CN103173655B - A kind of sclerous tissues bio-medical in-situ authigenic zirconium based composite material - Google Patents
A kind of sclerous tissues bio-medical in-situ authigenic zirconium based composite material Download PDFInfo
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- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 60
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 39
- 239000010955 niobium Substances 0.000 claims abstract description 39
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000002844 melting Methods 0.000 claims abstract description 37
- 230000008018 melting Effects 0.000 claims abstract description 37
- 239000010949 copper Substances 0.000 claims abstract description 34
- 229910052802 copper Inorganic materials 0.000 claims abstract description 33
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000001816 cooling Methods 0.000 claims abstract description 29
- 238000002360 preparation method Methods 0.000 claims abstract description 21
- 239000000956 alloy Substances 0.000 claims description 81
- 229910045601 alloy Inorganic materials 0.000 claims description 70
- 239000007789 gas Substances 0.000 claims description 40
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000203 mixture Substances 0.000 claims description 24
- 230000006835 compression Effects 0.000 claims description 21
- 238000007906 compression Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 18
- 229910052786 argon Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- 238000003723 Smelting Methods 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 9
- 238000012423 maintenance Methods 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 2
- 210000001519 tissue Anatomy 0.000 abstract description 23
- 239000000463 material Substances 0.000 abstract description 14
- 229910001069 Ti alloy Inorganic materials 0.000 abstract description 11
- 239000011159 matrix material Substances 0.000 abstract description 10
- 230000006378 damage Effects 0.000 abstract description 8
- 210000000988 bone and bone Anatomy 0.000 abstract description 5
- 229910000967 As alloy Inorganic materials 0.000 abstract description 4
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 150000002739 metals Chemical class 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- 238000001514 detection method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 239000003519 biomedical and dental material Substances 0.000 description 6
- 229910001093 Zr alloy Inorganic materials 0.000 description 5
- 239000002763 biomedical alloy Substances 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 239000007943 implant Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000003628 erosive effect Effects 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000012620 biological material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000035876 healing Effects 0.000 description 2
- 230000007774 longterm Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 231100000956 nontoxicity Toxicity 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910001040 Beta-titanium Inorganic materials 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229910020012 Nb—Ti Inorganic materials 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 208000030961 allergic reaction Diseases 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000002929 anti-fatigue Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
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- 238000012937 correction Methods 0.000 description 1
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- 239000000446 fuel Substances 0.000 description 1
- 230000036039 immunity Effects 0.000 description 1
- 230000008676 import Effects 0.000 description 1
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- 208000014674 injury Diseases 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
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Abstract
The invention discloses a kind of sclerous tissues bio-medical in-situ authigenic zirconium based composite material and preparation method thereof.Raw materials used component and weight percent are: copper 3.5% ~ 4.5%, niobium 0.1 ~ 1.20%, and surplus is zirconium sponge.Its preparation method first takes corresponding raw material according to the weight percent of each component, and fully mixed by raw material, then utilize non-consumable arc furnace to carry out melting, cooling obtains the cast metals of homogeneous microstructure.The present invention has the advantage of conventional medical titanium alloy, solves conventional medical titanium alloy in Young's modulus and the unmatched problem of human body natural's bone simultaneously, is expected to the damage that solution equivalent material causes human body because mechanical property is not mated.The present invention utilizes the Zr of in-situ authigenic
3cu is as wild phase, and niobium, as alloy element, is strengthened zirconium matrix, effectively improves the compressive strength of zirconium based composite material, compressive strength, plasticity, Young's modulus etc. simultaneously by regulating the content of niobium to change zirconium based composite material.
Description
Technical field
The invention belongs to metal-base composites technical field, be specifically related to bio-medical in-situ authigenic zirconium-based alloy material and preparation method thereof.
Background technology
Bio-medical material comprises medically can implantable bioartificial body or the material that can combine with bio-tissue, and biomaterial is used for treatment or replace original tissue and organ in living organism, revises and improves its function.Current biomedical metallic material is widespread use Srgery grafting material, has high intensity, 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 meet strict biological requirement as bio-medical material: (1) histocompatibility is good, nontoxicity, not aberration inducing, does not cause allergic reaction and disturbs the immunity of matrix, not destroying adjacent tissue etc.; (2) physicochemical property are stablized, the stable in properties such as intensity, elasticity, size, corrosion-resistant, wear resistance; (3) be easy to machine-shaping, easily make the shape of various needs.
Metal current material titanium and titanium alloys is widely used on biological and medicinal implant material, and especially the application of beta-titanium alloy is more extensive.But, along with the development of medical technology, the deficiency that titanium alloy exists in biomedical application embodies gradually, one of them is exactly that Young's modulus mates not with the Young's modulus of natural bone, easily cause stress shielding effect, be unfavorable for the long-term stability of bone healing and implant, easily damage is caused to human body.So the biomedical alloy material of development of new becomes a main research direction of bio-medical material now.
Zirconium alloy has that excellent corrosion resistance nature, mechanical property, histocompatibility are good, nontoxicity, mainly as reactor core structured material, as fuel sheath; Be commonly used for corrosion resistant container and pipeline, as penstock, support and duct pipe etc.The research of current zirconium alloy in bio-medical material is also quite rare, and most research is all as the alloying element added to promote the performance of titanium alloy using zirconium.And the present invention using the application of zirconium alloy on bio-medical as main research direction.The zirconium base alloy worked out is compared with traditional titanium alloy, and zirconium and alloy thereof have erosion resistance, the intensity better than titanium, and lower Young's modulus well compensate for the deficiency of conventional titanium alloy.
Summary of the invention
The object of this invention is to provide a kind of sclerous tissues bio-medical in-situ authigenic zirconium based composite material and preparation method thereof, it can substitute or the application of Some substitute titanium alloy on bio-medical, it has good biocompatibility, and to human non-toxic's evil, there is the Young's modulus matched with skeleton simultaneously, therefore can effectively reduce damage human body caused because mechanics does not mate.
Technical solution of the present invention is as follows:
A kind of sclerous tissues bio-medical in-situ authigenic zirconium based composite material, raw materials used component and weight percent are: copper 3.5% ~ 4.50%, niobium 0.1 ~ 1.2%, and surplus is zirconium sponge.Preferred feed composition and weight percent are: copper 4.00%, niobium 0.5 ~ 1.0%, and surplus is zirconium sponge, the biomedical alloy that this formula obtains, and every stable in properties is functional.
The purity of the zirconium sponge that the present invention adopts, copper and niobium, all more than 99.0%, all can commercially obtain.
The Young's modulus of sclerous tissues's bio-medical in-situ authigenic zirconium based composite material prepared by the present invention is 25 ~ 31GPa, and maximum compressive strength reaches 1100 ~ 1300MPa, and rate of compression is 20.0 ~ 28.0%, and yield strength is 750 ~ 1000MPa.
The preparation method of sclerous tissues of the present invention bio-medical in-situ authigenic zirconium based composite material, its preparation process is as follows:
(1) raw material takes, and the weight percent according to each feed composition takes zirconium sponge, copper and niobium respectively; Raw material particle size size control is below 2 centimetres;
(2) raw material mixing, mixes the raw material stirring weighed up;
(3) raw material melting, puts into the crucible of non-consumable arc furnace, then vacuumizes by the raw material mixed, vacuum degree control is 1 × 10
-2~ 1 × 10
-3pa; Pass into rare gas element again and carry out the residual air of gas washing removing; Finally under the protection of rare gas element, carry out melting, smelting temperature is 2800 ~ 3000 DEG C; Melting voltage is 220V, and melting current control is at 180 ~ 200A, and keep 100s ~ 150s, and then electric current is slowly adjusted to 0A, the time that electric current drops to 0A is 40 ~ 60s, and melt back like this more than 5 times, obtains thick alloy cast ingot; Vacuumizing of step (3) carries out 2 ~ 4 times repeatedly with gas washing;
(4) cooling of thick alloy cast ingot; under protection of inert gas; to crucible bottom water flowing; utilize the water of flowing to cool fast thick alloy cast ingot, thick alloy is 10 ~ 30 seconds by liquid state to solid-state cooling time, then continues maintenance to crucible bottom water flowing; alloy cast ingot is continued to be parked in stove and cools; take out after being cooled to room temperature, obtain sclerous tissues's bio-medical in-situ authigenic zirconium based composite material of homogeneous microstructure, 400 ~ 600 seconds whole cooling times.
The rare gas element that the present invention adopts is argon gas, and pressure is a standard atmospheric pressure.
Zr of the present invention as the matrix of matrix material, the Zr of in-situ authigenic
3cu is as wild phase, and improve alloy strength, niobium is as alloy element.Zr
3cu is at high temperature in process of cooling, because the solid solubility of Cu in Zr declines, separates out Zr
3cu, for this part Zr
3cu, near the crystal boundary mainly concentrating on zirconium, because Zr
3cu is in precipitation process, and Cu atom spreads to the grain boundary area that energy comparison is high, reduces the energy of grain boundary area with this.In addition, near 790 DEG C, eutectoid reaction occurs, and β-Zr changes Zr into
3cu and α-Zr.
Niobium, as alloy element, can produce significant solution strengthening effect in α-Zr matrix, and its consumption rationally can play the effect of crystal grain thinning and refinement second-phase, carries heavy alloyed comprehensive mechanical property.That is niobium adds zirconium alloy and can put forward heavy alloyed intensity and the plasticity and the processing characteristics that do not affect alloy, can strengthen the corrosion resistance nature of alloy.
Three kinds of elements, in the process of solid solution, second-phase strength, mainly play adjustment alloy mechanical performance, such as ultimate compression strength, Young's modulus, plastix strain etc.
Zirconium base biomedical alloy material of the present invention has the advantage of the standard biologic medical alloys such as conventional titanium alloy, it more mates at Young's modulus energy skeleton simultaneously, erosion resistance is strong, effectively can alleviate the corrosion of physiological environment alloy material, prevent metal ion from organizing diffusion towards periphery, material can be applied to biological and medicinal implant material, as the aspect such as artificial limb, artificial bone.
Advantage of the present invention:
1. matrix material of the present invention has good biocompatibility, and its Young's modulus (25-31GPa) is more mated with skeleton (10-40GPa), effectively can avoid the injury caused human body because mechanics does not mate.If when the Young's modulus of alloy material exceedes the Young's modulus of skeleton, because its rigidity is excessive, during as biomaterial, easily damage is caused to skeleton and muscle, be unfavorable for the long-term stability of bone healing and implant.The Young's modulus of a lot of biomedical alloy is higher at present, in actual application, causes certain damage to function of human body, produces the complication such as pain, hinders it to develop.The Young's modulus that therefore will control medical alloy material and skeleton mate mutually just can guarantee that material for a long time and human contact, can not produce damage to human body, can ensure again the normal effect of function of human body simultaneously.
2. the Zr of in-situ authigenic of the present invention
3cu plays second-phase strength effect as reinforcement, effectively raises the character such as the ultimate compression strength of matrix material; Adopt niobium as alloy element, control its reasonable volume, it plays solution strengthening effect, puies forward heavy alloyed intensity, strengthens the erosion resistance of alloy.Three kinds of element actings in conjunction can play the effect of the character such as ultimate compression strength, Young's modulus, plasticity, yield strength regulating matrix material, thus better adapt to the requirement of bio-medical material.
3. niobium used in zirconium based composite material of the present invention, copper are all to human non-toxic's side effect, zirconium alloy is also to human non-toxic's side effect, niobium, copper production cost are lower, the alloy element of medical alloy is in the past avoided to depend on noble metal unduly, reduce alloy research and development and production cost, have good development prospect.
4. matrix material of the present invention can substitute or the application of Some substitute titanium alloy on bio-medical, it has the every premium properties as bio-medical material, also the various advantages of conventional titanium alloy have been possessed, there is high mechanical strength and anti-fatigue performance, for biomedical materials field provides a kind of novel material.
Accompanying drawing explanation
Fig. 1 is the microstructure picture of the embodiment of the present invention 1.
Fig. 2 is the microstructure picture of the embodiment of the present invention 2.
Fig. 3 is the microstructure picture of the embodiment of the present invention 3.
Fig. 4 is the microstructure picture of the embodiment of the present invention 4.
Fig. 5 is the microstructure picture of the embodiment of the present invention 5.
Fig. 6 is the XRD spectral line of all embodiments of the present invention.
Specific embodiment
Below in conjunction with specific examples, the present invention is described further, but protection scope of the present invention does not limit to the scope that embodiment represents.
Embodiment 1
1. composition of raw materials: feed composition and weight percent are: zirconium sponge 96.00%, copper 4.00%, niobium 0.1%; The purity of zirconium sponge, copper and niobium is all more than 99%.
2. preparation method
(1) the taking of raw material, the weight percent according to each feed composition takes zirconium sponge, copper, niobium respectively; Raw material particle size size control is below 2 centimetres;
(2) raw material mixing, mixes the prepared using stirring mixing method weighed up;
(3) raw material melting, puts into the crucible of non-consumable arc furnace, then vacuumizes by the raw material mixed, vacuum tightness is 1 × 10
-2~ 1 × 10
-3pa; Pass into argon gas again and carry out gas washing; Vacuumize and repeatedly carry out 2 ~ 4 times with gas washing.Finally under the protection of rare gas element, carry out melting, smelting temperature is 2800 ~ 3000 DEG C; Melting voltage is 220V, and melting current control is at 180-200A, and keep 100s ~ 150s, and then electric current is slowly adjusted to 0A, the time that electric current drops to 0A is 40-60s, and melt back like this more than 5 times, obtains thick alloy cast ingot;
(4) cooling of thick alloy cast ingot; under argon shield; to crucible bottom water flowing; utilize the water of flowing to cool fast thick alloy cast ingot, thick alloy is 10 ~ 30 seconds by liquid state to solid-state cooling time, then continues maintenance to crucible bottom water flowing; alloy cast ingot is continued to be parked in stove and cools; take out after being cooled to room temperature, 400-600 second whole cooling time, obtain sclerous tissues's bio-medical in-situ authigenic zirconium based composite material.
3. the detection of alloy material
To sclerous tissues's bio-medical in-situ authigenic zirconium based composite material of obtaining of above-mentioned preparation method be adopted to utilize the omnipotent experimental system of Instron8801 to carry out the test of room temperature compression performance to the sample that specification is 5mm × 5mm × 10mm, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength be respectively 25.78GPa, 1174MPa, 26.92%, 796MPa.Fig. 1 is the microstructure picture of this alloy, in the microtexture of this sample as cast condition, can significantly see wild phase Zr
3cu.X=0 in Fig. 6 is the X ray diffracting spectrum of this sample, significantly can find out to there is wild phase Zr
3cu.
Embodiment 2
1. composition of raw materials: feed composition and weight percent are: zirconium sponge 95.70%, copper 4.00%, niobium 0.30%; The purity of zirconium sponge, copper and niobium is all more than 99%.
2. preparation method
(1) the taking of raw material, the weight percent according to each feed composition takes zirconium sponge, copper and niobium respectively; Raw material particle size size control is below 2 centimetres;
(2) raw material mixing, mixes the prepared using stirring mixing method weighed up;
(3) raw material melting, puts into the crucible of non-consumable arc furnace, then vacuumizes by the raw material mixed, vacuum tightness is 1 × 10
-2~ 1 × 10
-3pa; Pass into argon gas again and carry out gas washing; Vacuumize and repeatedly carry out 2 ~ 4 times with gas washing.Finally under the protection of rare gas element, carry out melting, smelting temperature is 2800 ~ 2900 DEG C; Melting voltage is 220V, and melting current control is at 180-190A, and keep 100s ~ 120s, and then electric current is slowly adjusted to 0A, the time that electric current drops to 0A is 40-60s, and melt back like this more than 5 times, obtains thick alloy cast ingot;
(4) cooling of thick alloy cast ingot; under argon shield; to crucible bottom water flowing; utilize the water of flowing to cool fast thick alloy cast ingot, thick alloy is 20 ~ 30 seconds by liquid state to solid-state cooling time, then continues maintenance to crucible bottom water flowing; alloy cast ingot is continued to be parked in stove and cools; take out after being cooled to room temperature, 500-600 second whole cooling time, obtain sclerous tissues's bio-medical in-situ authigenic zirconium based composite material.
3. the detection of alloy material
To sclerous tissues's bio-medical in-situ authigenic zirconium based composite material of obtaining of above-mentioned preparation method be adopted to utilize the omnipotent experimental system of Instron8801 to carry out the test of room temperature compression performance to the sample that specification is 5mm × 5mm × 10mm, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength be respectively 27.53GPa, 1189MPa, 25.44%, 815MPa.After contrasting with embodiment 1 niobium finding to the addition of 0.30%, compressive strength, the Young's modulus of metal slightly increase, and rate of compression declines a little.Fig. 2 is the microstructure picture of this alloy cast ingot.X=0.3 in Fig. 6 is the X ray diffracting spectrum of this sample.
Embodiment 3
1. composition of raw materials: feed composition and weight percent are: zirconium sponge 95.40%, copper 4.00%; Niobium 0.60%, the purity of zirconium sponge, copper and niobium is all more than 99%.
2. preparation method
(1) the taking of raw material, the weight percent according to each feed composition takes zirconium sponge, copper and niobium respectively; Raw material particle size size control is below 2 centimetres;
(2) raw material mixing, mixes the prepared using stirring mixing method weighed up;
(3) raw material melting, puts into the crucible of non-consumable arc furnace, then vacuumizes by the raw material mixed, vacuum tightness is 1 × 10
-2~ 1 × 10
-3pa; Pass into argon gas again and carry out gas washing; Vacuumize and repeatedly carry out 2 ~ 4 times with gas washing.Finally under the protection of rare gas element, carry out melting, smelting temperature is 2850 ~ 2950 DEG C; Melting voltage is 220V, and melting current control is at 190A, and keep 110s ~ 130s, and then electric current is slowly adjusted to 0A, the time that electric current drops to 0A is 40-60s, and melt back like this more than 5 times, obtains thick alloy cast ingot;
(4) cooling of thick alloy cast ingot; under argon shield; to crucible bottom water flowing; utilize the water of flowing to cool fast thick alloy cast ingot, thick alloy is 10 ~ 30 seconds by liquid state to solid-state cooling time, then continues maintenance to crucible bottom water flowing; alloy cast ingot is continued to be parked in stove and cools; take out after being cooled to room temperature, 400-600 second whole cooling time, obtain sclerous tissues's bio-medical in-situ authigenic zirconium based composite material.
3. the detection of alloy material
To sclerous tissues's bio-medical in-situ authigenic zirconium based composite material of obtaining of above-mentioned preparation method be adopted to utilize the omnipotent experimental system of Instron8801 to carry out the test of room temperature compression performance to the sample that specification is 5mm × 5mm × 10mm, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength be respectively 30.08GPa, 1271MPa, 21.68%, 892MPa.Found by comparative example 1,2, the rate of compression of this alloy cast ingot reduces, and Young's modulus slightly increases, and compressive strength strengthens to some extent.Fig. 3 is the microstructure picture of this alloy, and the x=0.6 in 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 95.1%, copper 4.00%, niobium 0.90%; The purity of zirconium sponge, copper and niobium is all more than 99%.
2. preparation method
(1) the taking of raw material, the weight percent according to each feed composition takes zirconium sponge, copper and niobium respectively; Raw material particle size size control is below 2 centimetres;
(2) raw material mixing, mixes the prepared using stirring mixing method weighed up;
(3) raw material melting, puts into the crucible of non-consumable arc furnace, then vacuumizes by the raw material mixed, vacuum tightness is 1 × 10
-2~ 1 × 10
-3pa; Pass into argon gas again and carry out gas washing; Vacuumize and repeatedly carry out 2 ~ 4 times with gas washing.Finally under the protection of rare gas element, carry out melting, smelting temperature is 2900 ~ 3000 DEG C; Melting voltage is 220V, and melting current control is at 190-200A, and keep 100s ~ 150s, and then electric current is slowly adjusted to 0A, the time that electric current drops to 0A is 40-60s, and melt back like this more than 5 times, obtains thick alloy cast ingot;
(4) cooling of thick alloy cast ingot; under argon shield; to crucible bottom water flowing; utilize the water of flowing to cool fast thick alloy cast ingot, thick alloy is 15 ~ 25 seconds by liquid state to solid-state cooling time, then continues maintenance to crucible bottom water flowing; alloy cast ingot is continued to be parked in stove and cools; take out after being cooled to room temperature, 450-550 second whole cooling time, obtain sclerous tissues's bio-medical in-situ authigenic zirconium based composite material.
3. the detection of alloy material
To sclerous tissues's bio-medical in-situ authigenic zirconium based composite material of obtaining of above-mentioned preparation method be adopted to utilize the omnipotent experimental system of Instron8801 to carry out the test of room temperature compression performance to the sample that specification is 5mm × 5mm × 10mm, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength be respectively 29.23GPa, 1245MPa, 20.90%, 951MPa.Fig. 4 is the microstructure picture of this alloy, and the x=0.9 in 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 94.8%, copper 4.00%, niobium 1.20%; The purity of zirconium sponge, copper and niobium is all more than 99%.
2. preparation method
(1) the taking of raw material, the weight percent according to each feed composition takes zirconium sponge, copper and niobium respectively; Raw material particle size size control is below 2 centimetres;
(2) raw material mixing, mixes the prepared using stirring mixing method weighed up;
(3) raw material melting, puts into the crucible of non-consumable arc furnace, then vacuumizes by the raw material mixed, vacuum tightness is 1 × 10
-2~ 1 × 10
-3pa; Pass into argon gas again and carry out gas washing; Vacuumize and repeatedly carry out 2 ~ 4 times with gas washing.Finally under the protection of rare gas element, carry out melting, smelting temperature is 2850 ~ 2950 DEG C; Melting voltage is 220V, and melting current control is at 190A, and keep 110s ~ 130s, and then electric current is slowly adjusted to 0A, the time that electric current drops to 0A is 40-60s, and melt back like this more than 5 times, obtains thick alloy cast ingot;
(4) cooling of thick alloy cast ingot; under argon shield; to crucible bottom water flowing; utilize the water of flowing to cool fast thick alloy cast ingot, thick alloy is 10 ~ 30 seconds by liquid state to solid-state cooling time, then continues maintenance to crucible bottom water flowing; alloy cast ingot is continued to be parked in stove and cools; take out after being cooled to room temperature, 400-600 second whole cooling time, obtain sclerous tissues's bio-medical in-situ authigenic zirconium based composite material.
3. the detection of alloy material
To sclerous tissues's bio-medical in-situ authigenic zirconium based composite material of obtaining of above-mentioned preparation method be adopted to utilize the omnipotent experimental system of Instron8801 to carry out the test of room temperature compression performance to the sample that specification is 5mm × 5mm × 10mm, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength be respectively 29.66GPa, 1222MPa, 20.83%, 847MPa.Fig. 5 is the microstructure picture of this alloy, and the x=1.2 in 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 95.40%, copper 3.50%; Niobium 0.60%, the purity of zirconium sponge, copper and niobium is all more than 99%.
2. preparation method
(1) the taking of raw material, the weight percent according to each feed composition takes zirconium sponge, copper and niobium respectively; Raw material particle size size control is below 2 centimetres;
(2) raw material mixing, mixes the prepared using stirring mixing method weighed up;
(3) raw material melting, puts into the crucible of non-consumable arc furnace, then vacuumizes by the raw material mixed, vacuum tightness is 1 × 10
-2~ 1 × 10
-3pa; Pass into argon gas again and carry out gas washing; Vacuumize and repeatedly carry out 2 ~ 4 times with gas washing.Finally under the protection of rare gas element, carry out melting, smelting temperature is 2900 ~ 3000 DEG C; Melting voltage is 220V, and melting current control is at 200A, and keep 100s ~ 150s, and then electric current is slowly adjusted to 0A, the time that electric current drops to 0A is 40-60s, and melt back like this more than 5 times, obtains thick alloy cast ingot;
(4) cooling of thick alloy cast ingot; under argon shield; to crucible bottom water flowing; utilize the water of flowing to cool fast thick alloy cast ingot, thick alloy is 15 ~ 25 seconds by liquid state to solid-state cooling time, then continues maintenance to crucible bottom water flowing; alloy cast ingot is continued to be parked in stove and cools; take out after being cooled to room temperature, 450-550 second whole cooling time, obtain sclerous tissues's bio-medical in-situ authigenic zirconium based composite material.
3. the detection of alloy material
To sclerous tissues's bio-medical in-situ authigenic zirconium based composite material of obtaining of above-mentioned preparation method be adopted to utilize the omnipotent experimental system of Instron8801 to carry out the test of room temperature compression performance to the sample that specification is 5mm × 5mm × 10mm, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength be respectively 31.28GPa, 1238MPa, 21.23%, 948MPa.
Embodiment 7
1. composition of raw materials: feed composition and weight percent are: zirconium sponge 95.40%, copper 4.50%; Niobium 0.60%, the purity of zirconium sponge, copper and niobium is all more than 99%.
2. preparation method
(1) the taking of raw material, the weight percent according to each feed composition takes zirconium sponge, copper and niobium respectively; Raw material particle size size control is below 2 centimetres;
(2) raw material mixing, mixes the prepared using stirring mixing method weighed up;
(3) raw material melting, puts into the crucible of non-consumable arc furnace, then vacuumizes by the raw material mixed, vacuum tightness is 1 × 10
-2~ 1 × 10
-3pa; Pass into argon gas again and carry out gas washing; Vacuumize and repeatedly carry out 2 ~ 4 times with gas washing.Finally under the protection of rare gas element, carry out melting, smelting temperature is 2800 ~ 2900 DEG C; Melting voltage is 220V, and melting current control is at 190A, and keep 110s ~ 130s, and then electric current is slowly adjusted to 0A, the time that electric current drops to 0A is 40-60s, and melt back like this more than 5 times, obtains thick alloy cast ingot;
(4) cooling of thick alloy cast ingot; under argon shield; to crucible bottom water flowing; utilize the water of flowing to cool fast thick alloy cast ingot, thick alloy is 20 ~ 30 seconds by liquid state to solid-state cooling time, then continues maintenance to crucible bottom water flowing; alloy cast ingot is continued to be parked in stove and cools; take out after being cooled to room temperature, 400-500 second whole cooling time, obtain sclerous tissues's bio-medical in-situ authigenic zirconium based composite material.
3. the detection of alloy material
To sclerous tissues's bio-medical in-situ authigenic zirconium based composite material of obtaining of above-mentioned preparation method be adopted to utilize the omnipotent experimental system of Instron8801 to carry out the test of room temperature compression performance to the sample that specification is 5mm × 5mm × 10mm, the Young's modulus of this alloy sample, maximum compressive strength, rate of compression, yield strength be respectively 29.58GPa, 1298MPa, 21.55%, 954MPa.
The β type Zr-Nb-Ti system biomedical alloy that above-described embodiment is made is prepared into through certain hospital of medical university and uses on volunteer at backbone correction device, correct for backbone, effect proves better than the Young's modulus of the titanium matrix composite of original import, to human zero damage, other character also meets medical material requirement, illustrates that material of the present invention meets medical science and human body requirement.
Claims (6)
1. sclerous tissues's bio-medical in-situ authigenic zirconium based composite material, is characterized in that: raw materials used component and weight percent are: copper 3.5% ~ 4.5%, niobium 0.1 ~ 1.2%, and surplus is zirconium sponge; Its preparation method comprises the steps:
(1) raw material takes, and the weight percent according to each feed composition takes zirconium sponge, copper and niobium respectively; Raw material particle size size control is below 2 centimetres;
(2) raw material mixing, mixes the raw material stirring weighed up;
(3) raw material melting, puts into the crucible of non-consumable arc furnace, then vacuumizes by the raw material mixed, vacuum degree control is 1 × 10
-2~ 1 × 10
-3pa; Pass into rare gas element again and carry out the residual air of gas washing removing; Finally under the protection of rare gas element, carry out melting, smelting temperature is 2800 ~ 3000 DEG C; Melting voltage is 220V, and melting current control is at 180 ~ 200A, and keep 100s ~ 150s, and then electric current is slowly adjusted to 0A, the time that electric current drops to 0A is 40 ~ 60s, and melt back like this more than 5 times, obtains thick alloy cast ingot;
(4) cooling of thick alloy cast ingot; under protection of inert gas; to crucible bottom water flowing; utilize the water of flowing to cool fast thick alloy cast ingot, thick alloy is 10 ~ 30 seconds by liquid state to solid-state cooling time, then continues maintenance to crucible bottom water flowing; alloy cast ingot is continued to be parked in stove and cools; take out after being cooled to room temperature, 400 ~ 600 seconds whole cooling times, obtain sclerous tissues's bio-medical in-situ authigenic zirconium based composite material.
2. sclerous tissues according to claim 1 bio-medical in-situ authigenic zirconium based composite material, it is characterized in that: raw materials used component and weight percent are: copper 4.0%, niobium 0.5 ~ 1.0%, surplus is zirconium sponge.
3. sclerous tissues according to claim 1 and 2 bio-medical in-situ authigenic zirconium based composite material, is characterized in that: the purity of titanium sponge, copper and niobium is all more than 99.0%.
4. sclerous tissues according to claim 3 bio-medical in-situ authigenic zirconium based composite material, it is characterized in that: the Young's modulus of sclerous tissues's bio-medical in-situ authigenic zirconium based composite material is 25 ~ 31GPa, maximum compressive strength reaches 1100 ~ 1300MPa, rate of compression is 20.0 ~ 28.0%, and yield strength is 750 ~ 1000MPa.
5. sclerous tissues according to claim 1 bio-medical in-situ authigenic zirconium based composite material, is characterized in that: described in vacuumize and repeatedly carry out 2 ~ 4 times with gas washing.
6. sclerous tissues according to claim 1 bio-medical in-situ authigenic zirconium based composite material, is characterized in that: described rare gas element is argon gas, and pressure is a standard atmospheric pressure.
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