CN110408815A - A kind of low elastic modulus, high-intensitive spinodal decomposition type Zr-Nb-Ti alloy material and preparation method thereof - Google Patents
A kind of low elastic modulus, high-intensitive spinodal decomposition type Zr-Nb-Ti alloy material and preparation method thereof Download PDFInfo
- Publication number
- CN110408815A CN110408815A CN201910772531.5A CN201910772531A CN110408815A CN 110408815 A CN110408815 A CN 110408815A CN 201910772531 A CN201910772531 A CN 201910772531A CN 110408815 A CN110408815 A CN 110408815A
- Authority
- CN
- China
- Prior art keywords
- alloy material
- preparation
- zirconium
- alloy
- bar
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- A61L27/047—Other specific metals or alloys not covered by A61L27/042 - A61L27/045 or A61L27/06
-
- 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
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- 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
-
- 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
- C22F1/186—High-melting or refractory metals or alloys based thereon of zirconium or alloys based thereon
Abstract
The invention discloses a kind of low elastic modulus, high-intensitive spinodal decomposition type Zr-Nb-Ti alloy material and preparation method thereof.Described its composition of Zr-Nb-Ti alloy material is as follows by atomic percentage: Ti:20~50%；Nb:15~45%；Surplus is Zr.Preparation method are as follows: match by design proportion and take titanium source, niobium source, zirconium source；Multiple melting obtains zircaloy ingot casting, zircaloy ingot casting inhale casting and obtains Zirconium alloy bar, Zirconium alloy bar is successively carried out to solution treatment, ageing treatment and obtains Zr-Nb-Ti alloy material, gained Zirconium alloy material of the invention has higher intensity and low elasticity modulus, wherein, intensity reaches as high as 1130.8 ± 8.5MPa, and elasticity modulus is maintained between 40~50GPa, close to the elasticity modulus of human body.
Description
Technical field
The invention belongs to medical zircaloy technical fields, and in particular to a kind of low elastic modulus, high-intensitive spinodal decomposition
Type Zr-Nb-Ti alloy material and preparation method thereof.
Technical background
In recent years, with the development of society and the raising of human living standard, people are for safe and reliable biological implantation
The demand of material increasingly increases, thus vast researcher implantable biological hard tissue material has been carried out it is deep
Research.Body implant's alloy is developed, requires the alloy that there is excellent biocompatibility first.Nowadays it is applied to give birth to
The biocompatible alloy element of object medical metal material mainly has Ti, Zr, Nb, Ta, Mo, Sn, Mg, Zn etc..Secondly, such is closed
The corrosion resistance that gold needs to have high-intensitive and excellent.On this basis, which also needs to have lower elasticity modulus with this
It can match with the elasticity modulus (15~30GPa) of skeleton.If the elasticity modulus of implant is excessively high, will cause
" stress shielding effect ", so as to cause implant premature failure or fracture, finally produces serious influence to human health.Cause
This, implant alloy material mechanical property mismatch is a urgent problem to be solved.
It can be seen that the design and development of safe and reliable human implantation's metal material, it is necessary to be based on good biofacies
Capacitive and biomechanical compatibility.And to make alloy that there is good biomechanical compatibility, alloy will have high-intensitive and low
Elasticity modulus, i.e., higher δ (δ=σys/ E) value.Currently, realizing this purpose, there are mainly two types of approach: first, reduce elasticity
Modulus.Domestic and foreign scholars are optimized by alloying component, are designed and are prepared low elastic modulus alloy.In addition, reducing alloy elastic
Another effective way of modulus is to introduce pore structure in the alloy, prepares porous alloy.Such as patent (CN 109847110
A) provide a kind of porous Ti-Nb-Zr composite artificial bone implant material and its preparation method and application, pass through a large amount of holes
It introduces, reduces alloy elastic modulus with can dramatically, but also considerably reduce the intensity of alloy simultaneously.And for dense alloy material
Material, the method for improving alloy strength are mainly to refine crystal grain by thermomechanical treatment or the second tiny phase is precipitated, and reach thin
Crystalline substance strengthens or the purpose of second-phase strength.But high elastic modulus phase, such as α phase and ω phase can be precipitated in alloy heat treatment,
Alloy is caused to show high elastic modulus.Therefore, high-intensitive and this contradiction of low elastic modulus how is solved to lead as the research
One hot issue in domain.
Spinodal decomposition refers to that solid solution due to infinitesimal undulating composition unstability or is decomposed into unlimited/non-local
A kind of even phase transition of ingredient difference, the identical two-phase of structure.From the point of view of thermodynamics, Gibbs free energy is with the two of composition transfer
When order derivative is negative, generates in alloy system and mutually separate.Compared with traditional phase transformation, when spinodal decomposition occurs, not forming core, fastly
Speed forms tiny ingredient difference, identical two phases of structure.The unique phase transformation mode of spinodal decomposition, makes itself and traditional forming core
Precipitation strength of growing up mode is compared, and has many excellent performances.The corrosion resisting property of modulation structure even tissue, alloy is higher,
Overaging will not be generated in normal ag(e)ing process or crystal grain is grown up；The mistake stacking of dislocation does not occur during spinodal decomposition
Product can reduce the sensibility of crackle generation and delay the extension of crackle.Therefore, it has become some engineering material Strengthening and Toughening processing
Effective means.More importantly component difference is little, the identical modulation structure of structure, it is ensured that the low elastic modulus of alloy,
And intensity significantly improves.
Summary of the invention
Low elastic modulus and high-intensitive problem, the purpose of the present invention are not can be implemented simultaneously for zircaloy in the prior art
It is to provide a kind of low elastic modulus, high-intensitive spinodal decomposition type Zr-Nb-Ti alloy material and preparation method thereof.
To achieve the goals above, the present invention adopts the following technical scheme that.It is a kind of low elastic modulus of the present invention, high-intensitive
Spinodal decomposition type Zr-Nb-Ti alloy material, composition are as follows by atomic percentage: Ti:20~50%；Nb:15~45%；
Surplus is Zr.
Low elastic modulus and high-intensitive problem are not can be implemented simultaneously for current zircaloy, the present invention provides one kind
Spinodal decomposition type zircaloy: Zr-Nb-Ti alloy material, there are the regions of spinodal decomposition in above-mentioned compositional ranges for the alloy；And
Spinodal decomposition does not need forming core, but quickly forms tiny even tissue and crystal structure is identical, ingredient is different two phases.
Therefore, alloy can guarantee low elasticity modulus while improving alloy strength.
Preferred scheme, the Zr-Nb-Ti alloy material, composition are as follows by atomic percentage: Ti:30~35%；
Nb:30~35%；Surplus is Zr.
In above-mentioned preferred range, spinodal decomposition is certainly existed.
The preparation method of a kind of low elastic modulus of the present invention, high-intensitive spinodal decomposition type Zr-Nb-Ti alloy material, packet
It includes following steps: matching by design proportion and take titanium source, niobium source, zirconium source；Multiple melting obtains zircaloy ingot casting, by zircaloy ingot casting into
Row inhales casting and obtains Zirconium alloy bar, and Zirconium alloy bar is successively carried out to solution treatment, ageing treatment and obtains Zr-Nb-Ti alloy
Material.
Preparation method of the invention first passes through multiple melting and obtains composition preparation and uniform zircaloy ingot casting, however inhales
Casting further increases uniformity, the supersaturated solid solution of Zirconium alloy bar is then obtained after solution treatment, then pass through timeliness
Processing makes material that even phase transition occur, and obtains spinodal decomposition phase.Due in the present invention solid solution and ageing treatment will not be precipitated
The higher phase of other elasticity modulus, such as α phase, ω are equal, but are not necessarily to forming core, quickly form tiny ingredient difference, knot
Identical two phases of structure.Therefore overaging will not be generated in normal ag(e)ing process or crystal grain is grown up, but component difference is not
Greatly, the identical modulation structure of structure can guarantee that intensity significantly improves while alloy low elasticity modulus in this way.
Preferred scheme, the titanium source are selected from the titanium grain that purity is not less than 99.99%；The niobium source is not less than selected from purity
99.99% niobium grain, the zirconium source are selected from the zirconium grain that purity is not less than 99.99%.
Preferred scheme, the melting electric current are 200~250A, and single melting suspension time is 60~90s, melting number
It is >=4 times.Further preferably 6 times.
By carrying out multiple melting in above-mentioned processing range, it can obtain that composition is accurate and uniform zircaloy ingot casting.
In the actual operation process, melting carries out in vacuum arc melting furnace with casting is inhaled.
Suction casting process can guarantee the uniformity of zircaloy more preferably, if directlying adopt ingot casting still has some dendrite materials
Material in order to solve the time that this inhomogeneities needs to increase solution treatment, leads to crystal grain so that material composition is uneven in this way
Become larger, influences material property.
Preferred scheme, the temperature of the solution treatment are 850~950 DEG C, and soaking time is 1~10h.
As a further preference, the temperature of the solution treatment is 860~900 DEG C, and soaking time is 3~6h.
Preferred scheme, the solution treatment carry out under vacuum conditions.
Zirconium alloy bar is placed in cryosel quenching-in water after the completion of the solution treatment heat preservation by preferred scheme.
Solid solution temperature can have a certain impact to the performance of material in the present invention, if solution treatment is excessively high to be made
Crystal grain fast growth influences the performance of material, the too low time that can lengthen solid solution, cannot quickly homogenize.In addition in brine ice
Middle rapid cooling quenching may insure to retain β phase, if the higher α phase of elasticity modulus and ω phase can be precipitated very much in cooling velocity slowly.
Preferred scheme, the detailed process of solution treatment are as follows: be placed on Zirconium alloy bar using the vitreosil seal of tube
Solution treatment is carried out in heat-treatment furnace, is then taken out Zirconium alloy bar and is placed in cryosel quenching-in water.
In the actual operation process, after the completion of solution treatment heat preservation, vitreosil pipe is taken out and is quickly smashed, bar is made
It falls into brine ice and is quenched.
Preferred scheme, the temperature of the ageing treatment are 500~600 DEG C, soaking time is 4~for 24 hours.
As a further preference, the temperature of the ageing treatment is 500~560 DEG C, and soaking time is 4~14h.
Preferred scheme, the ageing treatment carry out under vacuum conditions.
Zirconium alloy bar is placed in brine ice cooling by preferred scheme after the completion of the ageing treatment heat preservation.
Aging temperature has large effect to the performance of material in the present invention, if aging temp is not in this hair
In bright range, then spinodal decomposition phase can not be precipitated, while also need the cooling in brine ice, otherwise can not retain the amplitude modulation of precipitation
Decompose phase.
Preferred scheme, the ageing process are that the Zirconium alloy bar after solution treatment is used vitreosil pipe
Sealing, which is placed in heat-treatment furnace, carries out ageing treatment, then takes out Zirconium alloy bar and is placed in cooling in brine ice.
In the actual operation process, after the completion of ageing treatment heat preservation, vitreosil pipe is taken out and is quickly smashed, bar is made
It falls into brine ice and is cooled down.
The utility model has the advantages that
What the present invention initiated provides a kind of Zirconium alloy material with spinodal decomposition phase, on the one hand, passes through thermodynamics meter
It calculates and largely tests, the material composition range with spinodal decomposition phase is obtained, in combination with technique of the invention, it is ensured that material
Material during the preparation process, forms spinodal decomposition phase.Spinodal decomposition does not need forming core, but quickly formed tiny even tissue and
Two phases that crystal structure is identical, ingredient is different.Therefore, the alloy material that present invention gained supplies can improve alloy strength
Meanwhile guaranteeing low elasticity modulus.
Gained Zirconium alloy material of the invention has higher intensity and low elasticity modulus, wherein intensity reaches as high as
1130.8 ± 8.5MPa, and elasticity modulus is maintained between 40~50GPa, is closer to the elasticity modulus of human body.
The Zirconium alloy material that gained of the invention supplies is Zr-Nb-Ti ternary-alloy material, and compared with pure titanium, zircaloy has
The advantages that good ductility, wearability, lower magnetic susceptibility and tuneable elasticity modulus, be expected to substitute current use compared with
More titanium-based implantation piece and the novel bone substitute material for becoming next stage.
Detailed description of the invention
Fig. 1 is each stage sample XRD spectrum in embodiment 1；
Fig. 2 is sample TEM bright field image and selected diffraction figure after timeliness in embodiment 1；
Fig. 3 is each stage sample compression stress strain curve in embodiment 1；
Fig. 4 is sample TEM bright field image figure after timeliness in embodiment 2；
Fig. 5 is sample compression stress-strain diagram after 2 ageing treatment of embodiment；
Fig. 6 is sample TEM bright field image figure after timeliness in embodiment 3；
Fig. 7 is sample compression stress-strain diagram after 3 ageing treatment of embodiment.
Specific embodiment
Below with reference to example and attached drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to
This.
Embodiment 1
(1) it weighs: weighing raw material: being made by Elements Atom percentage composition 30%Ti, 30%Nb, surplus of Zr, point
Also known as take high purity titanium grain, High-purity Niobium grain, high purity zirconium grain.High purity titanium grain, High-purity Niobium grain, high purity zirconium grain purity be not less than
99.99%.
(2) melting: step (1) weighed raw material are put into vacuum arc melting furnace and carry out melting, melting electric current is
220A, melting suspension time are 65s.In order to improve the accuracy and uniformity of ingredient, ingot casting is needed melt back six times, is cast
Ingot.
(3) inhale casting: ingot casting obtained in step (2) is put into vacuum arc melting furnace carry out inhale casting obtain zirconium alloy bar
Material.
(4) microstructure regulates and controls: suction casting rod material obtained in step (3) being carried out solution treatment, solutionizing step will
The bar vitreosil seal of tube that casting obtains is inhaled, is put into Tubular thermal treatment furnace, 900 DEG C of heat preservation 3h is heated to, by quartz ampoule
It takes out and quickly smashes, fall into bar in brine ice and quenched, then the sample of solution treatment is subjected to ageing treatment, timeliness
The sample of the solution treatment vitreosil seal of tube is put into tube furnace by processing step, 500 DEG C of heat preservation 4h is heated to, by stone
English pipe takes out and quickly smashes, and falls into bar cooling in brine ice.
Fig. 1 is the sample XRD spectrum that example 1 is dissolved and is dissolved after added-time effect, as shown in Figure 1, alloy solid solution processing and solid
The phase of alloy is all β phase after molten processing plus ageing treatment, but is found out by enlarged drawing, sideband occurs after alloy aging processing
Peak, illustrating the alloy, there are spinodal decomposition tissues.Fig. 2 is the bright field image figure for being dissolved added-time effect treated sample transmission Electronic Speculum
Piece, it can be seen that apparent Modulated Structures, the tissue size are nanoscale.From Fig. 2 solid solution added-time effect treated sample constituency
Diffraction can see, and there are apparent satellite diffraction spots.It can be to have amplitude modulation in the sample after 1 ageing treatment of illustrated example by Fig. 2
Decompose phase.Compression test is carried out to stage sample each in this example, compression stress strain curve is as shown in Figure 3.It can be with by curve
Find out, the compression yield strength of sample is 795 ± 8.5MPa after solution treatment, and elasticity modulus is 40.8 ± 1.3GPa, and δ value is
0.019；Solid solution plus ageing treatment after sample compression yield strength be 1130.8 ± 8.5MPa, elasticity modulus be 45.5 ±
2.8GPa, δ value are 0.025, are obviously improved compared with solution treatment sample；It can thus be seen that after ageing treatment sample surrender
Intensity is significantly raised, and plays in the range that modulus is also maintained at lower.
Embodiment 2
(1) it weighs each component: weighing raw material: being Zr system by Elements Atom percentage composition 33%Ti, 31%Nb, surplus
At weighing high purity titanium grain, High-purity Niobium grain, high purity zirconium grain respectively.High purity titanium grain, High-purity Niobium grain, the purity of high purity zirconium grain is not low
In 99.99%.
(2) melting: step (1) weighed raw material are put into vacuum arc melting furnace and carry out melting, melting electric current is
200A, melting suspension time are 90s.In order to improve the accuracy and uniformity of ingredient, ingot casting is needed melt back six times, is cast
Ingot.
(3) inhale casting: ingot casting obtained in step (2) is put into vacuum arc melting furnace carry out inhale casting obtain zirconium alloy bar
Material.
(4) microstructure regulates and controls: suction casting rod material obtained in step (3) being carried out solution treatment, solutionizing step will
The bar vitreosil seal of tube that casting obtains is inhaled, is put into Tubular thermal treatment furnace, 860 DEG C of heat preservation 6h is heated to, by quartz ampoule
It takes out and quickly smashes, fall into bar in brine ice and quenched, then the sample of solution treatment is subjected to ageing treatment, timeliness
The sample of the solution treatment vitreosil seal of tube is put into tube furnace by processing step, is heated to 560 DEG C of heat preservation 14h, will
Quartz ampoule takes out and quickly smashes, and falls into bar cooling in brine ice.
TEM bright field image after this example ageing treatment by figure as shown in figure 4, can be illustrated there are Modulated Structures, at timeliness
The compression stress strain curve of sample is as shown in figure 5, the compression yield strength of sample is after ageing treatment as shown in Figure 5 after reason
998.9 ± 8.5MPa, elasticity modulus are 46.3 ± 2.1GPa, and δ value is 0.022.
Embodiment 3
(1) it weighs each component: weighing raw material: being Zr system by Elements Atom percentage composition 30%Ti, 30%Nb, surplus
At weighing high purity titanium grain, High-purity Niobium grain, high purity zirconium grain respectively.High purity titanium grain, High-purity Niobium grain, the purity of high purity zirconium grain is not low
In 99.99%.
(2) melting: step (1) weighed raw material are put into vacuum arc melting furnace and carry out melting, melting electric current is
230A, melting suspension time are 85s.In order to improve the accuracy and uniformity of ingredient, ingot casting is needed melt back six times, is cast
Ingot.
(3) inhale casting: ingot casting obtained in step (2) is put into vacuum arc melting furnace carry out inhale casting obtain zirconium alloy bar
Material.
(4) microstructure regulates and controls: suction casting rod material obtained in step (3) being carried out solution treatment, solutionizing step will
The bar vitreosil seal of tube that casting obtains is inhaled, is put into Tubular thermal treatment furnace, 950 DEG C of heat preservation 2h is heated to, by stone
English pipe takes out and quickly smashes, and falls into bar in brine ice and is quenched, then the sample of solution treatment is carried out ageing treatment,
The sample of the solution treatment vitreosil seal of tube is put into tube furnace by ageing treatment step, is heated to 500 DEG C of heat preservations
For 24 hours, quartz ampoule is taken out and is quickly smashed, fall into bar cooling in brine ice.
TEM bright field image after this example ageing treatment is as shown in fig. 6, can illustrate that there are spinodal decomposition phase, timeliness by figure
The compression stress strain curve of sample is as shown in fig. 7, the compression yield of sample is after ageing treatment as shown in Figure 7 after processing
899.6 ± 8.5MPa, elasticity modulus are 48.4 ± 1.9GPa, and δ value is 0.018, it may be possible to due to long-time heat preservation, group in alloy
It knits and grows up thicker, intensity is caused to decline, therefore δ value has relative to solution treatment sample and reduces by a small margin.
Comparative example 1
(1) it weighs: weighing raw material: being made by Elements Atom percentage composition 10%Ti, 10%Nb, surplus of Zr, point
Also known as take high purity titanium grain, High-purity Niobium grain, high purity zirconium grain.High purity titanium grain, High-purity Niobium grain, high purity zirconium grain purity be not less than
99.99%.
(2) melting: step (1) weighed raw material are put into vacuum arc melting furnace and carry out melting, melting electric current is
220A, melting suspension time are 65s.In order to improve the accuracy and uniformity of ingredient, ingot casting is needed melt back six times, is cast
Ingot.
(3) inhale casting: ingot casting obtained in step (2) is put into vacuum arc melting furnace carry out inhale casting obtain zirconium alloy bar
Material.
(4) microstructure regulates and controls: suction casting rod material obtained in step (3) being carried out solution treatment, solutionizing step will
The bar vitreosil seal of tube that casting obtains is inhaled, is put into Tubular thermal treatment furnace, 900 DEG C of heat preservation 3h is heated to, by quartz ampoule
It takes out and quickly smashes, fall into bar in brine ice and quenched, then the sample of solution treatment is subjected to ageing treatment, timeliness
The sample of the solution treatment vitreosil seal of tube is put into tube furnace by processing step, 500 DEG C of heat preservation 4h is heated to, by stone
English pipe takes out and quickly smashes, and falls into bar cooling in brine ice.
The ingredient of material is not within the scope of corresponding in this comparative example 1, therefore the zirconium obtained after solid solution+ageing treatment closes
Spinodal decomposition phase is not present in golden material, and compression yield is 780.6 ± 5.5MPa, and elasticity modulus is 55.7 ± 2.3GPa, and δ value is
0.014
Comparative example 2
(1) it weighs: weighing raw material: being made by Elements Atom percentage composition 30%Ti, 30%Nb, surplus of Zr, point
Also known as take high purity titanium grain, High-purity Niobium grain, high purity zirconium grain.High purity titanium grain, High-purity Niobium grain, high purity zirconium grain purity be not less than
99.99%.
(2) melting: step (1) weighed raw material are put into vacuum arc melting furnace and carry out melting, melting electric current is
220A, melting suspension time are 65s.In order to improve the accuracy and uniformity of ingredient, ingot casting is needed melt back six times, is cast
Ingot.
(3) inhale casting: ingot casting obtained in step (2) is put into vacuum arc melting furnace carry out inhale casting obtain zirconium alloy bar
Material.
(4) microstructure regulates and controls: suction casting rod material obtained in step (3) being carried out solution treatment, solutionizing step will
The bar vitreosil seal of tube that casting obtains is inhaled, is put into Tubular thermal treatment furnace, 900 DEG C of heat preservation 3h is heated to, by quartz ampoule
It takes out and quickly smashes, fall into bar in brine ice and quenched, then the sample of solution treatment is subjected to ageing treatment, timeliness
The sample of the solution treatment vitreosil seal of tube is put into tube furnace by processing step, 400 DEG C of heat preservation 4h is heated to, by stone
English pipe takes out and quickly smashes, and falls into bar cooling in brine ice.
Prevent it from spinodal decomposition phase occurs due to carrying out ageing treatment not within the scope of corresponding temperature in this comparative example 2
Become, there is no spinodal decomposition phases for the Zirconium alloy material obtained after solid solution+ageing treatment, and can analyse in the small timeliness of lower temperature
The higher α phase of elasticity modulus keeps its elasticity modulus significantly raised with ω phase out.Its compression yield is 950.9 ± 7.3MPa, elasticity
Modulus is 77.6 ± 1.2GPa, and δ value is 0.012
Comparative example 3
(1) it weighs: weighing raw material: being made by Elements Atom percentage composition 30%Ti, 30%Nb, surplus of Zr, point
Also known as take high purity titanium grain, High-purity Niobium grain, high purity zirconium grain.High purity titanium grain, High-purity Niobium grain, high purity zirconium grain purity be not less than
99.99%.
(2) melting: step (1) weighed raw material are put into vacuum arc melting furnace and carry out melting, melting electric current is
220A, melting suspension time are 65s.In order to improve the accuracy and uniformity of ingredient, ingot casting is needed melt back six times, is cast
Ingot.
(3) inhale casting: ingot casting obtained in step (2) is put into vacuum arc melting furnace carry out inhale casting obtain zirconium alloy bar
Material.
(4) microstructure regulates and controls: suction casting rod material obtained in step (3) being carried out solution treatment, solutionizing step will
The bar vitreosil seal of tube that casting obtains is inhaled, is put into Tubular thermal treatment furnace, 900 DEG C of heat preservation 3h is heated to, by quartz ampoule
It takes out and quickly smashes, fall into bar in brine ice and quenched, then the sample of solution treatment is subjected to ageing treatment, timeliness
The sample of the solution treatment vitreosil seal of tube is put into tube furnace by processing step, 500 DEG C of heat preservation 4h is heated to, by stone
English pipe takes out and smashes, and cools down bar in air.
Material carries out air-cooled after ageing treatment in this comparative example 3, and elasticity modulus can equally be precipitated during air-cooled
Higher α phase and ω phase, but can also retain some spinodal decomposition phases in material, it increase its elasticity modulus will not more, press
Contracting surrender is 966.9 ± 7.3MPa, and elasticity modulus is 64.6 ± 1.2GPa, and δ value is 0.014.
Claims (10)
1. a kind of low elastic modulus, high-intensitive spinodal decomposition type Zr-Nb-Ti alloy material, it is characterised in that: its composition is by original
Sub- percentages are as follows: Ti:20~50%；Nb:15~45%；Surplus is Zr.
2. Zr-Nb-Ti alloy material according to claim 1, it is characterised in that: its composition presses atomic percentage such as
Under: Ti:30~35%；Nb:30~35%；Surplus is Zr.
3. the method for preparing Zr-Nb-Ti alloy material as claimed in claim 1 or 2, which comprises the steps of:
Match by design proportion and takes titanium source, niobium source, zirconium source；Multiple melting obtains zircaloy ingot casting, and zircaloy ingot casting is carried out suction casting and is obtained
Zirconium alloy bar is successively carried out solution treatment, ageing treatment and obtains Zr-Nb-Ti alloy material by Zirconium alloy bar.
4. the preparation method of Zr-Nb-Ti alloy material according to claim 3, it is characterised in that: the melting electric current is
200~250A, single melting suspension time are 60~90s, and melting number is >=4 times.
5. the preparation method of Zr-Nb-Ti alloy material according to claim 3, it is characterised in that: the solution treatment
Temperature is 850~950 DEG C, and soaking time is 1~10h.
6. the preparation method of Zr-Nb-Ti alloy material according to claim 3 or 5, it is characterised in that: at the solid solution
After the completion of reason heat preservation, Zirconium alloy bar is placed in cryosel quenching-in water.
7. the preparation method of Zr-Nb-Ti alloy material according to claim 3 or 5, it is characterised in that: solution treatment
Detailed process are as follows: Zirconium alloy bar is placed in heat-treatment furnace using the vitreosil seal of tube and carries out solution treatment, is then taken
Zirconium alloy bar is placed in cryosel quenching-in water out.
8. the preparation method of Zr-Nb-Ti alloy material according to claim 3, it is characterised in that: the ageing treatment
Temperature be 500~600 DEG C, soaking time be 4~for 24 hours.
9. the preparation method of Zr-Nb-Ti alloy material according to claim 3 or 8, it is characterised in that: at the timeliness
After the completion of reason heat preservation, Zirconium alloy bar is placed in brine ice cooling.
10. the preparation method of Zr-Nb-Ti alloy material according to claim 3 or 8, it is characterised in that: at the timeliness
Reason process is to be placed in heat-treatment furnace the Zirconium alloy bar after solution treatment using the vitreosil seal of tube and carry out at timeliness
Reason then takes out Zirconium alloy bar and is placed in cooling in brine ice.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910772531.5A CN110408815B (en) | 2019-08-21 | 2019-08-21 | Low-elasticity-modulus and high-strength spinodal decomposition type Zr-Nb-Ti alloy material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910772531.5A CN110408815B (en) | 2019-08-21 | 2019-08-21 | Low-elasticity-modulus and high-strength spinodal decomposition type Zr-Nb-Ti alloy material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110408815A true CN110408815A (en) | 2019-11-05 |
| CN110408815B CN110408815B (en) | 2020-11-06 |
Family
ID=68368100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910772531.5A Active CN110408815B (en) | 2019-08-21 | 2019-08-21 | Low-elasticity-modulus and high-strength spinodal decomposition type Zr-Nb-Ti alloy material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110408815B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111763852A (en) * | 2020-05-20 | 2020-10-13 | 东南大学 | Biomedical implanted zirconium alloy and preparation method thereof |
| CN112410639A (en) * | 2020-10-16 | 2021-02-26 | 北京赛博泰科科技有限公司 | Non-evaporable low-temperature activated wide-range working getter alloy and preparation method thereof |
| CN112658528A (en) * | 2020-12-04 | 2021-04-16 | 四川大学 | Brazing filler metal for SiC ceramic brazing and preparation method thereof |
| CN113319530A (en) * | 2021-05-31 | 2021-08-31 | 西安泵阀总厂有限公司 | Preparation method of zirconium-niobium alloy plate spring |
| CN113403502A (en) * | 2021-07-28 | 2021-09-17 | 燕山大学 | Low-elasticity-modulus zirconium alloy and preparation method thereof |
| CN115747571A (en) * | 2022-11-10 | 2023-03-07 | 重庆大学 | Magnetic-compatible near-alpha-Zr biomedical alloy and preparation method and application thereof |
| CN116144981A (en) * | 2023-02-21 | 2023-05-23 | 昆明理工大学 | Stable beta-phase-containing titanium alloy cast ingot and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60200947A (en) * | 1984-03-23 | 1985-10-11 | Sumitomo Electric Ind Ltd | Sintered hard alloy |
| CN1461816A (en) * | 2002-05-30 | 2003-12-17 | 王新敏 | Ti-base trielement alloy product and application |
| CN1648268A (en) * | 2003-12-25 | 2005-08-03 | 中国科学院金属研究所 | Super elasticity low modulus titanium alloy and preparing and processing method |
| CN101003873A (en) * | 2007-01-19 | 2007-07-25 | 上海交通大学医学院附属第九人民医院 | Beta type Ti Nb Zr alloy with low modulus of elasticity, preparation method and application |
| CN101696480A (en) * | 2009-11-04 | 2010-04-21 | 天津科技大学 | Nickel-free biomedical titanium alloy Ti-Nb-Zr material and preparation method thereof |
| CN101984114A (en) * | 2010-07-05 | 2011-03-09 | 大连理工大学 | Low-elastic modulus high-strength BCC Zr-Ti-Nb alloy |
| CN109355531A (en) * | 2018-11-26 | 2019-02-19 | 西安圣泰金属材料有限公司 | A kind of preparation method of the high-intensitive nearly β type medical titanium alloy Ti-13Nb-13Zr of low elastic modulus |
| CN109847110A (en) * | 2018-12-19 | 2019-06-07 | 云南大学 | A kind of porous Ti-Nb-Zr composite artificial bone implant material and its preparation method and application |
-
2019
- 2019-08-21 CN CN201910772531.5A patent/CN110408815B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS60200947A (en) * | 1984-03-23 | 1985-10-11 | Sumitomo Electric Ind Ltd | Sintered hard alloy |
| CN1461816A (en) * | 2002-05-30 | 2003-12-17 | 王新敏 | Ti-base trielement alloy product and application |
| CN1648268A (en) * | 2003-12-25 | 2005-08-03 | 中国科学院金属研究所 | Super elasticity low modulus titanium alloy and preparing and processing method |
| CN101003873A (en) * | 2007-01-19 | 2007-07-25 | 上海交通大学医学院附属第九人民医院 | Beta type Ti Nb Zr alloy with low modulus of elasticity, preparation method and application |
| CN101696480A (en) * | 2009-11-04 | 2010-04-21 | 天津科技大学 | Nickel-free biomedical titanium alloy Ti-Nb-Zr material and preparation method thereof |
| CN101984114A (en) * | 2010-07-05 | 2011-03-09 | 大连理工大学 | Low-elastic modulus high-strength BCC Zr-Ti-Nb alloy |
| CN109355531A (en) * | 2018-11-26 | 2019-02-19 | 西安圣泰金属材料有限公司 | A kind of preparation method of the high-intensitive nearly β type medical titanium alloy Ti-13Nb-13Zr of low elastic modulus |
| CN109847110A (en) * | 2018-12-19 | 2019-06-07 | 云南大学 | A kind of porous Ti-Nb-Zr composite artificial bone implant material and its preparation method and application |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111763852A (en) * | 2020-05-20 | 2020-10-13 | 东南大学 | Biomedical implanted zirconium alloy and preparation method thereof |
| CN111763852B (en) * | 2020-05-20 | 2021-07-09 | 东南大学 | Biomedical implanted zirconium alloy and preparation method thereof |
| CN112410639A (en) * | 2020-10-16 | 2021-02-26 | 北京赛博泰科科技有限公司 | Non-evaporable low-temperature activated wide-range working getter alloy and preparation method thereof |
| CN112658528A (en) * | 2020-12-04 | 2021-04-16 | 四川大学 | Brazing filler metal for SiC ceramic brazing and preparation method thereof |
| CN113319530A (en) * | 2021-05-31 | 2021-08-31 | 西安泵阀总厂有限公司 | Preparation method of zirconium-niobium alloy plate spring |
| CN113403502A (en) * | 2021-07-28 | 2021-09-17 | 燕山大学 | Low-elasticity-modulus zirconium alloy and preparation method thereof |
| CN115747571A (en) * | 2022-11-10 | 2023-03-07 | 重庆大学 | Magnetic-compatible near-alpha-Zr biomedical alloy and preparation method and application thereof |
| CN115747571B (en) * | 2022-11-10 | 2024-02-09 | 重庆大学 | Magnetic compatible near alpha-Zr type biomedical alloy and preparation method and application thereof |
| CN116144981A (en) * | 2023-02-21 | 2023-05-23 | 昆明理工大学 | Stable beta-phase-containing titanium alloy cast ingot and preparation method thereof |
| CN116144981B (en) * | 2023-02-21 | 2024-02-27 | 昆明理工大学 | Stable beta-phase-containing titanium alloy cast ingot and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110408815B (en) | 2020-11-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110408815A (en) | A kind of low elastic modulus, high-intensitive spinodal decomposition type Zr-Nb-Ti alloy material and preparation method thereof | |
| CN107805740B (en) | A kind of medical embedded titanium alloy and preparation method of low elastic modulus high-fatigue strength | |
| CN105349839B (en) | A kind of low elastic modulus β-Zr type biomedical alloys and preparation method thereof | |
| CN102899528A (en) | Biomedical beta-titanium alloy material and preparation method | |
| CN101768685B (en) | Biomedical titanium-niobium-based shape memory alloy as well as preparation method, processing method and application method thereof | |
| CN108203778B (en) | Zr-based biomedical alloy and preparation method thereof | |
| CN105274393B (en) | A kind of β types Zr Ti Nb Sn systems alloy and preparation method thereof | |
| CN103184369A (en) | Beta type Zr-Nb-Ti biomedical alloy and preparation method thereof | |
| CN108486408A (en) | A kind of low elastic modulus dental filling beta titanium alloy and its manufacturing method | |
| CN101225489A (en) | Ti-Mo-Sn-Al series titanium alloy and preparation method thereof | |
| CN108456805A (en) | A kind of beta titanium alloy and its manufacturing method for being implanted into bone | |
| CN107090554A (en) | It is a kind of to have low elastic modulus and the β type Zr Ti Nb Ta Sn systems alloy of high intensity and preparation method thereof concurrently | |
| CN108642359B (en) | High-strength rapid-degradation biomedical Mg-Zn-Zr-Fe alloy material and preparation method thereof | |
| AU2023201949A1 (en) | Titanium based ceramic reinforced alloy | |
| CN109055819A (en) | A kind of Ti-Nb-Ta-Zr-Mn alloy and preparation method thereof | |
| CN103255318B (en) | Sclerous tissues of metastable β type Zr-Mo-Ti system biomedical alloy and preparation method thereof | |
| CN107119208B (en) | A kind of Ti-Nb-Mn alloy and preparation method thereof | |
| US9039963B2 (en) | Titanium based ceramic reinforced alloy for use in medical implants | |
| CN108149071A (en) | A kind of low magnetic susceptibility β type Zr-Nb-Ta systems alloy and preparation method thereof | |
| CN103173655B (en) | A kind of sclerous tissues bio-medical in-situ authigenic zirconium based composite material | |
| CN114164370B (en) | Mg-based biological material based on high-entropy alloy theory and preparation method and application thereof | |
| TW201331380A (en) | Method for enhancing mechanical strength of a titanium alloy by aging | |
| CN114277283B (en) | Omega-rich medical zirconium-based alloy and preparation method thereof | |
| KR101678750B1 (en) | '' method for increasing mechanical strength of titanium alloys having '' phase by cold working | |
| CN118028658A (en) | TiZrNbSn alloy with super elasticity and low modulus and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |