Summary of the invention
The objective of the invention is the deficiency that exists in above-mentioned prior art, the surgery implantation piece that a kind of Young's modulus is lower, intensity is higher, plasticity is better, cost is relatively low beta titanium alloy is provided.
The objective of the invention is to be achieved through the following technical solutions.
A kind of surgery implantation piece beta titanium alloy is characterized in that the weight percent of its alloy consists of: zirconium 0.1%-9.5%; Tin: 0.5%-9.5%; Molybdenum: 0.5%-9.5%; Niobium: 20%-30%, surplus is titanium and unavoidable impurities, wherein low gap constituent content carbon C≤0.03%; Nitrogen N≤0.04%; Hydrogen H≤0.003%; Oxygen O≤0.12%.
Surgery implantation piece of the present invention adopts a certain proportion of, as to have good biocompatibility zirconium, niobium, molybdenum and tin element as additive with beta titanium alloy, control surgery implantation piece is 7.2-11.9 with beta titanium alloy molybdenum equivalent, makes it form the stable nearly β type medical titanium alloy that is situated between.Thereby provide the surgery implantation piece that a kind of Young's modulus is lower, intensity is higher, plasticity is better, cost is relatively low beta titanium alloy.
The normal calculation formula of relevant molybdenum is as follows:
〔Mo〕eq=%〔Mo〕+%〔V/1.5〕+〔W〕/2+%〔Nb〕/3.6+%〔Ta〕/4.5+%〔Fe〕/0.35+%〔Cr〕/0.63+%〔Mn〕/0.65+%〔Ni〕/0.8-%〔Al〕
Above-mentioned design reasons is: Mo, Nb, Zr, Sn help alloy strengthening; Nb, Zr, Mo element are beneficial to the reduction Young's modulus; Zr, Sn, Nb element are little to the plasticity disadvantageous effect, even improve alloy plasticity; The Mo crystal grain thinning can improve the hot and cold plasticity of alloy; Nb is also favourable to improving toughness.But it is excessive that Mo, Nb element add, and increases the stable degree of alloy first, alloy solid solution aging effect is subsequently weakened or loses and can't realize alloy structure and performance adjustment; Second increase alloy density and raw material and melting tooling cost thereof, and be easy to occur the composition segregation during melting and tissue odds is even.For example to disclose a kind of Ti-Zr-Mo-Nb be biological titanium alloy to United States Patent (USP) (US5,871,595), and its alloy content is very high, and it forms weight ratio is Ti-Zr (10%-46%)-Mo (3%-15%)-Nb (29%-70%).And Mo, Nb, Zr, the Sn element of control suitable proportion make it form the stable nearly beta titanium alloy that is situated between, and adjust alloy property (as intensity, Young's modulus and unit elongation etc.) thereby can handle by solid solution aging; And this type of alloy easily brings out martensite in solution treatment or when loading and forms, and then causes the higher plasticity of alloy, is convenient to following process.
A kind of surgery implantation piece beta titanium alloy of the present invention, best composition scope is zirconium: 1.5%-4.5%; Tin: 0.5%-5.5%, molybdenum 1.5%-4.4%; Niobium 23.5%-26.5%, surplus is titanium and unavoidable impurities, molybdenum equivalent 7.2-11.9.
Alloy preparation process of the present invention is that refractory metal elements Mo, Nb are added with master alloy TiNb (Nb weight content 25%-55%) and TiMo (Mo weight content 10%-30%) form, or adds with Nb bar and pure Mo powder; Element Zr adds with zirconium sponge or pure zirconium strips; Element S n adds with pure Sn strips; Adopt the zero level titanium sponge with lower interstitial impurity constituent content in the control alloy substrate.Twice or three times of the melting in vacuum consumable electrode arc furnace of batching back.The ingot casting cogging is forged and to be chosen in 1000 ℃-1100 ℃ and to carry out, and selects 900 ℃-1000 ℃ to implement finished products forging or rolling etc.The solution treatment system is: temperature is controlled between-50 ℃~+ 100 ℃ of α/β transformation temperature, soaking time 0.5-1.5 hour, adopts shrend or air cooling; System of ageing treatment is: temperature is chosen in 480 ℃-640 ℃, is incubated 4-12 hour, air cooling.The performance data of its tensile strength, yield strength, unit elongation, reduction of area and Young's modulus and over-all properties all are better than advanced in the world at present medical beta titanium alloy, as Ti-13Nb-13Zr, Ti35Nb5Ta7Zr, the Ti16Nb10Hf of the U.S., the alloys such as Ti15Mo5Zr3Al, Ti29Nb13Ta5Zr of Japan.
Embodiment
A kind of surgery implantation piece beta titanium alloy is characterized in that the weight percent of its alloy consists of: zirconium 0.1%-9.5%; Tin: 0.5%-9.5%, molybdenum 0.5%-9.5%; Niobium 20%-30%, surplus is titanium and unavoidable impurities, wherein low gap constituent content carbon C≤0.03%; Nitrogen N≤0.04%; Hydrogen H≤0.003%; Oxygen O≤0.12%.Adopting refractory metal elements Mo, Nb is raw material twice or three times of melting in vacuum consumable electrode arc furnace with master alloy TiNb (Nb content 25-55wt) and TiMo (Mo content 10-30wt%), Nb bar and Mo powder, zirconium sponge or pure zirconium bar, pure Sn bar, zero level titanium sponge, ingot casting, cogging is forged and to be chosen in 1000 ℃-1100 ℃ and to carry out, and selects 900 ℃-1000 ℃ to implement finished products forging or rolling etc.The solution treatment system is: temperature is controlled between-50 ℃~+ 100 ℃ of α/β transformation temperature, soaking time 0.5-1.5 hour, adopts shrend or air cooling; System of ageing treatment is: temperature is chosen in 480 ℃-640 ℃, is incubated 4-12 hour, air cooling.Make alloy of the present invention.
Embodiment 1
Adopting 0 grade of titanium sponge Ti, nuclear power zirconium sponge Zr, pure easy Sn plate and Ti-15Mo and Ti-52Nb master alloy is raw material, after batch mixing is pressed into electrode, carries out twice melting in vacuum consumable electrode arc furnace.Wherein melting once voltage is 32 volts, melting electric current 1300 peaces; 35 volts of secondary smelting voltages, melting electric current 2200 peaces; Melting initial vacuum degree is not less than 10
-2Handkerchief makes alloy pig; The weight percent composition of alloy pig is: Zr:3%, and Sn:2%, Mo:3%,
Nb: 25%, surplus is Ti.Ingot casting carries out cogging and forges under 1050 ℃, after upsetting pull repeatedly, be swaged into a mouthful 42mm square rod earlier, is swaged into φ 37mm pole again.950 ℃ of continuous passage hot rollings of process down, make the thin rod of φ 12.5mm then, its original state property can be σ
b=790MPa; σ
0.2=435MPa; δ
s=21%%; ψ=56%; E=57.3GPa.At last according to service requirements, carry out 680 ℃/1 hour, the solution treatment of air cooling after, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=760MPa;σ
0.2=345MPa;δ
s=21.5%;ψ=74%;E=58GPa。
Embodiment 2
Other condition is with example 1, and the weight percent of alloy pig consists of Zr:3.5%, Sn:2%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out 750 ℃/1 hour, the solution treatment of air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=660MPa;σ
0.2=340MPa;σ
s=27.5%;ψ=79%;E=60.9GPa。
Embodiment 3
Other condition is with example 1, and the weight percent of alloy pig consists of Zr:2.5%, Sn:2%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out 820 ℃/1 hour, the solution treatment of air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=630MPa;σ
0.2=385MPa;δ
s=39%;ψ=82.5%;E=60.7GPa。
Embodiment 4
Other condition is with example 1, and the weight percent of alloy pig consists of Zr:2%, Sn:2%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 680 ℃/1 hour, the solution treatment of air cooling and 510 ℃/6 hours, air cooling, make alloy of the present invention, record alloy room temperature tensile mechanical property parameters and be:
σ
b=995MPa;σ
0.2=955MPa;δ
s=19%;ψ=79%;E=81.4GPa。
Embodiment 5
Other condition is with example 1, and the weight percent of alloy pig consists of Zr:3%, Sn:2.5%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 680 ℃/1 hour, the solution treatment of air cooling and 560 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=815MPa;σ
0.2=780MPa;δ
s=22%;E=78.9GPa。
Embodiment 6
Other condition is with example 1, and the weight percent of alloy pig consists of Zr:3%, Sn:3%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 680 ℃/1 hour, the solution treatment of air cooling and 610 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=710MPa;σ
0.2=640MPa;δ
s=21%;E=68GPa。
Embodiment 7
Other condition is with example 1, and the weight percent of alloy pig consists of Zr:3%, Sn:1.5%, Mo:3%, Nb:25%, surplus is Ti, after carrying out the timeliness thermal treatment of 750 ℃/1 hour, the solution treatment of air cooling and 560 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=710MPa;σ
0.2=815MPa;δ
s=21%;E=74.8GPa。
Embodiment 8
Other condition is with example 1, and the weight percent of alloy pig consists of Zr:3%, Sn:2%, and Mo:3.5%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 750 ℃/1 hour, the solution treatment of air cooling and 560 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=710MPa;σ
0.2=555MPa;δ
s=23%;E=78GPa。
Embodiment 9
Other condition is with example 1, and the weight percent of alloy pig consists of Zr:3%, Sn:2%, and Mo:2.5%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 750 ℃/1 hour, the solution treatment of air cooling and 610 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=685MPa;σ
0.2=325MPa;δ
s=23%;E=74.8GPa。
Embodiment 10
Other condition is with example 1, and the weight percent of alloy pig consists of Zr:3%, Sn:2%, and Mo:4%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 820 ℃/1 hour, the solution treatment of air cooling and 510 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=860MPa;σ
0.2=770MPa;δ
s=21.5%;E=79.5GPa。
Embodiment 11
Other condition is with example 1, and the weight percent of alloy pig consists of Zr:3%, Sn:2%, and Mo:3%, Nb:24%, surplus is Ti.After carrying out the timeliness thermal treatment of 820 ℃/1 hour, the solution treatment of air cooling and 560 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=700MPa;σ
0.2=465MPa;δ
s=22%;E=73.7GPa。
Embodiment 12
Other condition is with example 1, and the weight percent of alloy pig consists of Zr:3%, Sn:2%, and Mo:3%, Nb:26%, surplus is Ti.After carrying out the timeliness thermal treatment of 820 ℃/1 hour, the solution treatment of air cooling and 610 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=655MPa;σ
0.2=255MPa;δ
s=25%;E=73.8GPa。
Embodiment 13
Adopting 0 grade of titanium sponge Ti, pure zirconium bar, Zr, pure Nb, pure Mo and pure Sn plate is raw material, after batch mixing is pressed into electrode, carries out twice melting in vacuum consumable electrode arc furnace.Wherein melting once voltage is 32 volts, melting electric current 1300 peaces; 35 volts of secondary smelting voltages, melting electric current 2200 peaces; Melting initial vacuum degree is not less than the 10-2 handkerchief.The weight percent that makes alloy pig consists of: zirconium 1%; Tin: 4%; Molybdenum: 3%, niobium 25%; Surplus is Ti.Ingot casting carries out cogging and forges under 1050 ℃, after upsetting pull repeatedly, be swaged into a mouthful 42mm square rod earlier, is swaged into φ 37mm pole again.Then 950 ℃ down through continuous multi-pass hot rollings, (its original state property can be σ to make the thin rod of φ 12.5mm
b=1100MPa; σ
0.2=1060MPa; δ
s=13%%; ψ=71%; E=83.9GPa).At last according to service requirements, carry out 680 ℃/1 hour, the solution treatment of air cooling after, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=1010MPa;σ
0.2=975MPa;δ
s=13%;ψ=71%;E=76.1GPa。
Embodiment 14
Other condition is with example 13, and the weight percent of alloy pig consists of Zr:0.5%, Sn:4%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out 750 ℃/1 hour, the solution treatment of air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=990MPa;σ
0.2=975MPa;δ
s=12%;E=90.1GPa。
Embodiment 15
Other condition is with example 13, and the weight percent of alloy pig consists of Zr:1.5%, Sn:4%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out 820 ℃/1 hour, the solution treatment of air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=1060MPa;σ
0.2=910MPa;δ
s=15.5%;E=70.5GPa。
Embodiment 16
Other condition is with example 13, and the weight percent of alloy pig consists of Zr:2%, Sn:4%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 680 ℃/1 hour, the solution treatment of air cooling and 510 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=1010MPa;σ
0.2=950MPa;δ
s=20%;E=96.3GPa。
Embodiment 17
Other condition is with example 13, and the weight percent of alloy pig consists of Zr:1%, Sn:4.5%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 680 ℃/1 hour, the solution treatment of air cooling and 560 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=865MPa;σ
0.2=840MPa;δ
s=22.5%;E=88.7GPa。
Embodiment 18
Other condition is with example 13, and the weight percent of alloy pig consists of Zr:1%, Sn:3.5%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 680 ℃/1 hour, the solution treatment of air cooling and 610 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=785MPa;σ
0.2=765MPa:σ
s=24%;E=81.1GPa。
Embodiment 19
Other condition is with example 13, and the weight percent of alloy pig consists of Zr:1%, Sn:3%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 750 ℃/1 hour, the solution treatment of air cooling and 510 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=1050MPa;σ
0.2=955MPa;δ
s=19%;E=86.3GPa。
Embodiment 20
Other condition is with example 13, and the weight percent of alloy pig consists of Zr:1%, Sn:4%, and Mo:3.5%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 750 ℃/1 hour, the solution treatment of air cooling and 560 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=825MPa;σ
0.2=755MPa;δ
s=22%;E=86.7GPa。
Embodiment 21
Other condition is with example 13, and the weight percent of alloy pig consists of Zr:1%, Sn:4%, and Mo:4%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 750 ℃/1 hour, the solution treatment of air cooling and 610 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=740MPa;σ
0.2=700MPa;δ
s=22%;E=78.3GPa。
Embodiment 22
Other condition is with example 13, and the weight percent of alloy pig consists of Zr:1%, Sn:4%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 820 ℃/1 hour, the solution treatment of air cooling and 510 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=1050MPa;σ
0.2=975MPa;δ
s=16%;E=84.4GPa。
Embodiment 23
Other condition is with example 13, and the weight percent of alloy pig consists of Zr:1%, Sn:4%, and Mo:3%, Nb:25%, surplus is Ti.After carrying out the timeliness thermal treatment of 820 ℃/1 hour, the solution treatment of air cooling and 560 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=780MPa;σ
0.2=715MPa;δ
s=23%;E=78.9GPa。
Embodiment 24
Other condition is with example 13, and the weight percent of alloy pig consists of Zr:1%, Sn:4%, and Mo:3%, Nb:26%, surplus is Ti.After carrying out the timeliness thermal treatment of 610 ℃/1 hour, the solution treatment of air cooling and 610 ℃/6 hours, air cooling, make alloy of the present invention.Recording alloy room temperature tensile mechanical property parameters is:
σ
b=750MPa;σ
0.2=705MPa;σ
s=23%;E=80.1GPa。