CN103014389B - 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, the preparation method of the brilliant medical beta titanium alloy of high-strength nano that particularly a kind of orthopaedics is implanted.
Background technology
Along with 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, 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, 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 widespread use at present 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, after the long-term implant into body of above-mentioned titanium alloy, can and corrode Al ion, V ion and the Ni ion in discharging because of friction, human body cell and nerve are had to 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 is all the more than 2 times of people's flexible bone modulus, and consequent stress shielding easily causes bone resorption and implantation piece to become flexible; 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 applied as bio-medical material.
For above problem, the scientific research technician of this area has proposed various terms of settlement.
In Chinese patent CN101775632B, mention, by differential arc oxidation and hydrothermal treatment consists directly on medical titanium nickelalloy preparation 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 completely, still has serious potential safety hazard.
Since nontoxic TiNb (C.Baker, Metal Sci.5 (9) (1971) 92-100.) alloy of C.Baker discovery has shape memory effect, beta-titanium alloy has obtained broad research.Alloys such as the Ti-29Nb-13Ta-4.6Zr of Japanology and the Ti-15Mo of American Studies, Ti-13Nb-13Zr and Ti-35Nb-5Ta-7Zr.But these alloy strengths are on the low side, and Young's modulus is higher, super-elasticity recovery strain is less than normal, is unsuitable for human body and implants for a long time use.
Meanwhile, domestic also have related personnel to be studied β type TiNb alloy.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 contributes to put forward heavy alloyed intensity, reduces alloy Young's modulus, strengthens plasticity and increases super-elasticity recovery strain.Therefore under the condition of biocompatibility that does not affect alloy, alloy grain size refine to nano level and likely realizes high strength, low elastic modulus, and good plasticity and large super-elasticity recovery strain are unified.
What about titanium alloy grain refining research work, obtained at present, carries out widely.Large plastometric set (SPD Severe plastic deformation) is the grain refinement technology generally adopting.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) utilize the method for high pressure deformation technology (HPT) to obtain Ti-6Al-4V alloy that grain-size is 100nm and lower than the 100nm NiTi alloy of amorphous even.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) utilize multiway forging technology (MF) to prepare the Ti-6Al-3.2Mo alloy that grain-size is 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) adopt Equal Channel Angular Pressing technology (ECAP) to prepare the commercial pure titanium that grain-size is 40nm.Through large plastometric set, crystal grain is seriously broken, produces a large amount of dislocations, and alloy yield strength is greatly improved.But the nanometer crystal alloy plasticity that gross distortion obtains is poor, and preparation efficiency is low, therefore, titanium alloy grain refining work is still in laboratory development, development phase.
In Chinese patent CN1298874C, mention, by cold deformation complete processings such as cold rolling and hand-drawn wires, obtain block Ti-Nb-Zr and Ti-Nb-Zr-Sn nano material, realized high strength and low elastic modulus unified.But maximum plasticity is 10%, be unfavorable for cold-formed.Super-elasticity recovery strain is in 3% left and right, far below 8% of Ni-Ti alloy.
In sum, the no-toxicity medical titanium alloy nano material plasticity that technology prepares is at present low, poor processability, and preparation efficiency is low, in laboratory development, development phase.Therefore how keeping high intensity and low Young's modulus simultaneously, further improve its plasticity and elastic performance, is the problem that those skilled in the art will solve.
Summary of the invention
The object of this invention is to provide a kind of preparation method who implants the brilliant medical beta titanium alloy of high-strength nano for orthopaedics, further improve its intensity and elastic performance, keep high plasticity and low Young's modulus simultaneously, be more suitable for the manufacture of artificial bone.
In order to realize above-mentioned technical purpose, the preparation method of the brilliant medical beta titanium alloy of a kind 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 comprises the following steps:
1) Ti is equally divided into three parts, respectively with Nb element, Mo element and Sn element are placed in vacuum melting furnace melting and obtain Ti-Nb alloy, Ti-Mo alloy and Ti-Sn alloy;
2) by the Ti-Nb alloy obtaining; applying argon gas protection again after vacuumizing together with Ti-Mo alloy is placed in Ti-Sn alloy; melting in vacuum melting furnace, finally adopts mould cold process to carry out suction pouring and obtains 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 the alloy that average grain size is less than 100nm;
3) by step 2) in the alloy slice that obtains under cooled with liquid nitrogen, adopt 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; Direct Rolling is to final state, the further refinement of crystal grain, and grain-size is greatly about 20 ~ 50 nanometers;
4) by the alloy slice obtaining in step 3) at 873 ~ 1073K, timeliness 1 ~ 360s under argon shield, shrend, to room temperature, finally obtains the alloy that grain-size is less than 60nm.
In step 1) by three parts of Ti average marks respectively with Nb element, Mo element and Sn element are placed in the equal melt back of vacuum melting furnace and obtain Ti-Nb alloy three times, Ti-Mo alloy and Ti-Sn alloy.
Step 2) by the Ti-Nb alloy obtaining, after vacuumizing together with Ti-Mo alloy is placed in Ti-Sn alloy, applying argon gas protection again repeats melting five times in vacuum melting furnace, finally adopts mould cold process to inhale to cast and obtain 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 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 theoretical based on d-electronic orbit and first principle design obtains.
Vacuum melting treatment process described in the present invention, by Ti element respectively with Nb element, master alloy Ti-Nb alloy is prepared in Mo element and the melting of Sn element, Ti-Mo alloy and Ti-Sn alloy, then by Ti-Nb alloy, Ti-Mo alloy and Ti-Sn alloy melting obtain Ti-Nb-Mo-Sn alloy.Ti element, Nb element, Mo element and Sn element fusing point differ greatly, and without preparing master alloy, the Ti-Nb-Mo-Sn alloying constituent directly four kinds of element vacuum meltings being obtained is extremely inhomogeneous.
What in rapid solidification treatment process of the present invention, adopt is that 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.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 in the present invention, guarantees that alloy temperature in rolling process raises, and affects grain refining effect.Rolling strain rate is moderate strains rate, 2.9 ~ 7.5s
-1.Rolling strain rate is too little, and 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 in the present invention is chosen near the recrystallization temperature of β phase, and 873 ~ 1073K has just realized titanium alloy recrystallization annealing in 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 the α strengthening phase of nanoscale simultaneously.Moment, timeliness guaranteed, on the little basis of strength decreased, to have improved the plasticity of alloy.
The present invention is a kind of implants the brilliant medical beta titanium alloy of high-strength nano for orthopaedics, and is intended to improve alloy strength and improves 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, easily realizes production line and produces in enormous quantities.
The present invention processes rapid solidification effectively, and low temperature cold-rolling treatment and instantaneous ageing treatment combine, and prepare the bulk beta-titanium alloy that average grain size is less than 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 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, measures 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.
Below in conjunction with accompanying drawing, the invention will be further described.
Accompanying drawing explanation
Fig. 1 is the xrd collection of illustrative plates after 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
Below in conjunction with embodiment, be intended to further illustrate the present invention, and unrestricted the present invention.
Embodiment 1
The present embodiment preparation process is as follows: by weight percentage, and Nb13; Mo7; Sn4; Ti surplus weighs, by three parts of Ti average marks respectively with Nb element, Mo element and Sn element are placed in vacuum melting furnace melting and obtain Ti-Nb alloy, Ti-Mo alloy and Ti-Sn alloy; Then by the Ti-Nb alloy obtaining, after vacuumizing together with Ti-Mo alloy is placed in Ti-Sn alloy, applying argon gas protection again repeats melting five times in vacuum melting furnace, in water cooled copper mould moment suction casting, obtains average grain size and is 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 is processed to the alloy sheet material obtaining and under cooled with liquid nitrogen, adopt ℃ rolling of double-roll rolling mill low temperature-140, rolling strain rate is 5s-1, middle without tempering, the sheet material that Direct Rolling is 0.4mm to thickness (deformation quantity is 92%), grain-size is approximately 30 nanometers (Fig. 1); Alloy after cold treatment is at 873 timeliness 100s, and shrend, to room temperature, is finally prepared nanocrystalline titanium alloy average grain size and is approximately 40 nanometer (Fig. 2, Fig. 3), intensity is 1530MPa, and plasticity is 15%(Fig. 4), Young's modulus is 52GPa, and super-elasticity recovery strain is 4.8%(Fig. 5).
Embodiment 2
The preparation process of the present embodiment is as follows: as different from Example 1, rapid solidification is processed to the alloy sheet material obtaining and under cooled with liquid nitrogen, adopt double-roll rolling mill low temperature rolling, middle without tempering, the sheet material that Direct Rolling is 0.5mm to thickness (deformation quantity is 90%), grain-size is approximately 40 nanometers; Alloy after cold treatment, at 823K timeliness 200s, is finally prepared nanocrystalline titanium alloy average grain size and is approximately 45 nanometers (Fig. 6, Fig. 7), intensity is 1450MPa, plasticity is 17%(Fig. 8), Young's modulus is 47GPa, super-elasticity recovery strain is 4.4%(Fig. 9).
Embodiment 3
The preparation process of the present embodiment is as follows: as different from Example 1, rapid solidification is processed to the alloy sheet material obtaining and under cooled with liquid nitrogen, adopt double-roll rolling mill low temperature rolling, middle without tempering, the sheet material that Direct Rolling is 0.65mm to thickness (deformation quantity is 87%), grain-size is greatly about 20 ~ 50 nanometers; Alloy after cold treatment, at 923 timeliness 250s, is finally prepared nanocrystalline titanium alloy average grain size and is approximately 45 nanometers, and intensity is 1340MPa, and plasticity is 20%(Figure 10), Young's modulus is 41GPa, super-elasticity recovery strain is 4.1%(Figure 11).
Embodiment 4
The preparation process of the present embodiment is as follows: the alloy bar that embodiment 3 is prepared is implanted in bull new zealand rabbit bone, then raises for 12 week.Found that tinsel has a large amount of new osteogenesis around, and by titanium alloy tinsel coated (Figure 13, Figure 14).
Claims (2)
1. a preparation method for the brilliant medical beta titanium alloy of high-strength nano of implanting for orthopaedics, is characterized in that, comprises the following steps:
1) Ti is equally divided into three parts, respectively with Nb element, Mo element and Sn element are placed in the equal melt back of vacuum melting furnace and obtain Ti-Nb alloy three times, Ti-Mo alloy and Ti-Sn alloy;
2) by the Ti-Nb alloy obtaining; applying argon gas protection again after vacuumizing together with Ti-Mo alloy is placed in Ti-Sn alloy; in vacuum melting furnace, repeat melting five times; finally adopt mould cold process to carry out suction pouring and obtain Ti-Nb-Mo-Sn alloy slice, 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) by step 2) in the alloy slice that obtains under cooled with liquid nitrogen, adopt 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) by step 3) in the alloy slice that obtains at 873～1073K, timeliness 1～360s under argon shield, shrend is to room temperature.
2. method according to claim 1, is characterized in that, described nanocrystalline medical beta titanium alloy average grain size is less than 60 nanometers, intensity is 1200～1600MPa, plasticity is 15%～20%, and Young's modulus is 40～60GPa, and super-elasticity recovery strain is 4%～5%.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210592054.2A CN103014389B (en) | 2013-01-21 | 2013-01-21 | Preparation method of high-strength nanocrystalline type medical Beta titanium alloy for orthopaedic implanting |
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|---|---|---|---|
| CN201210592054.2A CN103014389B (en) | 2013-01-21 | 2013-01-21 | Preparation method of high-strength nanocrystalline type medical Beta titanium alloy for orthopaedic implanting |
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|---|---|
| CN103014389A CN103014389A (en) | 2013-04-03 |
| CN103014389B true CN103014389B (en) | 2014-11-19 |
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| 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 |
| CN104651829B (en) * | 2014-12-10 | 2018-07-03 | 湘潭大学 | A kind of preparation method of bio-medical Ti-Sn coats alloy and medical-dental alloy |
| CN105369063B (en) * | 2015-08-18 | 2018-04-03 | 赵丽 | A kind of preparation method of medical bone fixation means |
| DE102017005618A1 (en) * | 2017-06-14 | 2018-12-20 | Johannes Scherer | Dental implant system comprising at least one dental implant and a separate abutment |
| CN107904423B (en) * | 2017-12-06 | 2020-07-07 | 湘潭大学 | Preparation method of high-strength high-toughness 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 |
| CN111041395B (en) * | 2018-10-12 | 2021-07-06 | 南京理工大学 | Ultra-high density twin crystal titanium and preparation method thereof |
| 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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| CN101892403B (en) * | 2010-06-30 | 2011-12-14 | 大连理工大学 | Biomedical beta-titanium alloy with low Nb content |
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