WO2022011951A1 - 钨掺杂钛基复合多孔材料及其制备方法 - Google Patents

钨掺杂钛基复合多孔材料及其制备方法 Download PDF

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WO2022011951A1
WO2022011951A1 PCT/CN2020/135952 CN2020135952W WO2022011951A1 WO 2022011951 A1 WO2022011951 A1 WO 2022011951A1 CN 2020135952 W CN2020135952 W CN 2020135952W WO 2022011951 A1 WO2022011951 A1 WO 2022011951A1
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tungsten
titanium
based composite
composite porous
porous material
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English (en)
French (fr)
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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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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 [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D 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 [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D 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

Definitions

  • the invention relates to the technical field of preparation of a titanium-based composite porous material, in particular to a tungsten-doped titanium-based composite porous material and a preparation method thereof.
  • Titanium (Ti)-based composite porous materials have low density, high energy absorption properties and biocompatibility, and are materials that integrate structure and function.
  • Ti Titanium
  • higher requirements are put forward for their wear resistance, hardness and pore structure.
  • Ti-TiC composites prepared by adding TiC particles to Ti-based materials have higher performance, and their performance is better than that of pure Ti, especially the addition of high volume fraction of TiC particles can improve its strength and hardness, but its strength and hardness can be improved due to the addition of high volume Fractions of refractory TiC ceramic particles reduce the density, surface roughness and hardness of the material. This will cause the material to fall off and cause more serious damage when the material is used, especially in frictional conditions, which will significantly reduce the mechanical properties of the material, such as wear resistance and fatigue properties.
  • three-dimensional porous structures are divided into two types: three-dimensional porous structures with complex topological order and random structures.
  • Different types of three-dimensional porous structures have unique mechanical properties and functions, and can be selected according to different application environments.
  • the current commonly used laser additive manufacturing method is difficult to meet with the conventional melt method and sintering method: 1.
  • the Ti-based composite material prepared by adding high melting point material can obtain a porous material with high density and uniform structure; 2. It is difficult to prepare crystal grains Porous materials with small size, low surface roughness and excellent wear resistance; 3. It is difficult to provide effective solutions and processes according to different user needs to obtain complex topologically ordered three-dimensional pore structures and random structures to meet different application requirements .
  • the purpose of the present invention is to provide a tungsten-doped titanium-based composite porous material and a preparation method thereof.
  • Abrasion resistance which can be achieved by the method of direct ink-writing additive manufacturing or by the method of spark plasma sintering with the addition of pore-forming agents.
  • the first object of the present invention is to disclose the application of tungsten metal (W) in the preparation of tungsten-doped titanium-based composite porous materials.
  • the tungsten-doped titanium-based composite porous materials are distributed with a plurality of three-dimensional porous structures, and the plurality of porous structures are composed of Three-dimensional topological structure or random structure, the tungsten-doped titanium-based composite porous material includes Ti, TiC and W, wherein 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 a Ti-TiC composite material doped with W (ie, the Ti(W)-TiC material hereinafter), and the tungsten-doped titanium-based composite porous material is Ti-TiC as the The matrix, W is a superhard material.
  • W is a superhard material.
  • the particle size of W is 100 nm-2 ⁇ m; the particle size of titanium carbide is 15 ⁇ m or less.
  • the second object of the present invention is to provide a preparation method of a tungsten-doped titanium-based composite porous material.
  • the porous structure of the tungsten-doped titanium-based composite porous material forms a three-dimensional topology, and the preparation method includes the following steps:
  • step (1) the step of uniformly mixing tungsten powder, titanium carbide and metal titanium matrix includes:
  • the W and TiC are ball-milled to obtain W-doped TiC powder; and then the W-doped TiC powder is added to the metal titanium matrix to obtain the first mixed powder.
  • titanium matrix composite material is preferably a non-metallic titanium, titanium hydride (TiH 2), select TiH 2 TiH 2 is a low cost, high density benefits as metallic titanium substrate, the oxygen-containing The amount of tungsten-doped titanium-based composite porous material is low, and the dehydrogenation reaction occurs in the subsequent sintering process, and the mechanical properties of the obtained tungsten-doped titanium-based composite porous material are good.
  • step (1) the titanium carbide accounts for 1%-30% of the volume fraction of the titanium metal matrix.
  • the polymer solution includes water, polyvinyl alcohol and polyethylene glycol, and the mass ratio of water, polyvinyl alcohol and polyethylene glycol is (6-7.5): (3-1.5): 1.
  • a polymer solution is used as a solvent to disperse the first mixed powder.
  • the polymer solution includes polyvinyl alcohol and polyethylene glycol, which can endow the printing ink with good formability and make the final prepared tungsten-doped titanium-based composite porous
  • the material has good mechanical properties. Adjusting the amount of each component in the polymer solution can adjust the viscosity of the printing ink, thereby changing the formability of the printed preform. Exceeding the above ratio range, the printing ink will have problems such as drawing, air bubbles, and inability to form during the printing process, or poor formability such as broken filaments and clogging.
  • the molecular weight of polyvinyl alcohol is 10k-20k.
  • the molecular weight of polyethylene glycol is 600-2000.
  • step (2) an ultrasonic disperser is used for dispersion, the dispersion time is 30min-1h, and 3D printing is performed after standing for 30min-2h.
  • the printing speed is 5-15 mm/s
  • the printing diameter is 150-1000 ⁇ m
  • the extrusion pressure is 5-10 bar.
  • the print diameter refers to the diameter of the nozzle in the 3D printer.
  • step (3) sintering is performed in a vacuum environment or a protective atmosphere, which can prevent the oxidation of the titanium metal matrix.
  • the degree of vacuum is not less than 3 ⁇ 10 -5 Torr.
  • the protective atmosphere is preferably argon, and the flow rate of argon is 50-100 mL/min.
  • step (3) the temperature is raised from room temperature to 1000-1300°C at a heating rate of 2-10°C/min, and kept at 1000-1300°C for 0.1-4h.
  • the present 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 has an irregular structure, and the preparation method includes the following steps:
  • (S1) Mixing the tungsten powder, titanium carbide, titanium metal matrix and pore-forming agent uniformly to obtain a second mixed powder, wherein the titanium metal matrix includes pure titanium or titanium hydride, and the particle size of the tungsten powder in the second mixed powder is 100 nm -2 ⁇ m, the particle size of titanium carbide is less than 10 ⁇ m; the tungsten powder accounts for less than 3% of the mass fraction of the second mixed powder; the initial powder particle size for preparing the metal titanium matrix is less than 10 ⁇ m;
  • step (S1) the step of uniformly mixing tungsten metal particles, titanium carbide, metal titanium matrix and pore-forming agent includes:
  • the pore-forming agent includes NaCl and/or NH 4 HCO 3 .
  • step (S1) the pore-forming agent accounts for less than 90% of the volume fraction of the second mixed powder.
  • the porosity and mechanical properties of the final prepared tungsten-doped titanium-based composite porous material can be adjusted by changing the amount of the pore-forming agent.
  • step (S1) the titanium carbide accounts for 1%-30% of the volume fraction of the titanium metal matrix.
  • step (S2) sintering is performed in a graphite mold, and the temperature is raised from room temperature to 500-650°C at a heating rate of 50-100°C/min, and kept at 500-650°C for 10-30min.
  • the vacuum pressure of spark plasma sintering is 25-40MPa. The purpose of spark plasma sintering is to achieve powder activation and rapid sintering.
  • step (S2) when the pore-forming agent is NaCl, the step of removing the pore-forming agent comprises:
  • the product after spark plasma sintering is placed in water, and the pore-forming agent in the sintered product is dissolved with water to form a porous structure therein.
  • water treatment at 40-60° C. is used for 20-40 h.
  • step (S2) when the pore-forming agent is NH 4 HCO 3 , during the spark plasma sintering process, the pore-forming agent NH 4 HCO 3 is directly sintered and volatilized, and does not need to be soaked in water after the sintering is completed. The removal of the pore-forming agent is directly realized.
  • step (S2) sintering at 1000-1300° C. is performed in a vacuum environment or a protective atmosphere, and the sintering time is 1-3 h.
  • the present invention also claims to protect a tungsten-doped titanium-based composite porous material, which is characterized in that: a plurality of three-dimensional porous structures are distributed in the tungsten-doped titanium-based composite porous material, and the plurality of porous structures form a three-dimensional topology structure or a random structure, and the tungsten
  • the doped titanium-based composite porous material includes Ti, TiC and W, wherein 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 above two preparation methods.
  • the porosity of the tungsten-doped titanium-based composite porous material is 20%-90%.
  • TiC accounts for 1%-30% of the volume fraction of Ti.
  • the present invention has at least the following advantages:
  • the invention discloses the application of W in the preparation of tungsten-doped titanium-based composite porous materials, and doping a small amount of micro-nano-sized W can improve the density, hardness and wear resistance of the tungsten-doped titanium-based composite porous materials.
  • the invention provides a tungsten-doped titanium-based composite porous material, which has new composite components, and the preparation method is low in cost, and two types of porous structures with three-dimensional ordered and disordered pore shape distribution can be prepared according to requirements.
  • the preparation of lightweight Ti-based composite porous materials with high wear resistance can be achieved by the method of additive manufacturing by ink direct writing or the method of adding pore-forming agents combined with spark plasma sintering.
  • the porous Ti-based composite material prepared by the method of the present invention can be applied not only in the aerospace field, but also in In biomedical implants, it has a wide range of application value and potential.
  • Fig. 1 is the flow chart of the preparation process of the porous material of the three-dimensional porous structure with topology structure
  • Fig. 2 is a flow chart of the preparation process of a porous material having a three-dimensional porous structure with irregular pores;
  • Fig. 3 is the physical image of the prepared tungsten-doped titanium-based composite porous material, the SEM image of the mixed powder of TiC and W after ball milling, and the SEM image of Ti(W)-TiC after sintering;
  • FIG. 4 is an XRD pattern of the tungsten-doped titanium-based composite porous material prepared in Example 3.
  • the preparation method of the porous material with the three-dimensional porous structure of the topology structure is as follows:
  • the solution components are water, polyvinyl alcohol and polyethylene glycol
  • the mass ratio of water: polyvinyl alcohol: polyethylene glycol is ((6-7.5): (3-1.5): 1)
  • the mass ratio of the solid powder to the solution is (4-1): 1, dispersed by an ultrasonic disperser for 30min-1h, and then left for 30min-2h to obtain printing Ink; wherein, the molecular weight of polyvinyl alcohol is 10k-20k.
  • the molecular weight of polyethylene glycol is 600-2000;
  • the printing speed is 5-15mm/s
  • the printing diameter is 150-1000 ⁇ m
  • the extrusion pressure range is 5-10bar.
  • Heating the preform is 2-10°C/min
  • the heating temperature is 1000-1300°C
  • the holding time is 0.1-4h
  • the sintering environment is a vacuum environment or argon gas protection.
  • the preparation method of the porous material having the three-dimensional porous structure with irregular pores is as follows:
  • the spark plasma sintering method put the mixed powder obtained in step 2 into a graphite mold, the sintering temperature is 500-650°C, the heating rate is 50-100°C/min, the heat preservation is 10-30min, the vacuum environment, the pressure is 25- 40MPa.
  • the temperature is 40-60 °C, 20-40h, take out the sample and put it into a vacuum heating furnace, the temperature is 1000-1300 °C, and the holding time range is 1-3h , the sintering environment is a vacuum environment or argon protection, and finally a Ti(W)-TiC composite porous titanium material is obtained.
  • W-doped TiC powder Doping W into TiC and performing ball milling to obtain W-doped TiC powder. Specifically, the ball milling is carried out at room temperature with a ball-to-material ratio of 10:1 and a rotation speed of 300 rpm for 1 h. Before ball milling, the size of W is about 100 nm, and the size of TiC powder is about 10 ⁇ m.
  • the W-doped TiC powder added to the TiH 2 powder to obtain a mixed powder; wherein, W mixed powder mass fraction accounted for 1.0%, 15% TiC TiH 2 powder accounts for a volume fraction, particle size of about TiH 2 powder is 3 ⁇ m.
  • step 3 Import the ink synthesized in step 3 into the printer, and print the preform of the target design according to the printing model designed in step 4.
  • the printing speed range is 8mm/s
  • the printing diameter is 250 ⁇ m
  • the extrusion pressure range is 8bar.
  • the heating temperature is 1200°C
  • the holding time range is 2h
  • the heating rate is 2°C/min
  • the sintering environment is a vacuum environment
  • the vacuum degree is 5.9 ⁇ 10 -5 torr to obtain a three-dimensional porous structure with a topology structure. of porous materials.
  • W-doped TiC powder Doping W into TiC and performing ball milling to obtain W-doped TiC powder. Specifically, the ball milling is carried out at room temperature with a ball-to-material ratio of 10:1 and a rotation speed of 300 rpm for 1 h. After ball milling, the size of W is about 100 nm, and the size of TiC powder is about 10 ⁇ m.
  • the W-doped TiC powder added to the TiH 2 powder to obtain a mixed powder; wherein, W mixed powder mass fraction accounted for 1.0%, 30% TiC volume fraction representing the volume of TiH 2 powder, the particle size TiH 2 powder About ⁇ 3 ⁇ m.
  • step 5 Import the ink synthesized in step 3 into the printer, and print out the preform of the target design according to the printing model designed in step 4.
  • the printing speed range is 5mm/s
  • the printing diameter is 410 ⁇ m
  • the extrusion pressure range is 6bar.
  • the heating temperature is 1300°C
  • the holding time range is 2h
  • the heating rate is 10°C/min
  • the sintering environment is a vacuum environment
  • the vacuum degree is 6 ⁇ 10 -5 torr to obtain a three-dimensional porous structure with a topology structure. of porous materials.
  • W and TiC additives to pure Ti powder and mix by ball milling to obtain mixed powder.
  • W accounts for 3% of the mass fraction of the mixed powder
  • TiC accounts for 15% of the volume fraction of the pure Ti powder.
  • the size of W is 1 ⁇ m, and the size of TiC powder is about 10 ⁇ m; among them, the ball milling is specifically at room temperature, under the protection of argon, with a ball-to-material ratio of 10:1, and ball milling at 300 rpm for 3 hours.
  • step 2 Add the pore-forming agent NaCl into the mixed powder obtained in step 1 and mix to obtain a mixed powder containing the pore-forming agent, and the pore-forming agent accounts for 40% of the volume fraction of the mixed powder containing the pore-forming agent.
  • the mixed powder containing the pore-forming agent is 2:1 in the ratio of ball to material, the rotating speed is 150 rpm, and the mixing time is 0.5 h, and the mixed powder is taken out and waited for sintering.
  • the sintering temperature is 650° C.
  • the heating rate is 50° C./min
  • the temperature is kept for 10 minutes
  • the pressure is 30 MPa in a vacuum environment.
  • the temperature is 60°C
  • dissolve for 24h take out the sample and put it into a vacuum heating furnace
  • the temperature is 1200°C
  • the holding time is 2h
  • the heating rate is 10°C/min
  • the vacuum degree is 6 ⁇ 10 -5 torr
  • the Ti(W)-TiC composite porous titanium material with irregular porous structure is obtained.
  • W and TiC to the TiH 2 powder and mix by ball milling to obtain a mixed powder.
  • W representing the mass fraction of the mixed powder 3%, TiC accounting for 30% TiH 2 powder volume fraction.
  • the size of W before ball milling is 1 ⁇ m, the size of TiC powder is about 10 ⁇ m; the size of TiH 2 powder is about 3 ⁇ m.
  • the ball milling is carried out at room temperature, under the protection of argon gas, and the ball-to-material ratio is 5:1, and the ball is milled for 4 hours at a rotational speed of 350 rpm.
  • step 2 Add the pore-forming agent NH 4 HCO 3 into the mixed powder obtained in step 1 and mix to obtain a mixed powder containing the pore-forming agent, and the pore-forming agent accounts for 40% of the volume fraction of the mixed powder containing the pore-forming agent.
  • the mixed powder containing the pore-forming agent is 2:1 in the ratio of ball to material, the rotation speed is 100 rpm, and the mixing time is 1 h, and the powder is taken out and waited for sintering.
  • the sintering temperature is 1000°C
  • the heating rate is 10°C/min
  • the temperature is kept for 30 minutes
  • the sintering temperature is 1300°C
  • the heating rate is 5°C/min
  • heat preservation for 30min, vacuum environment, pressure is 30MPa
  • Ti(W)-TiC composite porous titanium material with irregular porous structure is obtained.
  • the size of the TiC powder before ball milling is about 10 ⁇ m.
  • the ball milling is performed at room temperature with a ball-to-material ratio of 10:1 and a rotation speed of 300 rpm for 1 h.
  • step 4 Import the ink synthesized in step 3 into the printer, and print the preform of the target design according to the printing model designed in step 4.
  • the printing speed range is 6mm/s
  • the printing diameter is 250 ⁇ m
  • the extrusion pressure range is 5bar.
  • the heating temperature is 1200°C
  • the holding time range is 4h
  • the heating rate is 10°C/min
  • the sintering environment is a vacuum environment
  • the vacuum degree is 6 ⁇ 10 -5 torr to obtain a topological structure without W.
  • TiC powder accounts for 15% of the volume fraction of TiH 2 powder.
  • the size of W is 1 ⁇ m, and the size of TiC powder is about 10 ⁇ m; the ball milling is specifically at room temperature, under the protection of argon, with a ball-to-material ratio of 10:1, and ball milling at 300 rpm for 3 hours.
  • step 2 Add the pore-forming agent NaCl into the mixed powder obtained in step 1 and mix to obtain a mixed powder containing the pore-forming agent, and the pore-forming agent accounts for 40% of the volume fraction of the mixed powder containing the pore-forming agent.
  • the mixed powder containing the pore-forming agent was 2:1 in the ratio of ball to material, the rotation speed was 150 rpm, and the mixing time was 0.5 h, and the powder was taken out and waited for sintering.
  • the sintering temperature is 650° C.
  • the heating rate is 50° C./min
  • the temperature is kept for 10 minutes
  • the pressure is 30 MPa in a vacuum environment.
  • the temperature is 60°C, 24h, take out the sample and put it in a vacuum heating furnace, the temperature is 1200°C, the holding time is 2h, the heating rate is 10°C/min, The vacuum degree is 6 ⁇ 10 -5 torr, and the Ti-TiC composite porous titanium material without W is obtained.
  • TiC powder was added to pure Ti powder were mixed, TiC powder comprises 15% TiH 2 powder volume fraction.
  • the lattice structure was prepared by selective laser melting method, and the preparation process conditions were that the laser power was 200W, the scanning speed was 300mm/s, and the energy density was 120J/mm 3 .
  • TiC powder to pure Ti powder for mixing, TiC powder accounts for 15% of the volume fraction of TiH 2 powder, and then add pore-forming agent NH 4 HCO 3 for mixing to obtain a mixed powder containing pore-forming agent, and the pore-forming agent accounts for pore-forming agent. 40% of the mixed powder volume fraction of the agent.
  • the mixed powder containing the pore-forming agent was cold-pressed at 600 MPa, the sintering temperature was 1375 °C, the temperature was kept for 3 h, and the heating rate was 5 °C/min.
  • Figure 3(a) is a physical image of the tungsten-doped titanium-based composite porous material prepared in Example 1
  • Figure 3(b) is a physical image of the tungsten-doped titanium-based composite porous material prepared in Example 3
  • Figure 3(c) is the SEM image of the mixed powder of TiC and W after ball milling in Step 1 of Example 1
  • FIG. 3(d) is the SEM image of Ti(W)-TiC after sintering in Step 6 of Example 1. It can be seen from Figures 3(a)-(b) that, by using the method of the present invention, a porous material having a three-dimensional porous structure with a topology structure and irregular pores can be obtained, respectively.
  • the bright white point pointed to by the arrow is W. It can be seen from Figure 3(c) that the TiC and W after ball milling are evenly mixed, and the micro-nano-sized W powder is dispersed between the TiC powders.
  • the bright white part is W
  • the black part represents TiC
  • the gray part represents Ti. It can be seen from Figure 3(d) that W has been relatively uniformly dissolved in the Ti-TiC matrix to form Ti(W)- TiC composite material, and the surface is dense, no pores are generated.
  • Figure 4 is the XRD pattern of the tungsten-doped titanium-based composite porous material prepared in Example 3. From the figure, characteristic diffraction peaks of Ti, TiC and W can be seen, indicating that the Ti-TiC material is successfully doped with W.
  • the test results of porosity, hardness and wear resistance were carried out on the materials prepared in the above examples and comparative examples, and the results are shown in Table 1.
  • the results show that the present invention is prepared in the tungsten-doped titanium-based composite porous material of more than 700 HV 0.2, the surface roughness S a ( ⁇ m) of less than 4, the average friction coefficient ([mu]) of less than 0.3, with high hardness, low surface roughness, and The friction coefficient, the material has the characteristics of high density, high strength and high wear resistance.
  • the method provided by the present invention is simple, low cost, safe, easy to operate, strong practicability, easy to prepare Ti-based composite porous material with high strength, low surface roughness and high wear resistance, and the product can not only be used in aerospace Fields can also be used in the biomedical field.

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Abstract

一种钨掺杂钛基复合多孔材料及其制备方法，公开了W在制备钨掺杂钛基复合多孔材料中的应用，在制备钨掺杂钛基复合多孔材料时，在其中掺杂少量微纳尺寸的W，可提高其致密度、显著提高基体硬度和耐磨性。钨掺杂钛基复合多孔材料中分布有多个三维多孔结构，多个三维多孔结构组成拓扑结构或随机结构，钨掺杂钛基复合多孔材料包括Ti、TiC和W，其中钨金属占钨掺杂钛基复合多孔材料质量分数的3％以下。钨掺杂钛基复合多孔材料通过墨水直写成型增材制造的方法或添加造孔剂结合放电等离子烧结的方法实现。

Description

钨掺杂钛基复合多孔材料及其制备方法 技术领域
本发明涉及一种钛基复合多孔材料的制备技术领域，尤其涉及一种钨掺杂钛基复合多孔材料及其制备方法。
背景技术
钛(Ti)基复合多孔材料具有低密度、高吸收能量特性和生物相容性，是集结构与功能为一体的材料。近些年，随着对材料不断提出高性能结构轻量化的新要求和其航空、航天与生物材料上的广泛应用，对其耐磨性、硬度和孔隙结构等条件提出更高的要求，因此，设计新的成分与结构适用不同应用需求的多孔钛基复合材料是重要的解决途径。
Ti基材料中添加TiC颗粒制备的Ti-TiC复合材料具有更高的性能，其性能较纯Ti更优异，特别是添加高体积分数的TiC颗粒可以提高其强度和硬度，但是其由于添加高体积分数的难熔TiC陶瓷颗粒会降低材料的致密度、表面粗糙度和硬度。这会导致材料在使用的时候，尤其是在摩擦工况下使用时，会造成磨屑脱落带来更严重的损伤从而显著降低材料的力学性能，如耐磨性与疲劳性能。
现如今三维多孔结构分为具有复杂拓扑有序的三维孔隙结构和随机结构两种，其不同类型的三维多孔结构具有独特的力学性能与功能，可以根据不同的应用环境进行选择。目前常用的激光增材制造法与常规的熔体法和烧结法难以满足：1.添加高熔点材料制备的Ti基复合材料获得致密度高和组织均匀的多孔材料；2.难以制备出晶粒尺寸小，表面粗糙度低和耐磨性能优异的多孔材料；3.难以根据不同用户需求提供有效的方案与工艺使其获得有复杂拓扑有序的三维孔隙结构和随机结构，适应不同的使用要求。
发明内容
为解决上述技术问题，本发明的目的是提供一种钨掺杂钛基复合多孔材料及其制备方法，本发明通过掺杂少量微纳尺寸的W提高钛基复合多孔材料的致密度、硬度和耐磨性，其可通过墨水直写成型增材制造的方法或添加造孔剂通过放电等离子烧结的方法实现。
本发明的第一个目的是公开钨金属(W)在制备钨掺杂钛基复合多孔材料中的应用，钨掺杂钛基复合多孔材料中分布有多个三维多孔结构，多个多孔结构组成三维拓扑结构或随机结构，钨掺杂钛基复合多孔材料包括Ti、TiC和W，其中W占钨掺杂钛基复合多孔材料质 量分数的3％以下。
本发明中，钨掺杂钛基复合多孔材料是掺杂了W的Ti-TiC复合材料(即下文中的Ti(W)-TiC材料)，钨掺杂钛基复合多孔材料以Ti-TiC为基体，W是一种超硬材料，在制备钨掺杂钛基复合多孔材料时，在其中掺杂少量微纳尺寸的W可以显著提高TiC的致密化过程，进而有效的提高致密度、显著提高基体硬度和耐磨性。
进一步地，W的粒径为100nm-2μm；碳化钛的粒径为15μm以下。
本发明的第二个目的是提供一种钨掺杂钛基复合多孔材料的制备方法，钨掺杂钛基复合多孔材料的多孔结构组成三维拓扑结构，其制备方法包括以下步骤：
(1)将钨粉末、碳化钛和金属钛基体混合均匀，得到第一混合粉末，其中，金属钛基体包括纯钛或氢化钛，钨粉末的粒径为100nm-1μm，碳化钛的粒径为15μm以下；钨粉末占第一混合粉末质量分数的3％以下；制备金属钛基体初始粉末的粒径为10μm以下；
(2)将第一混合粉末均匀分散于聚合物溶液中，合成墨水，其中，第一混合粉末和聚合物溶液的质量比为(4-1):1，聚合物溶液中包括水溶性聚合物和水；
(3)将墨水按照设计的打印参数进行3D打印得到预制体，将预制体在1000-1300℃下进行烧结，烧结完毕后得到钨掺杂钛基复合多孔材料，其中打印模型参数包括孔隙率参数和多孔材料中三维多孔结构的拓扑结构类型。
进一步地，在步骤(1)中，将钨粉末、碳化钛和金属钛基体混合均匀的步骤包括：
将W与TiC进行球磨，得到掺杂W的TiC粉末；然后把掺杂W的TiC粉末添加在金属钛基体中，得到第一混合粉末。
进一步地，在步骤(1)中，金属钛基体优选为钛的非金属复合材料氢化钛(TiH 2)，选择TiH 2作为金属钛基体的好处是TiH 2的成本低，致密度高，含氧量低，在后续烧结过程中发生脱氢反应，得到钨掺杂钛基复合多孔材料的力学性能好。
进一步地，在步骤(1)中，碳化钛占金属钛基体体积分数的1％-30％。
进一步地，在步骤(2)中，聚合物溶液中包括水、聚乙烯醇和聚乙二醇，水、聚乙烯醇和聚乙二醇的质量比为(6-7.5)：(3-1.5)：1。本发明中，采用聚合物溶液作为溶剂分散第一混合粉末，该聚合物溶液中包括聚乙烯醇和聚乙二醇，可以赋予打印墨水良好的成型性，使最终制备的钨掺杂钛基复合多孔材料具有良好的力学性能。调节聚合物溶液中各组分的用量，可以调节打印墨水的黏度，进而改变打印出的预制体的成型性。超出上述比例范围，打印墨水在打印过程中会产生拉丝、气泡和无法成型的等问题，或者出现断丝、塞积等成型性差问题。
进一步地，聚乙烯醇的分子量为10k-20k。聚乙二醇的分子量为600-2000。
进一步地，在步骤(2)中，采用超声波分散仪进行分散，分散时间为30min-1h，静置后30min-2h后再进行3D打印。
进一步地，在步骤(3)中，3D打印过程中，打印速度为5-15mm/s，打印直径为150-1000μm，挤出压力为5-10bar。其中，打印直径指的是3D打印机中喷嘴的直径。
进一步地，在步骤(3)中，在真空环境或保护气氛中进行烧结，可防止金属钛基体氧化。真空度不低于3×10 -5Torr。保护气氛优选氩气，氩气的流量为50-100mL/min。
进一步地，在步骤(3)中，以2-10℃/min的升温速度从室温升温至1000-1300℃，并在1000-1300℃下保温0.1-4h。
本发明还提供了另外一种钨掺杂钛基复合多孔材料的制备方法，钨掺杂钛基复合多孔材料的多孔结构组成不规则结构，其制备方法包括以下步骤：
(S1)将钨粉末、碳化钛、金属钛基体和造孔剂混合均匀，得到第二混合粉末，其中，金属钛基体包括纯钛或氢化钛，第二混合粉末中钨粉末的粒径为100nm-2μm，碳化钛的粒径为10μm以下；钨粉末占第二混合粉末质量分数的3％以下；制备金属钛基体的初始粉末粒径为10μm以下；
(S2)将第二混合粉末在500-650℃的真空条件下进行放电等离子烧结并去除造孔剂，然后再在1000-1300℃下进行烧结，烧结完毕后得到钨掺杂钛基复合多孔材料。
进一步地，在步骤(S1)中，将钨金属颗粒、碳化钛、金属钛基体和造孔剂混合均匀的步骤包括：
将W、TiC和金属钛基体进行球磨，然后向其中加入造孔剂，继续进行球磨，得到第二混合粉末。
进一步地，在步骤(S1)中，造孔剂包括NaCl和/或NH 4HCO 3。
进一步地，在步骤(S1)中，造孔剂占第二混合粉末体积分数的90％以下。改变造孔剂的用量，可调节最终制备的钨掺杂钛基复合多孔材料的孔隙率和力学性能。
进一步地，在步骤(S1)中，碳化钛占金属钛基体体积分数的1％-30％。进一步地，在步骤(S2)中，在石墨模具中进行烧结，以50-100℃/min的升温速率从室温升温至500-650℃，并在500-650℃下保温10-30min。放电等离子烧结的真空压强为25-40MPa。放电等离子烧结的目的是实现粉末的活化与快速烧结。
进一步地，在步骤(S2)中，当造孔剂为NaCl时，去除造孔剂的步骤包括：
将放电等离子烧结后的产物置于水中，利用水溶解烧结后的产物中的造孔剂，以在其中 形成多孔结构。优选地，采用40-60℃的水处理20-40h。
进一步地，在步骤(S2)中，当造孔剂为NH 4HCO 3时，在放电等离子烧结过程中，造孔剂NH 4HCO 3直接被烧结挥发，不需在烧结完毕后再经水浸泡而直接实现造孔剂的去除。
进一步地，在步骤(S2)中，在真空环境或保护气氛下进行1000-1300℃的烧结，烧结时间为1-3h。
本发明还要求保护一种钨掺杂钛基复合多孔材料，其特征在于：钨掺杂钛基复合多孔材料中分布有多个三维多孔结构，多个多孔结构组成三维拓扑结构或随机结构，钨掺杂钛基复合多孔材料包括Ti、TiC和W，其中W占钨掺杂钛基复合多孔材料质量分数的3％以下；钨掺杂钛基复合多孔材料由上述两种制备方法所制备得到。
进一步地，钨掺杂钛基复合多孔材料的孔隙率为20％-90％。
进一步地，TiC占Ti的体积分数的1％-30％。
由上述方案，本发明至少具有以下优点：
本发明公开了W在制备钨掺杂钛基复合多孔材料中的应用，掺杂少量微纳尺寸的W可以提高钨掺杂钛基复合多孔材料的致密度、硬度和耐磨性。
本发明提供了一种钨掺杂钛基复合多孔材料，其具有新的复合成分，其制备方法成本低，且可根据需求制备孔形分布三维有序和无序的两类多孔结构。具体可通过墨水直写成型增材制造的方法或添加造孔剂结合放电等离子烧结的方法实现高耐磨性的轻质Ti基复合多孔材料的制备。得益于本发明钨掺杂钛基复合多孔材料的高致密度、硬度和良好的耐磨性，本发明的方法制备的多孔Ti基复合材料既可以应用在航空航天领域中，也可以应用于生物医用植入体中，具有广泛的应用价值与潜能。
上述说明仅是本发明技术方案的概述，为了能够更清楚了解本发明的技术手段，并可依照说明书的内容予以实施，以下以本发明的较佳实施例并配合详细附图说明如后。
附图说明
图1是具有拓扑结构的三维多孔结构的多孔材料制备工艺流程图；
图2是具有不规则孔隙的三维多孔结构的多孔材料制备工艺流程图；
图3是制备的钨掺杂钛基复合多孔材料的实物图、球磨后的TiC与W的混合粉末的SEM图和烧结后的Ti(W)-TiC的SEM图；
图4是实施例3制备的钨掺杂钛基复合多孔材料的XRD图。
具体实施方式
如图1所示，本发明中，具有拓扑结构的三维多孔结构的多孔材料制备方法如下：
1.把W按照一定比例通过高速球磨工艺掺杂到TiC中，球磨具体是在常温下，以球料比5-10：1在转速150-300rpm下球磨1-4h。球磨前W的尺寸100nm-1μm，TiC粉末尺寸为＜15μm；
2.把掺杂W的TiC粉末按照一定比例添加在TiH 2或纯Ti粉末中，得到混合粉末；W占混合粉末的质量分数的3％以下；
3.配置溶液，溶液成分为水、聚乙烯醇和聚乙二醇，水：聚乙烯醇：聚乙二醇质量比为((6-7.5)：(3-1.5)：1)，把第2步得到的得到混合粉末添加到上述溶液中进行分散，其中固体粉末质量与溶液的质量比为(4-1):1，采用超声波分散仪分散30min-1h，然后静置30min-2h后得到打印墨水；其中，聚乙烯醇的分子量为10k-20k。聚乙二醇的分子量为600-2000；
4.通过计算机辅助软件设计的不同孔隙率的具有拓扑结构的三维多孔结构；
5.把静置后的打印墨水导入到打印机中，打印出目标设计的预制体，打印速度为5-15mm/s，打印直径为150-1000μm，挤出压力范围5-10bar。
6.对预制体进行加热，升温速度2-10℃/min，加热温度1000-1300℃，保温时间为0.1-4h，烧结环境为真空环境或氩气保护。
如图2所示，本发明中，具有不规则孔隙的三维多孔结构的多孔材料制备方法如下：
1.把W和TiC按照一定比例在TiH 2或纯Ti粉末中进行球磨混合，得到混合粉末。球磨前W的尺寸100nm-2μm，TiC粉末尺寸为＜10μm；球磨具体是在常温下，通入氩气保护，以球料比5-10：1在转速250-350rpm下球磨1-4h；W占混合粉末的质量分数的5％以下；
2.按照一定体积分数把造孔剂NaCl或NH 4HCO 3添加入混合粉末中混合，造孔剂占混合粉末体积分数的90％以下，以球料比2-5：1转速为100-150rpm，真空环境，混合时间为0.2-1h，取出粉末等待烧结；
3.采用放电等离子烧结方法，把步骤2得到的混合粉末装入石墨模具中，烧结温度为500-650℃，升温速率50-100℃/min，保温10-30min，真空环境，压强为25-40MPa。
4.把烧结后的试样放入恒温水浴锅中溶解，温度为40-60℃，20-40h，取出试样放入真空加热炉中，温度1000-1300℃，保温时间范围为1-3h，烧结环境为真空环境或氩气保护，最终获得Ti(W)-TiC复合多孔钛材料。
下面结合实施例，对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明，但不用来限制本发明的范围。
实施例1.Ti(W)-15％vol TiC点阵材料
1.把W掺杂到TiC中进行球磨，得到掺杂W的TiC粉末。其中，球磨具体是在常温下，以球料比10：1在转速300rpm下球磨1h，球磨前W的尺寸约为100nm，TiC粉末尺寸约为10μm。
2.把掺杂W的TiC粉末添加在TiH 2粉末中，得到混合粉末；其中，W占混合粉末质量分数的1.0％，TiC占TiH 2粉末体积分数的15％，TiH 2粉末的粒径约为3μm。
3.配置含水、聚乙烯醇和聚乙二醇的溶液，其中水：聚乙烯醇：聚乙二醇质量比为(6.5：3.5：1)，把步骤2中得到的混合粉末添加到上述溶液进行分散，其中步骤2中得到的混合粉末总质量与溶液的质量比为3:1，合成含有固体粉末的悬浮液，采用超声波分散仪分散50min，得到墨水，静置后1.5h后等待打印。
4.通过画图编程设计不同“丝线”间距和截面直径大小的晶格结构，以尺寸55mm×110×55mmmm(长×宽×高)为边界设计整体图形。
5.把步骤3中合成好的墨水导入到打印机中，按照步骤4中设计的打印模型打印出目标设计的预制体，打印速度范围为8mm/s，打印直径250μm，挤出压力范围8bar。
6.对预制体进行加热，加热温度1200℃，保温时间范围为2h，升温速度2℃/min，烧结环境：真空环境，真空度为5.9×10 -5torr，得到具有拓扑结构的三维多孔结构的多孔材料。
实施例2.Ti(W)-30％vol TiC点阵材料
1.把W掺杂到TiC中进行球磨，得到掺杂W的TiC粉末。其中，球磨具体是在常温下，以球料比10：1在转速300rpm下球磨1h，球磨后W的尺寸约为100nm，TiC粉末尺寸约为10μm。
2.把掺杂W的TiC粉末添加在TiH 2粉末中，得到混合粉末；其中，W占混合粉末质量分数的1.0％，TiC占TiH 2粉末体积分数体积的30％，TiH 2粉末的粒径约为～3μm。
3.配置含水、聚乙烯醇和聚乙二醇的溶液，其中水：聚乙烯醇：聚乙二醇质量比为(7：2：1)，把步骤2中得到的混合粉末添加到上述溶液进行分散，其中步骤2中得到的混合粉末总质量与溶液的质量比为2:1，合成含有固体粉末的悬浮液，采用超声波分散仪分散1h，得到墨水，静置后1h后等待打印。
4.通过画图编程设计不同“丝线”间距和截面直径大小的晶格结构，以尺寸55mm×110×55mmmm(长×宽×高)为边界设计整体图形。
5.把步骤3中合成好的墨水导入到打印机中，按照步骤4中设计的打印模型打印出目标 设计的预制体，打印速度范围为5mm/s，打印直径410μm，挤出压力范围6bar。
6.对预制体进行加热，加热温度1300℃，保温时间范围为2h，升温速度10℃/min，烧结环境：真空环境，真空度为6×10 -5torr，得到具有拓扑结构的三维多孔结构的多孔材料。
实施例3.Ti(W)-15％vol TiC复合多孔钛材料
1.把W和TiC添加在纯Ti粉末中进行球磨混合，得到混合粉末。其中，W占混合粉末质量分数的3％，TiC占纯Ti粉末体积分数的15％。球磨前W的尺寸1μm，TiC粉末尺寸约为10μm；其中，球磨具体是在常温下，通入氩气保护，以球料比10：1，转速300rpm下球磨3h。
2.把造孔剂NaCl添加入步骤1得到的混合粉末中混合，得到含造孔剂的混合粉末，造孔剂占含造孔剂的混合粉末体积分数的40％。将含造孔剂的混合粉末以球料比2：1，转速为150rpm，混合时间为0.5h，取出混合后的粉末等待烧结。
3.采用放电等离子烧结方法，把步骤2得到的混合后的粉末装入石墨模具中，烧结温度为650℃，升温速率50℃/min，保温10min，真空环境，压强为30MPa。
4.把烧结后的试样放入恒温水浴锅中溶解，温度为60℃，溶解24h，取出试样放入真空加热炉中，温度1200℃，保温时间范围为2h，升温速度10℃/min，真空度为6×10 -5torr，最终获得具有不规则多孔结构的Ti(W)-TiC复合多孔钛材料。
实施例4.Ti(W)-30％vol TiC复合多孔钛材料
1.把W和TiC添加在TiH 2粉末中进行球磨混合，得到混合粉末。其中，W占混合粉末质量分数的3％，TiC占TiH 2粉末体积分数的30％。球磨前W的尺寸1μm，TiC粉末尺寸约为10μm；TiH 2粉末尺寸约为3μm。其中，球磨具体是在常温下，通入氩气保护，以球料比5：1，转速350rpm下球磨4h。
2.把造孔剂NH 4HCO 3添加入步骤1得到的混合粉末中混合，得到含造孔剂的混合粉末，造孔剂占含造孔剂的混合粉末体积分数的40％。将含造孔剂的混合粉末以球料比2：1，转速为100rpm，混合时间为1h，取出粉末等待烧结。
3.采用放电等离子烧结方法，把步骤2得到的混合粉末装入石墨模具中，烧结温度为1000℃，升温速率10℃/min，保温30min，然后烧结温度为1300℃，升温速率5℃/min，保温30min，真空环境，压强为30MPa；最终具有不规则多孔结构的获得Ti(W)-TiC复合多孔钛材料。
对比例1.Ti-15％vol TiC点阵材料
1.把TiC粉末添加在TiH 2粉末中进行球磨，其中，TiC粉末占TiH 2粉末体积分数的15％。球磨前TiC粉末尺寸约为10μm，球磨具体是在常温下，以球料比10：1在转速300rpm下球磨1h。
2.配置含水、聚乙烯醇和聚乙二醇的溶液，其中水：聚乙烯醇：聚乙二醇质量比为(6.5：3.5：1)，把步骤1中得到的混合粉末添加到上述溶液进行分散，其中步骤1中得到的混合粉末总质量与溶液的质量比为2:1，合成含有固体粉末的悬浮液，采用超声波分散仪分散50min，静置后1.5h后等待打印。
3.通过画图编程设计不同“丝线”间距和截面直径大小的晶格结构，以尺寸55mm×110×55mmmm(长×宽×高)为边界设计整体图形。
4.把步骤3中合成好的墨水导入到打印机中，按照步骤4中设计的打印模型打印出目标设计的预制体，打印速度范围为6mm/s，打印直径250μm，挤出压力范围5bar。
5.对预制体进行加热，加热温度1200℃，保温时间范围为4h，升温速度10℃/min，烧结环境：真空环境，真空度为6×10 -5torr，得到不含W的具有拓扑结构的三维多孔结构的多孔材料。
对比例2.Ti-15％vol TiC复合多孔钛材料
1.把TiC粉末添加在纯Ti粉末中进行球磨混合，TiC粉末占TiH 2粉末体积分数的15％。球磨前W的尺寸1μm，TiC粉末尺寸约为10μm；球磨具体是在常温下，通入氩气保护，以球料比10：1，转速300rpm下球磨3h。
2.把造孔剂NaCl添加入步骤1得到的混合粉末中混合，得到含造孔剂的混合粉末，造孔剂占含造孔剂的混合粉末体积分数的40％。将含造孔剂的混合粉末以球料比2：1，转速为150rpm，混合时间为0.5h，取出粉末等待烧结。
3.把步骤2得到的粉末装入石墨模具中，烧结温度为650℃，升温速率50℃/min，保温10min，真空环境，压强为30MPa。
4.把烧结后的试样放入恒温水浴锅中溶解，温度为60℃，24h，取出试样放入真空加热炉中，温度1200℃，保温时间范围为2h，升温速度10℃/min，真空度为6×10 -5torr，获得不含W的Ti-TiC复合多孔钛材料。
对比例3.Ti-15％vol TiC点阵材料
将TiC粉末添加到纯Ti粉末进行混合，TiC粉末占TiH 2粉末体积分数的15％。采用选择性激光熔化法制备点阵结构，制备工艺条件为激光功率为200W，扫描速度300mm/s，能量密度为120J/mm 3。
对比例4.Ti-15％vol TiC复合多孔钛材料
将TiC粉末添加到纯Ti粉末进行混合，TiC粉末占TiH 2粉末体积分数的15％然后添加造孔剂NH 4HCO 3进行混合，得到含造孔剂的混合粉末，造孔剂占含造孔剂的混合粉末体积分数的40％。将含造孔剂的混合粉末把混合好的粉末在600MPa下进行冷压成型，烧结温度1375℃，保温3h，升温速度5℃/min。
图3(a)为实施例1制备的钨掺杂钛基复合多孔材料的实物图，图3(b)为实施例3制备的钨掺杂钛基复合多孔材料的实物图，图3(c)为实施例1步骤1中，球磨后的TiC与W的混合粉末的SEM图，图3(d)为实施例1步骤6中，烧结后的Ti(W)-TiC的SEM图。从图3(a)-(b)中可以看出，采用本发明的方法可分别得到具有拓扑结构和不规则孔隙的三维多孔结构的多孔材料。图3(c)中，箭头所指的亮白色处为W，从图3(c)可以看出，球磨后的TiC与W混合均匀，微纳尺寸的W粉末分散在TiC粉末之间，图3(d)中，亮白色处为W，黑色处代表TiC，灰色处代表Ti，从图3(d)可以看出，W已经较为均匀溶解在Ti-TiC基体中，形成Ti(W)-TiC复合材料，并且表面致密，没有气孔产生。
图4为实施例3制备的钨掺杂钛基复合多孔材料的XRD图，从图中可以看出Ti、TiC和W的特征衍射峰，表明Ti-TiC材料中成功掺杂了W。
对以上实施例和对比例制备的材料进行孔隙率、硬度、耐磨性测试结果，结果如表1所示。结果表明，本发明制备的钨掺杂钛基复合多孔材料HV 0.2超过700，表面粗糙度S a(μm)小于4，平均摩擦系数(μ)小于0.3，具有高硬度、表面粗糙度和较低摩擦系数，材料具有致密度高，高强、高耐磨性的特点。
表1 不同材料的性能测试结果
Figure PCTCN2020135952-appb-000001
Figure PCTCN2020135952-appb-000002
综上，本发明提供的方法简单、成本低、安全、易操作、实用性强、易于制备高强、低表面粗糙度和高耐磨性的Ti基复合多孔材料，该产品不但可以用于航空航天领域也可用于生物医用领域。
以上仅是本发明的优选实施方式，并不用于限制本发明，应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明技术原理的前提下，还可以做出若干改进和变型，这些改进和变型也应视为本发明的保护范围。

Claims (10)

  1. 钨金属在制备钨掺杂钛基复合多孔材料中的应用，所述钨掺杂钛基复合多孔材料中分布有不同类型三维多孔结构，多个所述多孔结构组成三维拓扑结构或随机结构，所述钨掺杂钛基复合多孔材料包括Ti、TiC和W，其中W占钨掺杂钛基复合多孔材料质量分数的3％以下。
  2. 一种钨掺杂钛基复合多孔材料的制备方法，其特征在于，所述钨掺杂钛基复合多孔材料的多孔结构组成三维拓扑结构，其制备方法包括以下步骤：
    (1)将钨粉末、碳化钛和金属钛基体混合均匀，得到第一混合粉末，其中，所述金属钛基体包括纯钛或氢化钛，所述钨粉末的粒径为100nm-1μm，碳化钛的粒径为15μm以下；钨粉末占第一混合粉末质量分数的3％以下；所述金属钛基体的粒径为10μm以下；
    (2)将所述第一混合粉末均匀分散于聚合物溶液中，合成墨水，其中，所述第一混合粉末和聚合物溶液的质量比为(4-1):1，所述聚合物溶液中包括水溶性聚合物和水；
    (3)将所述墨水按照设计的打印参数进行3D打印得到预制体，将所述预制体在1000-1300℃下进行烧结，烧结完毕后得到所述钨掺杂钛基复合多孔材料，其中打印参数包括孔隙率参数和多孔材料中三维多孔结构的拓扑结构类型。
  3. 根据权利要求2所述的制备方法，其特征在于：在步骤(2)中，所述聚合物溶液中包括水、聚乙烯醇和聚乙二醇，所述水、聚乙烯醇和聚乙二醇的质量比为(6-7.5)：(3-1.5)：1。
  4. 根据权利要求2所述的制备方法，其特征在于：在步骤(3)中，3D打印过程中，打印速度为5-15mm/s，打印直径为150-1000μm，挤出压力为5-10bar。
  5. 一种钨掺杂钛基复合多孔材料的制备方法，其特征在于，所述钨掺杂钛基复合多孔材料具有不规则孔隙结构，其制备方法包括以下步骤：
    (S1)将钨粉末、碳化钛、金属钛基体和造孔剂混合均匀，得到第二混合粉末，其中，所述金属钛基体包括纯钛或氢化钛，第二混合粉末中所述钨粉末的粒径为100nm-2μm，碳化钛的粒径为10μm以下；钨粉末占第二混合粉末质量分数的3％以下；金属钛基体的粒径为10μm以下；
    (S2)将所述第二混合粉末在500-650℃的真空条件下进行放电等离子烧结并去除造孔剂，然后再在1000-1300℃下进行烧结，烧结完毕后得到所述钨掺杂钛基复合多孔材料。
  6. 根据权利要求5所述的制备方法，其特征在于：在步骤(S1)中，所述造孔剂包括NaCl和/或NH 4HCO 3。
  7. 根据权利要求5所述的制备方法，其特征在于：在步骤(S1)中，造孔剂占第二混 合粉末体积分数的90％以下。
  8. 一种钨掺杂钛基复合多孔材料，其特征在于：所述钨掺杂钛基复合多孔材料中分布有多个三维多孔结构，多个所述多孔结构组成三维拓扑结构或随机结构，所述钨掺杂钛基复合多孔材料包括Ti、TiC和W，其中W占钨掺杂钛基复合多孔材料质量分数的3％以下；所述钨掺杂钛基复合多孔材料由权利要求1-7中任一项所述的制备方法所制备得到。
  9. 根据权利要求8所述的钨掺杂钛基复合多孔材料，其特征在于：所述钨掺杂钛基复合多孔材料的孔隙率为20％-90％。
  10. 根据权利要求8所述的钨掺杂钛基复合多孔材料，其特征在于：所述TiC占Ti的体积分数的1％-30％。
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