EP3197621A1 - Titanium-based compositions, methods of manufacture and uses thereof - Google Patents
Titanium-based compositions, methods of manufacture and uses thereofInfo
- Publication number
- EP3197621A1 EP3197621A1 EP15844380.4A EP15844380A EP3197621A1 EP 3197621 A1 EP3197621 A1 EP 3197621A1 EP 15844380 A EP15844380 A EP 15844380A EP 3197621 A1 EP3197621 A1 EP 3197621A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- titanium
- carbon
- composition
- composite
- powder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/0094—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with organic materials as the main non-metallic constituent, e.g. resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
- B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
- B22F2998/10—Processes characterised by the sequence of their steps
Definitions
- 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.
- 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.
- 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.
- the present disclosure includes a composition comprising:
- 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.
- the present disclosure includes a composition comprising:
- the present disclosure includes a composition comprising: a titanium-based powder;
- 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.
- the present disclosure includes a composite material comprising:
- 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.
- 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.
- 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.
- the present disclosure includes a method of manufacturing a titanium-based composite material, the method comprising:
- composition comprising a titanium-based powder and at least one of a carbon-based material and a binder
- 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.
- the present disclosure includes a method of manufacturing a titanium-based composite material, the method comprising:
- composition comprising a titanium-based powder and at least one of a carbon-based material and a binder
- 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.
- the present disclosure includes a process for producing a titanium-based composite material, the process comprising:
- 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.
- the present disclosure includes a process for producing a titanium-based composite material, the process comprising:
- the present disclosure includes a powder injection molding process for in-situ synthesis of titanium carbide, the process comprising:
- 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.
- the present disclosure includes a process for promoting densification of a titanium-based material, the process comprising:
- composition comprising a titanium-based powder and at least one of a carbon-based material and a binder
- 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.
- the present disclosure includes a process for promoting densification of a titanium-based material, the process comprising:
- composition comprising a titanium-based powder and at least one of a carbon-based material and a binder
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- 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.
- the present disclosure includes a product produced by a process comprising:
- 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.
- the present disclosure includes a product produced by a process comprising:
- 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.
- the present disclosure includes a product produced by a powder injection molding process, the process comprising:
- 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;
- 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.
- the present disclosure includes a kit comprising:
- composition comprising a titanium-based powder and at least one of a carbon-based material and a binder
- 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.
- the present disclosure includes a kit comprising:
- composition comprising a titanium-based powder and at least one of a carbon-based material and a binder
- 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.
- FIG. 1 is a graph illustrating the effect of carbon black concentration on the density of a titanium carbide-reinforced titanium composite ( ⁇ 6 ⁇ 4 ⁇ -45 ⁇ ) in accordance with an embodiment of the present disclosure.
- FIG. 2 is a block diagram illustrating the effect of carbon black addition
- FIG. 3 shows optical micrographs of the effect of carbon black addition
- 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 ( ⁇ -45 ⁇ ) in accordance with an embodiment of the present disclosure.
- FIG. 5 is a block diagram illustrating the effect of carbon black addition
- FIG. 6 is a block diagram illustrating the effect of carbon black addition
- FIG. 7 is a block diagram illustrating the effect of carbon black addition
- Ti6AI4V- 25 ⁇ (1 % wt.) on the wear of a titanium carbide-reinforced titanium composite (Ti6AI4V- 25 ⁇ ) in accordance with an embodiment of the present disclosure.
- titanium-based includes titanium alloys as well as substantially pure titanium.
- the composition can further comprise a binder.
- 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.
- the binder comprises mainly thermoplastic polymers and/or waxes.
- the binder comprises a thermoplastic polymer, a paraffin or mixtures thereof.
- the binder comprises at least one thermoplastic polymer, at least one wax, or mixtures thereof.
- 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.
- 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.
- the carbon-based material is chosen from graphite, graphene, elemental carbon, carbon black, amorphous carbon, semi-crystalline carbon, crystalline carbon and mixtures thereof.
- the carbon-based material can be carbon nanotubes.
- the carbon-based material can be chosen from single- walled nanotubes, functionalized single-walled nanotubes, multiwalled nanotubes, functionalized multiwalled nanotubes and mixtures thereof.
- the titanium-based powder comprises particles ranging from about 0.01 ⁇ to about 200 ⁇ , about 0.1 ⁇ to about 100 ⁇ ; about 0.1 ⁇ to about 45 ⁇ ; or about 0.1 ⁇ to about 25 ⁇ .
- the titanium-based powder has an average particle size of about 1 ⁇ to about 100 ⁇ , about 5 ⁇ to about 100 ⁇ ; about 5 ⁇ to about 45 ⁇ ; about 5 ⁇ to about 25 ⁇ ; or about 10 ⁇ to about 25 ⁇ .
- 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.
- 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.
- the composite material comprises in-situ synthesized titanium carbide.
- the titanium carbide is produced by a process comprising sintering.
- 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.
- 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.
- 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.
- the powder injection molding comprises injection of the composition into a mold to form a shape.
- 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.
- 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).
- the composites exhibit higher ultimate tensile strength (FIG. 5).
- the composites exhibit higher hardness (FIG. 6).
- the composites exhibit higher wear resistance (FIG. 7).
- the composites exhibit lower residual porosity.
- the composites exhibit higher density.
- 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.
- Pressureless sintering 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.
- 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.
- 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.
- 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.
- 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.
- the titanium carbide-reinforced titanium composites of the present disclosure are prepared by a powder injection molding process.
- a titanium-based powder, a carbon- based material and a binder are mixed to provide a composition.
- 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.
- 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.
- 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.
- 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.
- the titanium-based powder comprises particles ranging from 0.01 ⁇ to about 200 ; about 0.01 ⁇ to about 100 ⁇ ; about 0.1 ⁇ to about 45 ⁇ ; or about 0.1 ⁇ to about 25 ⁇ .
- 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
- 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.
- the carbon-based materials are chosen from graphite, graphene, elemental carbon, carbon black, amorphous carbon, semi-crystalline carbon, crystalline carbon and carbon nanotubes.
- the carbon nanotubes are chosen from single- walled nanotubes, functionalized single-walled nanotubes, multiwalled nanotubes and functionalized multiwalled nanotubes.
- the binder is chosen from thermoplastic polymers, paraffin, waxes, surface agents and mixtures thereof.
- 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.
- 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 1 1 .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.
- a first portion of the binder is removed by solvent debinding.
- 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.
- a second portion of the binder is removed by thermal debinding.
- 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.
- the composition is sintered.
- the sintering comprises heating at temperatures of about 1250°C.
- the sintering is performed at temperatures from about 1000°C to about 1500°C.
- the sintering is performed at temperatures from about 1 100°C to about 1400°C.
- the sintering is performed at temperatures from about 1200°C to about 1300°C.
- the sintering is performed at temperatures from about 1225°C to about 1275°C.
- 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 121 1 °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,
- the present disclosure includes a powder injection molding process for preparing a titanium carbide-reinforced titanium composite, the process comprising:
- binder 50% 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.
- antioxidant e.g. pentaerythritol tetrakis(3-(3 5-di-tert-butyl-4-hydroxyphenyl)propionate
- titanium powder AP&C; 64.4% vol.
- carbon black particles Monarch 880(CS-5820 from Cabot
- 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 .
- CpTi and Ti6AI4V were used as the titanium-based powders constituting the matrix material of the composites.
- the size connotations -25 ⁇ and -45 ⁇ refer to particles smaller than or equal to -25 ⁇ and -45 ⁇ respectively.
- the carbon-based material was carbon black.
- 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-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).
- the addition of graphite has an effect on the density of the titanium carbide-reinforced titanium composite ( ⁇ 6 ⁇ 4 ⁇ /-45 ⁇ ).
- the density significantly increased with increasing carbon black concentrations, reaching a peak value of 97.4 ⁇ 0.4% at 1 % carbon black concentration.
- 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.
- the densification effect observed for the titanium carbide-reinforced titanium composite could also be observed for titanium carbide-reinforced titanium composites ⁇ 6 ⁇ 4 ⁇ -25 ⁇ and ⁇ -45 ⁇ 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 ( ⁇ 6 ⁇ 4 ⁇ -25 ⁇ ).
- carbon black 1 % wt.
- the addition of carbon black (1 % wt.) significantly reduced the number of pores, which are shown as black dots on the micrographs.
- 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.
- the in-situ formation of titanium carbides further refines the titanium grain size in the composite material.
- 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 ( ⁇ 6 ⁇ 4 ⁇ /-25 ⁇ ).
- 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 ( ⁇ 6 ⁇ 4 ⁇ -25 ⁇ ).
- 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 (1 10 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).
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Abstract
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201462054012P | 2014-09-23 | 2014-09-23 | |
| PCT/CA2015/050932 WO2016044930A1 (en) | 2014-09-23 | 2015-09-22 | Titanium-based compositions, methods of manufacture and uses thereof |
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| EP3197621A1 true EP3197621A1 (en) | 2017-08-02 |
| EP3197621A4 EP3197621A4 (en) | 2018-01-03 |
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| US (1) | US20170283909A1 (en) |
| EP (1) | EP3197621A4 (en) |
| JP (1) | JP2017535667A (en) |
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| US20190062871A1 (en) * | 2017-08-25 | 2019-02-28 | The Boeing Company | Tailoring high strength aluminum alloys for additive manufacturing through the use of grain refiners |
| KR102271297B1 (en) * | 2018-12-12 | 2021-06-29 | 주식회사 포스코 | Composite of titanium-carbon, method of preparing same and sintering materil comprising same |
| CN110592429B (en) * | 2019-10-16 | 2021-03-05 | 西安稀有金属材料研究院有限公司 | High-hardness wear-resistant bimetallic titanium-based composite material with net structure and preparation method thereof |
| TWI710522B (en) * | 2019-11-25 | 2020-11-21 | 慧隆科技股份有限公司 | Graphene modifying method of metal |
| CN110923490B (en) * | 2019-12-09 | 2020-11-10 | 武汉理工大学 | A method for preparing high-strength micron porous metal titanium block by dealloying titanium-molybdenum alloy |
| CN111069614B (en) * | 2020-01-07 | 2022-10-18 | 西北工业大学 | Additive manufacturing method of in-situ synthesized micro-nano TiC reinforced titanium-based composite material |
| CN111451502B (en) * | 2020-04-10 | 2021-08-17 | 西北工业大学 | Partition control method of in situ in-situ TiC-reinforced titanium matrix composites for additive manufacturing |
| CN111961902B (en) * | 2020-08-14 | 2021-10-29 | 东南大学 | A kind of titanium matrix composite material with heterogeneous structure and its preparation method and application |
| CN115807179B (en) * | 2021-09-14 | 2024-04-26 | 中国石油天然气股份有限公司 | Titanium graphene composite material and preparation method and application thereof |
| CN116765383A (en) * | 2023-08-01 | 2023-09-19 | 江苏精研科技股份有限公司 | Preparation method of high-thermal-conductivity titanium alloy material |
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| JP2001049304A (en) * | 1999-08-04 | 2001-02-20 | Hitachi Metals Ltd | Titanium injection molded sintered body and method for producing the same |
| US8747515B2 (en) * | 2003-12-27 | 2014-06-10 | Advance Material Products, Inc | Fully-dense discontinuously-reinforced titanium matrix composites and method for manufacturing the same |
| JP4513520B2 (en) * | 2004-11-15 | 2010-07-28 | 三菱マテリアル株式会社 | Titanium alloy sponge sintered body with excellent compressive strength |
| DE102006005225B3 (en) * | 2006-01-26 | 2007-04-05 | Technische Universität Dresden | Titanium material and process for its preparation |
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| JP2017535667A (en) | 2017-11-30 |
| US20170283909A1 (en) | 2017-10-05 |
| CA2958409C (en) | 2017-11-07 |
| EP3197621A4 (en) | 2018-01-03 |
| WO2016044930A1 (en) | 2016-03-31 |
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