CN115488341A - Integrated preparation method of low-modulus biomedical titanium alloy with bionic structure - Google Patents
Integrated preparation method of low-modulus biomedical titanium alloy with bionic structure Download PDFInfo
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- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 30
- 239000011664 nicotinic acid Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 122
- 239000002245 particle Substances 0.000 claims abstract description 35
- 239000011812 mixed powder Substances 0.000 claims abstract description 34
- 238000003825 pressing Methods 0.000 claims abstract description 32
- 238000005245 sintering Methods 0.000 claims abstract description 31
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 239000000956 alloy Substances 0.000 claims abstract description 29
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 24
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 21
- 239000010936 titanium Substances 0.000 claims abstract description 17
- 238000001816 cooling Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052786 argon Inorganic materials 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 9
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 9
- 238000011049 filling Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 238000007873 sieving Methods 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003723 Smelting Methods 0.000 claims abstract description 6
- 238000007664 blowing Methods 0.000 claims abstract description 6
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
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- 238000010438 heat treatment Methods 0.000 description 6
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- 238000010521 absorption reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
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- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007943 implant Substances 0.000 description 2
- 238000001746 injection moulding Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
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- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
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- 238000005097 cold rolling Methods 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
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- 230000006698 induction Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
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- 238000004663 powder metallurgy Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000002490 spark plasma sintering Methods 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000004938 stress stimulation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- -1 titanium hydride Chemical compound 0.000 description 1
- QSGNKXDSTRDWKA-UHFFFAOYSA-N zirconium dihydride Chemical compound [ZrH2] QSGNKXDSTRDWKA-UHFFFAOYSA-N 0.000 description 1
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- 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
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
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- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
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Abstract
The invention provides a low-modulus biomedical titanium alloy integrated preparation method with a bionic structure, which comprises the following steps: s1, doping sponge titanium or sponge zirconium particles into Nb, sn, ta and/or Hf particles, uniformly mixing, and then putting into a molten pool for vacuum melting; after uniform smelting, blowing hydrogen-argon mixed gas into the molten pool and cooling the furnace to obtainTo (Ti/Zr-Nb/Sn/Ta/Hf) H x Hydrogenating the prealloyed mass; s2, mechanically crushing the hydrogen-containing alloy block into (Ti/Zr-Nb/Sn/Ta/Hf) H x Hydrogenating the pre-alloyed powder and sieving the powder; s3, mixing the hydrogenated pre-alloyed powder with TiH 2 Powder and ZrH 2 Mixing the powder evenly and pressing into a prefabricated blank; s4, placing the preformed blank into a mold cavity, filling pore-forming agent mixed powder around the powder blank, and performing secondary pressing to obtain a composite powder blank; and S5, performing vacuum sintering on the composite powder blank. The preparation method can obviously improve the structural component uniformity, the grain size control, the compactness and the mechanical property of the alloy.
Description
Technical Field
The invention relates to an integrated preparation method of a low-modulus biomedical titanium alloy with a bionic structure, belonging to the technical field of preparation of medical titanium alloys.
Background
The beta type titanium alloy has the characteristics of high specific strength, low elastic modulus, strong corrosion resistance, good biocompatibility and the like, and is very suitable for being used as a hard tissue repair material in a human body. At present, researchers mainly strive to develop metastable beta-type titanium alloy containing biological non-toxic elements such as Mo, zr, nb, sn, ta and the like, and prepare biomedical materials with complex shapes, approximate to final forming and high quality through advanced manufacturing technologies such as vacuum induction arc melting, selective laser melting, spark plasma sintering, powder injection molding, metal injection molding and the like; the performance of the alloy is improved through the hot mechanical processing and heat treatment processes such as cold rolling, hot rolling, homogenization, aging, solid solution and the like; the elastic modulus of the prepared alloy is mostly concentrated in 70-120GPa, the tensile strength is in the range of 600-1250MPa and is still far higher than the biomechanical property (20-30 GPa) of human bones, and long-term stress shielding and stress stimulation are easily caused after the alloy is implanted into a human body, so that the bone tissues around the implant are absorbed or shrunk. On the other hand, in order to ensure the activity of osteoblasts, it is generally required that the surface of the biological implant material has a through opening with a pore diameter of more than 100 μm, and the wall of the large pore is distributed with abundant micropores, i.e., a "dual-scale microporous structure". Therefore, in order to improve the inherent bio-inert surface and biomechanical properties of titanium alloy, it is necessary to perform surface coating on the titanium alloy by using other materials such as porous tantalum based on additive manufacturing technology to form a bionic microporous surface. The problems of complex alloy composition elements, high elastic modulus, complex processing and heat treatment processes, limitation of a surface modification method (such as weak binding force and poor film quality) and the like limit the wide application of the metastable beta-type titanium alloy in the field of biomedicine.
Although the powder metallurgy method has the advantages of simple process flow, low production cost, capability of accurately regulating and controlling material components as required, near net shape forming and the like, the problems of uneven tissue components, large grains, poor compactness, difficulty in forming a bionic porous structure and the like exist when preparing the alloy with large diffusion rate difference among elements; it is often used as a preparatory link for processes such as additive manufacturing or to improve the texture by subsequent thermomechanical processing and heat treatment to meet application requirements. The economic advantages of the method are greatly reduced by prolonging the process flow, equipment investment and energy loss.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the integrated preparation method of the low-modulus biomedical titanium alloy with the bionic structure, which can greatly relieve the problem of component uniformity of a sintered material caused by diffusion rate difference among different elements, so that the structural component uniformity, the grain size control, the compactness and the mechanical property of the alloy are obviously improved.
The scheme is realized by the following technical measures: an integrated preparation method of a low-modulus biomedical titanium alloy with a bionic structure comprises the following steps:
s1, doping sponge titanium or sponge zirconium particles into Nb, sn, ta and/or Hf particles, uniformly mixing, and then putting into a molten pool for vacuum melting; after uniform smelting, blowing hydrogen-argon mixed gas into the molten pool and furnace cooling to obtain (Ti/Zr-Nb/Sn/Ta/Hf) H x Hydrogenating the prealloyed mass;
s2, mechanically crushing the hydrogen-containing alloy block obtained in the step S1 into (Ti/Zr-Nb/Sn/Ta/Hf) H x Hydrogenating the pre-alloyed powder and sieving the powder;
s3, mixing the hydrogenated pre-alloyed powder obtained in the step S2 with TiH 2 Powder and ZrH 2 Mixing the powder uniformly, and pressing into a prefabricated blank;
s4, placing the preformed blank obtained in the step S3 into a mold cavity, filling pore-forming agent mixed powder around the powder blank, and performing secondary pressing to obtain a composite powder blank;
and S5, carrying out vacuum sintering on the composite powder blank obtained in the step S4.
Preferably, the particle size of the Nb, sn and Hf particles in step S1 is 1-5mm, and the particle size of the titanium sponge or zirconium sponge particles is 1-5mm.
Preferably, (Ti/Zr-Nb/Sn/Ta/Hf) H after the powder sieving in the step S2 x The grain size of the hydrogenated pre-alloyed powder is less than 88 mu m.
Preferably, in the step S3, the prealloyed powder and the TiH2 and ZrH2 with the corresponding mass are mixed for 2 to 6 hours according to the designed component mass ratio to obtain an initial mixed powder.
Preferably, the initial mixed powder is pressed into a prefabricated blank by adopting a mould pressing method, the mould pressing temperature is room temperature, and the mould pressing pressure is 200-500Mpa.
Preferably, the pore-forming agent mixed powder in the step S4 is made of TiH 2 Powder and NH 4 HCO 3 Mixing the powders, wherein, tiH 2 The mass percentage of the powder is 50 percent, and the TiH 2 The particle size of the powder is less than or equal to 88 mu m, NH 4 HCO 3 The mass percentage of the powder is 50 percent, NH 4 HCO 3 The particle size of the powder is 200-300 μm, and the mass ratio is based on the total mass of all components of the pore-forming agent mixed powder.
Preferably, the pressure of the secondary pressing in the step S4 is 150MPa.
Preferably, in step S5, the composite powder blank is placed in a vacuum sintering furnace for vacuum sintering, and when the vacuum degree in the vacuum sintering furnace reaches 1 × 10 -3 And pa, starting to heat up to 1100 ℃ at the speed of 10 ℃/min, keeping the temperature for 90-120min, and cooling the furnace to finish the integrated preparation of the biomedical titanium alloy with the bionic porous surface.
Preferably, the partial pressure of hydrogen in the hydrogen-argon gas mixture accounts for 50%.
The invention has the beneficial effects that: the invention reserves the beta configuration of the alloy at room temperature by doping certain amount of Nb, sn, ta and/or Hf elements into the titanium alloy so as to reduce the elasticity of the biomedical titanium alloyA modulus; hydrogenation pre-alloyed powder and TiH under the guidance of mixed element idea 2 Powder and ZrH 2 of Powder mixing is carried out, so that the accurate control of alloy components is realized; the Ti-Nb alloy or the Zr-Nb alloy is prepared by doping Ti or Zr with a certain proportion into Nb, sn or Hf, so that the problem of component uniformity of a sintered material caused by diffusion rate difference among different elements is greatly relieved; the high activity and hydrogen absorption characteristics of the molten titanium alloy material are utilized to realize the pre-alloying and hydrogenation of the material, and the pre-forming blank is provided with TiH 2 And ZrH 2 Similar thermodynamic behavior obviously improves the structural component uniformity, the grain size control, the compactness and the mechanical property of the alloy; by constructing a multi-layer composite powder blank and utilizing TiH 2 And NH 4 HCO 3 And (3) carrying out pore-forming on the surface of the alloy to realize the integrated preparation of the biomedical titanium alloy with the bionic porous surface. Therefore, compared with the prior art, the invention has prominent substantive features and remarkable progress, and the beneficial effects of the implementation are also obvious.
Drawings
FIG. 1 is a process flow diagram of an embodiment of the present invention.
Detailed Description
In order to clearly explain the technical features of the present solution, the present solution is explained below by means of specific embodiments and with reference to the accompanying drawings.
An integrated preparation method of a low-modulus biomedical titanium alloy with a bionic structure comprises the following steps:
s1, doping sponge titanium or sponge zirconium particles into Nb, sn, ta and/or Hf particles, uniformly mixing, and then putting into a molten pool for vacuum melting; after the smelting is uniform, blowing hydrogen-argon mixed gas into the molten pool and cooling the molten pool, preferably, the hydrogen partial pressure in the hydrogen-argon mixed gas accounts for 50 percent to obtain (Ti/Zr-Nb/Sn/Ta/Hf) H x Hydrogenating the prealloyed mass; wherein the grain diameter of Nb, sn and Hf grains is 1-5mm, and the grain diameter of the titanium sponge or zirconium sponge grains is 1-5mm;
s2, mechanically crushing the hydrogen-containing alloy block obtained in the step S1 into (Ti/Zr-Nb/Sn/Ta/Hf) H x Hydrogenation pre-synthesisGold powder and sieving powder, (Ti/Zr-Nb/Sn/Ta/Hf) H after sieving powder x The grain diameter of the hydrogenated pre-alloy powder is less than 88 mu m;
s3, mixing the hydrogenated pre-alloyed powder obtained in the step S2 with TiH 2 Powder and ZrH 2 Mixing the powder uniformly, specifically, according to the mass ratio of the designed components, mixing the prealloyed powder with the corresponding mass of TiH 2 And ZrH 2 Mixing powder for 2-6h to obtain initial mixed powder, and pressing into a prefabricated blank, specifically, pressing the initial mixed powder into the prefabricated blank by adopting mould pressing, wherein the mould pressing temperature is room temperature, and the mould pressing pressure is 200-500Mpa;
s4, placing the preformed blank obtained in the step S3 into a mold cavity, filling pore-forming agent mixed powder around the powder blank, and performing secondary pressing to obtain a composite powder blank, wherein the pressure of the secondary pressing is 150MPa; wherein the pore-forming agent mixed powder is prepared from TiH 2 Powder and NH 4 HCO 3 Mixing the powders, wherein, tiH 2 The mass percentage of the powder is 50 percent, and the TiH 2 The particle size of the powder is less than or equal to 88 mu m, NH 4 HCO 3 The mass percentage of the powder is 50 percent, NH 4 HCO 3 The particle size of the powder is 200-300 mu m, and the mass ratio is based on the total mass of all components of the pore-forming agent mixed powder;
s5, carrying out vacuum sintering on the composite powder blank obtained in the step S4: the composite powder blank is put into a vacuum sintering furnace for vacuum sintering, and when the vacuum degree in the vacuum sintering furnace reaches 1 multiplied by 10 -3 And pa, heating to 1100 ℃ at the speed of 10 ℃/min, keeping the temperature for 90-120min, and cooling the furnace to finish the integrated preparation of the biomedical titanium alloy with the bionic porous surface (namely the compact alloy prosthesis with the bionic micropore surface).
Example 1 (preparation of 55Zr-24Ti-21Nb alloy)
S1, uniformly mixing sponge titanium with the particle size of 4mm and Nb particles according to the mass ratio of 20Zr-21Nb, and putting the mixture into a molten pool for vacuum melting; blowing hydrogen-argon mixed gas into the molten pool after uniform smelting, cooling the furnace, taking out the furnace after cooling to obtain (Ti-Nb) H x Hydrogenating the prealloyed mass;
s2, mechanically crushing the hydrogen-containing alloy block obtained in the step S1 into (Ti-Nb) H x Hydrogenation pre-stageAlloying and sieving to obtain (Zr-Nb) H with particle size of 88 μm x Hydrogenating the pre-alloyed powder;
s3, according to the mass ratio of the designed components, the prealloying powder and the corresponding mass TiH 2 And ZrH 2 Mixing the powder for 4 hours to obtain initial mixed powder, and pressing the initial mixed powder into a prefabricated blank by adopting 300MPa mould pressing at room temperature;
s4, placing the preformed blank obtained in the step S3 into a mold cavity, and filling a pore-forming agent mixed powder into the periphery of the powder blank, wherein the pore-forming agent mixed powder is made of TiH 2 Powder and NH 4 HCO 3 Mixing the powders, wherein, tiH 2 The mass percentage of the powder is 50 percent, and the TiH 2 The particle size of the powder is 88 mu m, NH 4 HCO 3 The mass percentage of the powder is 50 percent, NH 4 HCO 3 The particle size of the powder is 200 mu m, the mass ratio is based on the total mass of all components of the pore-forming agent mixed powder, and a composite powder blank is obtained by secondary pressing at 150MPa;
s5, carrying out vacuum sintering on the composite powder blank obtained in the step S4: the composite powder blank is put into a vacuum sintering furnace for vacuum sintering, and when the vacuum degree in the vacuum sintering furnace reaches 1 multiplied by 10 -3 And pa, starting to heat up to 1100 ℃ at the speed of 10 ℃/min, keeping the temperature for 90min, and then cooling the furnace to finish the 55Zr-25Ti-20Nb dense alloy artificial prosthesis with the bionic porous surface.
Example 2 (preparation of 32Zr-36Ti-12Nb-12Ta-8Sn alloy)
S1, uniformly mixing sponge titanium with the particle size of 5mm, nb particles, ta particles and Sn particles according to the mass ratio of 20Ti-12Nb-12Ta-8Sn, and putting the mixture into a molten pool for vacuum melting; blowing hydrogen-argon mixed gas into the molten pool after uniform smelting, cooling the molten pool in a furnace, and taking out the molten pool after furnace cooling to obtain (Ti-Nb-Ta-Sn) H x Hydrogenating the prealloyed mass;
s2, mechanically crushing the hydrogen-containing alloy block obtained in the step S1 into (Ti-Nb-Ta-Sn) H x Hydrogenating the pre-alloyed powder and sieving to obtain (Ti-Nb-Ta-Sn) H with a particle size of 88 mu m x Hydrogenating the pre-alloyed powder;
s3, according to the mass proportion of the designed components, the prealloyed powder and the corresponding mass TiH are mixed 2 And ZrH 2 Mixing the powder for 4h to obtain initial mixed powderPressing into a prefabricated blank by adopting 300MPa mould pressing;
s4, placing the preformed blank obtained in the step S3 into a mold cavity, and filling a pore-forming agent mixed powder into the periphery of the powder blank, wherein the pore-forming agent mixed powder is made of TiH 2 Powder and NH 4 HCO 3 Mixing the powders, wherein, tiH 2 The mass percentage of the powder is 50 percent, and the TiH 2 The particle size of the powder is 88 mu m, NH 4 HCO 3 The mass percentage of the powder is 50 percent, NH 4 HCO 3 The particle size of the powder is 260 mu m, the mass ratio is based on the total mass of all components of the pore-forming agent mixed powder, and a composite powder blank is obtained by secondary pressing at 150MPa;
s5, carrying out vacuum sintering on the composite powder blank obtained in the step S4: the composite powder blank is put into a vacuum sintering furnace for vacuum sintering, and when the vacuum degree in the vacuum sintering furnace reaches 1 multiplied by 10 -3 And pa, starting heating to 1100 ℃ at the speed of 10 ℃/min, keeping the temperature for 1200min, and then cooling the furnace to finish the 32Zr-36Ti-12Nb-12Ta-8Sn compact alloy artificial prosthesis with the bionic porous surface.
COMPARATIVE EXAMPLE 1 (preparation of 55Zr-24Ti-21Nb alloy)
S1, mixing Nb powder with the particle size of 88 mu m and TiH according to the mass ratio of the designed components 2 And ZrH 2 Mixing powder for 4 hours to obtain initial mixed powder, and pressing the initial mixed powder into a prefabricated blank by adopting 300MPa mould pressing;
s2, placing the preformed blank obtained in the step S1 into a mold cavity, and filling a pore-forming agent mixed powder into the periphery of the powder blank, wherein the pore-forming agent mixed powder is made of TiH 2 Powder and NH 4 HCO 3 Mixing the powders, wherein, tiH 2 The mass percentage of the powder is 50 percent, and the TiH 2 The particle size of the powder is 88 mu m, NH 4 HCO 3 The mass percentage of the powder is 50 percent, NH 4 HCO 3 The particle size of the powder is 200 mu m, the mass ratio is based on the total mass of all components of the pore-forming agent mixed powder, and a composite powder blank is obtained by secondary pressing at 150MPa;
and S3, carrying out vacuum sintering on the composite powder blank obtained in the step S2: the composite powder blank is put into a vacuum sintering furnace for vacuum sintering, and when the vacuum degree in the vacuum sintering furnace reaches 1 multiplied by 10 -3 After pa, start to ramp up at a rate of 10 deg.C/minAnd (3) heating to 1250 ℃, preserving the heat for 240min, and cooling the furnace to finish the 55Zr-24Ti-21Nb dense alloy artificial prosthesis with the bionic porous surface.
COMPARATIVE EXAMPLE 2 (preparation of 32Zr-36Ti-12Nb-12Ta-8Sn alloy)
S1, mixing Nb powder, ta powder and Sn powder with the grain diameter of 88um and TiH2 powder and ZrH2 powder for 4 hours according to the designed component mass proportion to obtain initial mixed powder, and pressing the initial mixed powder into a prefabricated blank by adopting 300MPa mould pressing;
s2, placing the preformed blank obtained in the step S1 into a mold cavity, and filling a pore-forming agent mixed powder body which is made of TiH into the periphery of the powder blank 2 Powder and NH 4 HCO 3 Mixing the powders, wherein, tiH 2 The mass percentage of the powder is 50 percent, and the TiH 2 The particle size of the powder is 88 mu m, NH 4 HCO 3 The mass percentage of the powder is 50 percent, NH 4 HCO 3 The particle size of the powder is 260 mu m, the mass ratio is based on the total mass of all components of the pore-forming agent mixed powder, and a composite powder blank is obtained by secondary pressing at 150MPa;
and S3, carrying out vacuum sintering on the composite powder blank obtained in the step S2: the composite powder blank is put into a vacuum sintering furnace for vacuum sintering, and when the vacuum degree in the vacuum sintering furnace reaches 1 multiplied by 10 -3 After pa, the temperature starts to rise to 1250 ℃ at the speed of 10 ℃/min, and after the temperature is kept for 240min, the furnace is cooled, and the 32Zr-36Ti-12Nb-12Ta-8Sn compact alloy artificial prosthesis with the bionic porous surface is completed.
TABLE 1 Process conditions and Performance characterization of the examples and comparative examples
As can be seen from comparison of the process parameters and performance data of the examples and comparative examples in Table 1, the hydrogenated pre-alloyed powder prepared by utilizing the hydrogen absorption characteristic of the molten titanium alloy and the mixed powder consisting of titanium hydride and zirconium hydride show better mechanical properties after sintering: the ductility and the strength of the material are greatly improved; and the control of the sintering temperature and time leads the surface micropore size to be obviously refined, and the elastic modulus to be obviously reduced. The demonstration proves that the low-modulus biomedical titanium alloy artificial prosthesis with the bionic micropore structure prepared by the method has good application prospect.
Technical features not described in the present invention can be implemented by the prior art, and will not be described herein again. The present invention is not limited to the above-described embodiments, and variations, modifications, additions and substitutions which are within the spirit of the invention and the scope of the invention may be made by those of ordinary skill in the art are also within the scope of the invention.
Claims (9)
1. A low-modulus biomedical titanium alloy integrated preparation method with a bionic structure is characterized by comprising the following steps: it comprises the following steps:
s1, doping sponge titanium or sponge zirconium particles into Nb, sn, ta and/or Hf particles, uniformly mixing, and then putting into a molten pool for vacuum melting; after uniform smelting, blowing hydrogen-argon mixed gas into the molten pool and cooling the furnace;
s2, mechanically crushing the hydrogen-containing alloy block obtained in the step S1;
s3, mixing the hydrogenated pre-alloyed powder obtained in the step S2 with TiH 2 Powder and ZrH 2 Mixing the powder uniformly, and pressing into a prefabricated blank;
s4, placing the preformed blank obtained in the step S3 into a mold cavity, filling pore-forming agent mixed powder around the powder blank, and performing secondary pressing to obtain a composite powder blank;
and S5, carrying out vacuum sintering on the composite powder blank obtained in the step S4.
2. The integrated preparation method of the low-modulus biomedical titanium alloy with the bionic structure as claimed in claim 1, which is characterized in that: in the step S1, the grain diameter of Nb, sn and Hf grains is 1-5mm, and the grain diameter of titanium sponge or zirconium sponge grains is 1-5mm.
3. The integrated preparation method of the low-modulus biomedical titanium alloy with the bionic structure as claimed in claim 2, which is characterized in that: (Ti/Zr-Nb/Sn/Ta/Hf) H after powder sieving in the step S2 x The grain size of the hydrogenated pre-alloyed powder is less than 88 mu m.
4. The integrated preparation method of the low-modulus biomedical titanium alloy with the bionic structure as claimed in claim 3, which is characterized in that: in the step S3, the prealloyed powder and the corresponding mass TiH are mixed according to the mass ratio of the designed components 2 And ZrH 2 Mixing the powder for 2-6h to obtain initial mixed powder.
5. The integrated preparation method of the low-modulus biomedical titanium alloy with the bionic structure as claimed in claim 4, which is characterized in that: and the initial mixed powder is pressed into a prefabricated blank by adopting mould pressing, the mould pressing temperature is room temperature, and the mould pressing pressure is 200-500Mpa.
6. The integrated preparation method of the low-modulus biomedical titanium alloy with the bionic structure as claimed in claim 5, which is characterized in that: the pore-forming agent mixed powder in the step S4 is made of TiH 2 Powder and NH 4 HCO 3 Mixing the powders, wherein, tiH 2 The mass percentage of the powder is 50 percent, and the TiH 2 The particle size of the powder is less than or equal to 88 mu m, NH 4 HCO 3 The mass percentage of the powder is 50 percent, NH 4 HCO 3 The particle size of the powder is 200-300 μm, and the mass ratio is based on the total mass of all components of the pore-forming agent mixed powder.
7. The integrated preparation method of the low-modulus biomedical titanium alloy with the bionic structure as claimed in claim 6, wherein the integrated preparation method comprises the following steps: the pressure of the secondary pressing in the step S4 is 150MPa.
8. The integrated preparation method of the low-modulus biomedical titanium alloy with the bionic structure as claimed in claim 7, is characterized in that: in the step S5, the composite powder blank is placed into a vacuum sintering furnace for vacuum sintering, and when the vacuum degree in the vacuum sintering furnace reaches 1 multiplied by 10 -3 And pa, starting to heat up to 1100 ℃ at the speed of 10 ℃/min, keeping the temperature for 90-120min, and cooling the furnace to finish the integrated preparation of the biomedical titanium alloy with the bionic porous surface.
9. The integrated preparation method of the low-modulus biomedical titanium alloy with the bionic structure as claimed in claim 8, is characterized in that: the hydrogen partial pressure in the hydrogen-argon mixed gas accounts for 50 percent.
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