CN108893628A - A kind of low elastic modulus erosion resistant titanium alloy and preparation method thereof - Google Patents

A kind of low elastic modulus erosion resistant titanium alloy and preparation method thereof Download PDF

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CN108893628A
CN108893628A CN201810875259.9A CN201810875259A CN108893628A CN 108893628 A CN108893628 A CN 108893628A CN 201810875259 A CN201810875259 A CN 201810875259A CN 108893628 A CN108893628 A CN 108893628A
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titanium alloy
alloy
elastic modulus
low elastic
melting
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CN108893628B (en
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刘日平
刘曙光
周奕年
马明臻
张星
景勤
张新宇
罗雷
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China Polytron Technologies Inc Qinhuangdao Polytron Technologies Inc
Yanshan University
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China Polytron Technologies Inc Qinhuangdao Polytron Technologies Inc
Yanshan University
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C14/00Alloys based on titanium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/02Making non-ferrous alloys by melting
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C16/00Alloys based on zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/002Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working by rapid cooling or quenching; cooling agents used therefor
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing 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
    • C22F1/18High-melting or refractory metals or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing 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
    • C22F1/18High-melting or refractory metals or alloys based thereon
    • C22F1/183High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16Changing 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
    • C22F1/18High-melting or refractory metals or alloys based thereon
    • C22F1/186High-melting or refractory metals or alloys based thereon of zirconium or alloys based thereon

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Abstract

The present invention provides a kind of low elastic modulus erosion resistant titanium alloy and preparation method thereof, and based on mass content, titanium alloy includes the Ti of Al 5.5~6.5%, Nb 6.5~7.5%, Zr 5~45%, Ta≤0.5% and surplus.The content of strict control each element of the present invention, promotes the mechanical property of titanium alloy, properly increases alloy corrosion resistance energy;Meanwhile, it is capable to obtain elasticity modulus lower α " martensitic phase, there is performance to supply and castering action medical Ti alloy.The experimental results showed that the elasticity modulus of the modular ratio conventional titanium alloy of low elastic modulus erosion resistant titanium alloy provided by the invention, which reduces amplitude, is up to 18%.

Description

A kind of low elastic modulus erosion resistant titanium alloy and preparation method thereof
Technical field
The present invention relates to titanium alloy technical field, in particular to a kind of low elastic modulus erosion resistant titanium alloy and its preparation side Method.
Background technique
Titanium alloy has a wide range of applications advantage with a series of advantages such as its high specific strength, high ratio modulus, corrosion-resistant, The numerous areas such as ocean engineering, aerospace, biomedicine, metallurgy, chemical industry, light industry are paid attention to.
As titanium or titanium alloy is by wide hair application, the nowadays continuous development of medicine and the continuous concern to human health, life Object medical domain proposes more stringent requirement to the performance of titanium alloy, and conventional titanium alloy is in elasticity modulus and corrosion-resistant aspect Be difficult to meet the requirement of body implanting material instantly, as body implanting material, should have lower elasticity modulus, avoid due to Stress-shielding effect and the skeleton damage generated and generation situations such as osteoporosis, should also have excellent corrosion resistance Can, to meet the normal service situation under human body fluid environment for a long time.
Summary of the invention
In view of this, the purpose of the present invention is to provide a kind of low elastic modulus erosion resistant titanium alloys and preparation method thereof. Titanium alloy provided by the invention has good corrosion resistance, and elasticity modulus is low, meets body implanting material to springform The requirement of amount and corrosion resistance.
The present invention provides a kind of low elastic modulus erosion resistant titanium alloys, based on mass content, including Al 5.5~ 6.5%, the Ti of Nb 6.5~7.5%, Zr 5~45%, Ta≤0.5% and surplus.
Preferably, the low elastic modulus erosion resistant titanium alloy includes Al 5.7~6.3%, Nb 6.7~7.3%, Zr 15~35%, the Ti of Ta0.1~0.4% and surplus.
Preferably, the tissue of the low elastic modulus erosion resistant titanium alloy includes metastable β phase, α " martensitic phase and α ' geneva Body phase.
The present invention provides the preparation methods of the low elastic modulus erosion resistant titanium alloy described in above-mentioned technical proposal, including with Lower step:
(1) cast alloy base will be obtained after alloy raw material melting;
(2) the cast alloy ingot for obtaining the step (1) carries out solution treatment, obtains solid solution state base;
(3) the solid solution state base for obtaining the step (2) carries out cooling after ageing treatment, and it is corrosion-resistant to obtain low elastic modulus Titanium alloy.
Preferably, melting is vacuum arc melting in the step (1), the temperature of the vacuum arc melting is 2000~ 2500℃。
Preferably, melting is repeated 5 times or more in the step (1).
Preferably, the holding temperature of solution treatment is 800~950 DEG C in the step (2), the soaking time of solution treatment For 60~90min, the type of cooling of solution treatment is water quenching.
Preferably, the temperature of ageing treatment is 600~700 DEG C in the step (3), and the time of ageing treatment is 3~4h.
Preferably, in the insulating process of step (2) solution treatment and step (3) ageing treatment independently in protection gas It is carried out under atmosphere.
The present invention provides a kind of low elastic modulus erosion resistant titanium alloys, based on mass content, including Al5.5~6.5%, Nb 6.5~7.5%, Zr 5~45%, Ta≤0.5% and surplus Ti.The content of strict control each element of the present invention is promoted The mechanical property of titanium alloy, the addition of β phase stable element Nb can reduce titanium alloy phase transition temperature, adjustment alloy phase composition, Phase content enhances the harden ability and hot-working character of alloy, can also properly increase alloy corrosion resistance energy;Zr element adds simultaneously Add, effectively enhances the corrosion resistance of alloy, moreover it is possible to it is appropriate to reduce alloy phase transition temperature, to obtain springform by heat treatment Lower α " martensitic phase is measured, has performance to supply and castering action medical Ti alloy.
The experimental results showed that the modular ratio conventional titanium alloy of low elastic modulus erosion resistant titanium alloy provided by the invention Elasticity modulus reduce amplitude be up to 18%.
Detailed description of the invention
Fig. 1 is the metallographic optical microscopy map of titanium alloy made from embodiment 1;
Fig. 2 is the metallographic optical microscopy map of titanium alloy made from embodiment 2;
Fig. 3 is the metallographic optical microscopy map of titanium alloy made from embodiment 3;
Fig. 4 is the metallographic optical microscopy map of titanium alloy made from embodiment 4;
Fig. 5 is the metallographic optical microscopy map of titanium alloy made from embodiment 5;
Fig. 6 is tensile property of the present invention test tensile sample dimensional drawing.
Specific embodiment
The present invention provides the present invention provides a kind of low elastic modulus erosion resistant titanium alloys, based on mass content, including Al 5.5~6.5%, Nb 6.5~7.5%, Zr 5~45%, Ta≤0.5% and surplus Ti.
Low elastic modulus erosion resistant titanium alloy provided by the invention, based on mass content, including Al5.5~6.5%, preferably It is 5.7~6.3%, more preferably 6.1~6.3%.In the present invention, the Al is a kind of cheap but to titanium alloy strengthening effect Apparent α phase stable element, can greatly improve the specific strength of titanium alloy.
Low elastic modulus erosion resistant titanium alloy provided by the invention, based on mass content, including Nb6.5~7.5%, preferably It is 6.7~7.3%, more preferably 6.9~7.1%.In the present invention, the addition of β phase stable element Nb can reduce titanium alloy Phase transition temperature adjusts alloy phase composition, phase content, enhances the harden ability and hot-working character of alloy, can also properly increase conjunction Golden corrosion resistance, and it is nontoxic to the human body.
Low elastic modulus erosion resistant titanium alloy provided by the invention, based on mass content, including Zr 5~45%, preferably 15~35%, further preferably 20~30%, more preferably 22~28%.In the present invention, Zr and Ti belong to congeners, The physicochemical property of the two is close, and Zr and Ti can be infinitely dissolved, and the Zr element being dissolved into Ti matrix plays solution strengthening Effect;Simultaneously because the addition of Zr element can cause distortion of lattice, these defects be will lead in nucleation process, and nucleation point increases More, the density of forming core increases, play the role of crystal grain refinement to;The addition of Zr is remarkably improved the corrosion resistance of titanium alloy, makes it Inoic acid, alkali, salt medium in have excellent anti-corrosion capability, and the biocompatibility of Zr is excellent;Therefore, Zr element Addition, can not only promote the mechanical property of alloy by solution strengthening, refined crystalline strengthening mechanism, and optimized alloy microscopic structure increases The corrosion resistance of strong alloy, moreover it is possible to it is appropriate to reduce alloy phase transition temperature, it is lower to obtain elasticity modulus by heat treatment α " martensitic phase has performance to supply and castering action medical Ti alloy.
Low elastic modulus erosion resistant titanium alloy provided by the invention further includes Ta≤0.5%, and preferably 0.1~0.4%, into One step is preferably 0.2~0.3%.In the present invention, the addition of a small amount of Ta can also suitably promote alloy corrosion resistance energy and not Compound phase can be formed with matrix, avoid the generation of crisp phase, endanger alloy mechanical property.
Low elastic modulus erosion resistant titanium alloy provided by the invention, based on mass content, in addition to above-mentioned each element, including it is remaining The Ti of amount.
In the present invention, the tissue of the low elastic modulus erosion resistant titanium alloy be preferably metastable β phase, α " martensitic phase and α ' martensitic phase.In the present invention, metastable β phase is a kind of typical phase in titanium alloy, belongs to high-temperature-phase, therefore referred to as metastable Phase;In the present invention, the volume content of metastable β phase is preferably 10~50% in the titanium alloy;α ' geneva in the titanium alloy The volume content of body phase is preferably 50~90%, also contains a small amount of α " martensitic phase;Metastable β phase, α ' martensitic phase and α " horse The sum of volume fraction of family name's body phase is 100%.
The present invention also provides the preparation methods of the low elastic modulus erosion resistant titanium alloy described in above-mentioned technical proposal, including Following steps:
(1) cast alloy base will be obtained after alloy raw material melting;
(2) alloy pig for obtaining the step (1) carries out solution treatment, obtains solid solution state base;
(3) the solid solution state base for obtaining the step (2) carries out cooling after ageing treatment, and it is corrosion-resistant to obtain low elastic modulus Titanium alloy.
The present invention will obtain cast alloy base after alloy raw material melting.The present invention is to the type of the alloy raw material without spy Different restriction uses the alloy raw material of titanium alloy smelting well known to those skilled in the art can obtain the titanium alloy of target components Subject to.In the present invention, the alloy raw material preferably includes titanium sponge, sponge zirconium, fine aluminium, pure niobium and pure tantalum.The present invention is to each The ratio of kind alloy raw material does not have special restriction, and final alloying component can be made to meet the requirements.
In the present invention, the melting is preferably vacuum arc melting, and the temperature of the vacuum arc melting is preferably 2000~2500 DEG C, more preferably 2200~2400 DEG C, most preferably 2250~2300 DEG C;The time of the melting is preferably 3 ~5min, more preferably 4min.In the present invention, the vacuum degree of the vacuum arc melting is preferably 0.04~0.05MPa, It is carried out under the conditions of argon gas.When using vacuum arc melting, vacuum degree in furnace chamber is preferably first evacuated to 9 × 10 by the present invention-3Pa with Under, then it is passed through argon gas;The intake of the argon gas is to meet the amount of electric arc melting ionized gas.The present invention is to institute The specific embodiment for stating vacuum arc melting does not have particular/special requirement, using well-known to those skilled in the art.This hair It is bright using first vacuumize be passed through argon gas again by the way of can be avoided Ti and Zr first in the event of high temperatures, it is a large amount of to inhale hydrogen oxygen uptakes and inhale Nitrogen aoxidizes, moreover it is possible to provide ionized gas for electric arc melting.
5 times or more, further preferably 6~10 times are repeated in melting in the present invention, and cast alloy base is obtained after melting. In the present invention, when melting is repeated, progress of the melting preferably in vacuum arc melting furnace;Specifically:It will be golden Belong to raw material and carry out melting in arc-melting furnace, obtains melting liquid;Then cooling obtains slab, then is melted after overturning slab Refining, obtain melting liquid again, again cool down melting liquid, the slab obtained, with this 5 times or more repeatedly, it is ensured that obtained as cast condition base at Divide uniform.
The present invention in melting, grow up to the preferential forming core of β phase during Solid State Transformation by melting liquid, obtains β phase green body, is The phase transition of subsequent solution treatment and ageing treatment provides basis.
Before the melting, the alloy raw material is preferably cleaned by ultrasonic by the present invention;The present invention is to the ultrasonic cleaning Specific embodiment there is no particular/special requirement, using well-known to those skilled in the art.
After obtaining cast alloy base, the cast alloy base is carried out solution treatment by the present invention, obtains solid solution state base.At this In invention, the holding temperature of the solution treatment is preferably 800~950 DEG C, and further preferably 820~920 DEG C, 850~900 ℃.In the present invention, the soaking time of the solution treatment is preferably 60~90min, further preferably 65~85min, more Preferably 70~80min.In the present invention, the type of cooling of the solution treatment is preferably water quenching.The present invention is to the solid solution The specific embodiment of processing does not have particular/special requirement, using embodiment well-known to those skilled in the art.In this hair In bright, the insulating process of the solution treatment is preferably carried out under protective atmosphere, and the protective atmosphere is specially argon gas protection gas Atmosphere.In the present invention, the solution treatment retains metastable β phase as much as possible, to be changed into tool in subsequent ageing process There are the α ' martensitic phase of strengthening effect and α " martensitic phase to provide basic phase, drops low-alloyed springform so as to improve alloy strength Amount.
After obtaining solid solution state base, the present invention will be cooling after solid solution state base progress ageing treatment, obtains low elastic modulus Erosion resistant titanium alloy.In the present invention, the temperature of the ageing treatment is preferably 600~700 DEG C, further preferably 620~ 680 DEG C, more preferably 650~660 DEG C.In the present invention, the time of the ageing treatment is preferably 3~4h, further preferably For 3.5h.For the present invention in the ageing process, metastable β phase decomposition is α " martensitic phase, and makes α " Martensitic phase transformation It is α ' mutually with α phase, α ', which meets, also will continue to be converted into α phase, and final major part is decomposed into α phase, and it might have a small amount of α ' and mutually remain, There are also original β phases;The reply of α ' martensitic phase and α " martensitic phase is set to grow up simultaneously, to drop low-alloyed elasticity modulus and improve Alloy mechanical property and processing performance.
After ageing treatment, aging state alloy is preferably removed surface scale by the present invention, and it is corrosion-resistant to obtain low elastic modulus Titanium alloy.Present invention preferably employs the modes of polishing to remove surface scale.
In order to further illustrate the present invention, low elastic modulus corrosion-resistant titanium provided by the invention is closed below with reference to embodiment Gold and preparation method thereof is described in detail, but they cannot be interpreted as limiting the scope of the present invention.
Embodiment 1
By alloying component Ti-5Zr-6.5Al-6.5Nb-0.1Ta (mass percent) ingredient, technical grade titanium sponge is weighed 81.9g, sponge zirconium 5g, fine aluminium 6.5g, pure niobium 6.5g and pure tantalum 0.1g are dipped in dehydrated alcohol, are air-dried, are set after ultrasonic cleaning In the water jacketed copper crucible for entering non-consumable vacuum arc melting furnace, the vacuum degree in furnace chamber will be extracted into 8 × 10-3Pa is hereinafter, electric arc is molten After high-purity argon gas is filled with before refining as protection gas, arc temperature is about 2500 DEG C or so when each melting, and smelting time is about 3 Minute or so, it is cooling after each melting to obtain ingot casting, then overturning processing is carried out to ingot casting and carries out melting, it is poured with this melting- Casting ingot casting melt back and overturning ingot casting are more than six times to guarantee that the ingot casting ingredient finally obtained is uniform.
It then takes out alloy cast ingot and is put into vacuum/atmosphere tube type furnace (limited public affairs of the Tianjin SK-G06143 middle ring experimental electric furnace Department) in, solution treatment is carried out after being filled with protection gas argon gas:In 950 DEG C of heat preservation 60min, then from tube furnace take out and it is rapid Carry out water quenching.
Then the alloy cast ingot after solution treatment is placed again into vacuum/atmosphere tube type furnace and carries out ageing treatment, is controlled Aging temp is 700 DEG C, and soaking time 180min cools to room temperature with the furnace later.
It is taken out after alloy pig is completely cooling, careful polishes off the oxide layer of alloy ingot surface, and is cleaned and air-dried, Obtain low elastic modulus erosion resistant titanium alloy.
Embodiment 2
By alloying component Ti-15Zr-6.3Al-6.7Nb-0.2Ta (mass percent) ingredient, technical grade titanium sponge is weighed 71.8g, sponge zirconium 15g, fine aluminium 6.3g, pure niobium 6.7g and pure tantalum 0.2g are dipped in dehydrated alcohol, are air-dried, are set after ultrasonic cleaning In the water jacketed copper crucible for entering non-consumable vacuum arc melting furnace, the vacuum degree in furnace chamber will be extracted into 8 × 10-3Pa is hereinafter, electric arc is molten After high-purity argon gas is filled with before refining as protection gas, arc temperature is about 2500 DEG C or so when each melting, and smelting time is about 3 Minute or so, it is cooling after each melting to obtain ingot casting, then overturning processing is carried out to ingot casting and carries out melting, it is poured with this melting- It casts ingot casting melt back and overturns ingot casting six times to guarantee that the ingot casting ingredient finally obtained is uniform.
It then takes out alloy cast ingot and is put into vacuum/atmosphere tube type furnace (limited public affairs of the Tianjin SK-G06143 middle ring experimental electric furnace Department) in, solution treatment is carried out after being filled with protection gas argon gas:In 910 DEG C of heat preservation 70min, then from tube furnace take out and it is rapid Carry out water quenching.
Then the alloy cast ingot after solution treatment is placed again into vacuum/atmosphere tube type furnace and carries out ageing treatment, is controlled Aging temp is 680 DEG C, and soaking time 190min cools to room temperature with the furnace later.
It is taken out after alloy pig is completely cooling, careful polishes off the oxide layer of alloy ingot surface, and is cleaned and air-dried, Obtain low elastic modulus erosion resistant titanium alloy.
Embodiment 3
By alloying component Ti-25Zr-6.1Al-6.9Nb-0.3Ta (mass percent) ingredient, technical grade titanium sponge is weighed 61.7g, sponge zirconium 25g, fine aluminium 6.1g, pure niobium 6.9g and pure tantalum 0.3g are dipped in dehydrated alcohol, are air-dried, are set after ultrasonic cleaning In the water jacketed copper crucible for entering non-consumable vacuum arc melting furnace, the vacuum degree in furnace chamber will be extracted into 8 × 10-3Pa is hereinafter, electric arc is molten After high-purity argon gas is filled with before refining as protection gas, arc temperature is about 2500 DEG C or so when each melting, and smelting time is about 3 Minute or so, it is cooling after each melting to obtain ingot casting, then overturning processing is carried out to ingot casting and carries out melting, it is poured with this melting- It casts ingot casting melt back and overturns ingot casting 7 times to guarantee that the ingot casting ingredient finally obtained is uniform.
It then takes out alloy cast ingot and is put into vacuum/atmosphere tube type furnace (limited public affairs of the Tianjin SK-G06143 middle ring experimental electric furnace Department) in, solution treatment is carried out after being filled with protection gas argon gas:In 870 DEG C of heat preservation 75min, then from tube furnace take out and it is rapid Carry out water quenching.
Then the alloy cast ingot after solution treatment is placed again into vacuum/atmosphere tube type furnace and carries out ageing treatment, is controlled Aging temp is 650 DEG C, and soaking time 200min cools to room temperature with the furnace later.
It is taken out after alloy pig is completely cooling, careful polishes off the oxide layer of alloy ingot surface, and is cleaned and air-dried, Obtain low elastic modulus erosion resistant titanium alloy.
Embodiment 4
By alloying component Ti-35Zr-5.7Al-7.3Nb-0.4Ta (mass percent) ingredient, technical grade titanium sponge is weighed 51.6g, sponge zirconium 35g, fine aluminium 5.7g, pure niobium 7.3g and pure tantalum 0.4g are dipped in dehydrated alcohol, are air-dried, are set after ultrasonic cleaning In the water jacketed copper crucible for entering non-consumable vacuum arc melting furnace, the vacuum degree in furnace chamber will be extracted into 8 × 10-3Pa is hereinafter, electric arc is molten After high-purity argon gas is filled with before refining as protection gas, arc temperature is about 2500 DEG C or so when each melting, and smelting time is about 3 Minute or so, it is cooling after each melting to obtain ingot casting, then overturning processing is carried out to ingot casting and carries out melting, it is poured with this melting- It casts ingot casting melt back and overturns ingot casting 8 times to guarantee that the ingot casting ingredient finally obtained is uniform.
It then takes out alloy cast ingot and is put into vacuum/atmosphere tube type furnace (limited public affairs of the Tianjin SK-G06143 middle ring experimental electric furnace Department) in, solution treatment is carried out after being filled with protection gas argon gas:In 830 DEG C of heat preservation 80min, then from tube furnace take out and it is rapid Carry out water quenching.
Then the alloy cast ingot after solution treatment is placed again into vacuum/atmosphere tube type furnace and carries out ageing treatment, is controlled Aging temp is 620 DEG C, and soaking time 220min cools to room temperature with the furnace later.
It is taken out after alloy pig is completely cooling, careful polishes off the oxide layer of alloy ingot surface, and is cleaned and air-dried, Obtain low elastic modulus erosion resistant titanium alloy.
Embodiment 5
By alloying component Ti-45Zr-5.5Al-7.5Nb-0.5Ta (mass percent) ingredient, technical grade titanium sponge is weighed 41.5g, sponge zirconium 45g, fine aluminium 5.5g, pure niobium 7.5g and pure tantalum 0.5g are dipped in dehydrated alcohol, are air-dried, are set after ultrasonic cleaning In the water jacketed copper crucible for entering non-consumable vacuum arc melting furnace, the vacuum degree in furnace chamber will be extracted into 8 × 10-3Pa is hereinafter, electric arc is molten After high-purity argon gas is filled with before refining as protection gas, arc temperature is about 2500 DEG C or so when each melting, and smelting time is about 3 Minute or so, it is cooling after each melting to obtain ingot casting, then overturning processing is carried out to ingot casting and carries out melting, it is poured with this melting- It casts ingot casting melt back and overturns ingot casting six times to guarantee that the ingot casting ingredient finally obtained is uniform.
It then takes out alloy cast ingot and is put into vacuum/atmosphere tube type furnace (limited public affairs of the Tianjin SK-G06143 middle ring experimental electric furnace Department) in, solution treatment is carried out after being filled with protection gas argon gas:In 800 DEG C of heat preservation 90min, then from tube furnace take out and it is rapid Carry out water quenching.
Then the alloy cast ingot after solution treatment is placed again into vacuum/atmosphere tube type furnace and carries out ageing treatment, is controlled Aging temp is 600 DEG C, and soaking time 240min cools to room temperature with the furnace later.
It is taken out after alloy pig is completely cooling, careful polishes off the oxide layer of alloy ingot surface, and is cleaned and air-dried, Obtain low elastic modulus erosion resistant titanium alloy.
Metallographic structure observation is carried out to the titanium alloy that Examples 1 to 5 obtains respectively, as a result respectively as shown in Fig. 1~5.By Fig. 1~5 it is found that the tissue of titanium alloy obtained by different embodiments of the invention by more coarse Original β grain and from crystalline substance α " martensitic phase and α ' the martensitic phase composition that intragranular portion is precipitated.
Comparative example 1
It is Ti-6Al-7Nb titanium alloy that composition of alloy is prepared in the way of embodiment 1.
Titanium alloy made from Examples 1 to 5 and comparative example 1 is cut out into tensile sample as shown in FIG. 6 respectively with wire cutting, Tension test is carried out, thus to obtain its mechanical property related data, test result is as shown in table 1.
The Mechanics Performance Testing and crystallite dimension result for the titanium alloy that 1 Examples 1 to 5 of table and comparative example 1 obtain
As shown in Table 1, the α " martensitic phase and α ' martensitic phase being precipitated in Original β grain in the titanium alloy that the present invention obtains So that the intensity of alloy is greatly improved;Compared with the Ti-6Al-7Nb titanium alloy of actual measurement, what Examples 1 to 5 obtained For the tensile strength increase rate of titanium alloy up to 3.4~36.05%, elasticity modulus distinguishes fall up to 4.55%~18.18%.
Titanium alloy made from Examples 1 to 5 and comparative example 1 is cut out with wire cutting having a size of 10mm × 10mm respectively simultaneously The salt spray test sample of × 2mm, every piece of titanium alloy ingot cut out 5 samples, it is ensured that the repeatability of experiment;With the face 10mm × 10mm To be tested face, with bakelite powder at metallographic test pointing machine (XQ-1 of model Shanghai metallographic mechanical equipment Co., Ltd) In processing is sealed to other non-test faces, polished after tested face is polishing to 3000# with sand paper after taking-up, clean And surface is dried up, then using salt mist tester (BY-120A, Beijing win space Xiang and reaches Instrument Ltd.), with GB/T10125- 1997 be that test basis carries out neutral salt spray test under the sodium chloride solution environment that concentration is 5%, according to the test mark in table 2 It is quasi- successively to sample cleaning, weigh, place, observation, maintenance, adjustment etc., the test period is 1440 hours (two months), thus Its corrosive nature related data is obtained, test result is as shown in table 3.
Table 2:Salt spray test testing experiment standard of the present invention
The salt spray test test result for the titanium alloy that 3 Examples 1 to 5 of table and comparative example 1 obtain
As shown in Table 3, in the present invention, the increase of Zr content keeps its corrosion resistance more excellent, with same treatment technique The comparative alloy (Ti-6Al-7Nb) of acquisition compares, and the resistance to corrosion in sodium chloride solution is respectively increased amplitude and reaches 6.69%~62.78%.
As can be seen from the above embodiments, the present invention promotes the mechanical property of titanium alloy by the content of control each element, Meet under the requirement of titanium alloy corrosion resistance, significantly reduce the elasticity modulus of titanium alloy, it is made to meet the implantation of the human body of medical alloy The requirement of material.
The above is only a preferred embodiment of the present invention, it is not intended to limit the present invention in any form.It should It points out, for those skilled in the art, without departing from the principle of the present invention, if can also make Dry improvements and modifications, these modifications and embellishments should also be considered as the scope of protection of the present invention.

Claims (9)

1. a kind of low elastic modulus erosion resistant titanium alloy, based on mass content, including Al 5.5~6.5%, Nb 6.5~ 7.5%, the Ti of Zr 5~45%, Ta≤0.5% and surplus.
2. low elastic modulus erosion resistant titanium alloy according to claim 1, which is characterized in that the low elastic modulus corrosion resistant Erosion titanium alloy includes the Ti of Al 5.7~6.3%, Nb 6.7~7.3%, Zr 15~35%, Ta0.1~0.4% and surplus.
3. low elastic modulus erosion resistant titanium alloy according to claim 1 or 2, which is characterized in that the low elastic modulus The tissue of erosion resistant titanium alloy includes metastable β phase, α " martensitic phase and α ' martensitic phase.
4. the preparation method of low elastic modulus erosion resistant titanium alloy described in claims 1 to 3 any one, which is characterized in that Include the following steps:
(1) cast alloy base will be obtained after alloy raw material melting;
(2) the cast alloy ingot for obtaining the step (1) carries out solution treatment, obtains solid solution state base;
(3) the solid solution state base for obtaining the step (2) carries out cooling after ageing treatment, obtains the conjunction of low elastic modulus corrosion-resistant titanium Gold.
5. the preparation method according to claim 4, which is characterized in that melting is vacuum arc melting in the step (1), The temperature of the vacuum arc melting is 2000~2500 DEG C.
6. preparation method according to claim 4 or 5, which is characterized in that melting is repeated 5 times in the step (1) More than.
7. the preparation method according to claim 4, which is characterized in that the holding temperature of solution treatment in the step (2) It is 800~950 DEG C, the soaking time of solution treatment is 60~90min, and the type of cooling of solution treatment is water quenching.
8. the preparation method according to claim 4, which is characterized in that the temperature of ageing treatment is 600 in the step (3) ~700 DEG C, the time of ageing treatment is 3~4h.
9. the preparation method according to claim 4, which is characterized in that the insulating process of step (2) solution treatment and Ageing treatment independently carries out under protective atmosphere in step (3).
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CN113881886A (en) * 2021-10-25 2022-01-04 上海交通大学 High-specific-strength Ti-Al-Nb-Zr-Ta refractory high-entropy alloy
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