TITANIUM-BASED COMPOSITIONS, METHODS OF MANUFACTURE AND USES THEREOF

Titanium-based compositions as well as titanium composites such as carbide-reinforced titanium composites are disclosed herein. More specifically, composite materials comprising a titanium metal matrix and titanium carbide dispersed in the matrix are disclosed. The composite materials comprise about 0.5 wt. % to about 3.0 wt. % of carbon, based on the total weight of titanium and carbon in the composite materials. Compositions comprising a titanium-based powder and at least one of a carbon-based material and a binder are also disclosed. The compositions comprise about 0.5 wt. % to about 3.0 wt. % of carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

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Description
CROSS-REFERENCE TO RELATED APPLICATIONS

The present application claims priority to U.S. provisional application 62/054,012 filed on September, which is hereby incorporated by reference in its entirety.

FIELD

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

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.

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.

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 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.

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.

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

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. % 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.

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.

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.

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. % of carbon, based on the total weight of titanium and carbon in the composite material.

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.

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.

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;

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.

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. % 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.

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.

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. % of the carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

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.

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.

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.

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.

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.

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.

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. % to about 3.0 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

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.

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-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.

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.

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.

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.

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.

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 composite 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.

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.

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.

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. % of the carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

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.

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. % to about 3.0 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

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.

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.

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.

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
    • 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.

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.

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.

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.

BRIEF DESCRIPTION OF THE DRAWINGS

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.

FIG. 1 is a graph illustrating the effect of carbon black concentration on the density of a titanium carbide-reinforced titanium composite (Ti6Al4V-45 μm) in accordance with an embodiment of the present disclosure.

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 (Ti6Al4V-25 μm, Ti6Al4V-45 μm, and CpTi-45 μm) in accordance with an embodiment of the present disclosure.

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 (Ti6Al4V-25 μm) in accordance with an embodiment of the present disclosure.

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 μm) in accordance with an embodiment of the present disclosure.

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 (Ti6Al4V-25 μm, Ti6Al4V-45 μm, and CpTi-45 μm) in accordance with an embodiment of the present disclosure.

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 (Ti6Al4V-25 μm) in accordance with an embodiment of the present disclosure.

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 (Ti6Al4V-25 μm) in accordance with an embodiment of the present disclosure.

 DESCRIPTION

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.

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.

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.

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.

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 characteristic(s) of these features, elements, components, groups, integers, and/or steps.

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.

The term “titanium-based”, as used herein, includes titanium alloys as well as substantially pure titanium.

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.

For example, the binder comprises mainly thermoplastic polymers and/or waxes.

For example, the binder comprises a thermoplastic polymer, a paraffin or mixtures thereof.

For example, the binder comprises at least one thermoplastic polymer, at least one wax, or mixtures thereof.

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.

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 titanium-based powder; or about 60 vol. % to about 66 vol. % of the titanium-based powder, based on the total volume of the composition.

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.

For example, the carbon-based material can be carbon nanotubes.

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.

For example, the titanium-based powder comprises particles ranging from about 0.01 μm to about 200 μm, about 0.1 μm to about 100 μm, about 0.1 μm to about 45 μm, or about 0.1 μm to about 25 μm.

For example, the titanium-based powder has an average particle size of about 1 μm to about 100 μm, about 5 μm to about 100 μm, about 5 μm to about 45 μm, about 5 μm to about 25 μm, or about 10 μm to about 25 μm.

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.

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.

For example, the composite material comprises in-situ synthesized titanium carbide. For example, the titanium carbide is produced by a process comprising sintering.

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.

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.

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.

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.

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.

In an embodiment, the titanium carbide-reinforced titanium composites of the present disclosure may comprise from about 0.5 wt. % to about 3.0 wt. % 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.

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, 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.

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.

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.

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, 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.

In an embodiment of the present disclosure, the titanium-based powder comprises particles ranging from 0.01 μm to about 200 about 0.01 μm to about 100 urn, about 0.1 μm to about 45 μm, or about 0.1 μm to about 25 μm. 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, 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 μm, or any range derivable therein.

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.

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.

In non-limiting embodiments, for example, the binder is chosen from thermoplastic polymers, paraffin, waxes, surface agents and mixtures thereof.

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 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.

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.

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.

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 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

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:

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 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.

Injecting and molding the composition in an AB-400 pneumatic injection press—injection pressure of 22.5 MPa.

Removing of binder material by solvent debinding—7.5 h in hexane at 32° C. followed by drying in air for 24 h.

Removing of binder material by thermal debinding using the following procedure:

    • 25-300° C. at 2 C°/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.

Sintering at 1250° C. under vacuum for 8 h.

The sintering time can be about 30 minutes to about 10 hours.

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 Ti6Al4V were used as the titanium-based powders constituting the matrix material of the composites. The size connotations −25 μm and −45 μm refer to particles smaller than or equal to −25 μm and −45 μm 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.

TABLE 1 Titanium carbide-reinforced titanium composites and selected properties. Carbon black Concentration Example Ti-based powder (% wt.) FIG.1 1 Ti6Al4V-45 μm 0.0 1, 2, 5 2 Ti6Al4V-45 μm 0.5 1 3 Ti6Al4V-45 μm 1.0 1, 2, 5 4 Ti6Al4V-45 μm 2.0 1 5 Ti6Al4V-45 μm 3.0 1 6 Ti6Al4V-25 μm 0.0 2, 3, 5, 6, 7 7 Ti6Al4V-25 μm 1.0 2, 3, 5, 6, 7 8 CpTi-45 μm 0.0 2, 4, 5 9 CpTi-45 μm 1.0 2, 4, 5 1Selected properties of the composites are illustrated by the referenced figures

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).

As illustrated in FIG. 1, the addition of graphite has an effect on the density of the titanium carbide-reinforced titanium composite (Ti6Al4V-45 μm). 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.

As illustrated in FIG. 2, the densification effect observed for the titanium carbide-reinforced titanium composite (Ti6Al4V-45 μm) could also be observed for titanium carbide-reinforced titanium composites Ti6Al4V-25 μm and CpTi-45 μm 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.

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 (Ti6Al4V-25 μm). 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.

Selected mechanical properties were assessed by performing tensile tests on composite materials made from CpTi-45 μm, Ti6Al4V-45 μm and Ti6Al4V-25 μm 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.

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 (Ti6Al4V-25 μm). 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 (Ti6Al4V-25 μm). 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 1 Hz). 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).

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.

Claims

1. 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 carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

2. The composition of claim 1, further comprising a binder.

3. The composition of claim 2, wherein the composition comprises about 30 vol. % to about 50 vol. % of the binder, based on the total volume of the composition.

4. The composition of claim 2, wherein the composition comprises about 32 vol. % to about 45 vol. % of the binder, based on the total volume of the composition.

5. The composition of any one of claims 2 to 4, wherein the binder comprises at least one thermoplastic polymer, at least one wax or a mixture thereof.

6. The composition of any one of claims 1 to 5, wherein the composition comprises about 0.5 wt. % to about 2.0 wt. % of the carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

7. The composition of any one of claims 1 to 5, wherein the composition comprises about 0.5 wt. % to about 1.5 wt. % of the carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

8. The composition of any one of claims 1 to 5, wherein the composition comprises 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.

9. The composition of any one of claims 1 to 8, wherein the composition comprises about 50 vol. % to about 70 vol. % of the titanium-based powder, based on the total volume of the composition.

10. The composition of any one of claims 1 to 8, wherein the composition comprises about 58 vol. % to about 68 vol. % of the titanium-based powder, based on the total volume of the composition.

11. The composition of any one of claims 1 to 8, wherein the composition comprises about 60 vol. % to about 66 vol. % of the titanium-based powder, based on the total volume of the composition.

12. The composition of any one of claims 1 to 11, wherein the carbon-based material is chosen from graphite, graphene, elemental carbon, carbon black, amorphous carbon, semi-crystalline carbon crystalline carbon, and mixtures thereof.

13. The composition of any one of claims 1 to 11, wherein the carbon-based material is chosen from single-walled nanotubes, functionalized single-walled nanotubes, multiwalled nanotubes, functionalized multiwalled nanotubes and mixtures thereof.

14. The composition of any one of claims 1 to 13, wherein the titanium-based powder has an average particle size of about 5 μm to about 100 μm.

15. The composition of any one of claims 1 to 13, wherein the titanium-based powder has an average particle size of about 5 μm to about 45 μm.

16. The composition of any one of claims 1 to 13, wherein the titanium-based powder has an average particle size of about 10 μm to about 25 μm.

17. The composition of any one of claims 1 to 16, wherein the composition is a dry powder composition.

18. 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.

19. The composite material of claim 18, wherein the titanium carbide is in-situ synthesized titanium carbide.

20. The composite material of claim 18 or 19, wherein the titanium carbide is produced by a process comprising pressureless sintering.

21. The composite material of claim 18 or 19, wherein the titanium carbide is produced by powder injection molding.

22. The composite material of claim 21, wherein the powder injection molding comprises mixing a titanium-based powder, a carbon-based material and a binder to produce a composition and injecting the composition into a powder injection mould.

23. The composite material of claim 22, 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.

24. The composite material of claim 22, wherein the composition comprises about 0.5 wt. % to about 2.0 wt. % of the carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

25. The composite material of claim 22, wherein the composition comprises about 0.5 wt. % to about 1.5 wt. % of the carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

26. The composite material of claim 22, wherein the composition comprises 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.

27. The composite material of any one of claims 22 to 26, wherein the composition comprises about 50 vol. % to about 70 vol. % of the titanium-based powder, based on the total volume of the composition.

28. The composite material of any one of claims 22 to 26, wherein the composition comprises about 58 vol. % to about 68 vol. % of the titanium-based powder, based on the total volume of the composition.

29. The composite material of any one of claims 22 to 26, wherein the composition comprises about 60 vol. % to about 66 vol. % of the titanium-based powder, based on the total volume of the composition.

30. The composite material of any one of claims 22 to 29, wherein the composition comprises about 30 vol. % to about 50 vol. % of the binder, based on the total volume of the composition.

31. The composite material of any one of claims 22 to 29, wherein the composition comprises about 35 vol. % to about 45 vol. % of the binder, based on the total volume of the composition.

32. The composite material of any one of claims 22 to 31, wherein the carbon-based material is chosen from graphite, graphene, elemental carbon, carbon black, amorphous carbon, semi-crystalline carbon, crystalline carbon and mixtures thereof.

33. The composite material of any one of claims 22 to 31, wherein the carbon-based material is chosen from single-walled nanotubes, functionalized single-walled nanotubes, multiwalled nanotubes, functionalized multiwalled nanotubes and mixtures thereof.

34. The composite material of any one of claims 22 to 33, wherein the binder comprises at least one thermoplastic polymer, at least one wax, or mixtures thereof.

35. The composite material of any one of claims 18 to 34, wherein the composite material comprises about 0.5 wt. % to about 2.0 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

36. The composite material of any one of claims 18 to 34, wherein the composite material comprises about 0.5 wt. % to about 1.5 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

37. The composite material of any one of claims 18 to 34, wherein the composite material comprises about 0.7 wt. % to about 1.3 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

38. The composite material of any one of claims 18 to 37, wherein the composite material comprises about 97 wt. % to about 99.5 wt. % of titanium, based on the total weight of titanium and carbon in the composite material.

39. The composite material of any one of claims 18 to 37, wherein the composite material comprises about 98 wt. % to about 99.5 wt. % of titanium, based on the total weight of titanium and carbon in the composite material.

40. The composite material of any one of claims 18 to 37, wherein the composite material comprises about 98.5 wt. % to about 99.5 wt. % of titanium, based on the total weight of titanium and carbon in the composite material.

41. The composite material of any one of claims 18 to 37, wherein the composite material comprises about 98.7 wt. % to about 99.3 wt. % of titanium, based on the total weight of titanium and carbon in the composite material.

42. The composite material of any one of claims 22 to 41, wherein the titanium-based powder has an average particle size of about 5 μm to about 100 μm.

43. The composite material of any one of claims 22 to 41, wherein the titanium-based powder has an average particle size of about 5 μm to about 45 μm.

44. The composite material of any one of claims 20 to 41, wherein the titanium-based powder has an average particle size of about 10 μm to about 25 μm.

45. 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.

46. The composite of claim 45, wherein the titanium carbide is in-situ synthesized titanium carbide.

47. The composite of claim 45 or 46, wherein the titanium carbide is produced by a process comprising pressureless sintering

48. The composite of claim 45 or 46, wherein the titanium carbide is produced by powder injection molding.

49. The composite of claim 48, wherein the powder injection molding comprises mixing a titanium-based powder, a carbon-based material and a binder to produce a composition and injecting the composition into a powder injection mold.

50. The composite of claim 49, 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.

51. The composite of claim 49, wherein the composition comprises about 0.5 wt. % to about 2.0 wt. % of the carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

52. The composite of claim 49, wherein the composition comprises about 0.5 wt. % to about 1.5 wt. % of the carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

53. The composite of claim 49, wherein the composition comprises 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.

54. The composite of any one of claims 49 to 53, wherein the composition comprises about 50 vol. % to about 70 vol. % of the titanium-based powder, based on the total volume of the composition.

55. The composite of any one of claims 49 to 53, wherein the composition comprises about 58 vol. % to about 68 vol. % of the titanium-based powder, based on the total volume of the composition.

56. The composite of any one of claims 49 to 53, wherein the composition comprises about 60 vol. % to about 66 vol. % of the titanium-based powder, based on the total volume of the composition.

57. The composite of any one of claims 49 to 56, wherein the composition comprises about 30 vol. % to about 50 vol. % of the binder, based on the total volume of the composition.

58. The composite of any one of claims 49 to 56, wherein the composition comprises about 32 vol. % to about 45 vol. % of the binder, based on the total volume of the composition.

59. The composite of any one of claims 49 to 58, wherein the carbon-based material is chosen from graphite, graphene, elemental carbon, carbon black, amorphous carbon, semi-crystalline carbon, crystalline carbon and mixtures thereof

60. The composite of any one of claims 49 to 58, wherein the carbon-based material is chosen from single-walled nanotubes, functionalized single-walled nanotubes, multiwalled nanotubes, functionalized multiwalled nanotubes and mixtures thereof.

61. The composite of any one of claims 49 to 60, wherein the binder comprises at least one thermoplastic polymer, at least one wax, or mixtures thereof.

62. The composite of any one of claims 45 to 61, wherein the composite comprises about 0.5 wt. % to about 2.0 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

63. The composite of any one of claims 45 to 61, wherein the composite comprises about 0.5 wt. % to about 1.5 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

64. The composite of any one of claims 45 to 61, wherein the composite comprises about 0.7 wt. % to about 1.3 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

65. The composite of any one of claims 45 to 64, wherein the composite comprises about 97 wt. % to about 99.5 wt. % of titanium, based on the total weight of titanium and carbon in the composite material.

66. The composite of any one of claims 45 to 64, wherein the composite comprises about 98 wt. % to about 99.5 wt. % of titanium, based on the total weight of titanium and carbon in the composite material.

67. The composite of any one of claims 45 to 64, wherein the composite comprises about 98.5 wt. % to about 99.5 wt. % of titanium, based on the total weight of titanium and carbon in the composite material.

68. The composite of any one of claims 45 to 64, wherein the composite comprises about 98.7 wt. % to about 99.3 wt. % of titanium, based on the total weight of titanium and carbon in the composite material.

69. The composite of any one of claims 49 to 68, wherein the titanium-based powder has an average particle size of about 5 μm to about 100 μm.

70. The composite of any one of claims 49 to 68, wherein the titanium-based powder has an average particle size of about 5 μm to about 45 μm.

71. The composite of any one of claims 49 to 68, wherein the titanium-based powder has an average particle size of about 10 μm to about 25 μm.

72. 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.

73. The composite of any one of claims 18 to 72, wherein the composite has a porosity of about 0.1% to about 5%.

74. The composite of any one of claims 18 to 72, wherein the composite has a porosity of about 0.2% to about 5%.

75. The composite of any one of claims 18 to 72, wherein the composite has a porosity of about 0.3% to about 3%.

76. The composite of any one of claims 18 to 72, wherein the composite has a porosity of about 0.4% to about 2%.

77. The composite of any one of claims 18 to 72, wherein the composite has a porosity of about 0.5% to about 1.5%.

78. A method of manufacturing a titanium-based composite material, the method comprising:

providing a composition as defined in any one of claims 1 to 17; and
subjecting the composition to pressureless sintering.

79. A method of manufacturing a titanium-based composite material, the method comprising:

providing a composition as defined in any one of claims 1 to 17; and
subjecting the composition to a powder injection molding process.

80. The method of claim 79, wherein the powder injection molding process comprises heating the composition under conditions sufficient to melt the binder and generate a melt comprising a dispersion of the titanium and carbon-based materials.

81. The method of claim 80, further comprising heating molded product under conditions to produce in-situ titanium carbide, wherein the titanium carbide is dispersed within a titanium matrix.

82. 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 as defined in any one of claims 1 to 17; and
subjecting the composition to pressureless sintering.

83. 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 as defined in any one of claims 1 to 17; and
subjecting the composition to a powder injection molding process.

84. The process of claim 83, wherein the powder injection molding process comprises heating the composition under conditions sufficient to melt the binder and generate a melt comprising a dispersion of the titanium and carbon-based materials.

85. The process of claim 84, further comprising heating molded product under conditions to produce in-situ titanium carbide, wherein the titanium carbide is dispersed within a titanium matrix.

86. 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 as defined in any one of claims 1 to 17;
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.

87. The powder injection molding process of claim 86, wherein the feeding is carried out at pressures of about 0.1 MPa to about 30 MPa.

88. The powder injection molding process of claim 87, wherein the feeding is carried out at pressures of about 5 MPa to about 25 MPa.

89. The powder injection molding process of claim 88, wherein the feeding is carried out at pressures of about 10 MPa to about 23 MPa.

90. The powder injection molding process of any one of claims 86 to 89, wherein the heating comprises heating at a temperature sufficient to melt the binder and generate a melt comprising a dispersion of the titanium and carbon-based materials.

91. The powder injection molding process of claim 90, wherein the heating further comprises heating at a temperature sufficient to at least partially remove the binder.

92. A process for promoting densification of a titanium-based material, the process comprising:

providing a composition as defined in any one of claims 2 to 17; and
subjecting the composition to pressureless sintering.

93. A process for promoting densification of a titanium-based material, the process comprising:

providing a composition as defined in any one of claims 1 to 17; and
subjecting the composition to a powder injection molding process.

94. The process of claim 93, wherein the powder injection molding process comprises heating the composition under conditions sufficient to melt the binder and generate a molded product comprising a dispersion of the titanium and carbon-based materials.

95. The process of claim 94, wherein the powder injection molding process further comprises heating the molded product under conditions to produce in-situ titanium carbide, wherein the titanium carbide is dispersed within a titanium matrix.

96. 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.

97. 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.

98. Use of an effective amount of a carbon-based material in 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.

99. 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. % to about 3.0 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

100. The use of any one of claims 96 to 99, wherein the titanium composite material comprises about 0.5 wt. % to about 2.0 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

101. The use of any one of claims 96 to 99, wherein the titanium composite material comprises about 0.5 wt. % to about 1.5 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

102. The use of any one of claims 96 to 99, wherein the titanium composite material comprises about 0.7 wt. % to about 1.3 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

103. The use of any one of claims 96 to 99, wherein the titanium composite material comprises a titanium metal matrix and titanium carbide dispersed in the matrix.

104. 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.

105. 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-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.

106. 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.

107. 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.

108. 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.

109. 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.

110. The use of any one of claims 104 to 109, wherein the composition further comprises a binder.

111. The use of any one of claims 104 to 110, wherein the composition comprises about 0.5 wt. % to about 2.0 wt. % of the carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

112. The use of any one of claims 104 to 110, wherein the composition comprises about 0.5 wt. % to about 1.5 wt. % of the carbon-based material, based on the total weight of the titanium-based powder and the carbon-based material.

113. The use of any one of claims 104 to 110, wherein the composition comprises 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.

114. The use of any one of claims 104 to 113, wherein the composition comprises about 50 vol. % to about 70 vol. % of the titanium-based powder, based on the total volume of the composition.

115. The use of any one of claims 104 to 113, wherein the composition comprises about 58 vol. % to about 68 vol. % of the titanium-based powder, based on the total volume of the composition.

116. The use of any one of claims 104 to 113, wherein the composition comprises about 60 vol. % to about 66 vol. % of the titanium-based powder, based on the total volume of the composition.

117. The use of any one of claims 110 to 116, wherein the composition comprises about 30 vol. % to about 50 vol. % of the binder, based on the total volume of the composition.

118. The use of any one of claims 110 to 116, wherein the composition comprises about 32 vol. % to about 45 vol. % of the binder, based on the total volume of the composition.

119. The use of any one of claims 110 to 118, wherein the binder comprises mainly at least one thermoplastic polymer, at least one wax, or mixtures thereof.

120. The use of any one of claims 106 to 119, wherein the titanium 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.

121. The use of any one of claims 106 to 119, wherein the titanium composite material comprises about 0.5 wt. % to about 2.0 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

122. The use of any one of claims 106 to 119, wherein the titanium composite material comprises about 0.5 wt. % to about 1.5 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

123. The use of any one of claims 106 to 119, wherein the titanium composite material comprises about 0.7 wt. % to about 1.3 wt. % of carbon, based on the total weight of titanium and carbon in the composite material.

124. The use of claim 106 or 119, wherein the titanium composite material comprises a titanium metal matrix and titanium carbide dispersed in the matrix.

125. The use of claim 124, wherein the titanium carbide is in-situ synthesized titanium carbide

126. The use of any one of claims 96 to 125, wherein the carbon-based material is chosen from graphite, graphene, elemental carbon, carbon black, amorphous carbon, semi-crystalline carbon, crystalline carbon and mixtures thereof.

127. The use of any one of claims 96 to 125, wherein the carbon-based material is chosen from single-walled nanotubes, functionalized single-walled nanotubes, multiwalled nanotubes, functionalized multiwalled nanotubes and mixtures thereof.

128. The use of any one of claims 104 to 127, wherein the titanium-based powder has an average particle size of about 5 μm to about 100 μm.

129. The use of any one of claims 104 to 127, wherein the titanium-based powder has an average particle size of about 5 μm to about 45 μm.

130. The use of any one of claims 104 to 127, wherein the titanium-based powder has an average particle size of about 10 μm to about 25 μm.

131. Use of a composition as defined in any one of claims 1 to 17 for preparing a titanium composite material.

132. Use of a composition as defined in any one of claims 1 to 17 for preparing a titanium carbide reinforced titanium composite.

133. Use of a composition as defined in any one of claims 1 to 17 in a process comprising pressureless sintering.

134. Use of a composition as defined in any one of claims 1 to 17 in a powder injection molding process.

135. The use of any one of claims 96, 98, 104, 106, 108 and 133, wherein the pressureless sintering comprises at least one process chosen from metal injection molding, pressing and sintering, loose powder sintering, selective laser sintering, electron beam sintering and powder rolling.

136. A product comprising the composite material of any one of claims 18 to 44, 45 and 72.

137. A product produced by the process of any one of claims 82 to 85.

138. A product produced by the powder injection molding process of any one of claims 86 to 91.

139. A kit comprising a composition as defined in any one of claims 1 to 17 and instructions for use of the composition in a powder injection molding process.

Patent History
Publication number: 20170283909
Type: Application
Filed: Sep 22, 2015
Publication Date: Oct 5, 2017
Inventors: Eric BARIL (Montréal), Louis-Philippe LEFEBVRE (Ottawa)
Application Number: 15/512,460
Classifications
International Classification: C22C 1/04 (20060101); C22C 14/00 (20060101); B22F 3/22 (20060101); B22F 1/00 (20060101);