CN103014389A - Preparation method of high-strength nanocrystalline type medical Beta titanium alloy for orthopaedic implanting - Google Patents
Preparation method of high-strength nanocrystalline type medical Beta titanium alloy for orthopaedic implanting Download PDFInfo
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Abstract
The invention discloses a preparation method of a high high-strength nanocrystalline type medical Beta titanium alloy for orthopaedic implanting. The titanium alloy is the Ti-Nb-Mo-Sn alloy prepared by the following steps in sequence: treating the alloy ingredients in a vacuum arc melting furnace, and sequentially carrying out the processes of quickly solidifying, rolling at a low temperature and instantaneously ageing at a high temperature, thus obtaining the large-dimension nanocrystalline type titanium alloy. The alloy has the average crystalline dimension less than 60 nanometers, and has strength of 1200 to 1600MPa, plasticity of 15 to 20%, elasticity modulus of 40 to 60 GPa, and super-elasticity recovery strain of 4 to 5%. According to the preparation method, the treatment processes of quick solidifying, low-temperature rolling and instantaneous ageing are creatively combined to treat the titanium alloy, thus, the purpose of unifying high strength, excellent processing performance, low elasticity modulus and excellent super-elasticity performance is realized, and high technological effect and huge potential economic value are brought.
Description
Technical field
That the present invention relates to is a kind of preparation method of material of field of medical appliances, particularly a kind of preparation method of the brilliant medical beta titanium alloy of high-strength nano of orthopaedics implantation.
Background technology
Along with the human living standard improves and scientific and technical development, it is more and more higher that society implants hard tissue material's demand to human body.Titanium alloy has excellent human compatibility, specific tenacity is high, good corrosion resistance, alternative medical stainless steel, cobalt base alloy become hard tissue substituting material gradually, such as joint prosthesises such as hip, knee, shoulder, ankle, elbow, wrist, articulations digitorum manus, the bone wound products such as intramedullary nail, steel plate, screw, tooth implant, bracket, tooth orthopedic wire, the backbone correcting internal fixation system, heart valve prosthesis, Interventional angiocarpy bracket.With regard to over-all properties, at present also not than the better medical embedded metallic substance of titanium alloy.
The medical titanium alloy of at present widespread use has the titanium alloys such as Ti-6Al-4V, Ti-6Al-7Nb and Ni-Ti.Titanium alloy material remains in following several respects problem: 1, behind the long-term implant into body of above-mentioned titanium alloy, can be because of friction and corrosion Al ion, V ion and the Ni ion in discharging, human body cell and nerve are had toxicity, bring out cancer and senile dementia.2, Young's modulus is too high, does not mate with the Young's modulus of people's bone, and the Young's modulus of Ti-6Al-4V and Ti-6Al-7Nb alloy all is more than 2 times of people's flexible bone modulus, and consequent stress shielding easily causes bone resorption and implantation piece loosening; 3, shape-memory properties is poor, has greatly limited to a certain extent the alloys such as Ti-6Al-4V, Ti-6Al-7Nb and has used as bio-medical material.
For above problem, the scientific research technician of this area has proposed various terms of settlement.
Mention among the Chinese patent CN101775632B, by differential arc oxidation and hydrothermal treatment consists directly the preparation of medical titanium nickelalloy have biological activity and and the hydroxyapatite coating layer of high bonding force, can reduce the toxicity Ni ion of Ti-Ni alloy in human body long service process and discharge.The method of this surface modification can not be stopped the release of toxic ion fully, still has serious potential safety hazard.
Nontoxic TiNb (C.Baker, Metal Sci.5 (9) (1971) 92-100.) alloy of finding since C.Baker has had since the shape memory effect, and beta-titanium alloy has obtained broad research.Such as alloys such as Ti-15Mo, the Ti-13Nb-13Zr of the Ti-29Nb-13Ta-4.6Zr of Japanology and American Studies and Ti-35Nb-5Ta-7Zr.But these alloy strengths are on the low side, and Young's modulus is higher, and the super-elasticity recovery strain is less than normal, are unsuitable for human body and implant for a long time use.
Simultaneously, domestic also have the related personnel that β type TiNb alloy is studied.Strong (the Liqiang Wang of Wang Li for example, Weijie Lu, Jining Qin, Fan Zhang, Di Zhang, Journal of Alloys and Compounds469 (2009) 512-518) study and find that the grain-size that reduces beta-titanium alloy helps to put forward heavy alloyed intensity, reduces the alloy Young's modulus, strengthens plasticity and increases the super-elasticity recovery strain.Therefore under the condition of the biocompatibility that does not affect alloy, the alloy grain size refine to nano level might realize high strength, low elastic modulus, and good plasticity and large super-elasticity recovery strain are unified.
At present, about carrying out widely that titanium alloy grain refining research work has obtained.Large plastometric set (SPD Severe plastic deformation) is the grain refinement technology that generally adopts.Valiev R Z (Valiev R Z, Mukherjee A K.Nanostructures and unique properties in intermetalliccs, subjected to severe plastic deformation.Scr.Mater, 2001,44:1747) utilizing the method for high pressure deformation technology (HPT) to obtain grain-size is the Ti-6Al-4V alloy of 100nm and the NiTi alloy that is lower than 100nm even amorphous.Salishchev G A (Salishchev G A Production of subnicron-grained Ti-6Al-4V sheets with enhanced superplastic properties.Lutjering G, Albrecht J.Ti-2003Science and Technology, Hamburg Germany:DDGD, 2003:569) to utilize multiway forging technology (MF) to prepare grain-size be the Ti-6Al-3.2Mo alloy of 60nm.Stolyarov V V (Stolyarov V V.Valiev R Z, ZeipperL, et a1.Extraordinary properties of bulk ultrafine-grained CP Ti processed by severe plastic deformation.Lutjering G, Albrecht J.Ti2003Science and Technology, Hamburg Germ any:DDGD, 2003:1437) to adopt Equal Channel Angular Pressing technology (ECAP) to prepare grain-size be the commercial pure titanium of 40nm.Through large plastometric set, crystal grain is seriously broken, produces a large amount of dislocations, and the alloy yield strength is greatly improved.But the nanometer crystal alloy plasticity that gross distortion obtains is poor, and preparation efficiency is low, and therefore, titanium alloy grain refining work still is in laboratory development, development phase.
Mention among the Chinese patent CN1298874C, obtain block Ti-Nb-Zr and Ti-Nb-Zr-Sn nano material by cold deformation complete processings such as cold rolling and hand-drawn wires, realized that high strength and low elastic modulus are unified.But maximum plasticity is 10%, is unfavorable for cold-formed.The super-elasticity recovery strain is about 3%, far below 8% of Ni-Ti alloy.
In sum, the no-toxicity medical titanium alloy nano material plasticity that present technology prepares is low, poor processability, and preparation efficiency is low, is in laboratory development, development phase.Therefore how keeping simultaneously high intensity and low Young's modulus, further improve its plasticity and elastic performance, is the problem that those skilled in the art will solve.
Summary of the invention
The purpose of this invention is to provide a kind of preparation method for the brilliant medical beta titanium alloy of orthopaedics implantation high-strength nano, further improve its intensity and elastic performance, keep simultaneously high plasticity and low Young's modulus, be more suitable for the manufacturing of artificial bone.
In order to realize above-mentioned technical purpose, the preparation method of a kind of brilliant medical beta titanium alloy of high-strength nano of implanting for orthopaedics of the present invention, the mean sizes of this alloy is less than 60nm, and its preparation method may further comprise the steps:
1) Ti is equally divided into three parts, respectively with the Nb element, Mo element and Sn element place the vacuum melting furnace melting to obtain the Ti-Nb alloy, Ti-Mo alloy and Ti-Sn alloy;
2) with the Ti-Nb alloy that obtains; again applying argon gas protection after Ti-Mo alloy and Ti-Sn alloy place and vacuumize together; melting in vacuum melting furnace is adopted at last the mould cold process to carry out suction pouring and is obtained the Ti-Nb-Mo-Sn alloy slice, and the rate of cooling that mould cold process rapid solidification is processed is 10
4~ 10
6K/s; The quality proportioning of each metal component is: Nb is 11-15%, and Mo is 6-8%, and Sn is 2-5%, and surplus is Ti; Obtain average grain size less than the alloy of 100nm;
3) with step 2) in the alloy slice that obtains under cooled with liquid nitrogen, adopt the double-roll rolling mill low temperature rolling, rolling reduction is 85% ~ 95%; Low temperature rolling temperature range-160～-90 ℃ adopt liquid nitrogen spraying to keep low temperature; Rolling strain rate is 2.9 ~ 7.5s
-1Direct Rolling is to final state, the further refinement of crystal grain, and grain-size is greatly about 20 ~ 50 nanometers;
4) with the alloy slice that obtains in the step 3) at 873 ~ 1073K, timeliness 1 ~ 360s under the argon shield, shrend to room temperature gets final product, and finally obtains grain-size less than the alloy of 60nm.
In the step 1) with three parts of Ti average marks respectively with the Nb element, Mo element and Sn element place the equal melt back of vacuum melting furnace to obtain the Ti-Nb alloy three times, Ti-Mo alloy and Ti-Sn alloy.
Step 2) with the Ti-Nb alloy that obtains, again applying argon gas protection after Ti-Mo alloy and Ti-Sn alloy place and vacuumize together repeats melting five times in vacuum melting furnace, adopts at last the mould cold process to inhale casting and obtains the Ti-Nb-Mo-Sn alloy slice.
Nanocrystalline medical beta titanium alloy average grain size of the present invention is less than 60 nanometers, and intensity is 1200 ~ 1600MPa, and plasticity is 15% ~ 20%, and Young's modulus is 40 ~ 60GPa, and the super-elasticity recovery strain is 4% ~ 5%.
Alloy compositions quality proportioning of the present invention: Nb, 11-15%, Mo, 6-8%, Sn, 2-5%, surplus is Ti.Alloying constituent is based on d-electronic orbit theory and the first principle design obtains.
Vacuum melting treatment process described in the present invention, with the Ti element respectively with the Nb element, Mo element and the melting of Sn element prepare master alloy Ti-Nb alloy, Ti-Mo alloy and Ti-Sn alloy, then with the Ti-Nb alloy, Ti-Mo alloy and Ti-Sn alloy melting obtain the Ti-Nb-Mo-Sn alloy.The Ti element, the Nb element, Mo element and Sn element fusing point differ greatly, and without the preparation master alloy, the Ti-Nb-Mo-Sn alloying constituent that directly four kinds of element vacuum meltings is obtained is extremely inhomogeneous.
What adopt in the rapid solidification treatment process of the present invention is that the mould cold process is inhaled cast titanium alloy, and wherein rate of cooling is 10
4~ 10
6K/s.Rate of cooling is lower than 10
4The alloy grain size that K/s obtains is bigger than normal.Be higher than 10
6The rate of cooling of K/s is high to equipment requirements, is difficult to realize.
Low temperature rolling process using liquid nitrogen cooling among the present invention guarantees that alloy temperature in rolling process raises, and affects grain refining effect.Rolling strain rate is the moderate strains rate, 2.9 ~ 7.5s
-1Rolling strain rate is too little, and the crystal grain degree of crushing is little, and the dislocation of generation is also few.Rolling strain rate is too large, and rolling sample can be pricked to be split.Rolling reduction is 85% ~ 95%, and middle without tempering, Direct Rolling is to final state.
Moment aging technique temperature among the present invention is chosen near the recrystallization temperature of β phase, and 873 ~ 1073K has just realized titanium alloy recrystallization annealing in the ag(e)ing process.Aging time is 0 ~ 360s, and the time is oversize, and grain growth is unfavorable to putting forward heavy alloyed intensity.Both refinement crystal grain, reduced again dislocation desity, separated out simultaneously the α strengthening phase of nanoscale.Moment, timeliness guaranteed to have improved the plasticity of alloy on the little basis of strength decreased.
The present invention is a kind of to implant the brilliant medical beta titanium alloy of high-strength nano for orthopaedics, and is intended to improve alloy strength and improves the plasticity traditional method and compare, and its advantage is:
1, adopt rapid solidification to process, the method that low temperature rolling is processed and instantaneous ageing treatment combines successively alloy is processed, and falls significantly low-alloyed grain-size (average grain size is lower than 60 nanometers), has reduced the Young's modulus of alloy.2, low temperature rolling is processed and has been produced a large amount of dislocations, and instantaneous ageing treatment is separated out the α strengthening phase of nano-scale, has improved the intensity of alloy.3, nano level grain-size and α strengthening phase have improved alloy martensite phase change induction stress, have improved elastic performance.4, production cost is lower, and rapid solidification is processed, and low temperature rolling processing and instantaneous ageing treatment etc. are simple for process.5, aging time is short, realizes easily the production line production in enormous quantities.
The present invention processes rapid solidification effectively, and low temperature cold-rolling treatment and instantaneous ageing treatment combine, and prepare average grain size less than the bulk beta-titanium alloy of 60 nanometers, obtain high strength, low elastic modulus, high-ductility and high hyperelastic beta-titanium alloy.
The nanocrystalline medical beta titanium alloy average grain size that the present invention obtains is less than 60 nanometers, and intensity is 1200～1600MPa, and plasticity is 15% ~ 20%, and Young's modulus is 40 ~ 60GPa, and the super-elasticity recovery strain is 4% ~ 5%.Intensity, plasticity, Young's modulus and super-elasticity proportioning are much better than other beta-titanium alloys.
Alloying constituent involved in the present invention is measured by Rigaku D/MAX-RB X-ray diffraction instrument;
Alloy grain size involved in the present invention obtains by Rigaku D/MAX-RB X-ray diffraction instrument and JEM-2100 TEM (transmission electron microscope) analysis;
The mechanical property of alloy involved in the present invention and elastic performance are by 5569 electronic tensile test machine measurements determination.
The invention will be further described below in conjunction with accompanying drawing.
Description of drawings
Fig. 1 is the xrd collection of illustrative plates behind the rapid solidification Ti-13Nb-7Mo-4Sn alloy cold roller and deformed 92%;
Fig. 2 is that rapid solidification Ti-13Nb-7Mo-4Sn alloy is after cold roller and deformed 92%, at the xrd collection of illustrative plates of 823K timeliness 100s;
Fig. 3 is that rapid solidification Ti-13Nb-7Mo-4Sn alloy is after cold roller and deformed 92%, in the microstructure of 823K timeliness 100s;
Fig. 4 is that rapid solidification Ti-13Nb-7Mo-4Sn alloy is after cold roller and deformed 92%, at the stress-strain curve of 823K timeliness 100s;
Fig. 5 is that rapid solidification Ti-13Nb-7Mo-4Sn alloy is after cold roller and deformed 92%, at the loading and unloading curve of 823K timeliness 100s;
Fig. 6 is that rapid solidification Ti-13Nb-7Mo-4Sn alloy is after cold roller and deformed 90%, at the xrd collection of illustrative plates of 873K timeliness 200s;
Fig. 7 is that rapid solidification Ti-13Nb-7Mo-4Sn alloy is after cold roller and deformed 90%, in the microstructure of 873K timeliness 200s;
Fig. 8 is that rapid solidification Ti-13Nb-7Mo-4Sn alloy is after cold roller and deformed 90%, at the stress-strain curve of 873K timeliness 200s;
Fig. 9 is that rapid solidification Ti-13Nb-7Mo-4Sn alloy is after cold roller and deformed 90%, at the loading and unloading curve of 873K timeliness 200s;
Figure 10 is that rapid solidification Ti-13Nb-7Mo-4Sn alloy is after cold roller and deformed 87%, at the stress-strain curve of 923K timeliness 250s;
Figure 11 is that rapid solidification Ti-13Nb-7Mo-4Sn alloy is after cold roller and deformed 87%, at the loading and unloading curve of 923K timeliness 250s;
Figure 12 is that the present invention prepares the process flow sheet that orthopaedics is implanted high-strength nanocrystalline medical beta titanium alloy;
Figure 13 is after cold roller and deformed 87%, at the Ti-13Nb-7Mo-4Sn alloy of 923K timeliness 250s and the interface of bone;
Figure 14 is after cold roller and deformed 87%, at the Ti-13Nb-7Mo-4Sn alloy of 923K timeliness 250s and the radially section of bone.
Embodiment
Be intended to further specify the present invention below in conjunction with embodiment, and unrestricted the present invention.
Embodiment 1
The present embodiment preparation process is as follows: by weight percentage, and Nb13; Mo7; Sn4; The weighing of Ti surplus, with three parts of Ti average marks respectively with the Nb element, Mo element and Sn element place the vacuum melting furnace melting to obtain the Ti-Nb alloy, Ti-Mo alloy and Ti-Sn alloy; Then with the Ti-Nb alloy that obtains, again applying argon gas protection after Ti-Mo alloy and Ti-Sn alloy place and vacuumize together repeats melting five times in vacuum melting furnace, in water cooled copper mould moment suction casting, obtains average grain size less than 10 μ m, the alloy slice that 5mm is thick; The rate of cooling that mould cold process rapid solidification is processed is 10
6K/s; Then rapid solidification being processed the alloy sheet material that obtains adopts double-roll rolling mill low temperature-140 ℃ rolling under cooled with liquid nitrogen, rolling strain rate is 5s-1, middle Direct Rolling to thickness is the sheet material (deformation quantity is 92%) of 0.4mm without tempering, and grain-size is approximately 30 nanometers (Fig. 1); Alloy behind the cold treatment is at 873 timeliness 100s, and shrend is finally prepared nanocrystalline titanium alloy average grain size and is approximately 40 nanometer (Fig. 2 to room temperature, Fig. 3), intensity is 1530MPa, and plasticity is 15%(Fig. 4), Young's modulus is 52GPa, and the super-elasticity recovery strain is 4.8%(Fig. 5).
Embodiment 2
The preparation process of present embodiment is as follows: as different from Example 1, rapid solidification is processed the alloy sheet material that obtains under cooled with liquid nitrogen, adopt the double-roll rolling mill low temperature rolling, middle without tempering, Direct Rolling to thickness is the sheet material (deformation quantity is 90%) of 0.5mm, and grain-size is approximately 40 nanometers; Alloy behind the cold treatment is finally prepared nanocrystalline titanium alloy average grain size and is approximately 45 nanometers (Fig. 6, Fig. 7) at 823K timeliness 200s, intensity is 1450MPa, plasticity is 17%(Fig. 8), Young's modulus is 47GPa, the super-elasticity recovery strain is 4.4%(Fig. 9).
Embodiment 3
The preparation process of present embodiment is as follows: as different from Example 1, rapid solidification is processed the alloy sheet material that obtains under cooled with liquid nitrogen, adopt the double-roll rolling mill low temperature rolling, middle without tempering, Direct Rolling to thickness is the sheet material (deformation quantity is 87%) of 0.65mm, and grain-size is greatly about 20 ~ 50 nanometers; Alloy behind the cold treatment is finally prepared nanocrystalline titanium alloy average grain size and is approximately 45 nanometers at 923 timeliness 250s, and intensity is 1340MPa, and plasticity is 20%(Figure 10), Young's modulus is 41GPa, the super-elasticity recovery strain is 4.1%(Figure 11).
Embodiment 4
The preparation process of present embodiment is as follows: the alloy bar that embodiment 3 prepares is implanted in the bull new zealand rabbit bone, then raised for 12 week.Found that around the tinsel has a large amount of new osteogenesis, and the titanium alloy tinsel is coated (Figure 13, Figure 14).
Claims (4)
1. a preparation method who is used for the brilliant medical beta titanium alloy of high-strength nano of orthopaedics implantation is characterized in that, may further comprise the steps:
1) Ti is equally divided into three parts, respectively with the Nb element, Mo element and Sn element place the vacuum melting furnace melting to obtain the Ti-Nb alloy, Ti-Mo alloy and Ti-Sn alloy;
2) with the Ti-Nb alloy that obtains; again applying argon gas protection after Ti-Mo alloy and Ti-Sn alloy place and vacuumize together; melting in vacuum melting furnace is adopted at last the mould cold process to carry out suction pouring and is obtained the Ti-Nb-Mo-Sn alloy slice, and the rate of cooling that mould cold process rapid solidification is processed is 10
4~ 10
6K/s; The quality proportioning of each metal component is: Nb is 11-15%, and Mo is 6-8%, and Sn is 2-5%, and surplus is Ti;
3) with step 2) in the alloy slice that obtains under cooled with liquid nitrogen, adopt the double-roll rolling mill low temperature rolling, rolling reduction is 85% ~ 95%; Low temperature rolling temperature range-160～-90 ℃ adopt liquid nitrogen spraying to keep low temperature; Rolling strain rate is 2.9 ~ 7.5s
-1
4) with the alloy slice that obtains in the step 3) at 873 ~ 1073K, timeliness 1 ~ 360s under the argon shield, shrend to room temperature gets final product.
2. method according to claim 1 is characterized in that,
In the step 1) with three parts of Ti average marks respectively with the Nb element, Mo element and Sn element place the equal melt back of vacuum melting furnace to obtain the Ti-Nb alloy three times, Ti-Mo alloy and Ti-Sn alloy.
3. method according to claim 1 is characterized in that,
Step 2) with the Ti-Nb alloy that obtains, again applying argon gas protection after Ti-Mo alloy and Ti-Sn alloy place and vacuumize together repeats melting five times in vacuum melting furnace, adopts at last the mould cold process to inhale casting and obtains the Ti-Nb-Mo-Sn alloy slice.
4. method according to claim 1 is characterized in that, described nanocrystalline medical beta titanium alloy average grain size is less than 60 nanometers, and intensity is 1200 ~ 1600MPa, and plasticity is 15% ~ 20%, and Young's modulus is 40 ~ 60GPa, and the super-elasticity recovery strain is 4% ~ 5%.
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| CN103205663A (en) * | 2013-04-12 | 2013-07-17 | 西安交通大学 | Method for preparing difficultly-deformed metal block nanocrystalline material at low temperature |
| CN104651829A (en) * | 2014-12-10 | 2015-05-27 | 湘潭大学 | Preparation methods of biomedical Ti-Sn coating alloy and medical dental alloy |
| CN105369063A (en) * | 2015-08-18 | 2016-03-02 | 赵丽 | Manufacturing method for medical bone fixing device |
| CN107904423A (en) * | 2017-12-06 | 2018-04-13 | 湘潭大学 | A kind of preparation method of high-strength and high ductility medical titanium alloy plate |
| CN109082560A (en) * | 2018-08-29 | 2018-12-25 | 江苏沃钛有色金属有限公司 | A kind of titanium alloy sheet of stretch-proof and preparation method thereof |
| CN111041395A (en) * | 2018-10-12 | 2020-04-21 | 南京理工大学 | Ultra-high density twin crystal titanium and preparation method thereof |
| US20200121425A1 (en) * | 2017-06-14 | 2020-04-23 | Grammer Ag | Dental implant system with at least one tooth implant and separate abutment |
| CN113337744A (en) * | 2021-05-31 | 2021-09-03 | 上海大学 | Preparation method of Ti2448 biomedical alloy with low Young modulus |
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| CN103205663A (en) * | 2013-04-12 | 2013-07-17 | 西安交通大学 | Method for preparing difficultly-deformed metal block nanocrystalline material at low temperature |
| CN103205663B (en) * | 2013-04-12 | 2015-04-29 | 西安交通大学 | Method for preparing difficultly-deformed metal block nanocrystalline material at low temperature |
| CN104651829A (en) * | 2014-12-10 | 2015-05-27 | 湘潭大学 | Preparation methods of biomedical Ti-Sn coating alloy and medical dental alloy |
| CN105369063A (en) * | 2015-08-18 | 2016-03-02 | 赵丽 | Manufacturing method for medical bone fixing device |
| US20200121425A1 (en) * | 2017-06-14 | 2020-04-23 | Grammer Ag | Dental implant system with at least one tooth implant and separate abutment |
| CN107904423A (en) * | 2017-12-06 | 2018-04-13 | 湘潭大学 | A kind of preparation method of high-strength and high ductility medical titanium alloy plate |
| CN109082560A (en) * | 2018-08-29 | 2018-12-25 | 江苏沃钛有色金属有限公司 | A kind of titanium alloy sheet of stretch-proof and preparation method thereof |
| CN111041395A (en) * | 2018-10-12 | 2020-04-21 | 南京理工大学 | Ultra-high density twin crystal titanium and preparation method thereof |
| CN113337744A (en) * | 2021-05-31 | 2021-09-03 | 上海大学 | Preparation method of Ti2448 biomedical alloy with low Young modulus |
| CN113337744B (en) * | 2021-05-31 | 2022-05-06 | 上海大学 | Preparation method of Ti2448 biomedical alloy with low Young modulus |
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