Be used for medicinal oxygen-containing beta titanium alloy of orthopaedics implantation and preparation method thereof
Technical field
What the present invention relates to is material of a kind of medical equipment technical field and preparation method thereof, specifically is a kind of medicinal oxygen-containing beta titanium alloy that is used for the orthopaedics implantation and preparation method thereof.
Background technology
In current field of medical materials, being used in the orthopaedics made various joint prosthesises, artificial bone and various inside and outside fixed apparatus; The materials demand that being mainly used in the dentistry made artificial tooth, obturator, planting body, orthopedic wire and various assisting therapy devices is more and more.In all bio-medical materials.Metallic substance is used the earliest, and the application at present clinical is also still extensive.Being used for clinical metallic substance at first is the stainless steel with certain etch resistant properties, wherein the most commonly used is the 316L austenitic stainless steel, developed the Co-Cr alloy later on again, this series alloy has good erosion resistance and intensity in coenocorrelation, therefore is widely used in the bio-medical field.At the initial stage forties, Bothe etc. have delivered the article that reacts about between multiple metal planting body and the bone, subsequently titanium are introduced biomedical sector.They comprise several metals in the femur of titanium, stainless steel and Co-Cr alloy implantation mouse, found that no any untoward reaction between titanium and the bone, thereby have opened up titanium alloy in the New Times of giving birth to the body medical field.Because titanium alloy has advantages such as high biocompatibility, low density, low elastic modulus, high strength, anti-body fluid corrosion, is widely used in medical field.
(α, alpha+beta β), generally can roughly be divided into the three generations with the application and the development of biological medical titanium alloy according to the type of titanium alloy.The first-generation is representative with pure titanium and Ti-6Al-4V, and the ultralow gap of Ti-6Al-4V (ELI) alloy has better biocompatibility, and solidity to corrosion and mechanical property are most popular so far surgery embedded materials.The s-generation is to be the type alpha+beta alloy of representative with Ti-5Al-2.5Fe and Ti-6Al-7Nb, do not contain Ti-6Ai-7Nb and two kinds of alpha+beta titanium alloys of Ti-5Al-2.5Fe to the toxic element V of health, have with Ti-6Al-4V ELI alloy phase like mechanical property, also be widely used in surgical field.With respect to the Young's modulus of people's bone 10-30GPa, such titanium alloy has bigger Young's modulus, implants and causes " stress shielding " phenomenon easily.Therefore, exploitation has the developing direction that becomes the biological medical titanium alloy nineties than the third generation titanium alloy of low elastic modulus.Enter the initial stage nineties, Ti-Mo is that beta titanium alloy has obtained broad research as medical material.As Ti-12Mo-6Zr-2Fe, Ti-15Mo-5Zr-3Al and Ti-15Mo-3Nb-0.30 (21SRx) etc.Such alloy has higher tensile strength, fracture toughness property, better abrasion resistance properties, but the Young's modulus of this class alloy still is higher than the flexible bone modulus.Design and develop the emphasis that the beta-titanium alloy with lower Young's modulus becomes the medical titanium alloy developing material.Find that in the research of biological medical titanium alloy some metal ion meeting and human organ react, secular implanting can be caused toxic action to health.Therefore, reduce and avoid alloy element that the toxic action of health is seemed particularly important.
Find through retrieval prior art, Steinemann S.G, Corrosion of titanium and titaniumalloys for surgical implants.Titanium ' 84 Science and Technology, vol.2.Munich, Deutsche Gesellschaft Fur Metallkunde EV 1985,2:1373-1379. (surgery is implanted the erosion resistance research with titanium or titanium alloy) contrasted stainless steel, cobalt-chromium-molybdenum-nickelalloy, titanium, tantalum, zirconium, niobium, live body embedded material corrosive linear polarization results of study such as platinum, and provide the contrast of these data and experiment in vitro.The result shows that V, Ni, Co are biological toxic element, and titanium, tantalum, zirconium, elements such as niobium have good biological safety, is biological toxic element at the certain advantage of surgery vegetable material and V, Ni, Co.
Kawahara H, Cytotoxicity of implantable metals and alloys.Bull.Jpn.Inst.Met., 1992,31 (12): 1033-1039. (cytotoxicity of implant metallic substance) has put down in writing by the cell toxicity test of implant metallic substance is discovered, Al, Fe are to the toxic effect of human body., Al, Fe are to the toxic effect of human body.
Okazaki Y, Ito Y, Kyo K, Tateisi T, Corrosion resistance and corrosion fatiguestrength of new titanium alloys for medical implants without V and Al, Mater.Sci.Eng.A, 1996,213:138-147. do not put down in writing in (not containing the solidity to corrosion and the research of anti-corrosion fatigue strength of the novel implantation medical titanium alloy of V and Al element): show through a large amount of experiments, contrasted Ti-15Zr-4Nb-4Ta-0.2Pd-0.20-0.05N, Ti-15Sn-4Nb-2Ta-0.2Pd-0.20 alloy and low gap Ti-6A1-4V, the solidity to corrosion of Ti-6A1-2Nb-1Ta and pure titanium and anti-corrosion fatigue strength draw by Nb, Ta, elementary composition titanium alloy such as Zr and Sn has good solidity to corrosion and anti-corrosion fatigue strength.
In sum, thus the low elastic modulus beta-titanium alloy that contains elements such as Nb, Ta, Zr and Sn have bigger application potential.With Ti-Mo, Ti-Nb, Ti-Ta and Ti-Zr are that the beta-titanium alloy of matrix obtains extensive studies at present, other titanium alloys commonly used of comparing, and this class alloy combination can obtain low Young's modulus, perhaps has high intensity.Ti-Nb base alloy is the medical titanium alloy of the most potential exploitation use owing to have low Young's modulus and shape memory effect preferably.The meta titanium alloy of some Ti-Nb bases has obtained application, as Ti-13Nb-13Zr, and Ti-35Nb-5Ta-7Zr, Ti-29Nb-13Ta-4.6Zr, Ti-39Nb-5.1Ta-7.1Zr (TNTZ) and Ti-34Nb-9Zr-8Ta.These titanium alloys but cause alloy strength lower when obtaining low Young's modulus.The Young's modulus that has is higher, but the not enough 600MPa of the intensity of alloy, as Ti-35Nb-5Ta-7Zr.Outside the characteristics that satisfy the good biocompatibility of bio-medical material, also should make material have medium intensity and lower Young's modulus.In general, the tensile strength of material is greater than 650MPa, and Young's modulus can satisfy orthopaedics, the application in bio-medical fields such as dentistry below 70GPa.
Summary of the invention
The present invention is directed to the prior art above shortcomings, a kind of medicinal oxygen-containing beta titanium alloy that is used for the orthopaedics implantation and preparation method thereof is provided, the alloy safety non-toxic for preparing can be widely used in medical instruments fields such as orthopaedics, dentistry.
The present invention is achieved by the following technical solutions:
The present invention relates to a kind of medicinal oxygen-containing beta titanium alloy that orthopaedics is implanted that is used for, its mass percent is: oxygen element 0.13wt%-0.53wt%, the composition of described titanium alloy and mass percent are: Ti60%, Nb35%, Zr3% and Ta2%.
The present invention relates to the above-mentioned preparation method who is used for the medicinal oxygen-containing beta titanium alloy of orthopaedics implantation, by alloying ingredient is carried out vacuum consumable smelting handle obtain the Ti-Nb-Zr-Ta alloy after, after the non-consumable melting is handled, heat-treat successively and hot-work again, realize the preparation of medical beta-titanium alloy.
Described alloying ingredient is the Ti element of 60 weight parts, the Nb element of 35 weight parts, the Zr element of 3 weight parts and the Ta element of 2 weight parts.
Described vacuum consumable smelting is handled and is meant: after placing the vacuum consumable electrode arc furnace melt back to obtain ingot casting three times alloying ingredient, ingot casting is forged 950 ℃ of coggings, after through 780 ℃ of homogenizing annealing half an hour, obtain the Ti-Nb-Zr-Ta alloy.
Described non-consumable melting is handled and is meant: add TiO after the Ti-Nb-Zr-Ta alloy is cut into block sample
2Powder adopts vacuum non-consumable melting mode to prepare Ti-Nb-Zr-Ta-O button ingot.
Described vacuum non-consumable melting mode is meant: carry out hot rolling under 950 ℃ of environment, air cooling after 780 ℃ of solution treatment half an hour.
Described thermal treatment is meant: the alloy after the non-consumable melting is handled places air cooling after 780 ℃ of solution treatment half an hour.
Described hot-work is meant: adopt duo mill rolling after the alloy after the thermal treatment is placed 950 ℃ of half an hour, pass deformation rate is controlled at 5-15%, and rolling deformation is thickness 1.5-2.5mm, makes medical beta-titanium alloy.
The over-all properties of the Ti-Nb-Zr-Ta-O alloy of the different oxygen that melting obtains through the vacuum non-consumable improves significantly, the intensity of the Ti-Nb-Zr-Ta alloy of comparing, and the intensity of Ti-Nb-Zr-Ta-O alloy is significantly improved; The titanium alloy that the present invention prepares is chosen the biological safety element, make alloy have good cold-forming property by the beta stable element that adds high level, come reinforced alloys by the content that in alloy, increases oxygen element, optimize the oxygen element ratio by the interpolation of different content oxygen element, make alloy have higher-strength, have than low elastic modulus simultaneously.
Embodiment
Below embodiments of the invention are elaborated, present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1
Adopt vacuum non-consumable melting method to prepare the Ti-Nb-Zr-Ta-O alloy.The Ti-Nb-Zr-Ta alloy of vacuum consumable smelting is cut into block sample.Cut the 80g alloy block, add TiO
2Powder 0.27g.The weight percent of button ingot casting is: Ti:60%, Nb:35%, Zr:3%, Ta:2%, the melting in magnetic control tungsten electrode button electric arc furnace of O:0.13wt% raw material.Smelting furnace vacuum tightness is 6.6 * 10
-3Pa, the tungsten electrode lifting is driven by micromotor; Lighting arc method is the high-frequency spark scratch start, and electric arc is lighted the security device that the back cuts off high frequency automatically.The general work electric current is 700-800A, and maximum melting electric current is 1250A.In fusion process, use electromagnetic mixing apparatus, to guarantee that each component is fully reacted and melting is even.For guaranteeing the homogeneity of composition, after each sample melting, the remelting of overturning again, melt back four times.Be cast into the lath of 70mm * 30mm * 10mm at last.The square sample that melting is come out, surface quality is better, does not see big being mingled with and pore, and the sample of casting is rolled into the lath that thickness is 0.5mm at 950 ℃.Sample is 780 ℃ of solution treatment half an hour, and the chemical ingredients of sample is as shown in table 2.Cut into tension specimen with wire electric discharge, specimen size is shown in example 1.Recording the room temperature tensile performance data is:
Tensile strength: 771.62MPa, yield strength: 650.27MPa, Young's modulus: 58.97GPa, unit elongation: 9.75%.
Table 2Ti-35Nb-3Zr-2Ta-O (wt%) chemical ingredients
Embodiment 2
Other conditions add TiO with embodiment 1
2Powder 0.53g, the weight percent of button ingot casting is: Ti:65%, Nb:35%, Zr:3%, Ta:2%, the chemical ingredients of O:0.26wt% sample is as shown in table 3.Recording the room temperature tensile performance data is:
Tensile strength: 756.86MPa, yield strength: 558.33MPa, Young's modulus: 65.00GPa, unit elongation: 17.80%.
Table 3Ti-35Nb-3Zr-2Ta-O (wt%) chemical ingredients
Embodiment 3
Other conditions add TiO with embodiment 1
2Powder 0.80g, the weight percent of button ingot casting is: Ti:65%, Nb:35%, Zr:3%, Ta:2%, the chemical ingredients of O:0.40wt% sample is as shown in table 4.Recording the room temperature tensile performance data is:
Table 4Ti-35Nb-3Zr-2Ta-O (wt%) chemical ingredients
Embodiment 4
Other conditions add TiO with embodiment 1
2Powder 1.07g, the weight percent of button ingot casting is: Ti:65%, Nb:35%, Zr:3%, Ta:2%, the chemical ingredients of O:0.53% sample is as shown in table 5.Recording the room temperature tensile performance data is:
Tensile strength: 883.07MPa, yield strength: 726.00MPa, Young's modulus: 90.91Pa, unit elongation: 0.87%.
Table 5Ti-35Nb-3Zr-2Ta-O (wt%) chemical ingredients
Comparative Examples
Vacuum consumable smelting Ti-Nb-Zr-Ta alloy, Nb adds in master alloy TiNb (Nb content 50%wt) mode, and the Zr element adds in zirconium plate mode, and element T a adds in tantalum plate mode, adopts the one-level titanium sponge.Adopt argon arc welding to be connected at the electrode that suppresses with supporting electrode.For guarantee the ingot casting chemical ingredients evenly, ingot casting remelting three times at least.A melted ingot is used argon arc welding and supporting electrode seam after machining, again in the vacuum consumable electrode arc furnace melting.With alloy melt back three times in vacuum consumable electrode arc furnace after the proportioning in proportion, guarantee that composition is even.Ingot casting forges 950 ℃ of coggings, is swaged into the square billet of 180mm * 70mm * 30mm.After through 780 ℃ of homogenizing annealing half an hour, air cooling makes this alloy.The chemical ingredients of alloy is as shown in table 1.Be cut into tension specimen with line, and with abrasive paper for metallograph with surface grinding to eliminate surface imperfection.Tension specimen gauge length segment length is 20mm, and thickness is 1.5mm.Draw speed is 1.5 * 10-4s
-1, record alloy at room temperature tensile mechanical properties numerical value and be:
Tensile strength: 537.56MPa, yield strength: 325.39MPa, Young's modulus: 56.50GPa, unit elongation: 17.74%.
Table 1Ti-35Nb-3Zr-2Ta (wt%) chemical ingredients