CN111822721B - Tungsten-doped titanium-based composite porous material and preparation method thereof - Google Patents

Tungsten-doped titanium-based composite porous material and preparation method thereof Download PDF

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CN111822721B
CN111822721B CN202010675244.5A CN202010675244A CN111822721B CN 111822721 B CN111822721 B CN 111822721B CN 202010675244 A CN202010675244 A CN 202010675244A CN 111822721 B CN111822721 B CN 111822721B
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tungsten
porous material
based composite
titanium
composite porous
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CN111822721A (en
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宋滨娜
曹健
章顺虎
仲兆准
宋志轩
潘春鑫
吴芃睿
庞博
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Suzhou University
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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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • 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
    • B22F3/001—Starting from powder comprising reducible metal compounds
    • 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
    • B22F3/10—Sintering only
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • 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
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • 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
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B22F3/1134—Inorganic fillers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Abstract

The invention relates to a tungsten-doped titanium-based composite porous material and a preparation method thereof. The invention discloses application of W in preparation of a tungsten-doped titanium-based composite porous material, and when the tungsten-doped titanium-based composite porous material is prepared, a small amount of W with a micro-nano size is doped in the tungsten-doped titanium-based composite porous material, so that the compactness of the tungsten-doped titanium-based composite porous material can be improved, and the hardness and the wear resistance of a matrix can be obviously improved. The tungsten-doped titanium-based composite porous material is distributed with a plurality of three-dimensional porous structures, the three-dimensional porous structures form a topological structure or a random structure, the tungsten-doped titanium-based composite porous material comprises Ti, TiC and W, wherein tungsten metal accounts for less than 3% of the mass fraction of the tungsten-doped titanium-based composite porous material. The tungsten-doped titanium-based composite porous material is prepared by an ink direct-writing forming additive manufacturing method or a method of adding a pore-forming agent and combining discharge plasma sintering.

Description

Tungsten-doped titanium-based composite porous material and preparation method thereof
Technical Field
The invention relates to the technical field of preparation of titanium-based composite porous materials, in particular to a tungsten-doped titanium-based composite porous material and a preparation method thereof.
Background
The titanium (Ti) -based composite porous material has the characteristics of low density, high energy absorption and biocompatibility, and is a material integrating the structure and the function. In recent years, with the continuous new requirements of high performance and light structure on materials and the wide application of the materials in aviation, aerospace and biological materials, the requirements on the conditions of wear resistance, hardness, pore structure and the like are higher, and therefore, the design of a porous titanium-based composite material with new components and structures suitable for different application requirements is an important solution.
The Ti-TiC composite material prepared by adding TiC particles into the Ti-based material has higher performance, the performance is more excellent than that of pure Ti, particularly, the strength and the hardness of the composite material can be improved by adding the TiC particles with high volume fraction, but the compactness, the surface roughness and the hardness of the composite material can be reduced by adding the refractory TiC ceramic particles with high volume fraction. This can cause the abrasion dust to fall off and cause more serious damage when the material is used, especially under the friction working condition, thereby significantly reducing the mechanical properties of the material, such as wear resistance and fatigue resistance.
At present, three-dimensional porous structures are divided into three-dimensional pore structures with complicated topological order and random structures, and the three-dimensional porous structures of different types have unique mechanical properties and functions and can be selected according to different application environments. The existing common laser additive manufacturing method and the conventional melt method and sintering method are difficult to meet the following requirements: 1. a Ti-based composite material prepared by adding a high-melting-point material is added to obtain a porous material with high density and uniform tissue; 2. the porous material with small grain size, low surface roughness and excellent wear resistance is difficult to prepare; 3. it is difficult to provide an effective scheme and process according to different user requirements to obtain a three-dimensional pore structure and a random structure with complicated topological order, so as to adapt to different use requirements.
Disclosure of Invention
In order to solve the technical problems, the invention aims to provide a tungsten-doped titanium-based composite porous material and a preparation method thereof.
The first purpose of the invention is to disclose the application of tungsten metal (W) in preparing a tungsten-doped titanium-based composite porous material, wherein a plurality of three-dimensional porous structures are distributed in the tungsten-doped titanium-based composite porous material, the porous structures form a three-dimensional topological structure or a random structure, the tungsten-doped titanium-based composite porous material comprises Ti, TiC and W, and the W accounts for less than 3% of the mass fraction of the tungsten-doped titanium-based composite porous material.
In the invention, the tungsten-doped titanium-based composite porous material is a Ti-TiC composite material (namely Ti (W) -TiC material) doped with W, the Ti-TiC is used as a matrix of the tungsten-doped titanium-based composite porous material, and the W is a superhard material, and when the tungsten-doped titanium-based composite porous material is prepared, a small amount of W with micro-nano size is doped in the tungsten-doped titanium-based composite porous material, so that the TiC densification process can be obviously improved, the density is effectively improved, and the matrix hardness and the wear resistance are obviously improved.
Further, the particle size of W is 100nm-2 μm; the particle diameter of the titanium carbide is 15 μm or less.
The second purpose of the invention is to provide a preparation method of the tungsten-doped titanium-based composite porous material, wherein the porous structure of the tungsten-doped titanium-based composite porous material forms a three-dimensional topological structure, and the preparation method comprises the following steps:
(1) uniformly mixing tungsten powder, titanium carbide and a metal titanium matrix to obtain first mixed powder, wherein the metal titanium matrix comprises pure titanium or titanium hydride, the particle size of the tungsten powder is 100nm-1 mu m, and the particle size of the titanium carbide is less than 15 mu m; the tungsten powder accounts for less than 3% of the first mixed powder by mass; preparing the metal titanium matrix initial powder with the particle size of less than 10 mu m;
(2) uniformly dispersing the first mixed powder in a polymer solution to synthesize the ink, wherein the mass ratio of the first mixed powder to the polymer solution is (4-1):1, and the polymer solution comprises a water-soluble polymer and water;
(3) 3D printing is carried out on the ink according to designed printing parameters to obtain a prefabricated body, the prefabricated body is sintered at the temperature of 1000-1300 ℃, and the tungsten-doped titanium-based composite porous material is obtained after sintering, wherein the printing model parameters comprise porosity parameters and the topological structure type of a three-dimensional porous structure in the porous material.
Further, in the step (1), the step of uniformly mixing the tungsten powder, the titanium carbide and the metallic titanium matrix comprises:
ball-milling W and TiC to obtain W-doped TiC powder; then, the W-doped TiC powder is added to the metallic titanium matrix to obtain a first mixed powder.
Further, in the step (1), the metallic titanium matrix is preferably titanium hydride (TiH) which is a non-metallic composite material of titanium2) Selection of TiH2The advantage of being a metallic titanium substrate is TiH2The cost is low, the density is high, the oxygen content is low, and dehydrogenation reaction occurs in the subsequent sintering process, so that the tungsten-doped titanium-based composite porous material has good mechanical property.
Further, in the step (1), the titanium carbide accounts for 1-30% of the volume fraction of the metallic titanium matrix.
Further, in the step (2), the polymer solution comprises water, polyvinyl alcohol and polyethylene glycol, and the mass ratio of the water to the polyvinyl alcohol to the polyethylene glycol is (6-7.5): (3-1.5): 1. according to the invention, the polymer solution is used as a solvent to disperse the first mixed powder, and the polymer solution comprises polyvinyl alcohol and polyethylene glycol, so that good formability can be given to printing ink, and the finally prepared tungsten-doped titanium-based composite porous material has good mechanical properties. The viscosity of the printing ink can be adjusted by adjusting the dosage of each component in the polymer solution, so that the formability of the printed preform is changed. When the proportion is beyond the range, problems such as wire drawing, air bubbles and incapability of forming can be caused in the printing process of the printing ink, or problems such as wire breaking, plugging and poor formability can be caused.
Further, the molecular weight of polyvinyl alcohol is 10k to 20 k. The molecular weight of polyethylene glycol is 600-2000.
Further, in the step (2), an ultrasonic wave dispersing instrument is adopted for dispersing for 30min-1h, and 3D printing is carried out after 30min-2h after standing.
Further, in the step (3), during the 3D printing process, the printing speed is 5-15mm/s, the printing diameter is 150-. Wherein, the printing diameter refers to the diameter of the nozzle in the 3D printer.
Further, in the step (3), sintering is performed in a vacuum environment or a protective atmosphere, so that the metallic titanium substrate can be prevented from being oxidized. Vacuum degree of not less than 3X 10-5And (5) Torr. Preference is given to protective atmospheresArgon gas with the flow rate of 50-100 mL/min.
Further, in the step (3), the temperature is raised from room temperature to 1000-1300 ℃ at a heating rate of 2-10 ℃/min, and the temperature is maintained at 1000-1300 ℃ for 0.1-4 h.
The invention also provides another preparation method of the tungsten-doped titanium-based composite porous material, the porous structure of the tungsten-doped titanium-based composite porous material forms an irregular structure, and the preparation method comprises the following steps:
(S1) uniformly mixing tungsten powder, titanium carbide, a metal titanium matrix and a pore-forming agent to obtain second mixed powder, wherein the metal titanium matrix comprises pure titanium or titanium hydride, the particle size of the tungsten powder in the second mixed powder is 100nm-2 mu m, and the particle size of the titanium carbide is less than 10 mu m; the tungsten powder accounts for less than 3% of the second mixed powder by mass; preparing the metal titanium matrix, wherein the particle size of the initial powder is less than 10 mu m;
(S2) performing spark plasma sintering on the second mixed powder under the vacuum condition of 500-650 ℃ and removing the pore-forming agent, and then performing sintering at 1000-1300 ℃ to obtain the tungsten-doped titanium-based composite porous material after sintering.
Further, in the step (S1), the step of uniformly mixing the tungsten metal particles, the titanium carbide, the metallic titanium matrix, and the pore-forming agent includes:
w, TiC and the metallic titanium substrate are ball-milled, then a pore-forming agent is added into the mixture, and the ball-milling is continued to obtain second mixed powder.
Further, in the step (S1), the pore-forming agent includes NaCl and/or NH4HCO3。
Further, in the step (S1), the pore-forming agent accounts for 90% or less of the volume fraction of the second mixed powder. The porosity and the mechanical property of the finally prepared tungsten-doped titanium-based composite porous material can be adjusted by changing the dosage of the pore-forming agent.
Further, in the step (S1), the titanium carbide accounts for 1% to 30% of the volume fraction of the metallic titanium substrate. Further, in the step (S2), sintering is performed in the graphite mold, the temperature is raised from room temperature to 650 ℃ at a heating rate of 50-100 ℃/min, and the temperature is maintained at 650 ℃ of 500-30 min. The vacuum pressure of the spark plasma sintering is 25-40 MPa. The purpose of spark plasma sintering is to achieve activation and rapid sintering of the powder.
Further, in the step (S2), when the pore former is NaCl, the step of removing the pore former includes:
and (3) placing the product after spark plasma sintering in water, and dissolving the pore-forming agent in the sintered product by using water to form a porous structure in the sintered product. Preferably, water at 40-60 ℃ is used for treating for 20-40 h.
Further, in the step (S2), when the pore-forming agent is NH4HCO3In the spark plasma sintering process, a pore-forming agent NH4HCO3Directly volatilized by sintering, and the removal of the pore-forming agent can be directly realized without soaking in water after the sintering is finished.
Further, in the step (S2), sintering is performed at 1300 ℃ under a vacuum environment or a protective atmosphere for 1-3h at 1000-.
The invention also claims a tungsten-doped titanium-based composite porous material, which is characterized in that: the tungsten-doped titanium-based composite porous material is distributed with a plurality of three-dimensional porous structures, the porous structures form a three-dimensional topological structure or a random structure, and the tungsten-doped titanium-based composite porous material comprises Ti, TiC and W, wherein the W accounts for less than 3% of the mass fraction of the tungsten-doped titanium-based composite porous material; the tungsten-doped titanium-based composite porous material is prepared by the two preparation methods.
Further, the porosity of the tungsten-doped titanium-based composite porous material is 20% -90%.
Further, TiC accounts for 1-30% of the volume fraction of Ti.
By the scheme, the invention at least has the following advantages:
the invention discloses application of W in preparation of a tungsten-doped titanium-based composite porous material, and the density, hardness and wear resistance of the tungsten-doped titanium-based composite porous material can be improved by doping a small amount of W with a micro-nano size.
The invention provides a tungsten-doped titanium-based composite porous material which has new composite components, is low in cost in a preparation method, and can be used for preparing two types of porous structures with three-dimensional ordered and disordered pore-shaped distribution according to requirements. The preparation of the high-wear-resistance light Ti-based composite porous material can be realized by a method of ink direct-writing molding additive manufacturing or a method of adding pore-forming agent and combining discharge plasma sintering. The porous Ti-based composite material prepared by the method can be applied to the aerospace field and biomedical implants, and has wide application value and potential due to the high compactness, hardness and good wear resistance of the tungsten-doped titanium-based composite porous material.
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following description is made with reference to the preferred embodiments of the present invention and the accompanying detailed drawings.
Drawings
FIG. 1 is a flow chart of a process for preparing a porous material having a three-dimensional porous structure with a topological structure;
FIG. 2 is a flow chart of a process for preparing a porous material having a three-dimensional porous structure with irregular pores;
FIG. 3 is a pictorial view of prepared tungsten doped titanium based composite porous material, SEM picture of mixed powder of TiC and W after ball milling, and SEM picture of Ti (W) -TiC after sintering;
FIG. 4 is an XRD pattern of the tungsten doped titanium matrix composite porous material prepared in example 3.
Detailed Description
As shown in fig. 1, in the present invention, a porous material having a three-dimensional porous structure with a topological structure is prepared as follows:
1. doping W into TiC according to a certain proportion by a high-speed ball milling process, wherein the ball milling is carried out at normal temperature according to a ball-to-material ratio of 5-10: 1 ball milling for 1-4h at the rotation speed of 150-. The size of W before ball milling is 100nm-1 μm, and the size of TiC powder is less than 15 μm;
2. adding W-doped TiC powder into TiH according to a certain proportion2Or pure Ti powder to obtain mixed powder; w accounts for less than 3% of the mass fraction of the mixed powder;
3. preparing a solution, wherein the solution comprises the following components: polyvinyl alcohol: adding the mixed powder obtained in the step 2 into the solution for dispersion, wherein the mass ratio of the solid powder to the solution is (4-1):1, dispersing for 30min-1h by using an ultrasonic disperser, and then standing for 30min-2h to obtain printing ink; wherein the molecular weight of the polyvinyl alcohol is 10k-20 k. The molecular weight of the polyethylene glycol is 600-2000;
4. designing three-dimensional porous structures with different porosities and topological structures through computer-aided software;
5. and (3) introducing the printing ink after standing into a printer to print a prefabricated body with a target design, wherein the printing speed is 5-15mm/s, the printing diameter is 150-1000 mu m, and the extrusion pressure range is 5-10 bar.
6. Heating the prefabricated body at the heating speed of 2-10 ℃/min, the heating temperature of 1000-.
As shown in fig. 2, in the present invention, a porous material having a three-dimensional porous structure with irregular pores is prepared as follows:
1. the W and the TiC are mixed in TiH according to a certain proportion2Or ball milling and mixing the pure Ti powder to obtain mixed powder. The size of W before ball milling is 100nm-2 μm, and the size of TiC powder is less than 10 μm; the ball milling is carried out at normal temperature, argon is introduced for protection, and the ratio of balls to materials is 5-10: 1 ball milling for 1-4h at the rotation speed of 250-350 rpm; w accounts for less than 5% of the mass fraction of the mixed powder;
2. adding pore-forming agent NaCl or NH according to certain volume fraction4HCO3Adding the mixture into the mixed powder for mixing, wherein the pore-forming agent accounts for less than 90% of the volume fraction of the mixed powder, and the ratio of the ball material to the material is 2-5: 1, the rotating speed is 100-150rpm, the mixing time is 0.2-1h in a vacuum environment, and the powder is taken out to wait for sintering;
3. and (3) adopting a discharge plasma sintering method, loading the mixed powder obtained in the step (2) into a graphite mold, wherein the sintering temperature is 500-650 ℃, the heating rate is 50-100 ℃/min, the temperature is kept for 10-30min, and the pressure is 25-40MPa in a vacuum environment.
4. And (3) putting the sintered sample into a constant-temperature water bath kettle for dissolving at the temperature of 40-60 ℃ for 20-40h, taking out the sample, putting the sample into a vacuum heating furnace at the temperature of 1000-1300 ℃, keeping the temperature for 1-3h, and finally obtaining the Ti (W) -TiC composite porous titanium material under the vacuum environment or argon protection.
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1 lattice material of Ti (W) -15% vol TiC
1. And doping W into TiC and performing ball milling to obtain W-doped TiC powder. Wherein, the ball milling is specifically carried out at normal temperature according to a ball-material ratio of 10: 1, ball milling for 1h at the rotating speed of 300rpm, wherein the size of W before ball milling is about 100nm, and the size of TiC powder is about 10 mu m.
2. Adding W-doped TiC powder to TiH2Obtaining mixed powder from the powder; wherein, W accounts for 1.0 percent of the mass fraction of the mixed powder, and TiC accounts for TiH215% by volume of the powder, TiH2The particle size of the powder was about 3 μm.
3. Preparing a solution containing water, polyvinyl alcohol and polyethylene glycol, wherein the ratio of water: polyvinyl alcohol: and (3) adding the mixed powder obtained in the step (2) into the solution for dispersion, wherein the mass ratio of the total mass of the mixed powder obtained in the step (2) to the solution is 3:1, synthesizing a suspension containing solid powder, dispersing for 50min by using an ultrasonic disperser to obtain ink, standing for 1.5h, and waiting for printing.
4. Lattice structures of different "wire" pitch and cross-sectional diameter sizes were designed by drawing programming, and the overall pattern was designed with dimensions of 55mm × 110 × 55mmmm (length × width × height) as boundaries.
5. And (4) introducing the ink synthesized in the step (3) into a printer, and printing a prefabricated body with a target design according to the printing model designed in the step (4), wherein the printing speed range is 8mm/s, the printing diameter is 250 mu m, and the extrusion pressure range is 8 bar.
6. Heating the prefabricated body at 1200 ℃, keeping the temperature for 2h, heating up at a speed of 2 ℃/min, and sintering the environment: vacuum environment, trueThe void degree is 5.9 multiplied by 10-5And torr, obtaining the porous material with the three-dimensional porous structure of the topological structure.
Example 2 lattice material of Ti (W) -30% vol TiC
1. And doping W into TiC and performing ball milling to obtain W-doped TiC powder. Wherein, the ball milling is specifically carried out at normal temperature according to a ball-material ratio of 10: 1, ball milling for 1h at the rotating speed of 300rpm, wherein the size of W after ball milling is about 100nm, and the size of TiC powder is about 10 mu m.
2. Adding W-doped TiC powder to TiH2Obtaining mixed powder from the powder; wherein, W accounts for 1.0 percent of the mass fraction of the mixed powder, and TiC accounts for TiH 230% by volume of the powder, TiH2The particle size of the powder is about-3 μm.
3. Preparing a solution containing water, polyvinyl alcohol and polyethylene glycol, wherein the ratio of water: polyvinyl alcohol: adding the mixed powder obtained in the step 2 into the solution for dispersion, wherein the mass ratio of the total mass of the mixed powder obtained in the step 2 to the solution is 2:1, synthesizing a suspension containing solid powder, dispersing for 1h by using an ultrasonic disperser to obtain ink, standing for 1h, and waiting for printing.
4. Lattice structures of different "wire" pitch and cross-sectional diameter sizes were designed by drawing programming, and the overall pattern was designed with dimensions of 55mm × 110 × 55mmmm (length × width × height) as boundaries.
5. And (4) introducing the ink synthesized in the step (3) into a printer, and printing a prefabricated body with a target design according to the printing model designed in the step (4), wherein the printing speed range is 5mm/s, the printing diameter is 410 mu m, and the extrusion pressure range is 6 bar.
6. Heating the prefabricated body, wherein the heating temperature is 1300 ℃, the heat preservation time range is 2h, the heating rate is 10 ℃/min, and the sintering environment is as follows: vacuum environment with vacuum degree of 6 × 10-5And torr, obtaining the porous material with the three-dimensional porous structure of the topological structure.
Example 3 Ti (W) -15% vol TiC composite porous titanium Material
1. And adding W and TiC into the pure Ti powder for ball milling and mixing to obtain mixed powder. Wherein W accounts for 3 percent of the mass fraction of the mixed powder, and TiC accounts for 15 percent of the volume fraction of the pure Ti powder. The size of W is 1 μm before ball milling, and the size of TiC powder is about 10 μm; wherein, the ball milling is specifically that under normal temperature, argon is introduced for protection, and the ball material ratio is 10: 1, ball milling for 3 hours at the rotating speed of 300 rpm.
2. And (3) adding a pore-forming agent NaCl into the mixed powder obtained in the step (1) and mixing to obtain mixed powder containing the pore-forming agent, wherein the pore-forming agent accounts for 40% of the volume fraction of the mixed powder containing the pore-forming agent. Mixing the mixed powder containing the pore-forming agent according to a ball-material ratio of 2:1, the rotation speed is 150rpm, the mixing time is 0.5h, and the mixed powder is taken out to wait for sintering.
3. And (3) loading the mixed powder obtained in the step (2) into a graphite die by adopting a spark plasma sintering method, wherein the sintering temperature is 650 ℃, the heating rate is 50 ℃/min, the temperature is kept for 10min, and the pressure is 30MPa in a vacuum environment.
4. Placing the sintered sample into a constant temperature water bath kettle for dissolving at 60 ℃ for 24h, taking out the sample, placing the sample into a vacuum heating furnace at 1200 ℃, keeping the temperature for 2h, increasing the temperature at 10 ℃/min and keeping the vacuum degree at 6 x 10-5And (3) torr, and finally obtaining the Ti (W) -TiC composite porous titanium material with the irregular porous structure.
Example 4 Ti (W) -30% vol TiC composite porous titanium Material
1. Adding W and TiC to TiH2And performing ball milling and mixing on the powder to obtain mixed powder. Wherein W accounts for 3 percent of the mass fraction of the mixed powder, and TiC accounts for TiH 230% of the powder volume fraction. The size of W is 1 μm before ball milling, and the size of TiC powder is about 10 μm; TiH2The powder size was about 3 μm. Wherein, the ball milling is specifically that under normal temperature, argon is introduced for protection, and the ratio of ball to material is 5: 1, ball milling for 4 hours at the rotating speed of 350 rpm.
2. Adding a pore-forming agent NH4HCO3And (3) adding the mixed powder obtained in the step (1) and mixing to obtain mixed powder containing a pore-forming agent, wherein the pore-forming agent accounts for 40% of the volume fraction of the mixed powder containing the pore-forming agent. Mixing the mixed powder containing the pore-forming agent according to a ball-material ratio of 2:1, the rotation speed is 100rpm, the mixing time is 1h, and the powder is taken out to wait for sintering.
3. Loading the mixed powder obtained in the step 2 into a graphite die by adopting a spark plasma sintering method, wherein the sintering temperature is 1000 ℃, the heating rate is 10 ℃/min, the temperature is kept for 30min, then the sintering temperature is 1300 ℃, the heating rate is 5 ℃/min, the temperature is kept for 30min, and the pressure is 30MPa in a vacuum environment; finally obtaining the Ti (W) -TiC composite porous titanium material with an irregular porous structure.
Comparative example 1 Ti-15% vol TiC lattice material
1. Adding TiC powder to TiH2Ball milling is carried out in the powder, wherein TiC powder accounts for TiH215% by volume of the powder. The size of TiC powder is about 10 mu m before ball milling, and the ball milling is carried out at normal temperature according to the ball-to-material ratio of 10: 1 ball milling at 300rpm for 1 h.
2. Preparing a solution containing water, polyvinyl alcohol and polyethylene glycol, wherein the ratio of water: polyvinyl alcohol: and (3) adding the mixed powder obtained in the step (1) into the solution for dispersion, wherein the mass ratio of the total mass of the mixed powder obtained in the step (1) to the solution is 2:1, synthesizing a suspension containing solid powder, dispersing for 50min by using an ultrasonic disperser, standing for 1.5h, and waiting for printing.
3. Lattice structures of different "wire" pitch and cross-sectional diameter sizes were designed by drawing programming, and the overall pattern was designed with dimensions of 55mm × 110 × 55mmmm (length × width × height) as boundaries.
4. And (4) introducing the ink synthesized in the step (3) into a printer, and printing a prefabricated body with a target design according to the printing model designed in the step (4), wherein the printing speed range is 6mm/s, the printing diameter is 250 mu m, and the extrusion pressure range is 5 bar.
5. Heating the prefabricated body at 1200 ℃, keeping the temperature for 4h, heating up at a speed of 10 ℃/min, and sintering the environment: vacuum environment with vacuum degree of 6 × 10-5torr, obtaining the three-dimensional porous structure porous material without W and with topological structure.
Comparative example 2 Ti-15% vol TiC composite porous titanium material
1. Adding TiC powder into pure Ti powder for ball milling and mixing, wherein the TiC powder accounts for TiH215% by volume of the powder. The size of W is 1 μm before ball milling, and the size of TiC powder is about 10 μm; ball with ball-shaped sectionThe grinding is carried out at normal temperature under the protection of argon gas, and the ratio of balls to materials is 10: 1, ball milling for 3 hours at the rotating speed of 300 rpm.
2. And (3) adding a pore-forming agent NaCl into the mixed powder obtained in the step (1) and mixing to obtain mixed powder containing the pore-forming agent, wherein the pore-forming agent accounts for 40% of the volume fraction of the mixed powder containing the pore-forming agent. Mixing the mixed powder containing the pore-forming agent according to a ball-material ratio of 2:1, the rotation speed is 150rpm, the mixing time is 0.5h, and the powder is taken out to wait for sintering.
3. And (3) putting the powder obtained in the step (2) into a graphite die, wherein the sintering temperature is 650 ℃, the heating rate is 50 ℃/min, the temperature is kept for 10min, and the pressure is 30MPa in a vacuum environment.
4. Placing the sintered sample into a constant temperature water bath kettle for dissolving at 60 deg.C for 24 hr, taking out the sample, placing into a vacuum heating furnace at 1200 deg.C for 2 hr, heating at 10 deg.C/min, and vacuum degree of 6 × 10-5And torr, obtaining the W-free Ti-TiC composite porous titanium material.
Comparative example 3 Ti-15% vol TiC lattice material
Adding TiC powder into pure Ti powder for mixing, wherein the TiC powder accounts for TiH215% by volume of the powder. The lattice structure is prepared by a selective laser melting method under the conditions of laser power of 200W, scanning speed of 300mm/s and energy density of 120J/mm3。
Comparative example 4 Ti-15% vol TiC composite porous titanium material
Adding TiC powder into pure Ti powder for mixing, wherein the TiC powder accounts for TiH215 percent of the powder volume fraction is added with a pore-forming agent NH4HCO3And mixing to obtain mixed powder containing the pore-forming agent, wherein the pore-forming agent accounts for 40% of the volume fraction of the mixed powder containing the pore-forming agent. And (3) carrying out cold press molding on the mixed powder containing the pore-forming agent under 600MPa, wherein the sintering temperature is 1375 ℃, the heat preservation time is 3h, and the heating speed is 5 ℃/min.
Fig. 3(a) is a physical representation of the tungsten-doped titanium-based composite porous material prepared in example 1, fig. 3(b) is a physical representation of the tungsten-doped titanium-based composite porous material prepared in example 3, fig. 3(c) is a SEM representation of a mixed powder of TiC and W after ball milling in step 1 of example 1, and fig. 3(d) is a SEM representation of ti (W) -TiC after sintering in step 6 of example 1. As can be seen from fig. 3(a) - (b), the method of the present invention can be used to obtain a porous material having a three-dimensional porous structure with a topological structure and irregular pores, respectively. In fig. 3(c), W is indicated by arrows in bright white, and as can be seen from fig. 3(c), TiC after ball milling is uniformly mixed with W, W powder with micro-nano size is dispersed among TiC powder, in fig. 3(d), W is indicated in bright white, TiC is indicated in black, and Ti is indicated in gray, and as can be seen from fig. 3(d), W is relatively uniformly dissolved in the Ti-TiC matrix, so that a Ti (W) -TiC composite material is formed, and the surface is dense without pores.
FIG. 4 is an XRD pattern of the W-doped Ti-based composite porous material prepared in example 3, from which characteristic diffraction peaks of Ti, TiC and W can be seen, which indicates that W is successfully doped in the Ti-TiC material.
The materials prepared in the above examples and comparative examples were subjected to porosity, hardness, abrasion resistance test results, and the results are shown in table 1. The result shows that the tungsten doped titanium-based composite porous material HV prepared by the invention0.2Over 700, surface roughness SaThe (mu m) is less than 4, the average friction coefficient (mu) is less than 0.3, the material has the characteristics of high hardness, surface roughness and lower friction coefficient, and the material has high density, high strength and high wear resistance.
Table 1 results of performance testing of different materials
Figure BDA0002583813790000091
Figure BDA0002583813790000101
In conclusion, the method provided by the invention is simple, low in cost, safe, easy to operate, strong in practicability, and easy to prepare the Ti-based composite porous material with high strength, low surface roughness and high wear resistance, and the product can be used in the aerospace field and the biomedical field.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, it should be noted that, for those skilled in the art, many modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.

Claims (9)

1. A preparation method of a tungsten-doped titanium-based composite porous material is characterized in that a three-dimensional topological structure is formed by a porous structure of the tungsten-doped titanium-based composite porous material, and the preparation method comprises the following steps:
(1) uniformly mixing tungsten powder, titanium carbide and a metal titanium matrix to obtain first mixed powder, wherein the metal titanium matrix comprises pure titanium or titanium hydride, the particle size of the tungsten powder is 100nm-1 mu m, and the particle size of the titanium carbide is less than 15 mu m; the tungsten powder accounts for less than 3% of the first mixed powder by mass; the particle size of the metal titanium matrix is less than 10 mu m;
(2) uniformly dispersing the first mixed powder in a polymer solution to synthesize ink, wherein the mass ratio of the first mixed powder to the polymer solution is (4-1):1, and the polymer solution comprises a water-soluble polymer and water;
(3) and 3D printing the ink according to designed printing parameters to obtain a prefabricated body, sintering the prefabricated body at the temperature of 1000-1300 ℃, and obtaining the tungsten-doped titanium-based composite porous material after sintering, wherein the printing parameters comprise porosity parameters and the topological structure type of a three-dimensional porous structure in the porous material.
2. The method of claim 1, wherein: in the step (2), the polymer solution comprises water, polyvinyl alcohol and polyethylene glycol, and the mass ratio of the water to the polyvinyl alcohol to the polyethylene glycol is (6-7.5): (3-1.5): 1.
3. the method of claim 1, wherein: in the step (3), in the 3D printing process, the printing speed is 5-15mm/s, the printing diameter is 150-.
4. A preparation method of a tungsten-doped titanium-based composite porous material is characterized in that the tungsten-doped titanium-based composite porous material has an irregular pore structure, and the preparation method comprises the following steps:
(S1) uniformly mixing tungsten powder, titanium carbide, a metal titanium matrix and a pore-forming agent to obtain second mixed powder, wherein the metal titanium matrix comprises pure titanium or titanium hydride, the particle size of the tungsten powder in the second mixed powder is 100nm-2 mu m, and the particle size of the titanium carbide is less than 10 mu m; the tungsten powder accounts for less than 3% of the second mixed powder by mass; preparing the metal titanium matrix, wherein the particle size of the initial powder is less than 10 mu m;
(S2) performing spark plasma sintering on the second mixed powder under the vacuum condition of 500-650 ℃ and removing the pore-forming agent, and then performing sintering at 1000-1300 ℃ to obtain the tungsten-doped titanium-based composite porous material after sintering.
5. The method of claim 4, wherein: in the step (S1), the pore-forming agent includes NaCl and/or NH4HCO3。
6. The method of claim 4, wherein: in the step (S1), the pore-forming agent accounts for 90% or less of the volume fraction of the second mixed powder.
7. A tungsten-doped titanium-based composite porous material is characterized in that: the tungsten-doped titanium-based composite porous material is distributed with a plurality of three-dimensional porous structures, the porous structures form a three-dimensional topological structure or a random structure, and the tungsten-doped titanium-based composite porous material comprises Ti, TiC and W, wherein the W accounts for less than 3% of the mass fraction of the tungsten-doped titanium-based composite porous material; the tungsten-doped titanium-based composite porous material is prepared by the preparation method of any one of claims 1 to 6.
8. The tungsten-doped titanium-based composite porous material of claim 7, wherein: the porosity of the tungsten-doped titanium-based composite porous material is 20% -90%.
9. The tungsten-doped titanium-based composite porous material of claim 7, wherein: the TiC accounts for 1-30% of the volume fraction of Ti.
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Publication number Priority date Publication date Assignee Title
CN111468714B (en) * 2020-05-14 2022-05-24 苏州大学 Metal microarray structure material and preparation method thereof
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CN115747568A (en) * 2022-11-01 2023-03-07 西安理工大学 Three-dimensional pellet micro-configuration TiC reinforced titanium-based composite material and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104321154A (en) * 2012-05-31 2015-01-28 山特维克知识产权股份有限公司 Method of making a CBN material
CN106521219A (en) * 2017-01-05 2017-03-22 重庆大学 Preparation method for TiC particle reinforced titanium-based porous material
CN107460476A (en) * 2017-07-24 2017-12-12 中南林业科技大学 A kind of titanium alloy surface TiC enhancings titanium-based composite coat and preparation method thereof
EP3369831A1 (en) * 2015-10-30 2018-09-05 Sumitomo Electric Industries, Ltd. Sintered compact and method for producing same
CN109652709A (en) * 2017-10-12 2019-04-19 刘冰飞 A kind of WC-1.0TiC-3.1TaC-4.5Co hard alloy

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100346762B1 (en) * 1999-07-21 2002-07-31 한국기계연구원 PRODUCTION METHOD FOR NANOPHASE WC/TiC/Co COMPOSITE POWDER
KR100528046B1 (en) * 2003-08-26 2005-11-15 한국과학기술연구원 Fabrication method for ultrafine cermet alloys with a homogeneous solid solution grain structure
US7311873B2 (en) * 2004-12-30 2007-12-25 Adma Products, Inc. Process of direct powder rolling of blended titanium alloys, titanium matrix composites, and titanium aluminides
CN103290248B (en) * 2013-05-31 2015-12-02 西华大学 A kind of particle reinforce abradable porous titanium preparation method
CN103341291B (en) * 2013-06-30 2015-07-15 成都易态膜分离技术有限公司 Sintered porous material and filter element using same
JP2015048488A (en) * 2013-08-30 2015-03-16 昭和電工株式会社 Ti/TiC COMPOSITE MATERIAL AND PRODUCTION METHOD AND USE OF THE SAME
CN106077693B (en) * 2016-07-22 2018-07-03 合肥工业大学 A kind of high thermal shock W-TiC-Y2O3Composite material and preparation method thereof
CN106591671A (en) * 2016-12-12 2017-04-26 威海职业学院 TiC-Ti-Ni porous ceramic material and preparation method thereof
CN107159893A (en) * 2017-05-12 2017-09-15 昆明理工大学 A kind of prefabricated preparation of labyrinth ceramic particle
CN109943786A (en) * 2019-05-06 2019-06-28 哈尔滨工业大学 A method of titanium-based nano composite material is prepared based on precinct laser fusion 3D printing
CN111041258A (en) * 2019-12-11 2020-04-21 北京理工大学重庆创新中心 Enhanced light metal matrix composite based on tungsten nanoparticles and preparation method thereof
CN111375758A (en) * 2020-04-23 2020-07-07 王伟东 Sintering method of titanium or titanium alloy powder
CN111822721B (en) * 2020-07-14 2022-05-10 苏州大学 Tungsten-doped titanium-based composite porous material and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104321154A (en) * 2012-05-31 2015-01-28 山特维克知识产权股份有限公司 Method of making a CBN material
EP3369831A1 (en) * 2015-10-30 2018-09-05 Sumitomo Electric Industries, Ltd. Sintered compact and method for producing same
CN106521219A (en) * 2017-01-05 2017-03-22 重庆大学 Preparation method for TiC particle reinforced titanium-based porous material
CN107460476A (en) * 2017-07-24 2017-12-12 中南林业科技大学 A kind of titanium alloy surface TiC enhancings titanium-based composite coat and preparation method thereof
CN109652709A (en) * 2017-10-12 2019-04-19 刘冰飞 A kind of WC-1.0TiC-3.1TaC-4.5Co hard alloy

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