CN103184369A - Beta type Zr-Nb-Ti biomedical alloy and preparation method thereof - Google Patents
Beta type Zr-Nb-Ti biomedical alloy and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Beta type Zr-Nb-Ti biomedical alloy and a preparation method thereof. The biomedical alloy comprises the following raw material components by the weight percentage: 19.50% to 20.5% of niobium, 0.1 to 15.0% of titanium, and the balance of zirconium sponge. The preparation method comprises the following steps: weighing corresponding raw materials by respective percent; mixing the materials fully; smelting the mixed materials in a nonconsumable vacuum arc furnace; and cooling to obtain evenly formed alloy ingot. The Beta type Zr-Nb-Ti biomedical alloy and the preparation method thereof have the advantages of traditional medical alloy, solve the problem that the traditional medical alloy, in Young modulus, is not matched with natural human skeleton, and can hopefully solve the problem that due to the unmatched mechanical property, the substitute material causes damage to human body. The Beta type Zr-Nb-Ti biomedical alloy and the preparation method thereof utilize niobium and titanium as alloying elements to conduct solid solution strengthening for zirconium base body, so that the compression strength of zirconium alloy is effectively improved, and the compression strength, the plasticity, the Young modulus and the like of the zirconium alloy can be changed by adjusting the content of titanium.
Description
Technical field
The invention belongs to the metal-base composites technical field, be specifically related to zirconium base bio-medical Alloy And Preparation Method.
Background technology
Bio-medical material comprises that medical treatment goes up the material of can the implantable bioartificial body or can combine with bio-tissue, and biomaterial is used for original tissue and organ in treatment or the replacement living organism, revises and improves its function.The bio-medical metallic substance is widespread use surgery embedded material at present, has high strength, good toughness, counter-bending fatigue strength and good machine-shaping property, has the premium properties that other type medical material is difficult to substitute.Metallic substance must satisfy strict biological requirement as bio-medical material: good, the nontoxicity of (1) histocompatibility, and aberration inducing does not cause allergic reaction and disturbs the immunity of matrix, does not destroy adjacent tissue etc.; (2) physicochemical property are stable, stable in properties such as intensity, elasticity, size, corrosion-resistant, wear resistance; (3) be easy to machine-shaping, make the shape of various needs easily.
Metal current material titanium and alloy thereof have obtained using widely at biological and medicinal implant material, and especially the application of beta-titanium alloy is more extensive.But, development along with medical technology, titanium alloy highlights gradually in the deficiency that biomedical application exists, one of them is exactly that the Young's modulus of Young's modulus and natural bone mates inadequately, cause the stress shielding effect easily, cause planting and bone resorption occurs around the body, cause phenomenons such as planting the loosening or fracture of body, the long-term stability that is unfavorable for bone healing and implant causes damage easily to human body.So the new bio medical alloy material that exploitation and function of human body are more mated becomes a main research direction of current bio-medical material.
Zirconium alloy has superior corrosion resistance energy, mechanical property, good, the nontoxicity of histocompatibility, mainly as the reactor core structured material, as fuel sheath; Be commonly used for corrosion resistant container and pipeline, as penstock, support and duct pipe etc.But the research of zirconium alloy aspect bio-medical material is also quite rare, and most researchs all are the performances that promotes titanium alloy with zirconium as the alloying element that adds.And the present invention with the application of zirconium alloy on bio-medical as main research direction, the zirconium base alloy that works out is compared with traditional titanium alloy, zirconium and alloy thereof have than titanium more good anti-corrosion, intensity, and lower Young's modulus, have well remedied the deficiency of conventional titanium alloy.
Summary of the invention
The purpose of this invention is to provide a kind of β type Zr-Nb-Ti is the bio-medical Alloy And Preparation Method, it can substitute or the application of part instead of titanium alloy on bio-medical, it has excellent biological compatibility, and to the human body toxicological harmless, have the Young's modulus that is complementary with skeleton simultaneously, therefore can effectively reduce the damage that does not match human body is caused because of mechanics.
Technical solution of the present invention is as follows:
A kind of β type Zr-Nb-Ti is the bio-medical alloy, and raw materials used component and weight percent are: niobium 19.5%～20.5%, and titanium 0.1～15.0%, surplus is zirconium sponge.Preferred feed composition and weight percent are: niobium 20%, and titanium 10～15.00%, surplus is zirconium sponge, the bio-medical alloy that this prescription obtains, every stable in properties, functional.
The purity of zirconium sponge, niobium and titanium that the present invention adopts is all more than 99.0%, all can buy from the market to obtain.Titanium elements is provided by titanium sponge usually.
The β type Zr-Nb-Ti of the present invention's preparation is that the Young's modulus of bio-medical alloy is 27 ~ 32 GPa, and maximum compressive strength reaches 1000 ~ 1400 MPa, and rate of compression is 36.0 ~ 38.0%, and yield strength is 850 ~ 1100MPa.
β type Zr-Nb-Ti of the present invention is the preparation method of bio-medical alloy, and its preparation process is as follows:
(1) raw material takes by weighing, and takes by weighing zirconium sponge, titanium and niobium respectively according to the weight percent of each feed composition; The raw material particle size size control is below 3 centimetres;
(2) raw material mixes, and the raw material stirring that weighs up is mixed;
(3) raw material melting is put into the crucible of non-consumable arc furnace with the raw material that mixes, and vacuumizes then, and vacuum degree control is 1 * 10
-2～1 * 10
-3Pa; Feeding rare gas element again carries out gas washing and removes residual air; At last carry out melting under the protection of rare gas element, smelting temperature is 2800～3100 ℃; Melting voltage is 220V, and the melting current control keeps 120 s ~ 180 s at 190 ~ 210A, and then electric current slowly is adjusted to 0A, and the time that electric current drops to 0 A is 40 ~ 60s, and so melt back obtains thick alloy cast ingot more than 5 times; Vacuumizing with gas washing of step (3) carried out 2～4 times repeatedly;
(4) cooling of thick alloy cast ingot; under protection of inert gas; to the crucible bottom water flowing; utilize the water that flows that thick alloy cast ingot is cooled off fast, thick alloy is 10 ~ 30 seconds by liquid state to solid-state cooling time, and continuation keeps the crucible bottom water flowing then; alloy cast ingot is continued to be parked in the stove internal cooling; take out after being cooled to room temperature, the β type Zr-Nb-Ti that obtains homogeneous microstructure is the bio-medical alloy, 400-600 second whole cooling time.
The rare gas element that the present invention adopts is argon gas, and pressure is a standard atmospheric pressure.
Zirconium of the present invention is as alloy substrate, and niobium and titanium are used for regulating alloy property as alloy element.Niobium is the β phase stabilizing element of using always, niobium has identical allotropic substance with zirconium at high temperature, crystalline structure all is body-centered cubic, atomic radius and β-Zr are close, niobium and β-Zr can form continuous solid solution, add an amount of niobium, can significantly reduce β → α phase transition temperature, can obtain metastable β-Zr in room temperature, produce the solution strengthening effect simultaneously.Niobium adds that zirconium alloy can improve the intensity of alloy and the plasticity and the processing characteristics that do not influence alloy, and can strengthen the corrosion resistance nature of alloy.The content of alloy system niobium of the present invention is set to become branch near eutectoid reaction about 20 at%, is conducive to obtain metastable β-Zr completely in room temperature.
Titanium belongs to α phase stable element, and when high temperature, titanium has identical crystalline structure and approaching lattice parameter with zirconium, and is to dissolve each other fully, so performance is not remarkable aspect the stable alpha phase.Because titanium and zirconium lattice parameter approach, so as alloy element, when the zirconium matrix is carried out the solution strengthening effect, can not make the plasticity of body material that very big decline takes place, the adding of titanium can be played multielement enhanced effect.
Zirconium base bio-medical alloy material of the present invention has the advantage of conventional bio-medical alloys such as conventional titanium alloy, it can more mate by the human body bone in Young's modulus simultaneously, erosion resistance is strong, can effectively alleviate physiological environment to the corrosion of alloy material, prevent that metal ion from organizing diffusion towards periphery, material can be applied to biological and medicinal implant material, as aspects such as artificial limb, artificial bones.
Advantage of the present invention:
1. alloy material of the present invention has excellent biological compatibility, and its Young's modulus (27-32GPa) is more mated with skeleton (10-40 GPa), can effectively avoid the injury that does not match human body is caused because of mechanics.When if the Young's modulus of alloy material surpasses the Young's modulus of skeleton, because its rigidity is excessive, during as biomaterial, easily skeleton and muscle are caused damage, be unfavorable for the long-term stability of bone healing and implant.The Young's modulus of at present a lot of bio-medical alloys is higher, in actual application, function of human body is caused certain damage, produces complication such as pain, hinders its development.Therefore the Young's modulus that will control the medical alloy material is mated mutually with skeleton can guarantee that just material can contact with human body for a long time, and generation damages to human body, and the while can guarantee the normal effect of function of human body again.
2. the add-on by the control niobium reduces phase transition temperature, can obtain metastable β-Zr in room temperature, plays the solution strengthening effect.Niobium joins that zirconium alloy can improve the intensity of alloy and the plasticity and the processing characteristics that do not influence alloy plays the effect of the erosion resistance that strengthens alloy.When high temperature, titanium and the lattice parameter that zirconium has identical crystalline structure and approaches dissolve each other fully, and alloy is played the solution strengthening effect, can regulate the plasticity (rate of compression) of alloy.Two kinds of alloying element actings in conjunction can be played the effect of character such as the ultimate compression strength of regulating zirconium alloy, Young's modulus, plasticity, yield strength, thereby better adapt to the requirement of bio-medical material.Alloy material improves ultimate compression strength can make this material bear bigger external force effect, and material can not be damaged simultaneously, is conducive to the effect of maintenance biological hard tissue equivalent material steady in a long-term in human body.
3. alloy element niobium, the titanium in the zirconium base alloy of the present invention has no side effect to human body, zirconium alloy also has no side effect to human body, niobium, titanium production cost are lower, avoid in the past the alloy element of medical alloy to depend on noble metal unduly, reduced alloy research and development and production cost, good development prospect has been arranged.
4. alloy material of the present invention can substitute or the application of part instead of titanium alloy on bio-medical, it has the every premium properties as bio-medical material, the various advantages that also possessed conventional titanium alloy, have high mechanical strength and anti-fatigue performance, for biomedical materials field provides a kind of novel material.
Description of drawings
Fig. 1 is the microstructure picture of the embodiment of the invention 1.
Fig. 2 is the microstructure picture of the embodiment of the invention 2.
Fig. 3 is the microstructure picture of the embodiment of the invention 3.
Fig. 4 is the microstructure picture of the embodiment of the invention 4.
Fig. 5 is the microstructure picture of the embodiment of the invention 5.
Fig. 6 is the XRD spectral line of all embodiment of the present invention.
Specific embodiment
The present invention is described further below in conjunction with specific examples, but protection scope of the present invention is not limited to the scope that embodiment represents.
Embodiment 1
1. composition of raw materials: feed composition and weight percent are: zirconium sponge 79.90%, niobium 20.00%, titanium 0.1%; The purity of zirconium sponge, titanium and molybdenum is all more than 99%.
2. preparation method
(1) taking by weighing of raw material takes by weighing zirconium sponge, niobium and titanium respectively according to the weight percent of each feed composition; The raw material particle size size control is below 3 centimetres;
(2) raw material mixes, and the prepared using stirring mixing method that weighs up is mixed;
(3) raw material melting is put into the crucible of non-consumable arc furnace with the raw material that mixes, and vacuumizes then, and vacuum tightness is 1 * 10
-2～1 * 10
-3Pa; Feed argon gas again and carry out gas washing; Vacuumize with gas washing and carry out repeatedly 2～4 times.At last carry out melting under the protection of argon gas, smelting temperature is 2800～3100 ℃; Melting voltage is 220V, and the melting current control keeps 120 s ~ 180 s at 190-210A, and then electric current slowly is adjusted to 0A, and the time that electric current drops to 0 A is 40-60s, and so melt back obtains thick alloy cast ingot more than 5 times;
(4) cooling of thick alloy cast ingot; under argon shield; to the crucible bottom water flowing; utilize the water that flows that thick alloy cast ingot is cooled off fast, thick alloy is 10 ~ 30 seconds by liquid state to solid-state cooling time, and continuation keeps the crucible bottom water flowing then; alloy cast ingot is continued to be parked in the stove internal cooling; take out after being cooled to room temperature, 400-600 second whole cooling time, obtaining β type Zr-Nb-Ti is the bio-medical alloy.
3. the detection of alloy material
Be that the bio-medical alloy utilizes the omnipotent experimental system of Instron8801 that specification is carried out the test of room temperature compression performance for the sample of 5mm * 5mm * 10mm with the β type Zr-Nb-Ti that adopts above-mentioned preparation method to make, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength are respectively 28.89GPa, 1048MPa, 37.77%, 860MPa.Fig. 1 is the microstructure picture of this alloy, in the microtexture of Zr-Nb-Ti cast alloy, has tangible crystal boundary.X=0 among Fig. 6 is the X ray diffracting spectrum of this sample,, this sample has only phase, i.e. a β-Zr as can be seen.
1. composition of raw materials: feed composition and weight percent are: zirconium sponge 77.00%, niobium 20.00%; Titanium 3.00%; The purity of zirconium sponge, niobium and titanium is all more than 99%.
2. preparation method
(1) taking by weighing of raw material takes by weighing zirconium sponge, niobium and titanium respectively according to the weight percent of each feed composition; The raw material particle size size control is below 3 centimetres;
(2) raw material mixes, and the prepared using stirring mixing method that weighs up is mixed;
(3) raw material melting is put into the crucible of non-consumable arc furnace with the raw material that mixes, and vacuumizes then, and vacuum tightness is 1 * 10
-2～1 * 10
-3Pa; Feed argon gas again and carry out gas washing; Vacuumize with gas washing and carry out repeatedly 2～4 times.At last carry out melting under the protection of argon gas, smelting temperature is 2800～2900 ℃; Melting voltage is 220V, and the melting current control keeps 120 s ~ 150 s at 190A, and then electric current slowly is adjusted to 0A, and the time that electric current drops to 0 A is 40-60s, and so melt back obtains thick alloy cast ingot more than 5 times;
(4) cooling of thick alloy cast ingot; under argon shield; to the crucible bottom water flowing; utilize the water that flows that thick alloy cast ingot is cooled off fast, thick alloy is 10 ~ 20 seconds by liquid state to solid-state cooling time, and continuation keeps the crucible bottom water flowing then; alloy cast ingot is continued to be parked in the stove internal cooling; take out after being cooled to room temperature, 400-500 second whole cooling time, obtaining β type Zr-Nb-Ti is the bio-medical alloy.
3. the detection of alloy material
Be that the bio-medical alloy utilizes the omnipotent experimental system of Instron8801 that specification is carried out the test of room temperature compression performance for the sample of 5mm * 5mm * 10mm with the β type Zr-Nb-Ti that adopts above-mentioned preparation method to make, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength are respectively 29.22GPa, 1119MPa, 37.74%, 897MPa.After finding to have added 3.00% titanium with embodiment 1 contrast, the over-all properties of alloy improves significantly.Fig. 2 is the microstructure picture of this alloy cast ingot, and the x=3 among Fig. 6 is the X ray diffracting spectrum of this sample.
1. composition of raw materials: feed composition and weight percent are: zirconium sponge 73.00%, niobium 20.00%, titanium 7%; The purity of zirconium sponge, niobium and titanium is all more than 99%.
2. preparation method
(1) taking by weighing of raw material takes by weighing zirconium sponge, niobium and titanium respectively according to the weight percent of each feed composition; The raw material particle size size control is below 3 centimetres;
(2) raw material mixes, and the prepared using stirring mixing method that weighs up is mixed;
(3) raw material melting is put into the crucible of non-consumable arc furnace with the raw material that mixes, and vacuumizes then, and vacuum tightness is 1 * 10
-2～1 * 10
-3Pa; Feed argon gas again and carry out gas washing; Vacuumize with gas washing and carry out repeatedly 2～4 times.At last carry out melting under the protection of argon gas, smelting temperature is 2900～3000 ℃; Melting voltage is 220V, and the melting current control keeps 150 s ~ 180 s at 200-210A, and then electric current slowly is adjusted to 0A, and the time that electric current drops to 0 A is 40-60s, and so melt back obtains thick alloy cast ingot more than 5 times;
(4) cooling of thick alloy cast ingot; under argon shield; to the crucible bottom water flowing; utilize the water that flows that thick alloy cast ingot is cooled off fast, thick alloy is 20 ~ 30 seconds by liquid state to solid-state cooling time, and continuation keeps the crucible bottom water flowing then; alloy cast ingot is continued to be parked in the stove internal cooling; take out after being cooled to room temperature, 500-600 second whole cooling time, obtaining β type Zr-Nb-Ti is the bio-medical alloy.
3. the detection of alloy material
Be that the bio-medical alloy utilizes the omnipotent experimental system of Instron8801 that specification is carried out the test of room temperature compression performance for the sample of 5mm * 5mm * 10mm with the β type Zr-Nb-Ti that adopts above-mentioned preparation method to make, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength are respectively 30.15GPa, 1160MPa, 37.49%, 910MPa.Find that by comparative example 1,2 rate of compression of this alloy cast ingot descends a little, Young's modulus slightly rises, and compressive strength raises to some extent.Fig. 3 is the microstructure picture of this alloy, and the x=7 among Fig. 6 is the X ray diffracting spectrum of this sample.
Embodiment 4
1. composition of raw materials: feed composition and weight percent are: zirconium sponge 69.00%, niobium 20.00%, titanium 11.00%; The purity of zirconium sponge, niobium and titanium is all more than 99%.
2. preparation method
(1) taking by weighing of raw material takes by weighing zirconium sponge, niobium and titanium respectively according to the weight percent of each feed composition; The raw material particle size size control is below 3 centimetres;
(2) raw material mixes, and the prepared using stirring mixing method that weighs up is mixed;
(3) raw material melting is put into the crucible of non-consumable arc furnace with the raw material that mixes, and vacuumizes then, and vacuum tightness is 1 * 10
-2～1 * 10
-3Pa; Feed argon gas again and carry out gas washing; Vacuumize with gas washing and carry out repeatedly 2～4 times.At last carry out melting under the protection of argon gas, smelting temperature is 2850～2950 ℃; Melting voltage is 220V, and the melting current control keeps 140 s ~ 160 s at 200-210A, and then electric current slowly is adjusted to 0A, and the time that electric current drops to 0 A is 40-60s, and so melt back obtains thick alloy cast ingot more than 5 times;
(4) cooling of thick alloy cast ingot; under argon shield; to the crucible bottom water flowing; utilize the water that flows that thick alloy cast ingot is cooled off fast, thick alloy is 20 ~ 30 seconds by liquid state to solid-state cooling time, and continuation keeps the crucible bottom water flowing then; alloy cast ingot is continued to be parked in the stove internal cooling; take out after being cooled to room temperature, 450-550 second whole cooling time, obtaining β type Zr-Nb-Ti is the bio-medical alloy.
3. the detection of alloy material
Be that the bio-medical alloy utilizes the omnipotent experimental system of Instron8801 that specification is carried out the test of room temperature compression performance for the sample of 5mm * 5mm * 10mm with the β type Zr-Nb-Ti that adopts above-mentioned preparation method to make, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength are respectively 29.35GPa, 1222MPa, 38.11%, 1050MPa.Compare with the sample of front, the comprehensive mechanical property of this sample promotes to some extent, and Fig. 4 is the microstructure picture of this alloy, and the x=11 among Fig. 6 is the X ray diffracting spectrum of this sample.
Embodiment 5
1. composition of raw materials: feed composition and weight percent are: zirconium sponge 65.00%, niobium 20.00%, titanium 15.00%; The purity of zirconium sponge, niobium and titanium is all more than 99%.
2. preparation method
(1) taking by weighing of raw material takes by weighing zirconium sponge, niobium and titanium respectively according to the weight percent of each feed composition; The raw material particle size size control is below 3 centimetres;
(2) raw material mixes, and the prepared using stirring mixing method that weighs up is mixed;
(3) raw material melting is put into the crucible of non-consumable arc furnace with the raw material that mixes, and vacuumizes then, and vacuum tightness is 1 * 10
-2～1 * 10
-3Pa; Feed argon gas again and carry out gas washing; Vacuumize with gas washing and carry out repeatedly 2～4 times.At last carry out melting under the protection of argon gas, smelting temperature is 3000～3100 ℃; Melting voltage is 220V, and the melting current control keeps 160 s ~ 180 s at 190-210A, and then electric current slowly is adjusted to 0A, and the time that electric current drops to 0 A is 40-60s, and so melt back obtains thick alloy cast ingot more than 5 times;
(4) cooling of thick alloy cast ingot; under argon shield; to the crucible bottom water flowing; utilize the water that flows that thick alloy cast ingot is cooled off fast, thick alloy is 15 ~ 25 seconds by liquid state to solid-state cooling time, and continuation keeps the crucible bottom water flowing then; alloy cast ingot is continued to be parked in the stove internal cooling; take out after being cooled to room temperature, 500-600 second whole cooling time, obtaining β type Zr-Nb-Ti is the bio-medical alloy.
3. the detection of alloy material
Be that the bio-medical alloy utilizes the omnipotent experimental system of Instron8801 that specification is carried out the test of room temperature compression performance for the sample of 5mm * 5mm * 10mm with the β type Zr-Nb-Ti that adopts above-mentioned preparation method to make, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength are respectively 30.45GPa, 1325MPa, 37.69%, 1061MPa.Compare with embodiment 4, the compressive strength of this sample promotes to some extent, and rate of compression descends a little, and Fig. 5 is the microstructure picture of this alloy, and the x=15 among Fig. 6 is the X ray diffracting spectrum of this sample.
Embodiment 6
1. composition of raw materials: feed composition and weight percent are: zirconium sponge 69.00%, niobium 19.50%, titanium 11.00%; The purity of zirconium sponge, niobium and titanium is all more than 99%.
2. preparation method
(1) taking by weighing of raw material takes by weighing zirconium sponge, niobium and titanium respectively according to the weight percent of each feed composition; The raw material particle size size control is below 3 centimetres;
(2) raw material mixes, and the prepared using stirring mixing method that weighs up is mixed;
(3) raw material melting is put into the crucible of non-consumable arc furnace with the raw material that mixes, and vacuumizes then, and vacuum tightness is 1 * 10
-2～1 * 10
-3Pa; Feed argon gas again and carry out gas washing; Vacuumize with gas washing and carry out repeatedly 2～4 times.At last carry out melting under the protection of argon gas, smelting temperature is 2850～2950 ℃; Melting voltage is 220V, and the melting current control keeps 140 s ~ 160 s at 200-210A, and then electric current slowly is adjusted to 0A, and the time that electric current drops to 0 A is 40-60s, and so melt back obtains thick alloy cast ingot more than 5 times;
(4) cooling of thick alloy cast ingot; under argon shield; to the crucible bottom water flowing; utilize the water that flows that thick alloy cast ingot is cooled off fast, thick alloy is 20 ~ 30 seconds by liquid state to solid-state cooling time, and continuation keeps the crucible bottom water flowing then; alloy cast ingot is continued to be parked in the stove internal cooling; take out after being cooled to room temperature, 450-550 second whole cooling time, obtaining β type Zr-Nb-Ti is the bio-medical alloy.
3. the detection of alloy material
Be that the bio-medical alloy utilizes the omnipotent experimental system of Instron8801 that specification is carried out the test of room temperature compression performance for the sample of 5mm * 5mm * 10mm with the β type Zr-Nb-Ti that adopts above-mentioned preparation method to make, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength are respectively 29.25GPa, 1283MPa, 38.01%, 1043MPa.
1. composition of raw materials: feed composition and weight percent are: zirconium sponge 69.00%, niobium 20.50%, titanium 11.00%; The purity of zirconium sponge, niobium and titanium is all more than 99%.
2. preparation method
(1) taking by weighing of raw material takes by weighing zirconium sponge, niobium and titanium respectively according to the weight percent of each feed composition; The raw material particle size size control is below 3 centimetres;
(2) raw material mixes, and the prepared using stirring mixing method that weighs up is mixed;
(3) raw material melting is put into the crucible of non-consumable arc furnace with the raw material that mixes, and vacuumizes then, and vacuum tightness is 1 * 10
-2～1 * 10
-3Pa; Feed argon gas again and carry out gas washing; Vacuumize with gas washing and carry out repeatedly 2～4 times.At last carry out melting under the protection of argon gas, smelting temperature is 2900～3000 ℃; Melting voltage is 220V, and the melting current control keeps 150 s ~ 180 s at 200-210A, and then electric current slowly is adjusted to 0A, and the time that electric current drops to 0 A is 40-60s, and so melt back obtains thick alloy cast ingot more than 5 times;
(4) cooling of thick alloy cast ingot; under argon shield; to the crucible bottom water flowing; utilize the water that flows that thick alloy cast ingot is cooled off fast, thick alloy is 20 ~ 30 seconds by liquid state to solid-state cooling time, and continuation keeps the crucible bottom water flowing then; alloy cast ingot is continued to be parked in the stove internal cooling; take out after being cooled to room temperature, 500-600 second whole cooling time, obtaining β type Zr-Nb-Ti is the bio-medical alloy.
3. the detection of alloy material
Be that the bio-medical alloy utilizes the omnipotent experimental system of Instron8801 that specification is carried out the test of room temperature compression performance for the sample of 5mm * 5mm * 10mm with the β type Zr-Nb-Ti that adopts above-mentioned preparation method to make, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength are respectively 30.15GPa, 1365MPa, 38.03%, 1038MPa.
To be the bio-medical alloy through certain hospital of medical university be prepared at the backbone correction device β type Zr-Nb-Ti that above-described embodiment is made uses the volunteer, being used for backbone corrects, the effect proof is better than the Young's modulus of the titanium matrix composite of original import, to the human zero damage, other character also meets the medical material requirement, illustrates that material of the present invention meets medical science and human body requirement.
Claims (7)
1. a β type Zr-Nb-Ti is the bio-medical alloy, and it is characterized in that: raw materials used component and weight percent are: niobium 19.5%～20.5%, and titanium 0.1～15.0%, surplus is zirconium sponge.
2. β type Zr-Nb-Ti according to claim 1 is the bio-medical alloy, and it is characterized in that: raw materials used component and weight percent are: niobium 20%, and titanium 10～15.00%, surplus is zirconium sponge.
3. β type Zr-Nb-Ti according to claim 1 and 2 is the bio-medical alloy, it is characterized in that: the purity of zirconium sponge, niobium and titanium is all more than 99.0%.
4. β type Zr-Nb-Ti according to claim 3 is the bio-medical alloy, it is characterized in that: β type Zr-Nb-Ti is that the Young's modulus of bio-medical alloy is 27 ~ 32 GPa, maximum compressive strength reaches 1000 ~ 1400 MPa, rate of compression is 36.0 ~ 38.0%, and yield strength is 850 ~ 1100MPa.
5. one kind is the preparation method of bio-medical alloy as β type Zr-Nb-Ti as described in the claim 1 ~ 4, and it is characterized in that: its preparation process is as follows:
(1) raw material takes by weighing, and takes by weighing zirconium sponge, titanium and niobium respectively according to the weight percent of each feed composition; The raw material particle size size control is below 3 centimetres;
(2) raw material mixes, and the raw material stirring that weighs up is mixed;
(3) raw material melting is put into the crucible of non-consumable arc furnace with the raw material that mixes, and vacuumizes then, and vacuum degree control is 1 * 10
-2～1 * 10
-3Pa; Feeding rare gas element again carries out gas washing and removes residual air; At last carry out melting under the protection of rare gas element, smelting temperature is 2800～3100 ℃; Melting voltage is 220V, and the melting current control keeps 120 s ~ 180 s at 190 ~ 210A, and then electric current slowly is adjusted to 0A, and the time that electric current drops to 0 A is 40 ~ 60s, and melt back obtains thick alloy cast ingot more than 5 times;
(4) cooling of thick alloy cast ingot; under protection of inert gas; to the crucible bottom water flowing; utilize the water that flows that thick alloy cast ingot is cooled off fast; thick alloy is 10 ~ 30 seconds by liquid state to solid-state cooling time, and continuation keeps the crucible bottom water flowing then, and alloy cast ingot is continued to be parked in the stove internal cooling; take out after being cooled to room temperature, obtaining β type Zr-Nb-Ti is the bio-medical alloy.
6. β type Zr-Nb-Ti according to claim 5 is the preparation method of bio-medical alloy, it is characterized in that: described vacuumizing with gas washing carried out 2～4 times repeatedly.
7. β type Zr-Nb-Ti according to claim 5 is the preparation method of bio-medical alloy, it is characterized in that: described rare gas element is argon gas, and pressure is a standard atmospheric pressure.
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| CN105586507A (en) * | 2016-03-14 | 2016-05-18 | 广西大学 | Beta-type Zr-Nb-Si biomedical alloy and preparation method thereof |
| CN107090554A (en) * | 2017-03-31 | 2017-08-25 | 江苏大学 | 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 |
| CN107142444A (en) * | 2017-03-28 | 2017-09-08 | 广西大学 | A kind of preparation method of the medical zircaloy of β types of surface oxidation |
| CN107893176A (en) * | 2017-11-08 | 2018-04-10 | 大连理工大学 | A kind of Zr Nb based alloys and its application with good increasing material manufacturing forming property |
| CN108034846A (en) * | 2018-01-05 | 2018-05-15 | 中南大学 | A kind of high intensity low elastic modulus zirconium niobium titanium dentistry implant material and preparation method thereof |
| CN108203778A (en) * | 2018-01-15 | 2018-06-26 | 中南大学 | Zr base biomedical alloys and preparation method thereof |
| CN110714138A (en) * | 2019-11-04 | 2020-01-21 | 河北科技师范学院 | High-performance zirconium-titanium binary alloy and preparation method thereof |
| CN111647772A (en) * | 2020-06-02 | 2020-09-11 | 广西大学 | Medical zirconium-based composite material with low elastic modulus and high strength and preparation method thereof |
| CN111763852A (en) * | 2020-05-20 | 2020-10-13 | 东南大学 | Biomedical implanted zirconium alloy and preparation method thereof |
| CN111842917A (en) * | 2020-07-27 | 2020-10-30 | 安徽有研吸气材料有限公司 | Components of high-performance getter alloy and processing method thereof |
| CN112575222A (en) * | 2020-12-07 | 2021-03-30 | 北京理工大学 | Zr-Ti-X alloy and preparation method and application thereof |
| CN114277283A (en) * | 2021-12-28 | 2022-04-05 | 南京理工大学 | Omega-rich medical zirconium-based alloy and preparation method thereof |
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| CN105586507A (en) * | 2016-03-14 | 2016-05-18 | 广西大学 | Beta-type Zr-Nb-Si biomedical alloy and preparation method thereof |
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| CN107142444A (en) * | 2017-03-28 | 2017-09-08 | 广西大学 | A kind of preparation method of the medical zircaloy of β types of surface oxidation |
| CN107142444B (en) * | 2017-03-28 | 2019-09-06 | 广西大学 | A kind of preparation method of the medical zircaloy of β type of surface oxidation |
| CN107090554A (en) * | 2017-03-31 | 2017-08-25 | 江苏大学 | 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 |
| CN107893176A (en) * | 2017-11-08 | 2018-04-10 | 大连理工大学 | A kind of Zr Nb based alloys and its application with good increasing material manufacturing forming property |
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| CN110714138A (en) * | 2019-11-04 | 2020-01-21 | 河北科技师范学院 | High-performance zirconium-titanium binary alloy and preparation method thereof |
| 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 |
| CN111647772A (en) * | 2020-06-02 | 2020-09-11 | 广西大学 | Medical zirconium-based composite material with low elastic modulus and high strength and preparation method thereof |
| CN111842917A (en) * | 2020-07-27 | 2020-10-30 | 安徽有研吸气材料有限公司 | Components of high-performance getter alloy and processing method thereof |
| CN111842917B (en) * | 2020-07-27 | 2023-11-03 | 安徽有研吸气新材料股份有限公司 | High-performance getter alloy component and processing method thereof |
| CN112575222A (en) * | 2020-12-07 | 2021-03-30 | 北京理工大学 | Zr-Ti-X alloy and preparation method and application thereof |
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| CN114855016A (en) * | 2022-05-24 | 2022-08-05 | 深圳技术大学 | Zirconium alloy with nano/micron structure and preparation method thereof |
| CN114855016B (en) * | 2022-05-24 | 2022-12-30 | 深圳技术大学 | Zirconium alloy with nano/micron structure and preparation method thereof |
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