Note: Descriptions are shown in the official language in which they were submitted.
1
TITANIUM-BASED COMPOSITIONS, METHODS OF MANUFACTURE AND USES
THEREOF
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001]
FIELD
[0002] The present disclosure broadly relates to titanium-based
compositions
as well as to titanium composites such as carbide-reinforced titanium
composites.
The present disclosure also relates to processes for the preparation of the
compositions and composites as well as to uses thereof.
BACKGROUND
[0003] The following is not an admission that anything discussed below is
part
of the prior art or part of the common general knowledge of a person skilled
in the
art.
[0004] Titanium composites with carbon reinforcement have been produced
using different processes. Most studies consolidated titanium-graphite powder
mixtures under high temperature extrusion or forging. However, the impact or
benefit of graphite addition on densification has never been demonstrated.
Moreover, studies involving pressureless sintering of titanium-graphite powder
mixtures were not intended to produce dense titanium-TiC based composites and
did
not report on the positive effect of graphite on densification. Indeed, many
of the
materials produced contain residual carbon or graphites or were highly porous.
[0005] Several processes to produce high-strength titanium matrix
composites
with carbon reinforcement have been developed. For example, powder metallurgy
carbon-reinforced titanium composites have been prepared using spark plasma
sintering and hot extrusion. Moreover, pure titanium powders have been coated
with
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unbundled multiwall carbon nanotubes resulting in materials exhibiting
increased
tensile strengths. The strengthening effect was attributed to the dispersion
of
unbundled carbon nanotubes and in-situ synthesized titanium carbide (TiC)
particles.
[0006] Composite materials have been prepared by a procedure comprising
the following: preparing a solution containing a surfactant having both
hydrophilicity
and hydrophobicity; preparing a solution containing fine carbonaceous
particles;
mixing of the solution with metallic particles; drying; thermal decomposition
and
removal of the solution; and sintering of the resulting powder. Composites
were
produced by discharge plasma sintering. The improvement of the mechanical
properties of the resulting materials was generally attributed to grain
refinement of
the titanium matrix (Hall-Petch effect), carbon solid solution hardening, and
a
dispersion strengthening effect by in-situ synthesized TiC.
[0007] Varying concentrations of graphite particles have also been used as
reinforcing materials. The resulting materials were subsequently consolidated
by
spark plasma sintering and extrusion. Grain refinement, yield and ultimate
tensile
strengths gradually increased with increasing graphite content.
SUMMARY
[0008] In an aspect, the present disclosure includes a composition
comprising:
a titanium-based powder; and
at least one of a carbon-based material and a binder;
wherein the composition comprises about 0.5 wt. (:)/0 to about 3.0 wt. %
of the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
[0009] In an aspect, the present disclosure includes a composition
comprising:
a titanium-based powder; and
a carbon-based material;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt. %
of the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
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[0010] In an aspect, the present disclosure includes a composition
comprising:
a titanium-based powder;
a carbon-based material; and
a binder;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt. %
of the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
[0011] In an aspect, the present disclosure includes a composite material
comprising:
a titanium metal matrix; and
titanium carbide dispersed in the matrix;
wherein the composite material comprises about 0.5 wt. % to about 3.0
wt. A) of carbon, based on the total weight of titanium and carbon in the
composite
material.
[0012] In an aspect, the present disclosure includes a composite material
comprising in-situ synthesized titanium carbide dispersed in a titanium metal
matrix,
wherein the titanium carbide is produced by powder injection molding and
wherein
the composite material comprises from about 0.5 wt. % to about 3.0 wt. % of
carbon,
based on the total weight of titanium and carbon in the composite material.
[0013] In an aspect, the present disclosure includes a titanium carbide
reinforced titanium composite, wherein the composite comprises about 0.5 wt. %
to
about 3.0 wt. % of carbon, based on the total weight of titanium and carbon in
the
composite material.
[0014] In an aspect, the present disclosure includes a method of
manufacturing a titanium-based composite material, the method comprising:
providing a composition comprising a titanium-based powder and at
least one of a carbon-based material and a binder; and
subjecting the composition to pressureless sintering;
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wherein the composition comprises about 0.5 wt. % to about 3.0 wt.
% of the carbon-based material, based on the total weight of the titanium-
based
powder and the carbon-based material.
[0015] In an
aspect, the present disclosure includes a method of
manufacturing a titanium-based composite material, the method comprising:
providing a composition comprising a titanium-based powder and at
least one of a carbon-based material and a binder; and
subjecting the composition to a powder injection molding process;
wherein the composition comprises about 0.5 wt. 13/0 to about 3.0 wt.
% of the carbon-based material, based on the total weight of the titanium-
based
powder and the carbon-based material.
[0016] In an
aspect, the present disclosure includes a process for producing a
titanium-based composite material, the process comprising:
mixing a titanium-based powder with a least one of a carbon-based
material and a binder to produce a composition comprising a titanium-based
powder
and at least one of a carbon-based material and a binder; and
subjecting the composition to pressureless sintering;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt.
% of the carbon-based material, based on the total weight of the titanium-
based
powder and the carbon-based material.
[0017] In an
aspect, the present disclosure includes a process for producing a
titanium-based composite material, the process comprising:
mixing a titanium-based powder with a least one of a carbon-based
material and a binder to produce a composition comprising a titanium-based
powder
and at least one of a carbon-based material and a binder; and
subjecting the composition to a powder injection molding process;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt. `3/0
of the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
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[0018] In an
aspect, the present disclosure includes a powder injection
molding process for in-situ synthesis of titanium carbide, the process
comprising:
mixing a titanium-based powder with at least one of a carbon-based
material and a binder to produce a composition comprising a titanium-based
powder
and at least one of a carbon-based material and a binder; and
feeding the composition into a powder injection molding apparatus to
provide a molded product;
debinding the molded product; and
heating the molded product under conditions sufficient to produce in-
situ titanium carbide, wherein the titanium carbide is dispersed within a
titanium
matrix;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt. %
of the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
[0019] In an
aspect, the present disclosure includes a process for promoting
densification of a titanium-based material, the process comprising:
providing a composition comprising a titanium-based powder and at
least one of a carbon-based material and a binder;
subjecting the composition to pressureless sintering;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt. % of
the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
[0020] In an
aspect, the present disclosure includes a process for promoting
densification of a titanium-based material, the process comprising:
providing a composition comprising a titanium-based powder and at
least one of a carbon-based material and a binder;
subjecting the composition to a powder injection molding process;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt. %
of the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
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[0021] In an
aspect, the present disclosure includes the use of a carbon-
based material in a process comprising pressureless sintering for promoting
densification of a titanium composite material, the titanium composite
material
comprising about 0.5 wt. % to about 3.0 wt. % of carbon, based on the total
weight of
titanium and carbon in the composite material.
[0022] In an
aspect, the present disclosure includes the use of a carbon-
based material in a powder injection molding process for promoting
densification of a
titanium composite material, the titanium composite material comprising about
0.5
wt. % to about 3.0 wt. % of carbon, based on the total weight of titanium and
carbon
in the composite material.
[0023] In an
aspect, the present disclosure includes the use of an effective
amount of a carbon-based material in a process comprising pressureless
sintering
for in-situ synthesis of titanium carbide, wherein a titanium composite
material
produced by the process comprises about 0.5 wt. % to about 3.0 wt. % of
carbon,
based on the total weight of titanium and carbon in the composite material.
[0024] In an
aspect, the present disclosure includes the use of an effective
amount of a carbon-based material in a powder injection molding process for in-
situ
synthesis of titanium carbide, wherein a titanium composite material produced
by the
powder injection molding process comprises about 0.5 wt. A) to about 3.0 wt.
% of
carbon, based on the total weight of titanium and carbon in the composite
material.
[0025] In an
aspect, the present disclosure includes the use of a carbon-
based material in a process comprising pressureless sintering for in-situ
synthesis of
titanium carbide, the carbon-based material being used in admixture with at
least a
titanium-based powder so as to produce a composition comprising about 0.5 wt.
%
to about 3.0 wt. % of the carbon-based material, based on the total weight of
the
titanium-based powder and the carbon-based material.
[0026] In an
aspect, the present disclosure includes the use of a carbon-
based material in a powder injection molding process for in-situ synthesis of
titanium
carbide, the carbon-based material being used in admixture with at least a
titanium-
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based powder so as to produce a composition comprising about 0.5 wt. % to
about
3.0 wt. % of the carbon-based material, based on the total weight of the
titanium-
based powder and the carbon-based material.
[0027] In an
aspect, the present disclosure includes the use of a carbon-
based material in a process comprising pressureless sintering for promoting
densification of a titanium composite material, the carbon-based material
being used
in admixture with at least a titanium-based powder so as to produce a
composition
comprising about 0.5 wt. % to about 3.0 wt. % of the carbon-based material,
based
on the total weight of the titanium-based powder and the carbon-based
material.
[0028] In an
aspect, the present disclosure includes the use of a carbon-
based material in a powder injection molding process for promoting
densification of a
titanium composite material, the carbon-based material being used in admixture
with
at least a titanium-based powder so as to produce a composition comprising
about
0.5 wt. % to about 3.0 wt. % of the carbon-based material, based on the total
weight
of the titanium-based powder and the carbon-based material.
[0029] In an
aspect, the present disclosure includes the use of a carbon-
based material as a reinforcing agent effective to form a composition with at
least a
titanium-based powder in a process comprising pressureless sintering for
preparing
a titanium composite material, the composition comprising about 0.5 wt. % to
about
3.0 wt. % of the carbon-based material, based on the total weight of the
titanium-
based powder and the carbon-based material.
[0030] In an
aspect, the present disclosure includes the use of a carbon-
based material as a reinforcing agent effective to form a composition with at
least a
titanium-based powder in a powder injection molding process for preparing a
titanium composite material, the composition comprising about 0.5 wt. % to
about 3.0
wt. % of the carbon-based material, based on the total weight of the titanium-
based
powder and the carbon-based material.
[0031] In an
aspect, the present disclosure includes the use of a composition
comprising a titanium-based powder and at least one of a carbon-based material
and
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a binder for preparing a titanium composite material, wherein the composition
comprises about 0.5 wt. `)/0 to about 3.0 wt. % of the carbon-based material,
based
on the total weight of the titanium-based powder and the carbon-based
material.
[0032] In an
aspect, the present disclosure includes the use of a composition
comprising a titanium-based powder and at least one of a carbon-based material
and
a binder for preparing a titanium carbide reinforced titanium composite,
wherein the
composition comprises about 0.5 wt. % to about 3.0 wt. % of the carbon-based
material, based on the total weight of the titanium-based powder and the
carbon-
based material.
[0033] In an
aspect, the present disclosure includes the use of a composition
comprising a titanium-based powder and at least one of a carbon-based material
and
a binder in a process comprising pressureless sintering, wherein the
composition
comprises about 0.5 wt. % to about 3.0 wt. % of the carbon-based material,
based
on the total weight of the titanium-based powder and the carbon-based
material.
[0034] In an
aspect, the present disclosure includes the use of a composition
comprising a titanium-based powder and at least one of a carbon-based material
and
a binder in a powder injection molding process, wherein the composition
comprises
about 0.5 wt. % to about 3.0 wt. A) of the carbon-based material, based on
the total
weight of the titanium-based powder and the carbon-based material.
[0035] In an
aspect, the present disclosure includes a product comprising a
composite material comprising a titanium metal matrix and titanium carbide
dispersed in the matrix; wherein the composite material comprises about 0.5
wt. % to
about 3.0 wt. % of carbon, based on the total weight of titanium and carbon in
the
composite material.
[0036] In an
aspect, the present disclosure includes a product comprising a
composite material comprising in-situ synthesized titanium carbide dispersed
in a
titanium metal matrix, wherein the titanium carbide is produced by powder
injection
molding and wherein the composite material comprises from about 0.5 wt. A to
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about 3.0 wt. (:)/0 of carbon, based on the total weight of titanium and
carbon in the
composite material.
[0037] In an
aspect, the present disclosure includes a product comprising a
titanium carbide reinforced titanium composite, wherein the composite
comprises
about 0.5 wt. % to about 3.0 wt. % of carbon, based on the total weight of
titanium
and carbon in the composite material.
[0038] In an
aspect, the present disclosure includes a product produced by a
process comprising:
mixing a titanium-based powder with a least one of a carbon-based
material and a binder to produce a composition comprising a titanium-based
powder
and at least one of a carbon-based material and a binder; and
subjecting the composition to pressureless sintering;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt. %
of the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
[0039] In an
aspect, the present disclosure includes a product produced by a
process comprising:
mixing a titanium-based powder with a least one of a carbon-based
material and a binder to produce a composition comprising a titanium-based
powder
and at least one of a carbon-based material and a binder; and
subjecting the composition to a powder injection molding process;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt. %
of the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
[0040] In an
aspect, the present disclosure includes a product produced by a
powder injection molding process, the process comprising:
mixing a titanium-based powder with at least one of a carbon-based
material and a binder to produce a composition comprising a titanium-based
powder
and at least one of a carbon-based material and a binder; and
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feeding the composition into a powder injection molding apparatus to
provide a molded product;
debinding the molded product; and
heating the molded product under conditions sufficient to produce in-
situ titanium carbide, wherein the titanium carbide is dispersed within a
titanium
matrix;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt. %
of the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
[0041] In an aspect, the present disclosure includes a kit comprising:
a composition comprising a titanium-based powder and at least one
of a carbon-based material and a binder; and
instructions for use of the composition in a process comprising
pressureless sintering;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt. %
of the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
[0042] In an aspect, the present disclosure includes a kit comprising:
a composition comprising a titanium-based powder and at least one
of a carbon-based material and a binder; and
instructions for use of the composition in a powder injection molding
process;
wherein the composition comprises about 0.5 wt. % to about 3.0 wt. %
of the carbon-based material, based on the total weight of the titanium-based
powder
and the carbon-based material.
[0043] Other features and advantages of the present disclosure will become
apparent from the following detailed description. It should be understood,
however,
that the detailed description and the specific examples while indicating
preferred
embodiments of the disclosure are given by way of illustration only, since
various
changes and modifications within the spirit and scope of the disclosure will
become
apparent to those skilled in the art from this detailed description.
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BRIEF DESCRIPTION OF THE DRAWINGS
[0044] The
drawings included herewith are for illustrating various
embodiments of the present disclosure and are not intended to limit the scope
of
what is taught in any way.
[0045] FIG. 1 is a
graph illustrating the effect of carbon black concentration on
the density of a titanium carbide-reinforced titanium composite (Ti6A14V-45 m)
in
accordance with an embodiment of the present disclosure.
[0046] FIG. 2 is a
block diagram illustrating the effect of carbon black addition
(1% wt.) on the sintered density of various titanium carbide-reinforced
titanium
composites (Ti6A14V-251.tm; Ti6A14V-45 m; and CpTi-45 m) in accordance with an
embodiment of the present disclosure.
[0047] FIG. 3
shows optical micrographs of the effect of carbon black addition
(1% wt.) on the porosity, grain size and carbide formation of a titanium
carbide-
reinforced titanium composite (Ti6AI4V-25 m) in accordance with an embodiment
of
the present disclosure.
[0048] FIG. 4 is a
graph illustrating the effect of carbon black addition (1% wt.)
on the stress-strain response of a titanium carbide-reinforced titanium
composite
(CpTi-45 m) in accordance with an embodiment of the present disclosure.
[0049] FIG. 5 is a
block diagram illustrating the effect of carbon black addition
(1% wt.) on the ultimate tensile strength of various titanium carbide-
reinforced
titanium composites (Ti6AI4V-25 m; Ti6A14V-45 m; and CpTi-45 m) in accordance
with an embodiment of the present disclosure.
[0050] FIG. 6 is a
block diagram illustrating the effect of carbon black addition
(1% wt.) on the hardness of a titanium carbide-reinforced titanium composite
(Ti6A14V-25 m) in accordance with an embodiment of the present disclosure.
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[0051] FIG. 7 is a
block diagram illustrating the effect of carbon black addition
(1% wt.) on the wear of a titanium carbide-reinforced titanium composite
(Ti6A14V-
25j1m) in accordance with an embodiment of the present disclosure.
DESCRIPTION
[0052] In order to
provide a clear and consistent understanding of the terms
used in the present specification, a number of definitions are provided below.
Moreover, unless defined otherwise, all technical and scientific terms as used
herein
have the same meaning as commonly understood by one of ordinary skill in the
art
to which this specification pertains.
[0053] The word
"a" or "an" when used in conjunction with the term
"comprising" in the claims and/or the specification may mean "one", but it is
also
consistent with the meaning of "one or more", "at least one", and "one or more
than
one" unless the content clearly dictates otherwise. Similarly, the word
"another" may
mean at least a second or more unless the content clearly dictates otherwise.
[0054] As used in
this specification and claim(s), the words "comprising" (and
any form of comprising, such as "comprise" and "comprises"), "having" (and any
form of having, such as "have" and "has"), "including" (and any form of
including,
such as "include" and "includes") or "containing" (and any form of containing,
such
as "contain" and "contains"), are inclusive or open-ended and do not exclude
additional, unrecited elements or process steps.
[0055] As used in
this specification and claim(s), the word "consisting" and its
derivatives, are intended to be close ended terms that specify the presence of
stated
features, elements, components, groups, integers, and/or steps, and also
exclude
the presence of other unstated features, elements, components, groups,
integers
and/or steps.
[0056] The term
"consisting essentially of", as used herein, is intended to
specify the presence of the stated features, elements, components, groups,
integers,
and/or steps as well as those that do not materially affect the basic and
novel
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characteristic(s) of these features, elements, components, groups, integers,
and/or
steps.
[0057] Terms of
degree such as "about", "substantially" and "approximately" as
used herein mean a reasonable amount of deviation of the modified term such
that the
end result is not significantly changed. These terms of degree should be
construed as
including a deviation of 10% of the modified term if this deviation would not
negate
the meaning of the word it modifies.
[0058] The term
"titanium-based", as used herein, includes titanium alloys as
well as substantially pure titanium.
[0059] For
example, the composition can further comprise a binder. For
example, the composition can comprise about 30 vol. % to about 50 vol. % of
binder,
about 32 vol. % to about 45 vol. %or about 35 vol. % to about 45 vol. % of
binder,
based on the total volume of the composition.
[0060] For
example, the binder comprises mainly thermoplastic polymers
and/or waxes.
[0061] For
example, the binder comprises a thermoplastic polymer, a paraffin
or mixtures thereof.
[0062] For
example, the binder comprises at least one thermoplastic polymer,
at least one wax, or mixtures thereof.
[0063] For
example, the composition comprises about 0.5 wt. % to about 2.0
wt. % of the carbon-based material; about 0.5 wt. % to about 1.5 wt. % of the
carbon-based material; or about 0.7 wt. % to about 1.3 wt. % of the carbon-
based
material, based on the total weight of the titanium-based powder and the
carbon-
based material.
[0064] For
example, the composition comprises about 50 vol. % to about 70
vol. % of the titanium-based powder; about 58 vol. % to about 68 vol. % of the
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titanium-based powder; or about 60 vol. % to about 66 vol. % of the titanium-
based
powder, based on the total volume of the composition.
[0065] For example, the carbon-based material is chosen from graphite,
graphene, elemental carbon, carbon black, amorphous carbon, semi-crystalline
carbon, crystalline carbon and mixtures thereof.
[0066] For example, the carbon-based material can be carbon nanotubes.
[0067] For example, the carbon-based material can be chosen from single-
walled nanotubes, functionalized single-walled nanotubes, multiwalled
nanotubes,
functionalized multiwalled nanotubes and mixtures thereof.
[0068] For example, the titanium-based powder comprises particles ranging
from about 0.01 Rm to about 200 pm, about 0.1 Rm to about 100 Rm; about 0.1 Rm
to about 45 Rm; or about 0.1 Rm to about 25 Rm.
[0069] For example, the titanium-based powder has an average particle size
of about 1 m to about 100 m, about 5 m to about 100 m; about 5 m to about
45 m; about 5 m to about 25 m; or about 10 m to about 25 m.
[0070] For example, the composite material comprises about 0.5 wt. % to
about 2.0 wt. % of carbon; about 0.5 wt. % to about 1.5 wt. % of carbon; or
about 0.7
wt. % to about 1.3 wt. % of carbon, based on the total weight of titanium and
carbon
in the composite material.
[0071] For example, the composite material comprises about 97 wt. % to
about 99.5 wt. % of metallic phase; about 98 wt. % to about 99.5 wt. % of
metallic
phase; about 98.5 wt. % to about 99.5 wt. % of metallic phase or about 98.7
wt. % to
about 99.3 wt. % of metallic phase.
[0072] For example, the composite material comprises in-situ synthesized
titanium carbide. For example, the titanium carbide is produced by a process
comprising sintering.
14a
[0072A] For example, the composite material has a porosity of about 0.2%
to
about 5%.
[0072B] According to another example, the composite can have a porosity of
about 0.3% to about 3%.
[0072C] According to another example, the composite can have a porosity of
about 0.4% to about 2%.
[0072D] According to another example, the composite can have a porosity of
about 0.5% to about 1.5%.
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[0073] For
example, the powder injection molding comprises mixing a
titanium-based powder, a carbon-based material and a binder to produce a
composition and feeding the composition into a powder molding apparatus.
[0074] For
example, the composition is fed into the powder injection molding
apparatus at pressures of about 0.01 MPa to about 30 MPa; at pressures of
about 0.
1 MPa to about 30 MPa; at pressures of about 5 MPa to about 25 MPa; at
pressures
of about 10 MPa to about 25 MPa; at pressures of about 20 MPa to about 25 MPa;
at pressures of about 10 MPa to about 23 MPa or at pressures of about 20 MPa
to
about 23 MPa.
[0075] For
example, the powder injection molding comprises heating the
composition under conditions sufficient to melt the binder and generate a melt
comprising a dispersion of titanium and carbon-based materials. For example,
the
powder injection molding comprises injection of the composition into a mold to
form a
shape. For example, the powder injection molding comprises debinding (with a
solvent and/or heat) and sintering during which titanium carbide is formed in-
situ, the
titanium carbide being dispersed within a titanium matrix.
[0076] In an
embodiment, the titanium carbide-reinforced titanium composites
of the present disclosure have improved mechanical and/or physical properties.
It
was discovered that the addition of low concentrations of a carbon-based
material to
a titanium-based powder, typically from about 0.5 wt. % to about 3.0 wt. %
(based on
the total weight of the titanium-based powder and the carbon-based material),
followed by powder injection molding, debinding and sintering has a positive
impact
on the densification of the resulting composite material. It is believed that
the
aforementioned improved mechanical and/or physical properties are at least in
part
due to this enhanced densification. For example, the composites exhibit higher
stress-strain responses (FIG. 4). For example, the composites exhibit higher
ultimate tensile strength (FIG. 5). For example, the composites exhibit higher
hardness (FIG. 6). For example, the composites exhibit higher wear resistance
(FIG.
7). For example, the composites exhibit lower residual porosity. For example,
the
composites exhibit higher density.
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[0077] In an
embodiment of the present disclosure, a composition comprising
a titanium-based powder and a carbon-based material is subjected to sintering.
The
sintering produces in-situ titanium carbide as a result of a reaction between
titanium
and carbon. Pressureless sintering of a titanium/carbon-based material and the
positive impact of low concentrations of carbon, about 0.5 wt. % to about 3.0
wt. %
(based on the total weight of titanium-based powder and carbon-based
material), on
densification have not been reported. Pressureless sintering, as used herein,
refers
to sintering treatments done without the application of external forces and
where the
consolidation of the material results essentially from the effect of
temperature.
Pressureless sintering can be done under different atmospheres or under vacuum
conditions to prevent the reaction of titanium with the environment.
[0078] In an
embodiment, the titanium carbide-reinforced titanium composites
of the present disclosure may comprise from about 0.5 wt. 1% to about 3.0 wt.
1% of
carbon; about 0.5 wt. % to about 2.0 wt. % of carbon; about 0.5 wt. % to about
1.5
wt. % of carbon; or about 0.7 wt. % to about 1.3 wt. % of carbon, based on the
total
weight of titanium and carbon in the composite. In non-limiting embodiments,
for
example, the titanium carbide-reinforced titanium composites may comprise, for
example, about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0,
about 1.1,
about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8,
about 1.9,
about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6,
about 2.7,
about 2.8, about 2.9 or about 3.0 wt. % of carbon, or any range derivable
therein.
The carbon content of the titanium carbide-reinforced titanium composites of
the
present disclosure is substantially in the form of titanium carbide.
[0079] In an
embodiment, the titanium carbide-reinforced titanium composites
of the present disclosure may comprise from about 97.0 wt. % to about 99.5 wt.
% of
metallic phase; about 98 wt. % to about 99.5 wt. % of metallic phase; about
98.5 wt.
% to about 99.5 wt. % of metallic phase; or about 98.7 wt. % to about 99.3 wt.
% of
metallic phase. In non-limiting embodiments, for example, the titanium carbide-
reinforced titanium composites may comprise, for example, about 97.0, about
97.1,
about 97.2, about 97.3, about 97.4, about 97.5, about 97.6, about 97.7, about
97.8,
about 97.9, about 98.0, about 98.1, about 98.2, about 98.3, about 98.4, about
98.5,
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about 98.6, about 98.7, about 98.8, about 98.9, about 99.0, about 99.1, about
99.2,
about 99.3, about 99.4 or about 99.5 wt. % of metallic phase, or any range
derivable
therein. The titanium content of the titanium carbide-reinforced titanium
composites
of the present disclosure is substantially in the form of titanium metal and
titanium
carbide.
[0080] In an
embodiment, the titanium carbide-reinforced titanium composites
of the present disclosure are prepared by a powder injection molding process.
In an
aspect of the powder injection molding process, a titanium-based powder, a
carbon-
based material and a binder are mixed to provide a composition.
[0081] In an
embodiment of the present disclosure, the composition comprises
about 0.5 wt. % to about 3.0 wt. % of the carbon-based material; about 0.5 wt.
% to
about 2.0 wt. % of the carbon-based material; about 0.5 wt. % to about 1.5 wt.
% of
the carbon-based material; or about 0.7 wt. % to about 1.3 wt. % of the carbon-
based material, based on the total weight of titanium-based powder and the
carbon-
based material. In non-limiting embodiments, for example, the composition may
comprise about 0.5, about 0.6, about 0.7, about 0.8, about 0.9, about 1.0,
about 1.1,
about 1.2, about 1.3, about 1.4, about 1.5, about 1.6, about 1.7, about 1.8,
about 1.9,
about 2.0, about 2.1, about 2.2, about 2.3, about 2.4, about 2.5, about 2.6,
about 2.7,
about 2.8, about 2.9 or about 3.0 wt. % of the carbon-based material, or any
range
derivable therein.
[0082] In an
embodiment of the present disclosure, the composition comprises
about 50.0 vol. % to about 70.0 vol. % of the titanium-based powder; about 58
vol. %
to about 68 vol. % of the titanium-based powder; or about 60 vol. % to about
66 vol.
% of the titanium-based powder, based on the total volume of the composition.
In
non-limiting embodiments, for example, the composition may comprise about
50.0,
about 50.5, about 51.0, about 51.5, about 52.0, about 52.5, about 53.0, about
53.5,
about 54.0, about 54.5, about 55.0, about 55.5, about 56.0, about 56.5, about
57.0,
about 57.5, about 58.0, about 58.5, about 59.0, about 59.5, about 60.0, about
60.5,
about 61.0, about 61.5, about 62.0, about 62.5, about 63.0, about 63.5, about
64.0,
about 64.5, about 65.0, about 65.5, about 66.0, about 66.5, about 67.0, about
67.5,
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about 68.0, about 68.5, about 69.0, about 69.5 or about 70.0 vol. % of the
titanium-
based powder, or any range derivable therein.
[0083] In an
embodiment of the present disclosure, the titanium-based powder
comprises particles ranging from 0.01 pm to about 200 ; about 0.01 m to about
100
m; about 0.1 pm to about 45 pm; or about 0.1 pm to about 25 pm. In non-
limiting
embodiments, for example, the titanium titanium-based powder may comprise
particles of about 0.1, about 0.5, about 1.0, about 1.5, about 2.0, about 2.5,
about
3.0, about 3.5, about 4.0, about 4.5, about 5.0, about 5.5, about 6.0, about
6.5, about
7.0, about 7.5, about 8.0, about 8.5, about 9.0, about 9.5, about 10.0, about
10.5,
about 11.0, about 11.5, about 12.0, about 12.5, about 13.0, about 13.5, about
14.0,
about 14.5, about 15.0, about 15.5, about 16.0, about 16.5, about 17.0, about
17.5,
about 18.0, about 18.5, about 19.0, about 19.5, about 20.0, about 20.5, about
21.0,
about 21.5, about 22.0, about 22.5, about 23.0, about 23.5, about 24.0, about
24.5,
about 25.0, about 25.5, about 26.0, about 26.5, about 27.0, about 27.5, about
28.0,
about 28.5, about 29.0, about 29.5, about 30.0, about 30.5, about 31.0, about
31.5,
about 32.0, about 32.5, about 33.0, about 33.5, about 34.0, about 34.5, about
35.0,
about 35.5, about 36.0, about 36.5, about 37.0, about 37.5, about 38.0, about
38.5,
about 39.0, about 39.5, about 40.0, about 40.5, about 41.0, about 41.5, about
42.0,
about 42.5, about 43.0, about 43.5, about 44.0, about 44.5, about 45.0, about
45.5,
about 46.0, about 46.5, about 47.0, about 47.5, about 48.0, about 48.5, about
49.0,
about 49.5, about 50.0, about 50.5, about 51.0, about 51.5, about 52.0, about
52.5,
about 53.0, about 53.5, about 54.0, about 54.5, about 55.0, about 55.5, about
56.0,
about 56.5, about 57.0, about 57.5, about 58.0, about 58.5, about 59.0, about
59.5,
about 60.0, about 60.5, about 61.0, about 61.5, about 62.0, about 62.5, about
63.0,
about 63.5, about 64.0, about 64.5, about 65.0, about 65.5, about 66.0, about
66.5,
about 67.0, about 67.5, about 68.0, about 68.5, about 69.0, about 69.5, about
70.0,
about 70.5, about 71.0, about 71.5, about 72.0, about 72.5, about 73.0, about
73.5,
about 74.0, about 74.5, about 75.0, about 75.5, about 76.0, about 76.5, about
77.0,
about 77.5, about 78.0, about 78.5, about 79.0, about 79.5, about 80.0, about
80.5,
about 81.0, about 81.5, about 82.0, about 82.5, about 83.0, about 83.5, about
84.0,
about 84.5, about 85.0, about 85.5, about 86.0, about 86.5, about 87.0, about
87.5,
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about 88.0, about 88.5, about 89.0, about 89.5, about 90.0, about 90.5, about
91.0,
about 91.5, about 92.0, about 92.5, about 93.0, about 93.5, about 94.0, about
94.5,
about 95.0, about 95.5, about 96.0, about 96.5, about 97.0, about 97.5, about
98.0,
about 98.5, about 99.0, about 99.5, or about 100.0 jim, or any range derivable
therein.
[0084] In an
embodiment of the present disclosure, the composition comprises
about 30.0 vol. % to about 50.0 vol. % of binder; or about 35 vol. % to about
45 vol.
% of binder, based on the total volume of the composition. In non-
limiting
embodiments, for example, the composition may comprise about 30.0, about 30.5,
about 31.0, about 31.5, about 32.0, about 32.5, about 33.0, about 33.5, about
34.0,
about 34.5, about 35.0, about 35.5, about 36.0, about 36.5, about 37.0, about
37.5,
about 38.0, about 38.5, about 39.0, about 39.5, about 40.0, about 40.5, about
41.0,
about 41.5, about 42.0, about 42.5, about 43.0, about 43.5, about 44.0, about
44.5,
about 45.0, about 45.5, about 46.0, about 46.5, about 47.0, about 47.5, about
48.0,
about 48.5, about 49.0, about 49.5 or about 50.0 vol. % of the binder, or any
range
derivable therein.
[0085] In non-
limiting embodiments, for example, the carbon-based materials
are chosen from graphite, graphene, elemental carbon, carbon black, amorphous
carbon, semi-crystalline carbon, crystalline carbon and carbon nanotubes. In
non-
limiting embodiments, for example, the carbon nanotubes are chosen from single-
walled nanotubes, functionalized single-walled nanotubes, multiwalled
nanotubes
and functionalized multiwalled nanotubes.
[0086] In non-
limiting embodiments, for example, the binder is chosen from
thermoplastic polymers, paraffin, waxes, surface agents and mixtures thereof.
[0087] In an
aspect of the powder injection molding process, the composition
is fed into a powder injection molding apparatus at pressures ranging from
about
0.01 MPa to about 30 MPa; at pressures of about 10 MPa to about 25 MPa; of
about
20 MPa to about 25 MPa; or at pressures of about 20 MPa to about 23 MPa. In
non-
limiting embodiments, for example, the composition may be injected at a
pressure of
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about 1.0, about 2.0, about 3.0, about 4.0, about 5.0, about 6.0, about 7.0,
about 8.0,
about 9.0, about 10.0, about 11.0, about 12.0, about 13.0, about 14.0, about
15.0,
about 16.0, about 17.0, about 18.0, about 19.0, about 20.0, about 21.0, about
22.0,
about 23.0, about 24.0, about 25.0, about 26.0, about 27.0, about 28.0, about
29.0 or
about 30.0 MPa or any range derivable therein.
[0088] In an
aspect of the powder injection molding process, a first portion of
the binder is removed by solvent debinding. Non-limiting examples of suitable
solvents include low boiling hydrocarbon solvents such as pentane, and hexane
or
mixtures. Some polar solvents can also be used such as polar organic solvents,
water, or mixtures thereof.
[0089] In an
aspect of the powder injection molding process, a second portion
of the binder is removed by thermal debinding. In an embodiment of the present
disclosure, the thermal treatment comprises heating at temperatures ranging
from
about 25 C to about 800 C. In an embodiment of the present disclosure, the
thermal
treatment is performed at temperatures from about 25 C to about 900 C. In an
embodiment of the present disclosure, the thermal treatment is performed at
temperatures from about 25 C to about 850 C. In an embodiment of the present
disclosure, the thermal treatment is performed at temperatures from about 25 C
to
about 800 C. In an embodiment of the present disclosure, the thermal treatment
is
performed at temperatures from about 25 C to about 750 C. In an embodiment of
the present disclosure, the thermal treatment is performed at temperatures
from
about 25 C to about 700 C.
[0090] In an
aspect of the powder injection molding process, the composition
is sintered. In an embodiment of the present disclosure, the sintering
comprises
heating at temperatures of about 1250 C. In an embodiment of the present
disclosure, the sintering is performed at temperatures from about 1000 C to
about
1500 C. In an embodiment of the present disclosure the sintering is performed
at
temperatures from about 1100 C to about 1400 C. In an embodiment of the
present
disclosure the sintering is performed at temperatures from about 1200 C to
about
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21
1300 C. In an embodiment of the present disclosure the sintering is performed
at
temperatures from about 1225 C to about 1275 C. In non-limiting embodiments,
for
example, the sintering is performed at a temperature of about 1200 C, about
1201 C, about 1202 C, about 1203 C, about 1204 C, about 1205 C, about 1206 C,
about 1207 C, about 1208 C, about 1209 C, about 1210 C, about 1211 C, about
1212 C, about 1213 C, about 1214 C, about 1215 C, about 1216 C, about 1217 C,
about 1218 C, about 1219 C, about 1220 C, about 1221 C, about 1222 C, about
1223 C, about 1224 C, about 1225 C, about 1226 C, about 1227 C, about 1228 C,
about 1229 C, about 1230 C, about 1231 C, about 1232 C, about 1233 C, about
1234 C, about 1235 C, about 1236 C, about 1237 C, about 1238 C, about 1239 C,
about 1240 C, about 1241 C, about 1241 C, about 1243 C, about 1244 C, about
1245 C, about 1246 C, about 1247 C, about 1248 C, about 1249 C, about 1250 C,
about 1251 C, about 1252 C, about 1253 C, about 1254 C, about 1255 C, about
1256 C, about 1257 C, about 1258 C, about 1259 C, about 1260 C, about 1261 C,
about 1262 C, about 1263 C, about 1264 C, about 1265 C, about 1266 C, about
1267 C, about 1268 C, about 1269 C, about 1270 C, about 1271 C, about 1272 C,
about 1273 C, about 1274 C, about 1275 C, about 1276 C, about 1277 C, about
1278 C, about 1279 C, about 1280 C, about 1281 C, about 1282 C, about 1283 C,
about 1284 C, about 1285 C, about 1286 C, about 1287 C, about 1288 C, about
1289 C, about 1290 C, about 1291 C, about 1292 C, about 1293 C, about 1294 C,
about 1295 C, about 1296 C, about 1297 C, about 1298 C, about 1299 C or about
1300 C or any range derivable therein.
Method for Preparing Titanium Carbide-Reinforced Titanium Composites
[0091] In one of
its aspects, the present disclosure includes a powder injection
molding process for preparing a titanium carbide-reinforced titanium
composite, the
process comprising:
[0092] Mixing of
binder (40% paraffin wax, 27.5% polypropylene, 27.9%
polyethylene, 4.5% stearic acid, 0.005% antioxidant (e.g. pentaerythritol
tetrakis(3-(3
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5-di-tert-butyl-4-hydroxyphenyl)propionate)), titanium powder (AP&C; 64.4%
vol.)
and carbon black particles (Monarch 880(CS-5820 from Cabot) to produce a
composition.
[0093] Injecting
and molding the composition in an AB-400 pneumatic injection
press ¨ injection pressure of 22.5 M Pa.
[0094] Removing of
binder material by solvent debinding - 7.5h in hexane at
32 C followed by drying in air for 24h.
[0095] Removing of
binder material by thermal debinding using the following
procedure:
25-300 C at 2C /min; plateau at 300 C for 30 min;
300-360 C at 2 C /min; plateau at 360 C for 30 min;
360-420 C at 2 C /min; plateau at 420 C for 30 min;
420-480 C at 2 C /min; plateau at 480 C for 30 min;
480-800 C at 5 C /min; plateau at 800 C for 30 min; and
cooling to room temperature at 5 C/min.
[0096] Sintering at 1250 C under vacuum for 8h.
[0097] The sintering time can be about 30 minutes to about 10 hours.
[0098] Various
titanium carbide-reinforced titanium composites prepared in
accordance with an embodiment of the present disclosure are illustrated in
Table 1.
For example, CpTi and Ti6AI4V were used as the titanium-based powders
constituting the matrix material of the composites. The size connotations -
251.tm and
-45 ,m refer to particles smaller than or equal to -25 ,m and -45 m
respectively. In
the embodiments of Table 1, the carbon-based material was carbon black. It is
to be
understood that further composite materials can be prepared following the
above-
described powder injection molding process using other carbon-based materials.
Non-limiting examples of such other carbon-based materials include graphene,
elemental carbon, graphite, amorphous carbon, semi-crystalline carbon,
crystalline
carbon, carbon nanotubes and mixtures thereof.
23
[0099] Table 1:
Titanium carbide-reinforced titanium composites and selected
properties.
Example Ti-based powder Carbon black Figure'
Concentration
(% wt.)
1 Ti6AI4V-45 prn 0.0 1, 2, 5
2 Ti6AI4V-45 lam 0.5 1
3 Ti6AI4V-45 j.tm 1.0 1, 2, 5
4 Ti6A14V-451.1m 2.0 1
Ti6AI4V-45 3.0 1
6 Ti6A14V-251.i.m 0.0 2, 3, 5, 6, 7
7 Ti6AI4V-25 [im 1.0 2, 3, 5, 6, 7
8 CpTi-45 pm 0.0 2, 4, 5
9 CpTi-451im 1.0 2, 4, 5
'Selected properties of the composites are illustrated by the referenced
figures
[00100] Carbon-
based material in the form of carbon black was mixed with the
titanium-based powders and binder to produce powder compositions to be
subjected
to a powder injection molding process. The compositions comprises about 0.5
wt. %
to about 3.0 wt. % of the carbon-based material (e.g. graphite), based on the
total
weight of the titanium-based powders and the carbon-based material. The
composite materials produced following sintering comprise about 0.5 wt. % to
about
3 0 wt. % of carbon, based on the total weight of titanium and carbon in the
composite material. The effect of carbon black addition on density,
microstructure,
and mechanical properties was subsequently assessed (FIGS. 1-7).
[00101] As
illustrated in FIG. 1, the addition of carbon black has an effect on
the density of the titanium carbide-reinforced titanium composite (Ti6AI4V-45
m).
The density significantly increased with increasing carbon black
concentrations,
reaching a peak value of 97.4 0.4% at 1% carbon black concentration.
Furthermore, as illustrated in FIG. 1, carbon black concentrations in excess
of 1%
wt. resulted in the densities gradually decreasing to levels comparable to
that of
materials fabricated without carbon-based additives.
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[00102] As
illustrated in FIG. 2, the densification effect observed for the
titanium carbide-reinforced titanium composite (Ti6AI4V-45 m) could also be
observed for titanium carbide-reinforced titanium composites Ti6AI4V-25pm and
CpTi-45pm respectively. The effect of the addition of a carbon-based material
(about 0.5 wt. % to about 3.0 wt. %), for example carbon black, on the density
of the
resulting titanium-based composite material thus appears generally relevant to
any
titanium-based powder. This observation is consistent with the TiC particles
exhibiting high coherency and strong interface with a surrounding titanium
metal
matrix.
[00103] FIG. 3
shows optical micrographs illustrating the effect of carbon black
addition (1% wt.) on the porosity, grain size and carbide formation of a
titanium
carbide-reinforced titanium composite (Ti6AI4V-25pm). As can be readily
observed
from FIG. 3, the materials manufactured with and without the addition of
carbon-
based material show important structural differences. The addition of carbon
black
(1% wt.) significantly reduced the number of pores, which are shown as black
dots
on the micrographs. Moreover, titanium carbides produced during the sintering
of
the carbon black are shown as grey dots on the micrographs and are
substantially
evenly distributed throughout the microstructure. Furthermore, the in-situ
formation
of titanium carbides further refines the titanium grain size in the composite
material.
[00104] Selected
mechanical properties were assessed by performing tensile
tests on composite materials made from CpTi-45pm, Ti6AI4V-45pm and Ti6AI4V-
25pm powders with and without the addition of a carbon-based additive (FIGS. 4
and
5). An upward shift in the stress-strain response for composites prepared with
1%
carbon black additive was observed when compared to samples without carbon-
based additive. An improvement of elongation was also observed. This shift
translated into a significant increase in the ultimate tensile strength for
composites
prepared with 1% carbon black additive.
[00105] FIG. 6 is a
block diagram illustrating the effect of carbon black addition
(1% wt.) on the hardness of a titanium carbide-reinforced titanium composite
(Ti6A14V-25 m). FIG. 7 is a block diagram illustrating the effect of carbon
black
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addition (1% wt.) on the wear of a titanium carbide-reinforced titanium
composite
(Ti6AI4V-25 m). The addition of carbon black resulted in composite materials
exhibiting improved hardness, and reduced weight and volume losses when
samples
were subjected to wear tests (110 N Alumina ball with a 25 mm-long stoke for
30
minutes at 1Hz). The overall strengthening effect resulting from the addition
of 1%
wt. carbon black to the titanium-based powders can be associated with the
reduced
porosity, dispersion of in-situ synthesized titanium carbides, carbon solid
solution
hardening, and titanium grain size refinement (Hall-Petch effect).
[00106] While the
present disclosure has been described with reference to
what are presently considered to be the preferred examples, it is to be
understood
that the disclosure is not limited to the disclosed examples. In particular,
what has
been described herein has been intended to be illustrative and non-limiting
and it will
be understood by persons skilled in the art that other variants and
modifications may
be made without departing from the scope of the invention as defined in the
claims
appended hereto. The scope of the claims should not be limited by the
preferred
embodiments and examples, but should be given the broadest interpretation
consistent with the description as a whole.
