Note: Descriptions are shown in the official language in which they were submitted.
ANODE APPARATUS AND METHODS REGARDING THE SAME
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application claims benefit of U.S. provisional application No.
62/396,583, filed
September 19, 2016.
BACKGROUND
[0002] An inert anode is electrically connected to the electrolytic cell,
such that a conductor
rod is connected to the inert anode in order to supply current from a current
supply to the inert
anode, where the inert anode directs current into the electrolytic bath to
produce non-ferrous
metal (where current exits the cell via a cathode). In some embodiments,
during operation of
the cell, corrosive bath and/or vapor interacts with the anode assembly and
can impact the
effectiveness and longevity of the anode assembly (e.g. by weakening the
mechanical
connection, and/or increasing resistivity at the electrical connection).
FIELD OF THE INVENTION
[0003] Generally, the instant disclosure is directed towards an inert anode
apparatus. More
specifically, the instant disclosure is directed towards an inert anode
apparatus configured to
reduce, prevent, and/or eliminate corrosion of the pin and/or anode material
(e.g. by corrosive
vapors and/or molten electrolyte) in an electrolysis cell.
SUMMARY OF THE DISCLOSURE
[0004] Without being bound by a particular mechanism or theory, it is
believed that one or
more embodiments of the anode-pin-protective sealing material connection in
the instant
disclosure provide enhanced corrosion resistance to the anode assembly when
measured in at
least one of the following locations: (a) at the pin, inside the hole in the
anode body; (b) at the
anode body, along the inner diameter of the hole for the anode pin; and/or (c)
in the vapor zone
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where the pin extends above the anode body (i.e., above the bath, and/or in
the refractory
package).
[0005] Without being bound by a particular mechanism or theory, it is
believed that when the
sealing material is utilized in the anode assembly, it provides protection to
(1) mechanical
attachment site of the anode to pin and/or (2) the anode assembly components
(e.g. pin, anode
body, filler material, cement material) as the sealing material is configured
to accept reactive
fluoride species that are present in situ in the bath and/or bath vapor.
Without being bound by a
particular mechanism or theory, it is believed that by undergoing the chemical
transformation to
accept the fluoride species, the sealing material is transformed (at least
partially) from a solid to
a liquid material. In some embodiments, a sealing material is configured to
extend between the
inner surface of the hole in the anode body and the outer diameter of the pin.
[0006] In one aspect of the instant disclosure, an anode assembly is
provided, comprising: an
anode support; and an anode apparatus mechanically attached to the anode
support, wherein the
anode apparatus comprises: (a) an anode body comprising at least one outer
sidewall, wherein
the outer sidewall is configured to define a shape of the anode body, and to
perimetrically
surround a hole in the anode body, wherein the hole comprises an upper opening
in a top
surface of the anode body and wherein the hole axially extends into the anode
body; (b) a pin
comprising: a first end connected to a current supply, and a second end
opposite the first end,
wherein the second end extends downward into the upper end of the anode body
and into the
hole of the anode body; and (c) a sealing material comprising an aggregate and
a matrix,
wherein the sealing material is configured to cover at least a portion of at
least one of the
following: (1) an inner sidewall of the anode body; (2) the top surface of the
anode body; (3) the
pin; and (4) the anode support.
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[0007] In some embodiments of the instant disclosure, the sealing material
comprises at least
one of: water, polymers, organics, dispersants, or diluents.
[0008] In some embodiments of the instant disclosure, a sealing material is
configured to
cover at least a portion of at least one of the following: (1) an inner
sidewall of the anode body;
(2) the pin; and (3) a filler material.
[0009] In some embodiments of the instant disclosure, the first end of the
pin is configured to
be retained within an anode support.
[0010] In some embodiments of the instant disclosure, the filler is
retained in the hole
between the inner sidewall of the anode body and the pin.
[0011] In some embodiments of the instant disclosure, the sealing material
is configured to
enclose the conductive filler into the anode body between the inner sidewall
of the anode body
and the pin.
[0012] In some embodiments of the instant disclosure, the sealing material
is cast in place.
[0013] In some embodiments of the instant disclosure, the sealing material
is pre-cast and
screwed into the anode body.
[0014] In some embodiments of the instant disclosure, the sealing material
is sintered into
place during the sintering of the green form anode body into the final anode
body.
[0015] In some embodiments of the instant disclosure, the sealing material
is retained above
the top surface of the anode body.
[0016] In some embodiments of the instant disclosure, the sealing material
is retained in the
hole.
[0017] In some embodiments of the instant disclosure, above the top surface
of the anode
body includes extending along the pin.
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[0018] In some embodiments of the instant disclosure, above the top surface
of the anode
body includes extending along the pin and into the anode support.
[0019] In some embodiments of the instant disclosure, above the top surface
includes
extending across the top surface of the upper portion of the anode body.
[0020] In some embodiments of the instant disclosure, above the top surface
includes
extending across the top surface and extending down around the outer sidewall
of the anode
body.
[0021] In some embodiments of the instant disclosure, the sealing material
is applied to the
anode hole between the pin and the inner surface of the anode body in a
gradient, such that the
concentration of sealing material varies in a radial direction.
[0022] In some embodiments of the instant disclosure, the gradient is
configured such that
the concentration of sealing material is higher adjacent to the pin as
compared to adjacent to the
inner surface of the anode body.
[0023] In some embodiments of the instant disclosure, the gradient is
configured such that
the concentration of sealing material is lower adjacent to the pin as compared
to adjacent to the
inner surface of the anode body.
[0024] In some embodiments of the instant disclosure, the sealing material
is applied to the
anode hole between the pin and the inner surface of the anode body in a
gradient, such that the
concentration of sealing material varies in a lateral direction.
[0025] In some embodiments of the instant disclosure, the gradient is
configured such that
the concentration of sealing material is higher adjacent to the upper end as
compared to
adjacent to the lower end of the anode body.
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[0026] In some embodiments of the instant disclosure, the gradient is
configured such that
the concentration of sealing material is lower adjacent to the upper end as
compared to adjacent
to the lower end of the anode body.
[0027] In some embodiments of the instant disclosure, the sealing material
is configured with
a higher concentration at a position adjacent to the bath-vapor interface, as
compared to either
the upper end in the vapor phase or the lower end in the bath of the anode
body.
[0028] In some embodiments of the instant disclosure, the concentration of
sealing material
from a position just below the bath-vapor interface to a position adjacent to
the upper end of the
anode is higher than the portion of sealing material in the submerged portion
of the anode body.
[0029] In one aspect of the instant disclosure, an electrolysis cell,
comprising: a cell structure
comprising a cell bottom and a cell sidewall, wherein the cell sidewall is
configured to
perimetrically surround the cell bottom and extend in an upward direction from
the cell bottom
to define a control volume, wherein the control volume is configured to retain
a molten
electrolyte bath; and an anode assembly configured to direct current into the
molten electrolyte
bath, wherein the anode assembly comprises: an anode support; and an anode
apparatus
mechanically attached to the anode support, wherein the anode apparatus
comprises: (a) an
anode body comprising at least one outer sidewall, wherein the outer sidewall
is configured to
define the anode shape and to perimetrically surround a hole in the anode
body, wherein the
hole comprises an upper opening in the top of the anode body and wherein the
hole axially
extends into the anode body; and (b) an pin comprising: a first end connected
to a current
supply, and a second end opposite the first end, wherein the second end is
configured to extend
down into the upper end of the anode body and into the hole of the anode body;
and (c) a
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sealing material configured to cover at least a portion of at least one of the
following: an inner
sidewall of the anode body; the top surface of the anode body; the pin; and
the anode support.
BRIEF DESCRIPTION OF THE DRAWINGS
[0030] Embodiments of the present invention, briefly summarized above and
discussed in
greater detail below, can be understood by reference to the illustrative
embodiments of the
invention depicted in the appended drawings. It is to be noted, however, that
the appended
drawings illustrate only typical embodiments of this invention and are
therefore not to be
considered limiting of its scope, for the invention may admit to other equally
effective
embodiments.
[0031] Figure 1 depicts a block diagram of a generic anode assembly in
accordance an
embodiment of the instant disclosure.
[0032] Figure 2 depicts a schematic cut-away side view of an anode
apparatus in accordance
with an embodiment of the instant disclosure.
[0033] Figure 3 depicts a cut-away side view of an embodiment of an anode
apparatus of the
instant disclosure.
[0034] Figure 4 depicts a cut-away side view of an embodiment of an anode
apparatus of the
instant disclosure.
[0035] Figure 5 depicts a cut-away side view of an embodiment of an anode
apparatus of the
instant disclosure.
[0036] Figure 6 depicts a cut-away side view of an embodiment of an anode
apparatus of the
instant disclosure.
[0037] Figure 7 depicts a cut-away side view of an embodiment of an anode
apparatus of the
instant disclosure.
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[0038] Figure 8 depicts a cut-away side view of an embodiment of an anode
apparatus of the
instant disclosure.
[0039] Figure 9 depicts a cut-away side view of an embodiment of an anode
apparatus of the
instant disclosure.
[0040] Figure 10 depicts a cut-away side view of an embodiment of an anode
apparatus of
the instant disclosure.
[0041] Figure 11 depicts a cut-away side view of an embodiment of an anode
apparatus of
the instant disclosure.
[0042] Figure 12 depicts a cut-away side view of an embodiment of an anode
apparatus of
the instant disclosure.
[0043] Figure 13 depicts a cut-away side view of an embodiment of an anode
apparatus of
the instant disclosure.
[0044] Figure 14 depicts a cut-away side view of an embodiment of an anode
apparatus of
the instant disclosure.
[0045] Figure 15 depicts a cut-away side view of an embodiment of an anode
apparatus of
the instant disclosure.
[0046] To facilitate understanding, identical reference numerals have been
used, where
possible, to designate identical elements that are common to the figures. The
figures are not
drawn to scale and may be simplified for clarity. It is contemplated that
elements and features of
one embodiment may be beneficially incorporated in other embodiments without
further
recitation.
DETAILED DESCRIPTION
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[0047] Figure 1 depicts a block diagram of a generic anode assembly 10 in
accordance an
embodiment of the instant disclosure. In some embodiments of the instant
disclosure, the anode
assembly 10 comprises an anode support and an anode apparatus. In some
embodiments, the
anode apparatus is mechanically attached to the anode support (e.g. refractory
package,
structural support member, combination thereof). In some embodiments, the
anode apparatus
comprises: an anode body, a pin, and a sealing material.
[0048] In some embodiments, the anode assembly is a part of an electrolysis
cell comprising
a cell structure comprising a cell bottom and a cell sidewall. In some
embodiments, the cell
sidewall is configured to perimetrically surround the cell bottom and extend
in an upward
direction from the cell bottom to define a control volume. In some
embodiments, the control
volume is configured to retain a molten electrolyte bath.
[0049] In some embodiments, the anode body comprises at least one outer
sidewall. In some
embodiments, the outer sidewall is configured to define a shape of the anode
body and to
perimetrically surround a hole in the anode body. In some embodiments, the
hole comprises an
upper opening in a top surface of the anode body and the hole axially extends
into the anode
body. In some embodiments, the pin comprises a first end and a second end. In
some
embodiments, the first end is connected to a current supply. In some
embodiments, the second
end is opposite the first end. In some embodiments, the second end extends
downward into the
upper end of the anode body and into the hole of the anode body.
[0050] In some embodiments, the sealing material is configured to cover at
least a portion of
at least one of the following: an inner sidewall of the anode body; the top
surface of the anode
body; the pin; and the anode support. In some embodiments, the sealing
material is configured
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to cover at least a portion of at least one of the following: an inner
sidewall of the anode body;
the pin; and a filler material.
[0051] In some embodiments, the sealing material is configured to reduce,
prevent, or
eliminate corrosive constituents of the electrolysis process from contacting
(and corroding) (1)
the pin and/or (2) the mechanical attachment site of the anode body to the
pin. In some
embodiments, the sealing material is configured to be tailored (i.e. matched)
to the composition
of the anode body. In some embodiments, the sealing material is configured
such that aggregate
present in the sealing material is compositionally consistent with the anode
body composition.
In some embodiments, the sealing material is configured to substantially
overlap with the
coefficient of thermal expansion of the anode body.
[0052] In some embodiments, the sealing material is inserted into the anode
body (between
the inside of the anode body and the pin) as a particulate material. In some
embodiments, the
sealing material is inserted into the anode body (between the inside of the
anode body and the
pin) as a liquid/slurry applied to the anode body or pin. In some embodiments,
when the sealing
material is inserted into/added onto the anode body, it undergoes a chemical
and/or thermal cure
in order to form a solid sealing material. In some embodiments, the sealing
material is
positioned between the pin and the anode body.
[0053] In some embodiments, a sealing material is utilized around the upper
end of the anode
body, surrounding the outer surface of the pin and contacting the anode body
(e.g. inner portion
of the hole in the anode body, top surface of the anode body, upper portion of
the anode body,
and/or combinations thereof). In some embodiments, the sealing material
comprises a cement.
In some embodiments, the sealing material comprises a grout. In some
embodiments, the sealing
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material is configured to prevent corrosive vapors from entering into the
inner surface of the
anode body, proximal to the portion of the pin that is retained within the
anode body.
[0054] In some embodiments cement includes aggregate and a binder or
matrix. In some
embodiments, the aggregate is replaced with a sealing material in accordance
with the instant
disclosure (e.g. utilizing the commercially available binder and/or matrix).
In some
embodiments, the matrix or binder is replaced with a sealing material in
accordance with the
instant disclosure (e.g. utilizing the commercially available aggregate). In
some embodiments,
the matrix or binder and aggregate is replaced with a sealing material in
accordance with the
instant disclosure. Some non-limiting commercial examples of binders,
matrices, aggregates,
and/or combinations thereof include: A1203, SiO2, MgO, CaO, or the like.
[0055] In some embodiments, the sealing material includes at least one of:
water, polymers,
organics, dispersants, and/or diluents in order to promote a flowable sealing
material such that
the sealing material is formable/flowable into its desired location (e.g. in
the anode assembly
and/or anode body).
[0056] In some embodiments, the sealing material is configured to enclose
the conductive
filler into the anode body (i.e. between the inner sidewall of the anode body
and the pin). In
some embodiments, the sealing material is configured to provide a mechanical
attachment of the
anode body to the pin. In some embodiments, the sealing material is configured
to provide
structural support to the anode assembly and/or anode apparatus.
[0057] In some embodiments, the sealing material is cast in place. In some
embodiments, an
accelerant is utilized in combination with the sealing material in order to
reduce the curing time.
In some embodiments, the sealing material is pre-cast and screwed into the
anode body (e.g.
upper portion of the anode body) In some embodiments, the sealing material is
sintered into
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place while/during the sintering of the green form anode body into the final
anode body/anode
assembly (anode body, pin, and sealing material). In some embodiments, the
sealing material is
retained above the hole, proximal to the top surface of the upper end of the
anode. In some
embodiments, sealing material is retained in the hole (i.e. extending between
the pin and the
inner sidewall of the anode body) and above the top surface of the anode body.
[0058] In some embodiments, above the top surface of the anode body
includes extending
along the pin (i.e. portion of the pin that extends out of the anode body). In
some embodiments,
above the top surface of the anode body includes extending along the pin and
into the anode
support (i.e. portion of the pin that extends into the anode support, where
the pin is mechanically
attached). In some embodiments, above the top surface includes extending
across the top surface
of the upper portion of the anode body. In some embodiments, above the top
surface includes
extending across the top surface and extending down around the outer sidewall
of the anode
body (i.e. creating a collar around the upper end of the anode surface).
[0059] As used herein, "anode" means the positive electrode (or terminal)
by which current
enters an electrolytic cell. In some embodiments, the anodes (i.e. anode
bodies) are constructed
of electrically conductive materials. In some embodiments, the anode comprises
an inert anode
(e.g. non-reactive, dimensionally stable, and/or having a dissolution rate
(e.g. at the cell
operating parameters) less than that of a corresponding carbon anode).
[0060] As used herein, "anode body" means: the physical structure of the
anode (e.g
including the top, bottom, and sidewall(s)). Some non-limiting examples of
anode materials
include: metals, metal alloys, metal oxides, ceramics, cermets, and
combinations thereof. In
some embodiments, the anode body is oval, cylindrical, rectangular, square,
plate-shaped
(generally planar), other geometrical shapes (e.g. triangular, pentagonal,
hexagonal, and the like
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[0061] As used herein, "anode apparatus" means the anode or positive
electrode in the
electrolysis cell. In some embodiments, the anode apparatus includes: the
anode body and
anode pin, in some embodiments, the anode apparatus includes the anode body,
anode pin, and
filler/sealing materials (e.g. individually, or in combination: conductive
filler and/or sealing
material).
[0062] As used herein, "anode assembly" means at least one anode apparatus
(anode body,
pin, conductive filler, and/or sealing material) and an anode support, where
the at least one
anode apparatus is connected (e.g. mechanically and/or electrically) to the
anode support.
[0063] As used herein, "support" means a member that maintains another
object(s) in place.
In some embodiments, the support is the structure that retains the anode(s) in
place. In one
embodiment, the support facilitates the electrical connection of the
electrical bus work to the
anode(s). In one embodiment, the support is constructed of a material that is
resistant to attack
from the corrosive bath. For example, the support is constructed of insulating
material,
including, for example refractory material. In some embodiments, multiple
anodes are
connected (e.g. mechanically and electrically) to the support (e.g. removably
attached), which is
adjustable and can be raised, lowered, or otherwise moved in the cell. In some
embodiments,
the anode support includes a refractory material (e.g. block or assembly),
other bath resistant
materials, rail or beam support members, vertical adjustment components and
apparatuses,
and/or electrical bus work.
[0064] As used herein, "electrical bus work" refers to the electrical
connectors of one or
more component. For example, the anode, cathode, and/or other cell components
can have
electrical bus work to connect the components together. In some embodiments,
the electrical
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bus work includes pin connectors in the anodes, the wiring to connect the
anodes and/or
cathodes, electrical circuits for (or between) various cell components, and
combinations thereof.
[0065] As used herein, "sidewall" means: a surface that forms the wall of
an object.
[0066] As used herein, "perimetrically surrounding" means: surrounding the
outside edge of
a surface. As a non-limiting example, perimetrically surrounding includes
different geometries
(e.g. concentrically surrounding, circumscribing) and the like.
[0067] As used herein, "electrolyte bath" (sometimes interchangeably
referred to as bath)
refers to a liquefied bath having at least one species of metal to be reduced
(e.g. via an
electrolysis process). A non-limiting example of the electrolytic bath
composition (in an
aluminum electrolysis cell) includes: NaF-A1F3, NaF, A1F3, CaF2, MgF2, LiF,
KF, and
combinations thereof --with dissolved alumina.
[0068] As used herein, "molten" means in a flowable form (e.g. liquid)
through the
application of heat. As a non-limiting example, the electrolytic bath is in
molten form (e.g. at
least about 750 C). As another example, the metal product that forms at the
bottom of the cell
(e.g. sometimes called a "metal pad") is in molten form.
[0069] In some embodiments, the molten electrolyte bath/cell operating
temperature is: at
least about 750 C; at least about 800 C; at least about 850 C; at least about
900 C; at least
about 950 C; or at least about 975 C. In some embodiments, the molten
electrolyte bath/cell
operating temperature is: not greater than about 750 C; not greater than about
800 C; not
greater than about 850 C; not greater than about 900 C; not greater than about
950 C; or not
greater than about 975 C.
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[0070] As used herein, "vapor" means: a substance that is in the form of a
gas. hi some
embodiments, vapor comprises ambient gas mixed with caustic and/or corrosive
exhaust from
the electrolysis process.
[0071] As used herein, "vapor space" refers to the head space in an
electrolysis cell, above
the surface of the electrolyte bath.
[0072] As used herein, "interface" refers to a surface regarded as the
common boundary of
two bodies, spaces, or phases.
[0073] As used herein, "bath-vapor interface" refers to the surface of
bath, which is the
boundary of two phases, the vapor space and the liquid (molten) electrolyte
bath.
[0074] As used herein, "metal product" means the product which is produced
by electrolysis.
In one embodiment, the metal product forms at the bottom of an electrolysis
cell as a metal pad.
Some non-limiting examples of metal products include: aluminum, nickel,
magnesium, copper,
zinc, and rare earth metals.
[0075] As used herein, "at least" means greater than or equal to.
[0076] As used herein, "hole" means: an opening into something.
[0077] As used herein, "pin" means: a piece of material used to attach
things together. In
some embodiments, the pin is an electrically conductive material. In some
embodiments, the pin
is configured to electrically connect the anode body to the electrical buswork
in order to provide
current to an electrolysis cell (via the anode). In some embodiments, a first
end of the pin is
configured to fit into/be retained within an anode support (e.g. anode support
and at least one
anode apparatus is an anode assembly)In some embodiments, the pin is
configured to overlap
with the anode body. In some embodiments, the pin is configured to
structurally support the
anode body, as it is attached to and suspended from the pin. In some
embodiments, the pin is
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stainless steel, nickel, nickel alloy, Inconel, or a corrosion protected
steel. In some
embodiments, the pin is configured to extend into the anode body (e.g. into a
hole) to a certain
depth, in order to provide mechanical support and electrical communication to
the anode body.
In some embodiments, the length of the pin is sufficient (long enough) to
provide mechanical
support to the anode body and sufficient to (short enough) to prevent
corrosion on the pin inside
the hole (i.e. locate the pin above the bath-vapor interface) In some
embodiments, the pin is
oval, cylindrical, rectangular, square, plate-shaped (generally planar), other
geometrical shapes
(e.g. triangular, pentagonal, hexagonal, and the like).
[0078] As
used herein, "attach" means: to connect two or more things together. In some
embodiments, the pin is attached to the anode body. In some embodiments, the
pin is
mechanically attached to the anode body by: fastener(s), screw(s), a threaded
configuration (e.g.
on pin), a mating threaded configuration (e.g. on inner surface of hole in
anode body and on
pin), or the like. In some embodiments, the pin is attached to the anode body
via welding (e.g.
resistance welding or other types of welding). In some embodiments, the pin is
attached to the
anode body via a direct sinter (i.e. sintering the anode body onto the pin
directly).
[0079] As
used herein, "electrically conductive material" means: a material that has an
ability to move electricity (or heat) from one place to another.
[0080] As
used herein, "filler" means: a material that fills a space or void between two
other
objects. In some embodiments, the filler is configured to connect (e.g.,
electrically connect) the
anode body to the pin. In some embodiments, non-limiting examples of filler
include: a
particulate material, a liquid/slurry material, and combinations thereof. In
some embodiments,
the filler is incorporated/inserted into the desired location in a flowable
form, which then
hardens over time to yield a solid filler material.
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[0081] In some embodiments, the filler is a conductive material, also
referred to as
conductive filler. In some embodiments, the filler is configured to
electrically connect the pin to
the anode body. Non-limiting examples of electrically conductive filler
materials include: iron
oxides (hematite, magnetite, wustite), copper, copper alloys, nickel, nickel
alloys, precious
metals, (e.g., Pt, Pd, Ag, Au) and combinations thereof.
[0082] As used herein, "sealing material" means: a substance used to close
or secure an
object or component (e.g. in order to reduce, prevent, and/or eliminate the
transmittal of vapor
or liquid to the object or component). In some embodiments, the filler is
configured to seal the
upper portion hole in the anode body from corrosive vapors present in the
vapor space. Non-
limiting examples of a sealing material include: castable cement, concrete,
grout, mortar, and
combinations thereof.
[0083] In some embodiments, the sealing material is a substance/material
that includes at
least two components: (1) aggregate and (2) matrix cement (e.g., grout), where
the aggregate
includes large and/or fine aggregate sizes. In some embodiments, the sealing
material is applied
to an area in order to act as an adhesive, as it is configured to adhere
components together upon
hardening.
[0084] As used herein, "castable" means: a substance/material that includes
at least two
components: aggregate and cement, where the aggregate includes large and fine
aggregate sizes.
In some embodiments, the castable is applied to an area such in order to act
as an adhesive, as it
is configured to adhere components together upon hardening.
[0085] As used herein, "grout" means: a castable with matrix and finer
aggregate (as
compared to concrete or cement). In some embodiments, the grout includes a
viscosity
configured to fill cracks and crevices in the anode assembly and/or anode
apparatus. In some
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embodiments, the grout is configured as a bonding material that hardens in
place and is used to
bind things together.
[0086] As
used herein, "particulate material" means: a material composed of particles.
In
some embodiments, the particulate material is electrically conductive. In one
embodiment, the
particulate material is copper shot. Other non-limiting examples of
particulate materials
include: precious metals (e.g. platinum, palladium, gold, silver, and
combinations thereof). As
non-limiting examples, the particulate material includes: metal foam (e.g. Cu
foam), large or
small shot (e.g., configured to fit between the pin and the anode body and/or
in the anode hole),
paint, and/or powder. Other sizes and shapes of particulate materials are
utilizable, provided
they fill the void between the pin and the anode body (or portion below the
pin, in the hole of
the anode body) and promote an electrical connection between the anode body
and the pin to
provide current to the anode.
[0087] In
some embodiments, the sealing material is configured to reduce, prevent, or
eliminate corrosion from the anode apparatus (e.g. pin, anode body, conductive
filler, and/or
combinations thereof).
[0088] In
some embodiments, the sealing material includes aggregate that is configured
as
an anode-matched aggregate. In some embodiments, the sealing material is
configured as an off-
gas compatible aggregate (e.g., configured to react but not substantially
degrade the
effectiveness of the sealing material.
[0089] As
used herein, "anode-matched aggregate" (sometimes referred to as off gas
compatible aggregate) means aggregate that has an overlapping performance
characteristics as
the anode composition. In some embodiments, anode matched aggregate is
aggregate having the
same compositional constituent as the anode body (e.g. hematite, magnetite).
In some
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embodiments, anode matched aggregate is aggregate having a composition that is
consistent
with at least one major species (or compound) present in the anode (e.g. >30
wt. %). In some
embodiments, anode matched aggregate is aggregate having a compound or
component of an
off-gas compatible aggregate (e.g.
NiFe204, NiO, CuA1204, Cu0). Some non-limiting
examples of aggregating sealing materials include: spinels, magnetite,
hematite, copper
aluminate, nickel ferrite, or tin oxide_ and combinations thereof.
[0090] In
some embodiments, the sealing material comprises a castable ceramic or ceitnet
plug, where the aggregates (or at least a portion thereof) are replaced with
an anode-matched
aggregate and/or an off-gas compatible aggregate as the primary seal. As a non-
limiting
example, the sealing material comprises a castable ceramic or cermet
containing A1203, SiO2,
MgO, CaO, Na2O, and combinations thereof, where at least some of the silicates
and/or
aluminates are replaced with an aggregate specifically tailored/matched to the
anode body
and/or pin material, in accordance with the instant disclosure.
[0091] In
some embodiments, the aggregate is about 40 wt. % of the sealing material
(e.g. as
cured). In some embodiments, the matrix/binder is about 60 wt. % of the
sealing material (e.g.
as cured). In some embodiments, the aggregate is from about 5 wt. % to 100 wt.
% of the
sealing material. In some embodiments, the binder/matrix is from about 5 wt. %
to 100 wt. % of
the sealing material.
[0092] In
some embodiments, the percentage and/or quantity of aggregate or binder/matrix
is
quantified via SEM (scanning electron microscope) or EDS (energy dispersive
spectroscopy),
via viewing/observing a polished cross-section of sealing material. In this
embodiment, EDS is
configured to provide the chemical make-up of the cross-section.
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[0093] In some embodiments, the filler is conductive filler (e.g.
configured to promote
electrical communication between the pin and the anode body)
[0094] In some embodiments, within the hole, where the filler is configured
to extend
between the inner sidewall of the anode body and the pin (e.g. beneath the
sealing material).
[0095] In some embodiments, the sealing material comprises a thickness of:
from 1 mm to
not greater than 50 mm.
[0096] In some embodiments, the sealing material has a thickness of: at
least 1 mm; at least 2
mm; at least 3 mm; at least 4 mm; at least 5 mm; at least 6 mm; at least 7mm;
at least 8 mm; at
least 9 mm; or at least 10 mm.
[0097] In some embodiments, the sealing material has a thickness of: at
least about 5 mm; at
least about 10 mm; at least about 15 mm; at least about 20 mm; at least about
25 mm; at least
about 30 mm; at least about 35 mm; at least about 40 mm; at least about 45 mm;
or at least
about 50 mm.
[0098] In some embodiments, the sealing material has a thickness of: not
greater than 1 mm;
not greater than 2 mm; not greater than 3 mm; not greater than 4 mm; not
greater than 5 mm;
not greater than 6 mm; not greater than 7mm; not greater than 8 mm; not
greater than 9 mm; or
not greater than 10 mm.
[0099] In some embodiments, the sealing material has a thickness of: not
greater than about
mm; not greater than about 10 mm; not greater than about 15 mm; not greater
than about 20
mm; not greater than about 25 mm; not greater than about 30 mm; not greater
than about 35
mm; not greater than about 40 mm; not greater than about 45 mm; or not greater
than about 50
mm.
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[00100] In some embodiments, the sealing material has a thickness of: at
least about 50 mm;
at least about 100 mm; at least about 150 mm; at least about 200 mm; or at
least about 250 mm.
In some embodiments, the sealing material has a thickness of: not greater than
about 50 mm; not
greater than about 100 mm; not greater than about 150 mm; not greater than
about 200 mm; or
not greater than about 250 mm.
[00101] In some embodiments, the sealing material is configured as a
coating applied to the
anode pin. In some embodiments, the sealing material is configured as a
coating to the inner
surface of the anode body. In some embodiments, the sealing material is
configured as a coating
applied to the upper surface (e.g. top end) of the anode body.
[00102] In some embodiments, the sealing material is applied to one or more
components of
the anode apparatus and/or anode assembly via washing (e.g., painting) the
component directly
with the material.
[00103] In some embodiments, the sealing material is applied to one or more
components of
the anode apparatus and/or anode assembly via applying the sealing material to
the
component(s) as a slurry/suspension in combination with a binder or liquid.
[00104] In some embodiments, the sealing material is applied to one or more
of the anode
apparatus and the pin via applying/directing the aggregate into the desired
located (e.g. pouring
powder, particulate, or pellets), followed by adding the matrix, mechanically
agitating/combining, and allowing the sealing material to set/dry.
[00105] In some embodiments, the sealing material is applied to one or more
of the anode
apparatus and the pin via spraying.
[00106] In some embodiments, the sealing material is applied to one or more
of the anode
apparatus and the pin via gunning.
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[00107] In some embodiments, the sealing material is applied to one or more
of the anode
apparatus and the pin via slip casting. In some embodiments, the sealing
material is applied to
one or more of the anode apparatus and the pin via pressure casting. In some
embodiments, the
sealing material is applied to one or more of the anode apparatus and the pin
via vacuum
casting. In some embodiments, the sealing material is applied to one or more
of the anode
apparatus and the pin via slurry pressing. In some embodiments, the sealing
material is applied
to one or more of the anode apparatus and the pin via gel casting. In some
embodiments, the
sealing material is applied to one or more of the anode apparatus and the pin
via electrophoretic
casting.
[00108] In some embodiments, the anode matched aggregate and/or off-gas
compatible
aggregate is present in mixed form with the sealing material, where the
aggregate is from at
least 1 vol. % sealing material to not greater than 99.5 vol. % sealing
material.
[00109] In some embodiments, the aggregate is present in mixed form with
the sealing
material, where the aggregate is from at least 1 vol. % sealing material to
not greater than 100
vol. % sealing material.
[00110] As non-limiting examples, the aggregate comprises: at least 1 vol.
%; at least 5 vol.
%; at least 10 vol. ?/0; at least 15 vol. /0; at least 20 vol. /0; at least
25 vol. /0; at least 30 vol. %;
at least about 35 vol. %; at least 40 vol. ,43; at least 45 vol. %; at least
50 vol. %; at least 55 vol.
%; at least 60 vol. %; at least 65 vol. %; at least 70 vol.%; at least 75 vol.
%; at least 80 vol %;
at least 85 vol. %; at least 90 vol. %; or at least 95 vol. %; or at least 99
vol. % of the sealing
material.
[00111] As non-limiting examples, the aggregate comprises: not greater than
1 vol. %, not
greater than 5 vol. %; not greater than 10 vol. %; not greater than 15 vol. %;
not greater than 20
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vol. %; not greater than 25 vol. %; not greater than 30 vol. %; not greater
than about 35 vol. 9/0;
not greater than 40 vol. %; not greater than 45 vol. %; not greater than 50
vol %; not greater
than 55 vol. %; not greater than 60 vol. %; not greater than 65 vol. %; not
greater than 70 vol.%;
not greater than 75 vol. %; not greater than 80 vol. %; not greater than 85
vol. %; not greater
than 90 vol. %; or not greater than 95 vol. %; or not greater than 99 vol. %
of the sealing
material.
[00112] In some embodiments, a mixture of anode matched aggregate and/or off-
gas
compatible aggregate and sealing material includes an amount of aggregate
which is sufficient
to maintain the ability of the sealing material to adhere components of the
anode apparatus (e.g.,
anode body to pin) and/or anode assembly together (e.g., pin to anode
support).
[00113] In some embodiments, the sealing material is applied to the anode
hole (i.e. between
the pin and the inner surface of the anode body) in a gradient, such that the
concentration of
sealing material (with anode-matched aggregate and/or off-gas compatible
aggregate) varies in a
radial direction (i.e. differs from a position adjacent to the pin vs. a
position adjacent to the
anode sidewall).
[00114] In one embodiment, the gradient is configured such that the
concentration of sealing
material is (with anode-matched aggregate and/or off-gas compatible aggregate)
higher adjacent
to the pin as compared to adjacent to the inner surface of the anode body.
[00115] In one embodiment, the gradient is configured such that the
concentration of sealing
material (with anode-matched aggregate and/or off-gas compatible aggregate) is
lower adjacent
to the pin as compared to adjacent to the inner surface of the anode body.
[00116] In some embodiments, the sealing material is applied to the anode
hole (i.e. between
the pin and the inner surface of the anode body) in a gradient, such that the
concentration of
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sealing material varies in a lateral direction (i.e. differs from a position
adjacent to the opening
of the hole/upper surface of the anode body as compared to a position adjacent
to the lower end
of the anode body).
[00117] In one embodiment, the gradient is configured such that the
concentration of sealing
material is higher adjacent to the upper end as compared to adjacent to the
lower end of the
anode body.
[00118] In one embodiment, the gradient is configured such that the
concentration of sealing
material is lower adjacent to the upper end as compared to adjacent to the
lower end of the
anode body.
[00119] In some embodiments, the sealing material is configured with a
higher concentration
at a position adjacent to the bath-vapor interface, as compared to either the
upper end (in the
vapor phase) or lower end (in the bath) of the anode body.
[00120] In some embodiments, the concentration of sealing material from a
position just
below the bath-vapor interface to a position adjacent to the upper end of the
anode is higher than
the portion of (anode-matched aggregate and/or off-gas compatible aggregate in
the) sealing
material in the submerged portion of the anode body (e.g. submerged below the
bath-vapor
interface).
[00121] Figures 2-15 depict schematic cut-away side view of an exemplary
anode apparatus in
accordance with some embodiments of the instant disclosure. Figure 2 depicts
an anode
apparatus wherein the sealing material 50 covers a portion of the pin 12 in
vapor space 24, the
opening 32 and an entire top surface of the anode body 30. Figure 3 depicts an
anode apparatus
wherein the sealing material 50 covers an entirety of the pin 12 in vapor
space 24, the opening
32 and a portion of the top surface of the anode body 30. Figure 4 depicts an
anode apparatus
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wherein the sealing material 50 covers a portion of the pin 12 in vapor space
24, the opening 32,
and a portion of the top surface of the anode body 30. Figure 5 depicts an
anode apparatus
wherein the sealing material 50 covers an entirety of the pin 12 above the top
surface of the
anode body 30 (i.e. within the vapor space 24 and refractory portion 18), the
opening 32, and a
portion of the top surface of the anode body 30.
[00122] Figure 6 depicts an anode apparatus wherein the sealing material 50
covers an
entirety of the pin 12 in vapor space 24, the opening 32 and an entire top
surface of the anode
body 30. In Figure 6, the sealing material 50 extends beyond a peripheral edge
of the top
surface of the anode body and covers a portion of the sidewall 40 of the anode
body 30. Figure 7
depicts an anode apparatus wherein the sealing material 50 covers a portion of
the pin 12 in
vapor space 24, the opening 32, and an entire top surface of the anode body
30. In Figure 7, the
sealing material 50 extends beyond a peripheral edge of the top surface of the
anode body and
covers a portion of the sidewall 40 of the anode body 30.
[00123] Figure 8 depicts an anode apparatus wherein the sealing material 50
covers an
entirety of the pin 12 in vapor space 24. The sealing material 50 covers
opening 32 and an
entire top surface of the anode body 30. The sealing material 50 extends
beyond a peripheral
edge of the top surface of the anode body and covers a portion of the sidewall
40 of the anode
body 30. Sealing material 50 is also disposed between the vapor space 24 and
the refractory 18
to prevent corrosive chemicals from corroding exposed portions of the pin 12
(i.e. not covered
by sealing material 50).
[00124] Figure 9 depicts an anode apparatus wherein the sealing material 50
covers a portion
of the pin 12 in vapor space 24, the opening 32, and an entire top surface of
the anode body 30.
The sealing material 50 extends beyond a peripheral edge of the top surface of
the anode body
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and covers a portion of the sidewall 40 of the anode body 30. A portion of the
pin 12 in the
vapor phase 24 is not covered by sealing material 50. Sealing material 50 is
also disposed
between the vapor space 24 and the refractory 18 to prevent corrosive
chemicals from corroding
exposed portions of the pin 12 in the refractory 18.
[00125] Figure 10 depicts an anode apparatus wherein the sealing material
50 covers an
entirety of the pin 12 in vapor space 24. The sealing material 50 covers
opening 32 and an
entire top surface of the anode body 30. The sealing material 50 does not
extend beyond a
peripheral edge of the top surface of the anode body to cover a portion of the
sidewall 40 of the
anode body 30. Sealing material 50 is also disposed between the vapor space 24
and the
refractory 18 to prevent corrosive chemicals from corroding exposed portions
of the pin 12 (i.e.
not covered by sealing material 50).
[00126] Figure 11 depicts an anode apparatus wherein the sealing material
50 covers a portion
of the pin 12 in vapor space 24, the opening 32, and an entire top surface of
the anode body 30.
The sealing material 50 extends beyond a peripheral edge of the top surface of
the anode body
and covers a portion of the sidewall 40 of the anode body 30. The sealing
material extends
down the sidewall 40 of the anode body 30 proximate to the interface 22.
[00127] Figure 12 depicts an anode apparatus wherein the sealing material
50 covers a portion
of the pin 12 in vapor space 24, the opening 32 and an entire top surface of
the anode body 30.
[00128] Figure 13 depict an anode apparatus wherein the sealing material 50
covers a portion
of the pin 12 in vapor space 24, the opening 32 and an entire top surface of
the anode body 30.
The sealing material is also disposed within the hole 34 to cover a portion of
the pin 12 within
the anode body 30. The sealing material 50 covers a portion of the pin 12
within the anode
body 30 that is above the interface 22.
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[00129] Figure 14 depicts an anode apparatus wherein the sealing material
50 is disposed
within the hole 34 to cover a portion of the pin 12 within the anode body 30.
The sealing
material 50 covers a portion of the pin 12 within the anode body 30 that is
above the interface
22.
[00130] Figure 15 depicts an anode apparatus wherein the sealing material
50 is disposed
within the hole 34 to cover a portion of the pin 12 within the anode body 30.
The sealing
material 50 covers a portion of the pin 12 within the anode body 30 that is
above the interface
22. A filler material is disposed within the hole 34 below the sealing
material 50.
[00131] Reference will now be made in detail to prophetic examples, which
(in combination
with the accompanying drawings and previous descriptions thereof) at least
partially assist in
illustrating various pertinent embodiments of the present invention.
[00132] Example: Prophetic Anode Manufacture:
[00133] Non-limiting examples of producing the anode body include: press
sintering, fuse
casting, and casting, which is disclosed in corresponding US Patent 7,235,161,
which contents
are incorporated by reference herein by their entirety.
[00134] Once the anode body is formed, the pin and filler materials, if
being used, are
incorporated into the anode body. For example, if a filler (e.g. conductive
filler) is utilized, the
pin is placed in the hole of the anode body and filler (e.g. in the form of
particulate material) is
inserted into the void between the pin and the inner surface of the hole in
the anode body. Then
the sealing material (i.e., in order to provide a mechanical attachment and/or
seal the pin and/or
filler material into the hole in the anode body), is added to the upper end of
the anode body. In
some embodiments, the sealing material is configured to extend at least
partially into the hole in
the anode body. In some embodiments, the sealing material is configured to sit
on top of the
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anode body, proximal to the upper end of the hole, and surrounding the pin as
it extends upward
from the anode body. In some embodiments, the sealing material is placed on
top of the anode
body in a position surrounding the pin.
[00135] In some embodiments, the sealing material is configured to extend a
portion of the
way into the hole at the upper end of the anode. In some embodiments, the
sealing material is
configured to cover the top portion of the anode body. In some embodiments,
the sealing
material is configured to contact at least a portion of the outer perimetrical
sidewall of the anode
body. In some embodiments, the sealing material is configured to contact the
pin, the inner
portion of the anode body (hole), the upper portion/top surface of the anode
body, and the upper
portion of at least a portion of the outside perimetrical wall of the anode
body.
[00136] While various embodiments of the present invention have been
described in detail, it
is apparent that modifications and adaptations of those embodiments will occur
to those skilled
in the art. However, it is to be expressly understood that such modifications
and adaptations are
within the spirit and scope of the present invention.
[00137] Prophetic Comparative Example:
[00138] Two anode assemblies (AA1 = prior art and AA2 = an embodiment in
accordance
with the instant disclosure) are made with: the same anode body dimensions and
composition in
accordance with that set out in disclosures of US Patent Nos. 7,507,322 and
7,235,161; the same
pin material (copper or copper alloy); and different sealing materials.
[00139] In AA1 the first instance (prior art), the sealing material is in
accordance with the
disclosure of US 7,169,270. In the second instance (instant disclosure), the
sealing material has
wt. % to 100 wt. % the sealing material is a castable ceramic or cermet
containing A1203,
SiO2, MgO, CaO, Na2O, and combinations thereof, where at least some of the
silicate and/or
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aluminate aggregates in the sealing material (e.g. castable ceramic) are
replaced with a
magnetite aggregate (e.g. anode-matched/anode compatible aggregate),
configured with
comparable sizing as the aggregate appropriate sizing as the aggregate in the
prior art run.
[00140] Both anode assemblies are configured as the embodiment shown in Figure
2. Both
anode assemblies were incorporated into an aluminum electrolysis cell and
operated as
electrodes (anodes) extending across the bath-vapor interface for a sufficient
length of time in
order to evaluate whether any reactions occur as a result of the interaction
of the reactive species
present in the vapor space of the cell with the sealing material and/or
components thereof.
[00141] Anode assemblies are pulled out of the cell and evaluated in order
to evaluate and/or
quantify corrosion on the various anode apparatus components (e.g. sealing
material). It will be
found that the sealing material of AA2, i.e. sealing material with aggregate
tailored (i.e.
matched) to the anode body, performed better (exhibits less corrosion) than
the prior art sealing
material. Also, it will be found that the pin of AA2 performed better
(exhibits less corrosion)
than the pin of AA1 (the prior art anode apparatus).
[00142] Without being bound by a particular mechanism or theory, it is
believed that during
cell operating conditions (i.e. at elevated temperature and in a corrosive
environment in the
vapor space, which contains reactive fluoride gas, oxygen gas, and/or other
reactive vapor
species), the silica (e.g. SiO2 present as aggregate in the sealing material)
creates pockets of
reactive silicates available to interact with the reactive species present in
the vapor space.
[00143] Without being bound by a particular mechanism or theory, it is
believed that the
reactive silicates in the aggregates of the sealing material (i.e. AA1) will
react with fluoride gas
present in the vapor space of the cell, in turn creating silicon
tetrafluoride, which is in turn
corrosive to the pin. Without being bound by a particular mechanism or theory,
it is believed
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that as the reactive silicon fluoride species further interacts/reacts with
the pin, pockets or holes
are created in the sealing material (i.e. reducing the mechanical
strength/structural support of the
sealing material, and yielding pores/holes where the reactive species can
further penetrate into
and react with the sealing material, or other components of the anode
apparatus. Without being
bound by a particular mechanism or theory, as the silicon fluoride species
react with the pin
materials, initiation sites of corrosion occur on the pin and the structural
integrity of the anode
apparatus and/or the electrical efficiency of this component are further
reduced).
[00144] Without being bound by a particular mechanism or theory, it is
believed that during
cell operating conditions (i.e. at elevated temperature and in a corrosive
environment in the
vapor space, which contains reactive fluoride gas, oxygen gas, and/or other
reactive vapor
species), the magnetite aggregate (e.g. SiO2 and/or A1203 replacement in the
sealing material)
creates pockets of aggregate tailored to not undergo significant reactions
with the reactive
species (and thus, will not form pores in the sealing material and/or further
attribute to pin
corrosion).
[00145] Without being bound by a particular mechanism or theory, it is
believed that the
reactive silicates in the aggregates of the sealing material (i.e. AA1) will
react with fluoride gas
present in the vapor space of the cell, in turn creating silicon
tetrafluoride, which is in turn
corrosive to the pin.
[00146] Various ones of the inventive aspects noted hereinabove may be
combined to yield
inert anode apparatuses having a pin which provides a mechanical and
electrical connection to
the anode body, where the pin extends down into the hole of the anode body and
is positioned
such that the lower end of the pin is located above the vapor-bath interface.
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[00147] These and other aspects, advantages, and novel features of the
invention are set forth
in part in the description that follows and will become apparent to those
skilled in the art upon
examination of the following description and figures, or may be learned by
practicing the
invention.
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Reference Numbers
Anode Assembly 10
Pin 12
First end 14
Second end 16
Anode support 18
Current supply 20
Bath-vapor interface 22
Vapor space 24
Bath 26
Anode apparatus 28
Anode body 30
Upper opening 32
Anode inner sidewall (defining the hole) 34
Upper end of anode 36
Lower end of anode 38
Anode outer sidewall 40
Conductive filler 42
Particulate (conductive filler) material 44
Liquid/Slurry (conductive filler) material 46
Top surface of anode 48
Sealing material 50
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Aggregate 52 (large and/or small fines, e.g., aggregate particulate, powder)
Matrix/Binder material 54
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