CN108456805A - A kind of beta titanium alloy and its manufacturing method for being implanted into bone - Google Patents
A kind of beta titanium alloy and its manufacturing method for being implanted into bone Download PDFInfo
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- CN108456805A CN108456805A CN201810356386.8A CN201810356386A CN108456805A CN 108456805 A CN108456805 A CN 108456805A CN 201810356386 A CN201810356386 A CN 201810356386A CN 108456805 A CN108456805 A CN 108456805A
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L27/00—Materials for grafts or prostheses or for coating grafts or prostheses
- A61L27/02—Inorganic materials
- A61L27/04—Metals or alloys
- A61L27/06—Titanium or titanium alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/18—High-melting or refractory metals or alloys based thereon
- C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
Abstract
It is a kind of for being implanted into the beta titanium alloy of bone, it is characterised in that the alloying component is respectively according to weight percent：Nb：21‑22、Mo：10.5‑11.5、Zr：5‑6、Al：1.1‑1.2、Cr：0.8‑1.0、Ag：0.7‑0.8、Fe：0.2‑0.3、Ta：0.4‑0.7、Cu 0.15‑0.2、V：0.3~0.45, Sn：0.2~0.4, Sc+La：0.05 0.08, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and inevitable impurity composition, and average crystallite particle diameter is 15 25 μm in the beta titanium alloy after heat treatment formed；1000 1150MPa of yield strength, 1100 1250MPa of tensile strength, elongation percentage 18 20%, 50 70GPa of Young's modulus, primary alpha phase volume fraction are 18 21%, and grain size of α phase is 46 microns, secondaryαphase volume fraction is 17 19%, and secondaryαphase size is 0.5 1.5 microns.
Description
Technical field
The invention belongs to alloy field, more particularly to a kind of beta titanium alloys for being implanted into bone.
Background technology
Titanium alloy is due to higher intensity, lower elasticity modulus, good biocompatibility and excellent resistance to
Corrosive nature, having gradually replaced stainless steel and cobalt-base alloys becomes the alternative materials of bone.It clinically applies at present the widest
General titanium alloy is alpha+beta type Ti-6Al-4V, but the alloy can discharge after being implanted into human body certain time due to wearing and corroding
The Al ions for providing cytotoxicity and neurotoxicity, cause the symptoms such as osteomalacia, anaemia and neurological disorders, and V is also recognized in addition
For the element for being toxic to organism；And the elasticity modulus of the alloy is still much higher than the elasticity of people's bone in 115GPa or so
Modulus (is less than 40 GPa).Therefore, scientists from all over the world are dedicated to researching and developing that biocompatibility is more preferable, springform since the nineties
Lower beta-titanium alloy is measured, and the nontoxic element such as Nb, Ta, Zr, Sn and Mo is increasingly becoming the main adding elements of alloy.
The fusing point of titanium is 1668 DEG C, and there are two types of ppolymorphism crystal for tool, are in hcp lattices when temperature is less than 882 DEG C
Structure, referred to as α-Ti；It is in bcc lattice structures, referred to as β-Ti when temperature is higher than 882 DEG C or more.There is solid matter six using titanium
Side and the characteristics of body-centered cubic structure changes phase transition temperature by adding a certain proportion of alloying element, acquisition different tissues at
The titanium alloy divided.According to beta stable element content and phase constitution under metastable condition, titanium alloy is divided into three categories：α type titaniums close
Gold, (alpha+beta) Type Titanium Alloy and beta titanium alloy, the trade mark are respectively TA, TC, TB.Near β titanium alloy, metastable β Titanium-alloy and stable β
Titanium alloy is referred to as beta-titanium alloy, is most widely used a kind of titanium alloy.Beta-titanium alloy has highest specific strength, is far above
High-strength magnesium alloy, aluminium alloy, high temperature alloy and high-tensile structural steel, high specific strength meet modern aircraft and mitigate architecture quality
With the requirement for improving flying speed.There is beta-titanium alloy low elasticity modulus and thermal coefficient, elasticity modulus there was only two points of steel
One of or so, and apparent anisotropy is shown, strength and toughness matching is excellent.
Material using titanium alloy material as implantation bone is very universal, but this kind of titanium alloy material how to be made to have
Good intensity, wearability, plasticity, biocompatibility, low cost are always the target of research.Beta-titanium alloy is biomedical neck
Domain has many uses general.
The manufacture of usual metal material can be the technologies such as molten metal casting, powder metallurgy and superplastic forming, 3D printing.
Wherein, it is casting using most technologies in clinical medicine, although the principle of the technology is simple, is easy to be grasped by operator,
But its tedious process, and it is difficult to accurate, the accurate manufacture of composite dental one kind material.Although 3D printing is conducive to manufacture
The implantation human material of precise measure, but production cost is higher.Powder metallurgy can overcome the segregation of alloying element, be produced into
This is relatively low.
Invention content
The present invention develops implantation bone beta titanium on the basis of conventional titanium alloy, by composition adjustment and process modification
Alloy and its manufacturing method, which has excellent mechanical property and corrosion resisting property, and avoids the damage to health
Evil, matches special heat treatment process in conjunction with traditional sintering process, titanium alloy institutional framework after control heat treatment, can it is low at
This manufacture is implanted into the beta titanium alloy of bone, meets the needs of medical treatment of different income level crowds, has important society and warp
Ji meaning.
The present invention specifically provides a kind of beta titanium alloy for being implanted into bone, it is characterised in that the alloying component is pressed
It is respectively according to weight percent：Nb：21-22、Mo：10.5-11.5、Zr：5-6、Al：1.1-1.2、Cr：0.8-1.0、Ag：0.7-
0.8、Fe：0.2-0.3、Ta：0.4-0.7、Cu 0.15-0.2、V：0.3~0.45, Sn：0.2~0.4, Sc+La：0.05-
0.08, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are that Ti and inevitable impurity are constituted, Sc with
La mass ratioes are 2: 1, and average crystallite particle diameter is 15-25 μm in the beta titanium alloy after heat treatment formed；Yield strength 1000-
1150MPa, tensile strength 1100-1250MPa, elongation percentage 18-20%, Young's modulus 50-70GPa, primary alpha phase volume fraction are
18-21%, grain size of α phase are 4-6 microns, and secondaryαphase volume fraction is 17-19%, and secondaryαphase size is 0.5-1.5 microns.
Preferably a kind of beta titanium alloy for being implanted into bone, it is characterised in that the alloying component is according to weight hundred
Point ratio is respectively：Nb：21-21.8、Mo：10.5-11.2、Zr：5-5.8、Al：1.1-1.18、Cr：0.8-0.9、Ag：0.7-
0.75、Fe：0.2-0.25、Ta：0.4-0.6、Cu 0.15-0.18、V：0.35~0.45, Sn：0.25~0.35, Sc+La：
0.06-0.07, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder is Ti and inevitable impurity is constituted,
Sc is 2: 1 with La mass ratioes.
Preferably a kind of beta titanium alloy for being implanted into bone, it is characterised in that the alloying component is according to weight hundred
Point ratio is respectively：Nb：21、Mo：10.5、Zr：5、Al：1.1、Cr：0.8、Ag：0.7、Fe：0.2、Ta：0.4、Cu 0.15、V：
0.3、Sn：0.2、Sc+La：0.05, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and can not keep away
The impurity exempted from is constituted, and Sc is 2: 1 with La mass ratioes.
Preferably a kind of beta titanium alloy for being implanted into bone, it is characterised in that the alloying component is according to weight hundred
Point ratio is respectively：Nb：21.8、Mo：11.2、Zr：5.8、Al：1.18、Cr：0.9、Ag：0.75、Fe：0.25、Ta： 0.6、Cu
0.18、V： 0.45、Sn： 0.35、Sc+La：0.07, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are
Ti and inevitable impurity are constituted, and Sc is 2: 1 with La mass ratioes.
Preferably a kind of beta titanium alloy for being implanted into bone, it is characterised in that the alloying component is according to weight hundred
Point ratio is respectively：Nb 22、Mo：11.5、Zr：6、Al：1.2、Cr：1.0、Ag：0.8、Fe：0.3、Ta：0.7、Cu 0.2、V：
0.45、Sn：0.4、Sc+La：0.08, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and can not keep away
The impurity exempted from is constituted, and Sc is 2: 1 with La mass ratioes.
The above-mentioned manufacturing method for being implanted into the beta titanium alloy of bone, which is characterized in that include the following steps：
(1) raw material preparation：Nb, Mo, Ta, V in the form of low melting point intermediate alloy as raw material, Ti-Al intermediate alloys, among this
Al mass ratioes are 75% in alloy；Ti-Zr intermediate alloys, Zr mass ratioes are 55% in the intermediate alloy；Ti-Cr intermediate alloys, should
Cr mass ratioes are 49% in intermediate alloy；Ti-Fe intermediate alloys, Fe mass ratioes are 30% in the intermediate alloy； Ag、Cu、Sc、La、
Sn exists in the form of metal simple-substance；The main sources Ti are provided with titanium sponge, by adjusting raw material, it is contemplated that melting loss of elements,
The ultimate constituent is set to meet target titanium alloy product ingredient；
（2）Melting is sequentially added load weighted each raw material in medium frequency induction melting furnace by the sequence of fusing point from low to high, is taken out
Vacuum is to≤10Pa；It is then charged with inert gas, is 1 × 10 in inert gas pressure-2It is 100- that Pa, which protects melting, melting electric current,
110 A, smelting time are 25 ~ 30 min；Vacuumize refining after material completion is clear, after having refined by alloy melt be cast into
Under 200 ± 5 DEG C of environment in preheated mold, a diameter of 40mm is obtained, length is the metal bar of 40cm, as self-consuming electricity
Pole；
（3）Powder processed is by step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains meeting product cleanliness factor
Titanium alloy solution；Ensure that the degree of superheat is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid
Flow velocity rate is 10kg/min~15kg/min, and atomizing medium is nitrogen, and increasing atomizing gas pressure is 10MPa~15MPa, and atomization is quick
A diameter of 3mm~the 4mm of atomizer of condensing unit；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere
Point, obtain titanium alloy powder of the grain size at 15-25 microns；
（4）When sintering is sintered alloy powder using discharge plasma sintering system, specific process conditions are as follows：
Sintering current type：DC pulse current；Sintering temperature：1200 DEG C~1400 DEG C；Soaking time：10-12min；Sintering pressure
Power：200-300MPa；Heating rate：60~100 DEG C/min；
（5）Heat treatment is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 890-900 DEG C, when heat preservation
Between be 20-25 minutes, water hardening 10-15 seconds；660 DEG C~670 DEG C guarantors are heated to the heating rate of 10-30 DEG C/min later
Warm 0.2-0.3 hours progress artificial aging processing, it is air-cooled later to obtain low elastic modulus implantation bone beta titanium alloy.
It is preferably used in the manufacturing method of the beta titanium alloy of implantation bone, it is characterised in that：Step（3）Powder processed is by step
（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains the titanium alloy solution for meeting product cleanliness factor；Ensure overheat
Degree is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid flowing rate is 13kg/min, mist
Change medium is nitrogen, and increasing atomizing gas pressure 12.5MPa is atomized a diameter of 3.5mm of atomizer of rapid condensation device；Atomization
After wait for that powder is completely cooling, sieved in nitrogen protection atmosphere, obtain titanium alloy powder of the grain size at 20 microns.
It is preferably used in the manufacturing method of the beta titanium alloy of implantation bone, it is characterised in that：Step（4）Using electric discharge etc.
When ion sintering system is sintered alloy powder, specific process conditions are as follows：Sintering current type：DC pulse
Stream；Sintering temperature：1300℃；Soaking time：11min；Sintering pressure：250MPa；Heating rate：80℃/min.
It is preferably used in the manufacturing method of the beta titanium alloy of implantation bone, it is characterised in that：Step（5）Heat treatment is true
Reciprocal of duty cycle is to be heat-treated within 100Pa, and the temperature of solution treatment is 900 DEG C, and soaking time is 25 minutes, water hardening 15
Second；665 DEG C of heat preservations are heated to the heating rate of 20 DEG C/min later and carry out within 0.2 hour artificial aging processing, it is air-cooled later to obtain
It is implanted into bone beta titanium alloy to low elastic modulus.
The effect of each element is as follows in titanium alloy provided by the present invention：
Mo and β titaniums lattice types having the same, are infinitely dissolved in β titaniums.Mo, Nb and Ti outer electronic structure are close, atom
Radius is small, dissolves in and forms substitution solid solution in titanium, and distortion of lattice is small, and outer layer d electronics is less than 5, and electronics, shape can only be shared with titanium
At metallic bond, thus outer-shell electron is evenly distributed between ion, has high-ductility；Mo, Nb make ppolymorphism transformation temperature simultaneously
Degree declines, referred to as β stabilizing elements.More containing β phase stable elements in alloying element, the metastable β phases for quenching acquisition are more,
Ageing strengthening effect is bigger.Mo, Nb element can improve alloy strength and plasticity, advantageously reduce the elasticity modulus of alloy, Nb
Also advantageous to improving toughness, Mo can be with crystal grain thinning, and then improves the hot and cold formability of alloy.Nb has ductility, usually works as
Nb is added to titanium alloy, and titanium alloy is i.e. with flexibility, low elasticity.It, can be with Zr using Nb as the ingredient of titanium alloy of the present invention
Collaboration promotes the corrosion resistance of titanium alloy together.The content of Nb is Nb in the present invention：21-22%, preferably Nb：21-21.8%.
The content of Mo is 10.5-11.5%, preferably Mo in the present invention：10.5-11.2%.
When Zr is exposed in air, fine and close oxide skin(coating) is formed on the surface of Zr.Zr has excellent corrosion resistance.
Moreover, corrosion resistances of the Zr in high-temperature water is apparently higher than other metals.Zr is by forming oxide skin(coating) stabilization and not reacting, Zr
With excellent corrosion resistance.With excellent corrosion resistance and acid proof Zr as the biological alloy group often added
Point.The titanium alloy of the present invention, when the content of Zr is less than 5%, machinability reduces.When Zr contents are higher than 6%, corrosion resistance carries
High degree reduces, considering cost and performance, and the content of Zr is Zr in the present invention：5-6%, preferably Zr：5-5.8%.
Beta-titanium alloy will generally add a small amount of Al, crisp with hexagoinal lattice to promote to be generated by metastable β phase decompositions
Property ω phase transition is at α phases.According to Ti-Al binary phase diagramls, limit of solubility of the aluminium in titanium is 7.5%, therefore adds aluminum amount that must not surpass
7% is crossed, prevents from forming ordered phase Ti3Al, the ordered phase are unfavorable for the plasticity, toughness and stress corrosion resistant ability of alloy.In addition,
The density of Al is small with atomic radius ratio Ti's, and the Binding Forces Between Atoms of beta-titanium alloy solid solution can be made to enhance, improve the ratio of alloy
Intensity, and plasticity is without being substantially reduced；The inoxidizability that alloy can also be improved simultaneously, significantly improves its recrystallization temperature, improves
It is stability.Therefore Al takes 1.1-1.2%, preferably Al in the present invention：1.1-1.18%.
Cr elements are one of eutectoid elements of titanium alloy, also there is stronger beta stability, the high-strength beta-titanium alloy of the overwhelming majority
Cr elements are all employed as its stable element, Cr may be dissolved in α and β phases, form TiCr2Compound.Cr is in β titaniums
Solubility it is very high.So Cr elements improve the mechanical performance of titanium alloy in titanium alloy in a manner of solid solution strength,
The addition of Cr elements can also cause to be segregated.Cr elements can also play a role the refinement of alloy structure, Cr in the present invention：0.8-
1.0%, preferably Cr：0.8-0.9%.
Ag elements can all form limit solid solution with α-Ti, β-Ti, and Ag makes beta transus temperature decline, and also belongs to β phases and stablizes
Element.Suitable Ag elements are added in the present invention, processability and plasticity can be improved.Furthermore, it is contemplated that titanium alloy and skin
It is in close contact, the anti-microbial property of titanium alloy can also be improved using Ag.Ag in the present invention：0.7-0.8%, preferably Ag：0.7-
0.75%。
Strong β phases formation element Fe is added in titanium alloy, can promote the formation of metastable β phases at room temperature, and control
The martensitic transformation temperature Ms of titanium alloy.Fe replaces part Nb, both reduces cost of alloy, and can adjust the phase of α phases/β phases
Temperature and martensitic transformation temperature Ms so that alloy can obtain metastable β phases at room temperature；And cold change can be passed through
Shape stress induces the martensitic traoformation of the opposite α phase transition of β.In this way, can both meet processing technology of the Alloy At Room Temperature cold-drawn at silk
It is required that meanwhile, and because obtained martensitic phase is relatively soft so that the Young's modulus of alloy further decreases so that the poplar of alloy
The adjustable range of family name's modulus increases, and achievees the purpose that its Young's modulus is continuously adjustable.Fe in the present invention：0.2-0.3, it is excellent
Choosing is Fe：0.2-0.25%.
Ta and β titaniums lattice types having the same, are infinitely dissolved in β titaniums.The property of the elements such as V and Ti are extremely close,
Atomic radius difference is little, therefore can form continuous solid solution.In the present invention, Mo, Ta, V are added in titanium alloy, it can
Realize excellent formability, and improve corrosion resistance, heat resistance simultaneously etc..Ta in the present invention：0.4-0.7%、V：0.3~
0.45%, preferably Ta：0.4-0.6%、V：0.35~0.45%.
β eutectoid element Cu, which is added, can stablize a certain amount of β phase to room temperature, while energy refining alloy crystal grain, and it is strong to play fine grain
Change acts on so that alloy keeps higher intensity and plasticity, improves Wear Resistance, also, the Ti2Cu solid particles being precipitated also can
Effectively improve wearability.Cu 0.15-0.2% in the present invention, preferably 0.15-0.18%.
Although Sn has effect identical with the Al, but since the hardness under β states will not be increased as Al, because
This is replaced by reducing Al with Sn, so that it may to inhibit deformation drag to increase.The effect if the content of addition Sn is less than 0.2%
Unobvious, but when Sn contents are more than 0.4%, due to or the hardness of the alloy after βization can be increased, it is of the invention in Sn：0.2
~0.4%, preferably Sn：0.25~0.35%.
Rare earth is added in titanium alloy and plays reinforced alloys, impurity is reduced, changes form and the distribution of field trash, is improved anti-
The effects that burn into antioxygenic property, welding performance, cold-workability, phase transformation super-elasticity.Specifically rare earth can mitigate nonmetallic
The adverse effect of inevitable impurity.Hydrogen is harmful inevitable impurity of titanium alloy, leads to occur intercrystalline crack, loose
With the hydrogen-induced defects such as pin hole.In addition rare earth also has the effect for reducing oxygen content in alloy.Easily make with gas, nonmetallic and metal
With, the compound that generation is accordingly stablized, these compounds, fusing point height, light specific gravity, floating slagging.And their small particle
The nucleation point for then becoming alloy crystallization process, plays the role of crystal grain thinning.The present invention selects common rare earth Sc+La,
Production cost is saved, it is ensured that the balance of performance and cost.Sc+La：0.05-0.08, preferably Sc+La：0.06-0.07%.
It is got well than single rare earth element effect with compound rare-earth.
Low-alloyed deformability can drop in O, and the generation of crackle, deformation drag can be caused in the cold rolling processing for carrying out intensity
Also increase.Although the fewer its amount the better, it is typically set at 0.05% or less.
H can make ductility and degraded toughness, more fewer better, therefore be set as to 0.01% or less.
C can be such that ductility i.e. deformability substantially reduces, more fewer better, therefore be set as to 0.02% or less.
The fewer N the better due to that deformability can be made to substantially reduce, therefore is set as to 0.01% or less.
When the carry out alloy manufacture of different elements, the difficulty of melting can be increased, be also easy to generate component segregation, the present invention adopts
It uses many master alloyed powders as manufacture raw material, is completely melt when being conducive to melting, makes solution composition evenly；Alloy melting
And the degree of superheat of the titanium alloy solution obtained after fusing is controlled at 180-200 DEG C；The appropriate of the degree of superheat of titanium alloy solution is set
It sets, condensation time of the titanium alloy powder in atomization process can be increased so that when the effect on surface tension retracting drop surface
Between increase, be more readily available spherical powder, although theoretically, the degree of superheat is higher, condensation time is longer, and surface tension is made to receive
The action time of contracting droplet surface is longer, and the probability for obtaining spherical powder is bigger.The control of the degree of superheat should not exceed 200 DEG C,
If more than 200 DEG C, while it is desirable to condensation time it is longer, but surface tension contraction is excessively drastically, is not easy instead
Shape to spherical powder, powder is mostly irregular.The grain size that the present invention selects both was kept away in 15-25 microns of titanium alloy powder
Exempt from less than 15 microns fine powder processes of grain size to the high request of production equipment, production technology, cost, also meets sintering to powder
Requirement because the granule-morphology of inorganic powder will as possible close to spheroidal, and particle size need it is moderate, ball powder particles
Locomotivity is strong, and convenient for uniformly sprawling for powder, while ball is conducive to binder and is flowed in powder gap, improves binder
Seepage velocity.A small amount of fluoropolymer resin is added as binder, consumption of binder accounts for the 2-3% of titanium alloy powder total amount.
Heat treatment process is extremely important in titanium alloy product manufacture, and titanium alloy group is woven in volume fraction and modal difference
It is different to have apparent influence to its mechanical property.There are primary alpha phases and secondary α in alloy after two-phase section fixation rates
Phase, primary alpha phase is softer in high-strength high-ductility titanium alloy, and the influence to alloy strength is smaller.It is sliding when alloy Tensile load acts on
It moves system to be easy to start in primary alpha phase, and with the increasing of deformation extent, is opened in the shaft-like primary alpha phase such as neighbouring others
It is dynamic.Primary α volume fraction is bigger, and stress more disperses, and the plastic deformation ability of alloy is stronger.So with primary α volume point
The elongation of several increases, alloy gets a promotion.The raising of primary α volume fraction, which improves alloy strength, to be influenced less, but is stretched
Long rate significantly increases, and alloy can be more plastically deformed before fracturing, so Tension toughness is in increased trend, shows alloy
Fracture occurs under tensile load to need to absorb more work(.Ballistic work is divided into crack forming energy and crack expansion power two parts,
Crack forming energy is mainly consumed in the formation of the elasticity, plastic deformation and micro-crack of sample.Alloy be hit load effect when,
Although impact velocity is quickly, plastic deformation still will produce, and plastic deformation is transferred to another place from one makes deformation increase, simultaneously
Strain-hardening is generated, crack forming energy is caused to increase.Alloy plastic deformation's ability can be improved in the volume fraction increase of primary alpha phase,
So crack forming energy is in raising trend.Primary alpha phase volume fraction is 18-21% in the present invention, and grain size of α phase is that 4-6 is micro-
Rice, secondaryαphase volume fraction are 17-19%, and secondaryαphase size is 0.5-1.5 microns.
To sum up, the beneficial effects of the invention are as follows：
1, the present invention is implanted into the raw material of bone beta titanium alloy using a variety of intermediate alloys as low elastic modulus, is conducive to melting
When raw material be completely melt, can avoid generate segregation phenomena, make solution composition evenly, reduce the loss of alloying element.
2, the present invention obtains best particle size range, helps to be sintered by the stringent control to powder by atomization technique
Forming avoids the inadequate defect of implantation material precision that conventional casting methods bring.
3. by strictly controlling heat treatment process so that final titanium alloy institutional framework is that primary alpha phase volume fraction is
18-21%, grain size of α phase are 4-6 microns, and secondaryαphase volume fraction is 17-19%, and secondaryαphase size is 0.5-1.5 microns.
Have both good intensity, plasticity, toughness, elongation.
4. by clearly being limited raw materials for metallurgy, it is ensured that just alloying element is made to be completely melt in lower temperature, it is full
Foot-eye product composition reduces the loss of element while requirement, which has excellent mechanical property and corrosion resisting property,
And avoid damage to health.
Specific implementation mode
It elaborates to technical solution of the present invention below with reference to example embodiment.However, example embodiment can
Implement in a variety of forms, and is not understood as limited to embodiment set forth herein；On the contrary, providing these embodiments makes
It is of the invention more comprehensively and completely, and the design of example embodiment is comprehensively communicated to those skilled in the art.
Embodiment 1
It is a kind of for being implanted into the beta titanium alloy of bone, it is characterised in that the alloying component is respectively according to weight percent：
Nb：21、Mo：10.5、Zr：5、Al：1.1、Cr：0.8、Ag：0.7、Fe：0.2、Ta：0.4、Cu 0.15、V：0.3、Sn：0.2、Sc
+La：0.05, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and inevitable impurity composition,
Sc is 2: 1 with La mass ratioes.
Manufacturing method includes the following steps：
(1) raw material preparation：Nb, Mo, Ta, V in the form of low melting point intermediate alloy as raw material, Ti-Al intermediate alloys, among this
Al mass ratioes are 75% in alloy；Ti-Zr intermediate alloys, Zr mass ratioes are 55% in the intermediate alloy；Ti-Cr intermediate alloys, should
Cr mass ratioes are 49% in intermediate alloy；Ti-Fe intermediate alloys, Fe mass ratioes are 30% in the intermediate alloy； Ag、Cu、Sc、La、
Sn exists in the form of metal simple-substance；The main sources Ti are provided with titanium sponge, by adjusting raw material, it is contemplated that melting loss of elements,
The ultimate constituent is set to meet target titanium alloy product ingredient；
（2）Melting is sequentially added load weighted each raw material in medium frequency induction melting furnace by the sequence of fusing point from low to high, is taken out
Vacuum is to≤10Pa；It is then charged with inert gas, is 1 × 10 in inert gas pressure-2It is 100- that Pa, which protects melting, melting electric current,
110 A, smelting time are 25 ~ 30 min；Vacuumize refining after material completion is clear, after having refined by alloy melt be cast into
Under 200 ± 5 DEG C of environment in preheated mold, a diameter of 40mm is obtained, length is the metal bar of 40cm, as self-consuming electricity
Pole；
（3）Powder processed is by step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains meeting product cleanliness factor
Titanium alloy solution；Ensure that the degree of superheat is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid
Flow velocity rate is 10kg/min~15kg/min, and atomizing medium is nitrogen, and increasing atomizing gas pressure is 10MPa~15MPa, and atomization is quick
A diameter of 3mm~the 4mm of atomizer of condensing unit；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere
Point, obtain titanium alloy powder of the grain size at 15-25 microns；
（4）When sintering is sintered alloy powder using discharge plasma sintering system, specific process conditions are as follows：
Sintering current type：DC pulse current；Sintering temperature：1200 DEG C~1400 DEG C；Soaking time：10-12min；Sintering pressure
Power：200-300MPa；Heating rate：60~100 DEG C/min；
（5）Heat treatment is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 890-900 DEG C, when heat preservation
Between be 20-25 minutes, water hardening 10-15 seconds；660 DEG C~670 DEG C guarantors are heated to the heating rate of 10-30 DEG C/min later
Warm 0.2-0.3 hours progress artificial aging processing, it is air-cooled later to obtain low elastic modulus implantation bone beta titanium alloy.
Embodiment 2
It is a kind of for being implanted into the beta titanium alloy of bone, it is characterised in that the alloying component is respectively according to weight percent：
Nb：21.8、Mo：11.2、Zr：5.8、Al：1.18、Cr：0.9、Ag：0.75、Fe：0.25、Ta： 0.6、Cu 0.18、V：
0.45、Sn： 0.35、Sc+La：0.07, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and can not
The impurity avoided is constituted, and Sc is 2: 1 with La mass ratioes.
Manufacturing method includes the following steps：
(1) raw material preparation：Nb, Mo, Ta, V in the form of low melting point intermediate alloy as raw material, Ti-Al intermediate alloys, among this
Al mass ratioes are 75% in alloy；Ti-Zr intermediate alloys, Zr mass ratioes are 55% in the intermediate alloy；Ti-Cr intermediate alloys, should
Cr mass ratioes are 49% in intermediate alloy；Ti-Fe intermediate alloys, Fe mass ratioes are 30% in the intermediate alloy； Ag、Cu、Sc、La、
Sn exists in the form of metal simple-substance；The main sources Ti are provided with titanium sponge, by adjusting raw material, it is contemplated that melting loss of elements,
The ultimate constituent is set to meet target titanium alloy product ingredient；
（2）Melting is sequentially added load weighted each raw material in medium frequency induction melting furnace by the sequence of fusing point from low to high, is taken out
Vacuum is to≤10Pa；It is then charged with inert gas, is 1 × 10 in inert gas pressure-2It is 100- that Pa, which protects melting, melting electric current,
110 A, smelting time are 25 ~ 30 min；Vacuumize refining after material completion is clear, after having refined by alloy melt be cast into
Under 200 ± 5 DEG C of environment in preheated mold, a diameter of 40mm is obtained, length is the metal bar of 40cm, as self-consuming electricity
Pole；
（3）Powder processed is by step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains meeting product cleanliness factor
Titanium alloy solution；Ensure that the degree of superheat is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid
Flow velocity rate is 10kg/min~15kg/min, and atomizing medium is nitrogen, and increasing atomizing gas pressure is 10MPa~15MPa, and atomization is quick
A diameter of 3mm~the 4mm of atomizer of condensing unit；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere
Point, obtain titanium alloy powder of the grain size at 15-25 microns；
（4）When sintering is sintered alloy powder using discharge plasma sintering system, specific process conditions are as follows：
Sintering current type：DC pulse current；Sintering temperature：1200 DEG C~1400 DEG C；Soaking time：10-12min；Sintering pressure
Power：200-300MPa；Heating rate：60~100 DEG C/min；
（5）Heat treatment is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 890-900 DEG C, when heat preservation
Between be 20-25 minutes, water hardening 10-15 seconds；660 DEG C~670 DEG C guarantors are heated to the heating rate of 10-30 DEG C/min later
Warm 0.2-0.3 hours progress artificial aging processing, it is air-cooled later to obtain low elastic modulus implantation bone beta titanium alloy.
Embodiment 3
It is a kind of for being implanted into the beta titanium alloy of bone, it is characterised in that the alloying component is respectively according to weight percent：Nb
22、Mo：11.5、Zr：6、Al：1.2、Cr：1.0、Ag：0.8、Fe：0.3、Ta：0.7、Cu 0.2、V：0.45、Sn：0.4、Sc+
La：0.08, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and inevitable impurity composition, Sc
It is 2: 1 with La mass ratioes.
Manufacturing method includes the following steps：
(1) raw material preparation：Nb, Mo, Ta, V in the form of low melting point intermediate alloy as raw material, Ti-Al intermediate alloys, among this
Al mass ratioes are 75% in alloy；Ti-Zr intermediate alloys, Zr mass ratioes are 55% in the intermediate alloy；Ti-Cr intermediate alloys, should
Cr mass ratioes are 49% in intermediate alloy；Ti-Fe intermediate alloys, Fe mass ratioes are 30% in the intermediate alloy； Ag、Cu、Sc、La、
Sn exists in the form of metal simple-substance；The main sources Ti are provided with titanium sponge, by adjusting raw material, it is contemplated that melting loss of elements,
The ultimate constituent is set to meet target titanium alloy product ingredient；
（2）Melting is sequentially added load weighted each raw material in medium frequency induction melting furnace by the sequence of fusing point from low to high, is taken out
Vacuum is to≤10Pa；It is then charged with inert gas, is 1 × 10 in inert gas pressure-2It is 100- that Pa, which protects melting, melting electric current,
110 A, smelting time are 25 ~ 30 min；Vacuumize refining after material completion is clear, after having refined by alloy melt be cast into
Under 200 ± 5 DEG C of environment in preheated mold, a diameter of 40mm is obtained, length is the metal bar of 40cm, as self-consuming electricity
Pole；
（3）Powder processed is by step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains meeting product cleanliness factor
Titanium alloy solution；Ensure that the degree of superheat is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid
Flow velocity rate is 10kg/min~15kg/min, and atomizing medium is nitrogen, and increasing atomizing gas pressure is 10MPa~15MPa, and atomization is quick
A diameter of 3mm~the 4mm of atomizer of condensing unit；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere
Point, obtain titanium alloy powder of the grain size at 15-25 microns；
（4）When sintering is sintered alloy powder using discharge plasma sintering system, specific process conditions are as follows：
Sintering current type：DC pulse current；Sintering temperature：1200 DEG C~1400 DEG C；Soaking time：10-12min；Sintering pressure
Power：200-300MPa；Heating rate：60~100 DEG C/min；
（5）Heat treatment is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 890-900 DEG C, when heat preservation
Between be 20-25 minutes, water hardening 10-15 seconds；660 DEG C~670 DEG C guarantors are heated to the heating rate of 10-30 DEG C/min later
Warm 0.2-0.3 hours progress artificial aging processing, it is air-cooled later to obtain low elastic modulus implantation bone beta titanium alloy.
Comparative example 1
It is a kind of for being implanted into the beta titanium alloy of bone, it is characterised in that the alloying component is respectively according to weight percent：
Nb：15、Mo：9、Zr：3、Al：0.5、Cr：0.5、Ag：0.4、Fe：0.2、Ta：0.4、Cu 0.15、V：0.3、Sn：0.2、Sc+
La：0.05, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and inevitable impurity composition, Sc
It is 2: 1 with La mass ratioes.
Manufacturing method includes the following steps：
(1) raw material preparation：Nb, Mo, Ta, V in the form of low melting point intermediate alloy as raw material, Ti-Al intermediate alloys, among this
Al mass ratioes are 75% in alloy；Ti-Zr intermediate alloys, Zr mass ratioes are 55% in the intermediate alloy；Ti-Cr intermediate alloys, should
Cr mass ratioes are 49% in intermediate alloy；Ti-Fe intermediate alloys, Fe mass ratioes are 30% in the intermediate alloy； Ag、Cu、Sc、La、
Sn exists in the form of metal simple-substance；The main sources Ti are provided with titanium sponge, by adjusting raw material, it is contemplated that melting loss of elements,
The ultimate constituent is set to meet target titanium alloy product ingredient；
（2）Melting is sequentially added load weighted each raw material in medium frequency induction melting furnace by the sequence of fusing point from low to high, is taken out
Vacuum is to≤10Pa；It is then charged with inert gas, is 1 × 10 in inert gas pressure-2It is 100- that Pa, which protects melting, melting electric current,
110 A, smelting time are 25 ~ 30 min；Vacuumize refining after material completion is clear, after having refined by alloy melt be cast into
Under 200 ± 5 DEG C of environment in preheated mold, a diameter of 40mm is obtained, length is the metal bar of 40cm, as self-consuming electricity
Pole；
（3）Powder processed is by step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains meeting product cleanliness factor
Titanium alloy solution；Ensure that the degree of superheat is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid
Flow velocity rate is 10kg/min~15kg/min, and atomizing medium is nitrogen, and increasing atomizing gas pressure is 10MPa~15MPa, and atomization is quick
A diameter of 3mm~the 4mm of atomizer of condensing unit；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere
Point, obtain titanium alloy powder of the grain size at 15-25 microns；
（4）When sintering is sintered alloy powder using discharge plasma sintering system, specific process conditions are as follows：
Sintering current type：DC pulse current；Sintering temperature：1200 DEG C~1400 DEG C；Soaking time：10-12min；Sintering pressure
Power：200-300MPa；Heating rate：60~100 DEG C/min；
（5）Heat treatment is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 890-900 DEG C, when heat preservation
Between be 20-25 minutes, water hardening 10-15 seconds；660 DEG C~670 DEG C guarantors are heated to the heating rate of 10-30 DEG C/min later
Warm 0.2-0.3 hours progress artificial aging processing, it is air-cooled later to obtain low elastic modulus implantation bone beta titanium alloy.
Comparative example 2
It is a kind of for being implanted into the beta titanium alloy of bone, it is characterised in that the alloying component is respectively according to weight percent：
Nb：21.8、Mo：11.2、Zr：5.8、Al：1.18、Cr：0.9、Ag：0.75、Fe：0.05、Ta： 0.2、Cu 0.08、V：
0.05、Sn： 0.05、Sc+La：0.01, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and can not
The impurity avoided is constituted, and Sc is 2: 1 with La mass ratioes.
Manufacturing method includes the following steps：
(1) raw material preparation：Nb, Mo, Ta, V in the form of low melting point intermediate alloy as raw material, Ti-Al intermediate alloys, among this
Al mass ratioes are 75% in alloy；Ti-Zr intermediate alloys, Zr mass ratioes are 55% in the intermediate alloy；Ti-Cr intermediate alloys, should
Cr mass ratioes are 49% in intermediate alloy；Ti-Fe intermediate alloys, Fe mass ratioes are 30% in the intermediate alloy； Ag、Cu、Sc、La、
Sn exists in the form of metal simple-substance；The main sources Ti are provided with titanium sponge, by adjusting raw material, it is contemplated that melting loss of elements,
The ultimate constituent is set to meet target titanium alloy product ingredient；
（2）Melting is sequentially added load weighted each raw material in medium frequency induction melting furnace by the sequence of fusing point from low to high, is taken out
Vacuum is to≤10Pa；It is then charged with inert gas, is 1 × 10 in inert gas pressure-2It is 100- that Pa, which protects melting, melting electric current,
110 A, smelting time are 25 ~ 30 min；Vacuumize refining after material completion is clear, after having refined by alloy melt be cast into
Under 200 ± 5 DEG C of environment in preheated mold, a diameter of 40mm is obtained, length is the metal bar of 40cm, as self-consuming electricity
Pole；
（3）Powder processed is by step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains meeting product cleanliness factor
Titanium alloy solution；Ensure that the degree of superheat is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid
Flow velocity rate is 10kg/min~15kg/min, and atomizing medium is nitrogen, and increasing atomizing gas pressure is 10MPa~15MPa, and atomization is quick
A diameter of 3mm~the 4mm of atomizer of condensing unit；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere
Point, obtain titanium alloy powder of the grain size at 15-25 microns；
（4）When sintering is sintered alloy powder using discharge plasma sintering system, specific process conditions are as follows：
Sintering current type：DC pulse current；Sintering temperature：1200 DEG C~1400 DEG C；Soaking time：10-12min；Sintering pressure
Power：200-300MPa；Heating rate：60~100 DEG C/min；
（5）Heat treatment is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 890-900 DEG C, when heat preservation
Between be 20-25 minutes, water hardening 10-15 seconds；660 DEG C~670 DEG C guarantors are heated to the heating rate of 10-30 DEG C/min later
Warm 0.2-0.3 hours progress artificial aging processing, it is air-cooled later to obtain low elastic modulus implantation bone beta titanium alloy.
Comparative example 3
It is a kind of for being implanted into the beta titanium alloy of bone, it is characterised in that the alloying component is respectively according to weight percent：Nb
22、Mo：11.5、Zr：6、Al：1.2、Cr：1.0、Ag：0.8、Fe：0.3、Ta：0.7、Cu 0.2、V：0.45、Sn：0.4、Sc+
La：0.08, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and inevitable impurity composition, Sc
It is 2: 1 with La mass ratioes.
Manufacturing method includes the following steps：
(1) raw material preparation：Nb, Mo, Ta, V in the form of low melting point intermediate alloy as raw material, Ti-Al intermediate alloys, among this
Al mass ratioes are 75% in alloy；Ti-Zr intermediate alloys, Zr mass ratioes are 55% in the intermediate alloy；Ti-Cr intermediate alloys, should
Cr mass ratioes are 49% in intermediate alloy；Ti-Fe intermediate alloys, Fe mass ratioes are 30% in the intermediate alloy； Ag、Cu、Sc、La、
Sn exists in the form of metal simple-substance；The main sources Ti are provided with titanium sponge, by adjusting raw material, it is contemplated that melting loss of elements,
The ultimate constituent is set to meet target titanium alloy product ingredient；
（2）Melting is sequentially added load weighted each raw material in medium frequency induction melting furnace by the sequence of fusing point from low to high, is taken out
Vacuum is to≤10Pa；It is then charged with inert gas, is 1 × 10 in inert gas pressure-2It is 100- that Pa, which protects melting, melting electric current,
110 A, smelting time are 25 ~ 30 min；Vacuumize refining after material completion is clear, after having refined by alloy melt be cast into
Under 200 ± 5 DEG C of environment in preheated mold, a diameter of 40mm is obtained, length is the metal bar of 40cm, as self-consuming electricity
Pole；
（3）Powder processed is by step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains meeting product cleanliness factor
Titanium alloy solution；Ensure that the degree of superheat is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid
Flow velocity rate is 3-5kg/min, and atomizing medium is nitrogen, and increasing atomizing gas pressure 5-8MPa is atomized the atomization of rapid condensation device
Nozzle diameter is 3mm~4mm；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere, obtain grain size and exist
25-30 microns of titanium alloy powder；
（4）When sintering is sintered alloy powder using discharge plasma sintering system, specific process conditions are as follows：
Sintering current type：DC pulse current；Sintering temperature：1200 DEG C~1400 DEG C；Soaking time：10-12min；Sintering pressure
Power：200-300MPa；Heating rate：60~100 DEG C/min；
（5）Heat treatment is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 890-900 DEG C, when heat preservation
Between be 20-25 minutes, water hardening 10-15 seconds；660 DEG C~670 DEG C guarantors are heated to the heating rate of 10-30 DEG C/min later
Warm 0.2-0.3 hours progress artificial aging processing, it is air-cooled later to obtain low elastic modulus implantation bone beta titanium alloy.
Comparative example 4
It is a kind of for being implanted into the beta titanium alloy of bone, it is characterised in that the alloying component is respectively according to weight percent：Nb
22、Mo：11.5、Zr：6、Al：1.2、Cr：1.0、Ag：0.8、Fe：0.3、Ta：0.7、Cu 0.2、V：0.45、Sn：0.4、Sc+
La：0.08, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and inevitable impurity composition, Sc
It is 2: 1 with La mass ratioes.
Manufacturing method includes the following steps：
(1) raw material preparation：Nb, Mo, Ta, V in the form of low melting point intermediate alloy as raw material, Ti-Al intermediate alloys, among this
Al mass ratioes are 75% in alloy；Ti-Zr intermediate alloys, Zr mass ratioes are 55% in the intermediate alloy；Ti-Cr intermediate alloys, should
Cr mass ratioes are 49% in intermediate alloy；Ti-Fe intermediate alloys, Fe mass ratioes are 30% in the intermediate alloy； Ag、Cu、Sc、La、
Sn exists in the form of metal simple-substance；The main sources Ti are provided with titanium sponge, by adjusting raw material, it is contemplated that melting loss of elements,
The ultimate constituent is set to meet target titanium alloy product ingredient；
（2）Melting is sequentially added load weighted each raw material in medium frequency induction melting furnace by the sequence of fusing point from low to high, is taken out
Vacuum is to≤10Pa；It is then charged with inert gas, is 1 × 10 in inert gas pressure-2It is 100- that Pa, which protects melting, melting electric current,
110 A, smelting time are 25 ~ 30 min；Vacuumize refining after material completion is clear, after having refined by alloy melt be cast into
Under 200 ± 5 DEG C of environment in preheated mold, a diameter of 40mm is obtained, length is the metal bar of 40cm, as self-consuming electricity
Pole；
（3）Powder processed is by step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains meeting product cleanliness factor
Titanium alloy solution；Ensure that the degree of superheat is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid
Flow velocity rate is 10kg/min~15kg/min, and atomizing medium is nitrogen, and increasing atomizing gas pressure is 10MPa~15MPa, and atomization is quick
A diameter of 3mm~the 4mm of atomizer of condensing unit；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere
Point, obtain titanium alloy powder of the grain size at 15-25 microns；
（4）When sintering is sintered alloy powder using discharge plasma sintering system, specific process conditions are as follows：
Sintering current type：DC pulse current；Sintering temperature：800 DEG C~1100 DEG C；Soaking time：5-7min；Sintering pressure：
100-180MPa；Heating rate：40-60℃/min；
（5）Heat treatment is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 890-900 DEG C, when heat preservation
Between be 20-25 minutes, water hardening 10-15 seconds；660 DEG C~670 DEG C guarantors are heated to the heating rate of 10-30 DEG C/min later
Warm 0.2-0.3 hours progress artificial aging processing, it is air-cooled later to obtain low elastic modulus implantation bone beta titanium alloy.
Comparative example 5
It is a kind of for being implanted into the beta titanium alloy of bone, it is characterised in that the alloying component is respectively according to weight percent：Nb
22、Mo：11.5、Zr：6、Al：1.2、Cr：1.0、Ag：0.8、Fe：0.3、Ta：0.7、Cu 0.2、V：0.45、Sn：0.4、Sc+
La：0.08, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and inevitable impurity composition, Sc
It is 2: 1 with La mass ratioes.
Manufacturing method includes the following steps：
(1) raw material preparation：Nb, Mo, Ta, V in the form of low melting point intermediate alloy as raw material, Ti-Al intermediate alloys, among this
Al mass ratioes are 75% in alloy；Ti-Zr intermediate alloys, Zr mass ratioes are 55% in the intermediate alloy；Ti-Cr intermediate alloys, should
Cr mass ratioes are 49% in intermediate alloy；Ti-Fe intermediate alloys, Fe mass ratioes are 30% in the intermediate alloy； Ag、Cu、Sc、La、
Sn exists in the form of metal simple-substance；The main sources Ti are provided with titanium sponge, by adjusting raw material, it is contemplated that melting loss of elements,
The ultimate constituent is set to meet target titanium alloy product ingredient；
（2）Melting is sequentially added load weighted each raw material in medium frequency induction melting furnace by the sequence of fusing point from low to high, is taken out
Vacuum is to≤10Pa；It is then charged with inert gas, is 1 × 10 in inert gas pressure-2It is 100- that Pa, which protects melting, melting electric current,
110 A, smelting time are 25 ~ 30 min；Vacuumize refining after material completion is clear, after having refined by alloy melt be cast into
Under 200 ± 5 DEG C of environment in preheated mold, a diameter of 40mm is obtained, length is the metal bar of 40cm, as self-consuming electricity
Pole；
（3）Powder processed is by step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains meeting product cleanliness factor
Titanium alloy solution；Ensure that the degree of superheat is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid
Flow velocity rate is 10kg/min~15kg/min, and atomizing medium is nitrogen, and increasing atomizing gas pressure is 10MPa~15MPa, and atomization is quick
A diameter of 3mm~the 4mm of atomizer of condensing unit；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere
Point, obtain titanium alloy powder of the grain size at 15-25 microns；
（4）When sintering is sintered alloy powder using discharge plasma sintering system, specific process conditions are as follows：
Sintering current type：DC pulse current；Sintering temperature：1200 DEG C~1400 DEG C；Soaking time：10-12min；Sintering pressure
Power：200-300MPa；Heating rate：60~100 DEG C/min；
（5）Heat treatment is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 860-880 DEG C, when heat preservation
Between be 10-15 minutes, water hardening 10-15 seconds；560 DEG C~650 DEG C guarantors are heated to the heating rate of 10-30 DEG C/min later
Warm 0.5-0.6 hours progress artificial aging processing, it is air-cooled later to obtain low elastic modulus implantation bone beta titanium alloy.
Comparative example 6
It is a kind of for being implanted into the beta titanium alloy of bone, it is characterised in that the alloying component is respectively according to weight percent：Nb
22、Mo：11.5、Zr：6、Al：1.2、Cr：1.0、Ag：0.8、Fe：0.3、Ta：0.7、Cu 0.2、V：0.45、Sn：0.4、Sc：
0.08, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and inevitable impurity composition.
Manufacturing method includes the following steps：
(1) raw material preparation：Nb, Mo, Ta, V in the form of low melting point intermediate alloy as raw material, Ti-Al intermediate alloys, among this
Al mass ratioes are 75% in alloy；Ti-Zr intermediate alloys, Zr mass ratioes are 55% in the intermediate alloy；Ti-Cr intermediate alloys, should
Cr mass ratioes are 49% in intermediate alloy；Ti-Fe intermediate alloys, Fe mass ratioes are 30% in the intermediate alloy； Ag、Cu、Sc、La、
Sn exists in the form of metal simple-substance；The main sources Ti are provided with titanium sponge, by adjusting raw material, it is contemplated that melting loss of elements,
The ultimate constituent is set to meet target titanium alloy product ingredient；
（2）Melting is sequentially added load weighted each raw material in medium frequency induction melting furnace by the sequence of fusing point from low to high, is taken out
Vacuum is to≤10Pa；It is then charged with inert gas, is 1 × 10 in inert gas pressure-2It is 100- that Pa, which protects melting, melting electric current,
110 A, smelting time are 25 ~ 30 min；Vacuumize refining after material completion is clear, after having refined by alloy melt be cast into
Under 200 ± 5 DEG C of environment in preheated mold, a diameter of 40mm is obtained, length is the metal bar of 40cm, as self-consuming electricity
Pole；
（3）Powder processed is by step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains meeting product cleanliness factor
Titanium alloy solution；Ensure that the degree of superheat is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid
Flow velocity rate is 10kg/min~15kg/min, and atomizing medium is nitrogen, and increasing atomizing gas pressure is 10MPa~15MPa, and atomization is quick
A diameter of 3mm~the 4mm of atomizer of condensing unit；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere
Point, obtain titanium alloy powder of the grain size at 15-25 microns；
（4）When sintering is sintered alloy powder using discharge plasma sintering system, specific process conditions are as follows：
Sintering current type：DC pulse current；Sintering temperature：1200 DEG C~1400 DEG C；Soaking time：10-12min；Sintering pressure
Power：200-300MPa；Heating rate：60~100 DEG C/min；
（5）Heat treatment is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 890-900 DEG C, when heat preservation
Between be 20-25 minutes, water hardening 10-15 seconds；660 DEG C~670 DEG C guarantors are heated to the heating rate of 10-30 DEG C/min later
Warm 0.2-0.3 hours progress artificial aging processing, it is air-cooled later to obtain low elastic modulus implantation bone beta titanium alloy.
Performance detection is carried out in the following manner to embodiment 1-4, comparative example 1-4 products obtained therefroms：
1, Mechanics Performance Testing
Mechanical property (intensity and elongation percentage, Young's modulus) in testing example and comparative example, correlated results is shown in Table 1.
2, anti-microbial property, corrosion resistance detection
According to " JIS Z 2801-2000《Antibacterial fabricated product-antibiotic property test method and antibacterial effect》、GB/T21510-
2008《Nano inorganic material anti-microbial property detection method》" etc. standards regulation, alloy is to common bacteria shown in quantitative test table 1
Sterilizing rate after (Escherichia coli, staphylococcus aureus etc.) effect.Anti-microbial property testing result is shown in Table 2, wherein sterilizing rate
Calculation formula is：Sterilizing rate (%)=[(control sample viable count-antibacterial titanium alloy viable count)/control sample viable count] ×
100, control sample viable count is that the viable count after Bacteria Culture is carried out on 1 sample of comparative example, and antibacterial titanium alloy viable count refers to β
The viable count after Bacteria Culture is carried out on Type Titanium Alloy.
The variation of pitting potential in being detected according to electrochemical corrosion performance can reflect material microbial corrosion resistance ability
Just.Corrosion resisting property detection is carried out to the titanium alloy of embodiment and comparative example, that is, uses stainless steel pitting potential measurement method (state
Family's standard：GB/T 17899-1999) anodic polarization curves are obtained, its corrosion resisting property is measured, test result is shown in Table 2.
Table 1
| Type | Yield strength（MPa） | Tensile strength（MPa） | Elongation percentage（%） | Young's modulus（GPa） |
| Embodiment 1 | ≥1000 | ≥1100 | ≥20 | ≤70 |
| Embodiment 2 | ≥1100 | ≥1190 | ≥18.4 | ≤57.1 |
| Embodiment 3 | ≥1150 | ≥1250 | ≥18 | ≤50.4 |
| Comparative example 1 | ≥630 | ≥740 | ≥14 | ≤80 |
| Comparative example 2 | ≥710 | ≥850 | ≥13.5 | ≤67 |
| Comparative example 3 | ≥930 | ≥1020 | ≥15 | ≤63.5 |
| Comparative example 4 | ≥1000 | ≥1100 | ≥15.5 | ≤60.4 |
| Comparative example 5 | ≥1020 | ≥1120 | ≥16 | ≤68 |
| Comparative example 6 | ≥1100 | ≥1200 | ≥17.5 | ≤64 |
Table 2
| Type | Anti-microbial property（Sterilizing rate, %） | Corrosion resistance（Spot corrosion point, mv） |
| Embodiment 1 | ≥96 | ≥940 |
| Embodiment 2 | ≥98 | ≥990 |
| Embodiment 3 | ≥99 | ≥1040 |
| Comparative example 1 | ≥51 | ≥680 |
| Comparative example 2 | ≥67 | ≥730 |
| Comparative example 3 | ≥74 | ≥770 |
| Comparative example 4 | ≥85 | ≥860 |
| Comparative example 5 | ≥88 | ≥880 |
| Comparative example 6 | ≥92 | ≥920 |
Although above the present invention is described in detail with a general description of the specific embodiments, in this hair
On the basis of bright, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore, exist
Without departing from these modifications or improvements on the basis of spirit of that invention, the scope of protection of present invention is belonged to.
Claims (9)
1. a kind of for being implanted into the beta titanium alloy of bone, it is characterised in that the alloying component is respectively according to weight percent：
Nb：21-22、Mo：10.5-11.5、Zr：5-6、Al：1.1-1.2、Cr：0.8-1.0、Ag：0.7-0.8、Fe：0.2-0.3、Ta：
0.4-0.7、Cu 0.15-0.2、V：0.3~0.45, Sn：0.2~0.4, Sc+La：0.05-0.08、O≤0.05、H≤0.01、C
≤ 0.02, N≤0.01%, remainder are Ti and inevitable impurity is constituted, and Sc is 2: 1 with La mass ratioes, thermally treated
Average crystallite particle diameter is 15-25 μm in the beta titanium alloy formed afterwards；Yield strength 1000-1150MPa, tensile strength 1100-
1250MPa, elongation percentage 18-20%, Young's modulus 50-70GPa, primary alpha phase volume fraction are 18-21%, grain size of α phase 4-
6 microns, secondaryαphase volume fraction is 17-19%, and secondaryαphase size is 0.5-1.5 microns.
2. a kind of beta titanium alloy for being implanted into bone as described in claim 1, it is characterised in that the alloying component according to
Weight percent is respectively：Nb：21-21.8、Mo：10.5-11.2、Zr：5-5.8、Al：1.1-1.18、Cr：0.8-0.9、Ag：
0.7-0.75、Fe：0.2-0.25、Ta：0.4-0.6、Cu 0.15-0.18、V：0.35~0.45, Sn：0.25~0.35, Sc+
La：0.06-0.07, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder are Ti and inevitable impurity structure
At Sc is 2: 1 with La mass ratioes.
3. a kind of beta titanium alloy for being implanted into bone as claimed in claim 2, it is characterised in that the alloying component according to
Weight percent is respectively：Nb：21、Mo：10.5、Zr：5、Al：1.1、Cr：0.8、Ag：0.7、Fe：0.2、Ta：0.4、Cu
0.15、V：0.3、Sn：0.2、Sc+La：0.05, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder be Ti and
Inevitable impurity is constituted, and Sc is 2: 1 with La mass ratioes.
4. a kind of beta titanium alloy for being implanted into bone as claimed in claim 2, it is characterised in that the alloying component according to
Weight percent is respectively：Nb：21.8、Mo：11.2、Zr：5.8、Al：1.18、Cr：0.9、Ag：0.75、Fe：0.25、Ta：
0.6、Cu 0.18、V： 0.45、Sn： 0.35、Sc+La：0.07, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, surplus
Remaining part is divided into Ti and inevitable impurity is constituted, and Sc is 2: 1 with La mass ratioes.
5. a kind of beta titanium alloy for being implanted into bone as claimed in claim 2, it is characterised in that the alloying component according to
Weight percent is respectively：Nb 22、Mo：11.5、Zr：6、Al：1.2、Cr：1.0、Ag：0.8、Fe：0.3、Ta：0.7、Cu
0.2、V：0.45、Sn：0.4、Sc+La：0.08, O≤0.05, H≤0.01, C≤0.02, N≤0.01%, remainder be Ti and
Inevitable impurity is constituted, and Sc is 2: 1 with La mass ratioes.
6. the manufacturing method of the beta titanium alloy described in claim any one of 1-5 for being implanted into bone, which is characterized in that including
Following steps：
(1) raw material preparation：Nb, Mo, Ta, V in the form of low melting point intermediate alloy as raw material, Ti-Al intermediate alloys, in this
Between in alloy Al mass ratioes be 75%；Ti-Zr intermediate alloys, Zr mass ratioes are 55% in the intermediate alloy；Ti-Cr intermediate alloys,
Cr mass ratioes are 49% in the intermediate alloy；Ti-Fe intermediate alloys, Fe mass ratioes are 30% in the intermediate alloy； Ag、Cu、Sc、
La, Sn exist in the form of metal simple-substance；The main sources Ti are provided with titanium sponge, by adjusting raw material, it is contemplated that first biscuiting
Damage, makes the ultimate constituent meet target titanium alloy product ingredient；
（2）Melting is sequentially added load weighted each raw material in medium frequency induction melting furnace by the sequence of fusing point from low to high, is taken out
Vacuum is to≤10Pa；It is then charged with inert gas, is 1 × 10 in inert gas pressure-2It is 100- that Pa, which protects melting, melting electric current,
110 A, smelting time are 25 ~ 30 min；Vacuumize refining after material completion is clear, after having refined by alloy melt be cast into
Under 200 ± 5 DEG C of environment in preheated mold, a diameter of 40mm is obtained, length is the metal bar of 40cm, as electric from great formula
Pole；
（3）Powder processed is by step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains meeting product cleanliness factor
Titanium alloy solution；Ensure that the degree of superheat is 180-200 DEG C, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid
Flow velocity rate is 10kg/min~15kg/min, and atomizing medium is nitrogen, and increasing atomizing gas pressure is 10MPa~15MPa, and atomization is quick
A diameter of 3mm~the 4mm of atomizer of condensing unit；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere
Point, obtain titanium alloy powder of the grain size at 15-25 microns；
（4）When sintering is sintered alloy powder using discharge plasma sintering system, specific process conditions are as follows：
Sintering current type：DC pulse current；Sintering temperature：1200 DEG C~1400 DEG C；Soaking time：10-12min；Sintering pressure
Power：200-300MPa；Heating rate：60~100 DEG C/min；
（5）Heat treatment is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 890-900 DEG C, when heat preservation
Between be 20-25 minutes, water hardening 10-15 seconds；660 DEG C~670 DEG C guarantors are heated to the heating rate of 10-30 DEG C/min later
Warm 0.2-0.3 hours progress artificial aging processing, it is air-cooled later to obtain low elastic modulus implantation bone beta titanium alloy.
7. the manufacturing method of the beta titanium alloy for being implanted into bone as claimed in claim 6, it is characterised in that：Step（3）Powder processed
By step（2）Self-consuming electrode later carries out remelting, refines, skims, and obtains the titanium alloy solution for meeting product cleanliness factor；It protects
It is 180-200 DEG C to demonstrate,prove the degree of superheat, carries out powder by atomization later, the specific process parameter of powder by atomization is：Liquid flowing rate is 13kg/
Min, atomizing medium are nitrogen, and the atomizer of increasing atomizing gas pressure 12.5MPa, atomization rapid condensation device are a diameter of
3.5mm；It waits for that powder is completely cooling after atomization, is sieved in nitrogen protection atmosphere, obtain titanium alloy of the grain size at 20 microns
Powder.
8. the manufacturing method of the beta titanium alloy for being implanted into bone as claimed in claim 6, it is characterised in that：Step（4）Using
When discharge plasma sintering system is sintered alloy powder, specific process conditions are as follows：Sintering current type：Direct current
Pulse current；Sintering temperature：1300℃；Soaking time：11min；Sintering pressure：250MPa；Heating rate：80℃/min.
9. the manufacturing method of the beta titanium alloy for being implanted into bone as claimed in claim 6, it is characterised in that：Step（5）At heat
Reason is to be heat-treated within 100Pa in vacuum degree, and the temperature of solution treatment is 900 DEG C, and soaking time is 25 minutes, water cooling
Quenching 15 seconds；665 DEG C of heat preservations are heated to the heating rate of 20 DEG C/min later and carry out artificial aging processing within 0.2 hour, later
It is air-cooled to obtain low elastic modulus implantation bone beta titanium alloy.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111235430A (en) * | 2020-03-02 | 2020-06-05 | 北京理工大学 | Ti-Al alloy shaped charge liner material and powder metallurgy preparation method thereof |
| CN111270102A (en) * | 2020-03-25 | 2020-06-12 | 中国航空制造技术研究院 | Near β ultrahigh-strength titanium alloy with tensile strength of more than 1450MPa and preparation method thereof |
| CN113897512A (en) * | 2021-09-15 | 2022-01-07 | 东北大学 | Iron-containing antibacterial titanium alloy and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490421A (en) * | 2003-08-08 | 2004-04-21 | 西北有色金属研究院 | Beta type titanium alloy for vascular stent |
| CN103649350A (en) * | 2012-05-30 | 2014-03-19 | 韩国机械研究院 | Beta titanium alloy with low elasticity and high strength |
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2018
- 2018-04-20 CN CN201810356386.8A patent/CN108456805A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1490421A (en) * | 2003-08-08 | 2004-04-21 | 西北有色金属研究院 | Beta type titanium alloy for vascular stent |
| CN103649350A (en) * | 2012-05-30 | 2014-03-19 | 韩国机械研究院 | Beta titanium alloy with low elasticity and high strength |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111235430A (en) * | 2020-03-02 | 2020-06-05 | 北京理工大学 | Ti-Al alloy shaped charge liner material and powder metallurgy preparation method thereof |
| CN111270102A (en) * | 2020-03-25 | 2020-06-12 | 中国航空制造技术研究院 | Near β ultrahigh-strength titanium alloy with tensile strength of more than 1450MPa and preparation method thereof |
| CN111270102B (en) * | 2020-03-25 | 2021-09-10 | 中国航空制造技术研究院 | Near-beta ultrahigh-strength titanium alloy with tensile strength of more than 1450MPa and preparation method thereof |
| CN113897512A (en) * | 2021-09-15 | 2022-01-07 | 东北大学 | Iron-containing antibacterial titanium alloy and preparation method thereof |
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