total composition) up to
about 5.0%
by weight of the total composition.
[00440] The preferable treating solution contains a silane, Silquest A1100
from
Momentive and has the following chemical formula, H2NCH2CH2CH2Si(OCH2CH3)3.
[00441] To treat proppant the following procedure may be utilized. Wash the
Proppant in water (current procedure) to remove fines, Wash the Proppant in
Silane/Antistat aqueous solution for 5min (at 25C). Remove Proppant and save
all the
excess Silane/Antistat solution for multiple use. Dry the Proppant at 105-110C
for
30mins-1hr (preferably it should be completely dry).
[00442] By way of example, 40 mesh proppant having a crush strength of
13,200 psi was treated using the above procedure and exhibited crush strengths
that
exceeded 17,600 psi, and more. The fine percentage for these silane treated
proppants was less than 1.7%, and lower.
[00443] EXAMPLE 50 ¨ Off Shore Hydrocarbon Recovery
[00444] In PsDC hydraulic fracturing treatments of offshore deep water wells
is
conducted using embodiments of the proppants of these examples, e.g., Example
2, 16,
17, 18, 21, 23, 35, 42, 49, 53, 54, and 55.
[00445] Existing proppants, and in particular generally used higher strength
proppants, that typically have specific gravities of 2.5 and greater (e.g.,
FIG. 66) are
failing to meet the needs of the deep water offshore hydrocarbon E&P. Such
proppants
increase the weight of the fracturing fluid to such an extent that pumps have
great
difficulty, and in many cases cannot reverse the flow of the fracturing fluid
and pump the
fluid from the well, if need be, during a fracturing treatment. This inability
to reverse,
back off, or have full control of the fracturing fluid, can result delays,
cost increases, and
in some cases in severe and costly damage to the well. For example, this
problem can
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arise in water depths of 5,000 feet, and increases as the water depth, and
thus the
length of the riser, and column of fracturing fluid in the riser increases.
Thus, the
problem becomes more pronounced in water depths of 7,000 feet and greater,
8,000
feet and greater, and 10,000 feet and greater. The problem is further
complicated by
the MD of the wells, which further increases the total weight of the column of
fracturing
fluid that must be backed off, reverse flowed, or otherwise controlled. Thus,
MDs of
10,000 feet and greater, 15,000 feet and greater, and 20,000 feet and greater
provide
significant addition weight, especially when combined with a 5,000 foot and
greater
column of fracture fluid in the riser.
[00446] The low specific gravity, e.g., less than 2.5, and more preferably
less
than 2.0, and low specific gravity to high strength ratio, provided by the
synthetic
proppants of the present inventions, greatly reduces the weight of the column
of
fracturing fluid providing the ability to back off, circulate, reverse flow,
and otherwise
control the movement of the fracturing fluid, and thus solves this developing,
significant
and potentially severe problem with prior proppants, as E&P activities move
into deeper
and deeper waters.
[00447] EXAMPLE 50a
[00448] Turning to FIG. 70 there is shown a perspective view of an off shore
well. An off shore rig 7000, e.g., a dynamically positioned drill ship, has
fracturing
equipment 7002. The drill ship 7000 is located on the surface 7003 of a body
of water
7004. A riser 7006 extends down from the drill ship 7000 to a BOP 7008 located
on the
sea floor 7005. The borehole 7101 extends below the sea floor 7005 to a
fracture area
7012. The MD for the borehole from the sea floor to the fracture area 7012 is
10,000
feet (unless stated otherwise, in off shore wells MD is from the sea floor as
the
reference point). The sea floor is at a depth of about 8,000 feet and the
riser has a
length of about that same same distance. The proppant of Example 54 is used to
perform a hydraulic fracturing treatment on the fracturing area 7012.
[00449] EXAMPLE 50b
[00450] Turning to FIG. 71 there is shown a cross sectional view of an off
shore well. An off shore rig 7100, e.g., a dynamically positioned semi-
submersible, has
a vessel 7101 having fracturing equipment. The rig 7100 is located on the
surface 7103
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of a body of water 7104. A riser 7106 extends down from the drill ship 7100 to
a BOP
7108 located on the sea floor 7105. The borehole extends below the sea floor
7105 to
a fracture area 7112. The borehole has casings 7109, 7110. A pipe 7107 for
transporting the fracturing fluid to the fracturing area 7112 extends from the
rig 7100 to
the fracture area 7112. Perforations, e.g., 7113 are present in the fracture
area 7112.
An annulus 7111 is located around the pipe 7107 and extends from the fracture
area
7112 to the drill ship 7100 (during different stages, points of the fracturing
treatment is is
understood that packers may be engaged, and disengaged, at strategic points in
the
annulus). The MD at the fracture area 7112 is about 15,000 feet. The sea floor
is at a
depth of about 9,000 feet and the riser has a length of about that same same
distance.
The proppant of Example 55 is used to perform a hydraulic fracturing treatment
on the
fracturing area 7012.
[00451] EXAMPLE 51
[00452] In a PsDC hydraulic fracturing treatment the PsDC proppants are
added in a controlled manner, and at a controlled lbs/gal, using volumetric
metering
devices.
[00453] EXAMPLE 52
[00454] In a PsDC hydraulic fracturing treatment the PsDC proppants are
added using volumetric metering devices. The proppant is metered into the high
pressure line, in a controlled manner. In this manner the pumps are not
required to
pump fracturing fluid containing proppant.
[00455] EXAMPLE 53
[00456] A PsDC proppant of the type of Example 42 has the following features:
high in strength resulting in less crushing, optimizing conductivity and
minimizing fines
generation; lower specific gravity enabling the proppant to travel further
into the
formation, creating longer propped fracture half-lengths and more propped
surface area,
resulting in greater access to reserves in place generating higher initial
production (IP)
and increased estimated ultimate recovery (EUR); performs well at temperatures
to
>2,000 F (1,100 C), enabling usage in virtually all O&G reservoirs; is round
and has a
uniform mesh distribution, maximizing conductivity and increasing the free
flow of
formation liquids; lowers total well costs per unit of production; not harmful
to the
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environment and could reduce the number of wells producers must drill given
its ability
to access more of the reserves in place.
[00457] The proppant has a sieve analysis ( /0 retained) of +35 Mesh/420
microns ¨ 0.1%; -35+40 mesh/354 microns ¨ 72.8%; -40+45 mesh/297 microns ¨
27.1 /o; -45 mesh/250 microns ¨ 0%. The proppant has a roundness of about 1.0,
a
sphericity of about 1.0, a bulk density of 75.15 (lbs/ft3) 1.20 (g/cc), a
specific gravity of
1.98, an absolute volume of 0.61 (gal/lb), a solubility in 12/3 HCl/HF Acid (
/0 weight
loss) 5.7, API crush test, % of fines generated @ 15,000 psi 0.3.
[00458] The proppant has the long term conductivity data of Tables 4a and 4b
[00459] Table 4a
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md-ft (millidarcy ¨
Closure Stress (psi) feet) @ 250 F
2 lbs/ft2 40 mesh
2,000 2,743
4,000 2,510
6,000 2,228
8,000 1,697
10,000 1,607
12,000 1,544
14,000 1,366
15,000 1,228
[00460] Table 4b
Closure stress (psi) Darcies @ 250 F
2 lbs/ft3 40 mesh
2,000 133
4,000 124
6,000 113
8,000 86
10,000 84
12,000 82
14,000 74
15,000 67
[00461] EXAMPLE 54
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[00462] An embodiment of the proppant of Example 39 has a bulk density of
1.17 g/cc, a specific gravity of 1.93, a particle size distribution of 0.1 /o
at 35 mesh,
75.2% at 40 mesh, 24.6% at 45 mesh, and 0.1 /o at 50 mesh, and an ISO Crush
Analysis ( /0 fines) 4Ib/ft2@ 15,000 psi of 0.6. The sample exhibits
exceptional long
term conductivity performance data as shown in Table 5.
[00463] Table 5
Stress (psi) Time (hrs) @ Total test time Conductivity (md-
Permeability Pack Height
stress (hrs) ft) (Darcy)
(Test cell
plate
separation)
(in)
1,000 24 24 2263 111
0.246
2,000 74 1977 99
0.240
4,000 50 124 1841 93
0.237
6,000 50 174 1940 100
0.233
8,000 50 224 1769 93
0.229
10,000 50 274 1762 94
0.226
12,000 50 324 1638 89
0.221
14,000 50 374 1381 77
0.215
15,000 50 424 1187 68
0.209
[00464] EXAMPLE 55
[00465] An embodiment of the proppant of Example 35 has a bulk density of
1.24 g/cc, a specific gravity of 1.95, a particle size distribution of 0.1% at
35 mesh,
10 91.6% at 40 mesh, 8.2% at 45 mesh, and 0.1 /o at 50 mesh, and an ISO
Crush Analysis
( /0 fines) 4Ib/ft2@ 15,000 psi of 0.4. A 400x photograph of these proppants
is shown in
FIG. 69. The sample exhibits exceptional long term conductivity performance
data as
shown in Table 6.
[00466] Table 6
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Stress (psi) Time (hrs) @ Total test time Conductivity (md-
Permeability Pack Height
stress (hrs) ft) (Darcy)
(Test cell
plate
separation)
(in)
1,000 24 24 2777 127
0.262
2,000 50 74 2344 110
0.256
4,000
50 124 2051 98
0.251
6,000 50 174 1912 93
0.247
8,000 50 224 1681 82
0.245
10,000 50 274 1916 94
0.244
12,000 50 324 1717 86
0.240
14,000 50 374 1461 75
0.233
15,000 50 424 1247 65
0.229
[00467] EXAMPLE 56
[00468] Embodiments of a PsDC formulations of Examples 35, 39 and 42 are
formed into pucks. The pucks are cures and pyrolized to a ceramic. The ceramic
pucks
are broken apart, into small particles. The particles are sieved if need be,
to have the
majority of all particles smaller than 100 mesh. These particles are not
spherical, are
irregular and varied in shape, and have planar surfaces. These particles are
PsDC
proppants
[00469] EXAMPLE 57
[00470] Embodiments of a PsDC formulations of Examples 35, 39 and 42 are
formed into pucks. The pucks are cures and pyrolized to a ceramic. The ceramic
pucks
are broken apart, into small particles. The particles are sieved if need be,
to have the
majority of all particles smaller than 200 mesh. These particles are not
spherical, are
irregular and varied in shape, and have planar surfaces. These particles are
PsDC
proppants
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[00471] EXAMPLE 58
[00472] Embodiments of the proppants of these examples, e.g., Examples 56,
57, 59 and 60, are used in a hydraulic fracture treatment of an unconventional
shale
well. The fractures are propped with a monolayer or partial monolayer
distribution of
proppant. It is theorized that a self-bridging diverting phenomena takes place
in
situ. Prior proppants, now generally in use, do not get very far from the well
bore due to
settling because of their density. Embodiments of proppants of the present
inventions
can accomplish this due to, among other things, their size and lower density.
[00473] EXAMPLE 59
[00474] Embodiments of a PsDC formulations of Examples 35, 39 and 42 are
formed into small spheres using emulsion polymerization techniques. The
precursor
formulation is emulsified using water, alcohol, glycol, or any polar liquid
having a low
partition coefficient, and in which the precursor formulation is not soluble,
as the
emulsifier. Once formed the emulsion is broken and the small sphere are cured
and
pyrolized into PsDC proppants. The spheres are smaller than 100 mesh.
[00475] EXAMPLE 60
[00476] Embodiments of a PsDC formulations are formed into small spheres
using emulsion polymerization techniques. The precursor formulation is
emulsified
using water, alcohol, glycol, or any polar liquid having a low partition
coefficient, and in
which the precursor formulation is not soluble, as the emulsifier. Once formed
the
emulsion is broken and the small sphere are cured and pyrolized into PsDC
proppants.
The spheres are smaller than 100 mesh. In other embodiments the spheres are
smaller
than 150 mesh. In other embodiments the spheres are smaller than 200 mesh, and
smaller.
[00477] EXAMPLE 61
[00478] A jack-up off shore rig has fracturing equipment operationally
associated with it. The rig is located above the surface of a body of water
having a
depth of 200 feet. A riser extends down from the rig to a BOP on the sea
floor, and has
a length of about 200 feet. A borehole extends below the sea floor into the
earth to a
fracture area at a MD of about 8,000 feet. The proppant of Example 55 is used
to
perform a hydraulic fracturing treatment on the fracturing area.
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[00479] It is noted that there is no requirement to provide or address the
theory
underlying the novel and groundbreaking conductivities, performance or other
beneficial
features and properties that are the subject of, or associated with,
embodiments of the
present inventions. Nevertheless, various theories are provided in this
specification to
further advance the art in this important area, and in particular in the
important area of
hydrocarbon exploration and production. These theories put forth in this
specification,
and unless expressly stated otherwise, in no way limit, restrict or narrow the
scope of
protection to be afforded the claimed inventions. These theories many not be
required
or practiced to utilize the present inventions. It is further understood that
the present
inventions may lead to new, and heretofore unknown theories to explain the
conductivities, fractures, drainages, resource production, and function-
features of
embodiments of the methods, articles, materials, devices and system of the
present
inventions; and such later developed theories shall not limit the scope of
protection
afforded the present inventions.
[00480] The various embodiments of formulations, batches, devices, systems,
proppants, PsDCs, methods, hydraulic fracture treatments, hydrocarbon
recovery,
activities and operations set forth in this specification may be used for
various oil field
operations, other mineral and resource recovery fields, as well as other
activities and in
other fields. Additionally, these embodiments, for example, may be used with:
oil field
systems, operations or activities that may be developed in the future; and
with existing
oil field systems, operations or activities which may be modified, in-part,
based on the
teachings of this specification. Further, the various embodiments set forth in
this
specification may be used with each other in different and various
combinations. Thus,
for example, the configurations provided in the various embodiments of this
specification may be used with each other; and the scope of protection
afforded the
present inventions should not be limited to a particular embodiment,
configuration or
arrangement that is set forth in a particular embodiment, example, or in an
embodiment
in a particular Figure.
[00481] Although this specification focuses on proppants, it should be
understood that the formulations, material systems, small volumetric shapes,
and
methods of making them, taught and disclosed herein, may have applications and
uses
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for many other activities in addition to hydraulic fracturing, for example, as
pigments and
additives.
[00482] The invention may be embodied in other forms than those specifically
disclosed herein without departing from its spirit or essential
characteristics. The
described embodiments are to be considered in all respects only as
illustrative and not
restrictive.
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