CN113750288A - Ceramic particle reinforced Ti-Ta-based bone implantation composite material and preparation method thereof - Google Patents
Ceramic particle reinforced Ti-Ta-based bone implantation composite material and preparation method thereof Download PDFInfo
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- 239000002245 particle Substances 0.000 title claims abstract description 40
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 210000000988 bone and bone Anatomy 0.000 title claims abstract description 30
- 239000000919 ceramic Substances 0.000 title claims abstract description 25
- 238000002513 implantation Methods 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000000463 material Substances 0.000 claims abstract description 21
- 239000002002 slurry Substances 0.000 claims abstract description 18
- 238000005245 sintering Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- 239000000843 powder Substances 0.000 claims abstract description 15
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 229910033181 TiB2 Inorganic materials 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims abstract description 9
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims abstract description 9
- JAGQSESDQXCFCH-UHFFFAOYSA-N methane;molybdenum Chemical compound C.[Mo].[Mo] JAGQSESDQXCFCH-UHFFFAOYSA-N 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 8
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001868 water Inorganic materials 0.000 claims abstract description 7
- 238000010791 quenching Methods 0.000 claims abstract description 6
- 230000000171 quenching effect Effects 0.000 claims abstract description 6
- 238000007599 discharging Methods 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 4
- 239000011261 inert gas Substances 0.000 claims abstract description 4
- 238000000748 compression moulding Methods 0.000 claims abstract description 3
- 239000007943 implant Substances 0.000 claims description 16
- 238000004321 preservation Methods 0.000 claims description 10
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 239000011812 mixed powder Substances 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 5
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 5
- QIQXTHQIDYTFRH-GTFORLLLSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCC[14C](O)=O QIQXTHQIDYTFRH-GTFORLLLSA-N 0.000 claims description 2
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- 239000000956 alloy Substances 0.000 description 12
- 229910045601 alloy Inorganic materials 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
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- 238000005452 bending Methods 0.000 description 7
- 238000009826 distribution Methods 0.000 description 6
- 239000010936 titanium Substances 0.000 description 5
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 4
- 229910039444 MoC Inorganic materials 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052715 tantalum Inorganic materials 0.000 description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910003178 Mo2C Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- 208000024827 Alzheimer disease Diseases 0.000 description 1
- 229910000531 Co alloy Inorganic materials 0.000 description 1
- 206010039966 Senile dementia Diseases 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000003013 cytotoxicity Effects 0.000 description 1
- 231100000135 cytotoxicity Toxicity 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000013001 point bending Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
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- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/10—Ceramics or glasses
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- 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
- B22F3/02—Compacting only
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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
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
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- 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
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/04—Making non-ferrous alloys by powder metallurgy
- C22C1/05—Mixtures of metal powder with non-metallic powder
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- 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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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
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- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
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Abstract
The invention discloses a ceramic particle reinforced Ti-Ta based bone implantation composite material and a preparation method thereof, wherein the method comprises the following steps: mixing dimolybdenum carbide or titanium diboride with titanium powder, tantalum powder and nickel carbonyl powder, preparing slurry with a dispersant and a grinding ball, mixing, separating the grinding ball, drying the slurry, and performing compression molding; sintering under a vacuum condition, namely, firstly heating the furnace temperature to 600 ℃ from room temperature at the speed of 10 ℃/min, then preserving the heat for 30min, then heating to 1250-1300 ℃ at the speed of 10 ℃/min, preserving the heat for 60min, and finally cooling to room temperature at the speed of-20 ℃/min; keeping the temperature at 850-940 ℃ in closed high-pressure equipment, keeping the pressure at 90-140 MPa by using inert gas, cooling to 265 ℃ along with the furnace, and discharging; and (3) performing water quenching after the temperature is kept at 900-1200 ℃, and performing air cooling after the temperature is kept at 450-700 ℃. The uniformity, the corrosion resistance and the material strength of elements in the composite material are all improved.
Description
Technical Field
The invention relates to a bone implantation composite material, in particular to a ceramic particle reinforced Ti-Ta based bone implantation composite material and a preparation method thereof.
Background
The titanium alloy material for bone implantation mainly comprises alpha type and beta type, wherein the alpha type is Ti-6AL-4V alloy, the beta type is Ti-5AL-2.5Fe and Ti-6AL-7Nb alloy, the alpha type and the beta type are applied to bone implantation, but V and Al elements contained in the alloy are harmful to human bodies, V is used as a beta phase and is a stable alloy element, the cost is high, the cytotoxicity is high, and the Al element easily causes senile dementia after being existed in the human bodies for a long time. From the medical application point of view, the most important criteria for bone implant alloys are not only the non-toxicity, corrosion resistance and cost of the alloy elements. Therefore, it is important to develop a titanium alloy free from harmful elements such as Al.
Among the bone-implanted titanium alloys without harmful elements such as V and Al, Ti-Ta alloy is one of the most promising alloys. The excellent biocompatibility and corrosion resistance of pure titanium and pure tantalum have been widely accepted by many medical researchers, and compared to pure Ta, Ti-Ta alloys are lighter and cheaper, and are superior materials to replace Ta. Among the currently used bone implant materials, the Ti — Ta alloy has the lowest young's modulus and strength comparable to that of the cobalt-based alloy.
In the powder metallurgy of Ti-Ta alloys, sintering the mixed Ti and Ta powders does not fully guarantee the homogeneity of the alloy despite the high sintering temperatures used (from 1200 to 1500 ℃). Therefore, Ti-Ta powder is not fully diffused in the sintering process, so that Ti-rich and Ta-rich areas in the alloy are alternately distributed, and the problem of uneven element distribution can be effectively solved by utilizing an initial mechanical alloying method and then sintering at the temperature lower than the melting point of titanium. In the process of preparing the titanium alloy through powder metallurgy, the porosity (the porosity is 5-20%) can be controlled by adjusting powder components and sintering parameters, so that the Ti-Ta alloy with low elastic modulus is obtained, and is suitable for bone implant, but the strength and the fatigue resistance of the alloy surface are reduced, and even harmful substances in the chemical treatment process remain in pores, so that the problem of obtaining the Ti-Ta alloy with proper pores, high bending strength and good corrosion resistance is a great problem.
Disclosure of Invention
The invention aims to provide a ceramic particle reinforced Ti-Ta based bone implantation composite material and a preparation method thereof.
In order to achieve the above objects, the present invention provides a method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite, the method comprising: and (2) mixing the following components in a mass ratio of 84-88: 8: 4-8: 1-5 parts of dimolybdenum carbide or titanium diboride, titanium powder, tantalum powder and nickel carbonyl powder are uniformly mixed, and the mixed powder, a dispersing agent and a grinding ball are mixed according to a mass ratio of 1:1:1, preparing slurry, mixing at a temperature of between 5 ℃ below zero and 2 ℃ below zero, separating the slurry from grinding balls after the completion of the mixing, drying the slurry, and performing compression molding under the pressure of 180 to 240 MPa; at 10-3～10-2Sintering under the Pa vacuum degree, firstly heating the furnace temperature from room temperature to 600 ℃ at the heating rate of 10 ℃/min, then preserving the heat for 30min, then heating to 1250-1300 ℃ at the heating rate of 10 ℃/min, preserving the heat for 60min, and finally cooling to the room temperature at the speed of-20 ℃/min; placing the sintered material in a closed high-pressure device, keeping the temperature at 850-940 ℃, keeping the pressure at 90-140 MPa through inert gas, keeping for 2 hours, cooling to 265 ℃ along with the furnace, and discharging; and then, carrying out heat preservation on the material at 900-1200 ℃ for 40min, then carrying out water quenching, then carrying out heat preservation at 450-700 ℃ for 5h, and then carrying out air cooling to obtain the ceramic particle reinforced Ti-Ta based bone implantation composite material.
Preferably, the pressure maintaining time is 5min when the material is pressed and formed under 180-240 MPa.
Preferably, the dimolybdenum carbide or titanium diboride is mixed with titanium powder, tantalum powder and nickel carbonyl powder in an ultrasonic mode, and the ultrasonic frequency is 35 Hz.
Preferably, the dispersant is octadecanoic acid.
Preferably, the grinding balls are zirconia balls.
Preferably, the mixing time is 24 hours at-5 to-2 ℃.
Preferably, the temperature at which the slurry is dried is 72 ℃.
The invention also aims to provide a ceramic particle reinforced Ti-Ta based bone implant composite material prepared by the method.
The ceramic particle reinforced Ti-Ta based bone implantation composite material and the preparation method thereof have the following advantages:
the ceramic particle reinforced Ti-Ta based bone implantation composite material is prepared by mixing ceramic particles Mo2C or TiB2The Ti-Ta alloy is used as reinforcing particles and added into the Ti-Ta alloy, so that the uniformity, the corrosion resistance and the material strength of elements in the composite material are improved. Wherein added Mo2The C particles are distributed in the matrix material in a criss-cross mode, so that the crack expansion in the material can be effectively hindered, and the bending strength of the material can be favorably improved. Added Mo2The wetting property between the C particles and the matrix is strong, the swelling phenomenon of the material can be eliminated, and the uniformity of particle distribution is improved. Ta and Mo are beneficial to alloy to generate a passivation layer, and the corrosion resistance of the material is also improved.
Drawings
FIG. 1 is a schematic diagram of sintering temperatures for various embodiments of the present invention.
Fig. 2 is the EDS element distribution test results of the composite material of example 1 of the present invention.
Fig. 3 is the EDS elemental distribution test results for the composite of example 4 of the invention.
FIG. 4 is a polarization impedance for various embodiments of the present invention.
FIG. 5 is a graph of the flexural strength of composite materials prepared in various examples of the invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A ceramic particle reinforced Ti-Ta based bone implantation composite material is prepared by the following steps:
(1) titanium powder (average particle size of 35 microns) with the purity of 95%, tantalum powder (average particle size of 10 microns), nickel carbonyl powder (average particle size of 10 microns) and molybdenum carbide (average particle size of 6 microns) are mixed together to prepare mixed powder, the mass of the mixed powder is 84g, 8g, 4g and 1g respectively, the mixed powder is subjected to ultrasonic treatment by an ultrasonic cleaning machine and is convenient to mix uniformly, the treatment frequency is 35Hz, and the treatment time is 43 min. Stearic acid and zirconia balls are respectively used as a dispersing agent and a grinding ball, and the mixed powder, stearic acid and the grinding ball are prepared into slurry according to the mass ratio of 1:1: 1.
(2) And (2) completely putting the slurry prepared in the step (1) into a three-dimensional space rotary mixer for mixing for 24 hours at the mixing temperature of-2 ℃. And after the powder mixing is finished, pouring the slurry out, separating the slurry from the grinding balls, placing the slurry in a drying oven at 72 ℃ for baking for 24 hours to remove the octadecanoic acid dispersing agent in the slurry, and carrying out press forming on the dried powder under the pressure of 180MPa for 5 minutes.
(3) Firing the pressed green body in a vacuum sintering furnace at 10 deg.C to reduce the adverse effects of harmful components such as nitrogen, oxygen and water in the atmosphere on the workpiece-2And sintering under Pa vacuum degree, wherein the sintering temperature is shown in figure 1, the furnace temperature is firstly increased from 25 ℃ to 600 ℃ at the heating rate of 10 ℃/min and then is kept for 30min, then is increased to 1250 ℃ at the heating rate of 10 ℃/min and is kept for 60min, and finally is reduced to 25 ℃ at the room temperature at the speed of-20 ℃/min.
(4) And (4) putting the material prepared in the step (3) into a closed high-pressure device, keeping the temperature at 850 ℃, keeping the pressure at 90MPa through inert gas, keeping for 2 hours, cooling to 265 ℃ along with the furnace, and discharging.
(5) And (3) putting the material prepared in the step (4) into a furnace at 900 ℃ for heat preservation for 40min, then carrying out water quenching, then carrying out heat preservation at 450 ℃ for 5h, and then carrying out air cooling to obtain the ceramic particle reinforced Ti-Ta based bone implantation composite material.
Example 2
A ceramic particle reinforced Ti-Ta based bone implant composite prepared substantially as in example 1, except that:
in the step (1), the mass of the titanium powder, the mass of the tantalum powder, the mass of the nickel carbonyl powder and the mass of the molybdenum carbide are respectively 86g, 8g, 6g and 3 g;
in the step (2), the mixing temperature of the slurry is-3 ℃; the pressure for carrying out press forming on the dried powder is 210MPa, and the pressure maintaining time is 5 min;
in step (3), at 10-3Sintering under Pa vacuum degree, wherein the sintering temperature is shown in figure 1, the furnace temperature is firstly increased from 25 ℃ to 600 ℃ at the heating rate of 10 ℃/min and then is kept for 30min, then is increased to 1275 ℃ at the heating rate of 10 ℃/min and is kept for 60min, and finally is reduced to 25 ℃ at the temperature of-20 ℃/min;
in the step (4), the temperature is maintained at 900 ℃, and the pressure is maintained at 120 MPa;
in the step (5), the material is put into 1100 ℃ for heat preservation for 40min, then water quenching is carried out, and then heat preservation is carried out for 5h at 600 ℃ and then air cooling is carried out.
Example 3
A ceramic particle reinforced Ti-Ta based bone implant composite prepared substantially as in example 1, except that:
in the step (1), the mass of the titanium powder, the mass of the tantalum powder, the mass of the nickel carbonyl powder and the mass of the molybdenum carbide are respectively 88g, 8g and 5 g;
in the step (2), the mixing temperature of the slurry is-5 ℃; the pressure for press forming the dried powder is 240 MPa;
in step (3), at 10-3Sintering under Pa vacuum degree, wherein the sintering temperature is shown in figure 1, the furnace temperature is firstly increased from 25 ℃ to 600 ℃ at the heating rate of 10 ℃/min and then is kept for 30min, then is increased to 1300 ℃ at the heating rate of 10 ℃/min and is kept for 60min, and finally is reduced to 25 ℃ at the room temperature at the speed of-20 ℃/min;
in the step (4), keeping the temperature at 940 ℃ and the pressure at 140 MPa;
in the step (5), the material is subjected to heat preservation at 1200 ℃ and then water quenching, and then is subjected to heat preservation at 700 ℃ and then air cooling.
Example 4
A ceramic particle reinforced Ti-Ta based bone implant composite prepared substantially as in example 1, except that: titanium diboride (average particle size 10 μm) was substituted for dimolybdenum carbide.
Example 5
A ceramic particle reinforced Ti-Ta based bone implant composite prepared substantially as in example 2, except that: titanium diboride (average particle size 10 μm) was substituted for dimolybdenum carbide.
Example 6
A ceramic particle reinforced Ti-Ta based bone implant composite prepared substantially as in example 3, except that: titanium diboride (average particle size 10 μm) was substituted for dimolybdenum carbide.
Uniformity test of elemental distribution for example 1 and example 4
EDS element distribution tests are carried out on the samples prepared in the example 1 and the example 4, and the test results are shown in a figure 2 and a figure 3, wherein in the example 1, C is converted from molybdenum carbide and is distributed in a material in a fine particle shape, other elements are uniformly distributed, and the structure has no obvious pores; in example 4, B is converted from titanium diboride, and the elements are uniformly distributed without obvious pores in the structure.
Corrosion resistance testing of examples 1-6
The corrosion resistance of the material is tested by adopting a dynamic potential polarization experimental method, the test specification refers to ASTM G59-97, the electrolyte is 0.5mol/L sulfuric acid aqueous solution, the auxiliary electrode is platinum, Ag/AgCl is a reference electrode, and the area of a corrosion test sample is 0.8cm2。
The polarization resistance of each example is shown in FIG. 4, where the polarization resistance is the greatest and the corrosion resistance is the best in example 3, followed by example 6, surface Mo2C and TiB2The addition of (2) is beneficial to improving the corrosion resistance of the composite material.
Flexural Strength testing of examples 1-6
The bending strength test adopts a three-point bending strength experimental method for measurement, the measurement specification refers to ASTM B528-2016, the loading rate is 2mm/min, the width, the height and the length of a tested sample are respectively 5.5mm, 6mm and 200mm, and the span of two supporting points below the test sample is 25.4 mm.
The bending strength calculation formula is as follows:
TRS＝(3×P×L)/(2×T2×W)
wherein P is the measured breaking load (N), L is the span (mm) of two fulcrums under the sample, T is the height (mm) of the sample, and W is the width (mm) of the sample.
As shown in FIG. 5, for the flexural strength of the composite materials prepared in the respective examples, it can be seen that Mo was contained in examples 1, 2 and 32The content of C particles is increased in sequence, the bending strength is also increased, and Mo is shown2The addition of the C particles can effectively prevent the crack from expanding, thereby improving the bending strength of the material. TiB in example 4, example 5 and example 62The particle content increases in turn when TiB2The particles are enlarged to a certain degree, and the bending strength of the material is improved.
While the present invention has been described in detail with reference to the preferred embodiments, it should be understood that the above description should not be taken as limiting the invention. Various modifications and alterations to this invention will become apparent to those skilled in the art upon reading the foregoing description. Accordingly, the scope of the invention should be determined from the following claims.
Claims (8)
1. A method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite, the method comprising:
and (2) mixing the following components in a mass ratio of 84-88: 8: 4-8: 1-5 parts of dimolybdenum carbide or titanium diboride, titanium powder, tantalum powder and nickel carbonyl powder are uniformly mixed, and the mixed powder, a dispersing agent and a grinding ball are mixed according to a mass ratio of 1:1:1, preparing slurry, mixing at a temperature of between 5 ℃ below zero and 2 ℃ below zero, separating the slurry from grinding balls after the completion of the mixing, drying the slurry, and performing compression molding under the pressure of 180 to 240 MPa;
at 10-3～10-2Sintering under Pa vacuum degree, heating furnace temperature from room temperature to 600 deg.C at a heating rate of 10 deg.C/min, maintaining for 30min, and sintering at high temperatureHeating to 1250-1300 ℃ at the speed of 10 ℃/min, preserving the heat for 60min, and finally cooling to room temperature at the speed of-20 ℃/min;
placing the sintered material in a closed high-pressure device, keeping the temperature at 850-940 ℃, keeping the pressure at 90-140 MPa through inert gas, keeping for 2 hours, cooling to 265 ℃ along with the furnace, and discharging; and then, carrying out heat preservation on the material at 900-1200 ℃ for 40min, then carrying out water quenching, then carrying out heat preservation at 450-700 ℃ for 5h, and then carrying out air cooling to obtain the ceramic particle reinforced Ti-Ta based bone implantation composite material.
2. The method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite material according to claim 1, wherein the pressure maintaining time is 5min when the composite material is press-molded at 180 to 240 MPa.
3. The method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite material according to claim 1, wherein the dimolybdenum carbide or titanium diboride is mixed with titanium powder, tantalum powder and nickel carbonyl powder in an ultrasonic manner, and the ultrasonic frequency is 35 Hz.
4. The method of claim 1, wherein the dispersant is octadecanoic acid.
5. The method of claim 1, wherein the grinding balls are zirconia balls.
6. The method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite according to claim 1, wherein the mixing time at-5 to-2 ℃ is 24 hours.
7. The method for preparing a ceramic particle reinforced Ti-Ta based bone implant composite according to claim 1, wherein the temperature at which the slurry is dried is 72 ℃.
8. A ceramic particle reinforced Ti-Ta based bone implant composite prepared according to the method of any one of claims 1 to 7.
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