CN104674093B - Medical high-toughness corrosion-resistant magnesium based composite material and preparation method thereof - Google Patents
Medical high-toughness corrosion-resistant magnesium based composite material and preparation method thereof Download PDFInfo
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- CN104674093B CN104674093B CN201310635857.6A CN201310635857A CN104674093B CN 104674093 B CN104674093 B CN 104674093B CN 201310635857 A CN201310635857 A CN 201310635857A CN 104674093 B CN104674093 B CN 104674093B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
- B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
- B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
Abstract
The invention discloses a medical high-toughness corrosion-resistant magnesium based composite material and a preparation method thereof. The method comprises the following steps: S1, determining the components of the magnesium based composite material; S2, preparing an intermediate alloy ingot from high-melting point components; S3, drying the intermediate alloy ingot and low-melting point components; and S4, preparing the magnesium based composite material. As the magnesium based composite material comprises RE which is capable of increasing the percentage of an amorphous matrix in the magnesium based composite material, the corrosion and degradation speeds of the magnesium based composite material are low; in addition, the magnesium based composite material is composed of an a-Mg crystal phase and the amorphous matrix, so that the degradation speed of the magnesium based composite material can be further reduced due to the existence of the crystal phase and the amorphous matrix; and besides, the magnesium based composite material also has the advantages of high strength and good plasticity.
Description
Technical field
The present invention relates to the tough corrosion-resistant magnesium base composite material of new bio medical metal material, more particularly, to medical high-strength, further relate to the preparation method of this magnesium base composite material.
Background technology
The biomedical metal material being applied to clinic at present mainly includes rustless steel, cochrome and titanium alloy, there are some drawbacks in them, as these materials because internal friction produces abrasive dust and because corrosion produces poisonous ion, cause local anaphylaxises or inflammation, reduce biocompatibility.Additionally, these materials are non-degradable material, for being temporarily implanted material, after tissue functional rehabilitation, need to be taken out by second operation, increase misery and the medical expense burden of patient.
The research and development of magnesio bio-medical material receive the close attention of people in recent years.Compared with other common metal base biological medical materials, magnesium base alloy has following main advantage: (1), the magnesium normal contents in human body are 25g, and half is present in skeleton, and the density of magnesium and magnesium alloy is far below titanium alloy, close with people's bone density.(2), magnesium is the cation in human body cell, and its content is only second to potassium, and the synthesis that magnesium participates in protein can activate multiple enzymes in vivo, adjusts the activity of neuromuscular and central nervous system, ensures myocardium normal contraction and thermoregulation.(3), the standard electrode potential of magnesium is low, corrodible degraded in the human physiological environment containing chloride ion, is degraded by absorption with the self-healing of human body, without second operation after implantation human body.(4), magnesium and magnesium alloy have high specific strength and specific stiffness, and Young's moduluss are 41 ~ 45gpa, can effectively alleviate stress-shielding effect.
However, magnesium alloy is its corrosion degradation excessive velocities as the subject matter that bio-medical material is faced, the too fast decay of mechanical strength during one's term of military service is led to cause support function to lose efficacy；Catabolite h2Quick release make human body have little time to carry out normal metabolism process and cause blood magnesium to increase, the unfavorable phenomenon such as alkalosis and rimhole.
The magnesium base amorphous alloy of fast solidification technology preparation is due to its homogeneous phase structure, no Second Phase Precipitation, also no crystal boundary exists, therefore even tissue, it is substantially absent from the surface activity points such as field trash, the end of dislocation of easy induction corrosion, decrease the minute corrosive cell in corrosive medium, and be conducive to forming the passivation film of the improved corrosion performance that high uniformity is combined closely with matrix from the teeth outwards, corrosion resistance is substantially better than the as-cast magnesium alloy of routine.But this kind of material does not almost have macroscopical plastic deformation just to rupture, limit quoting as bio-medical material.
Content of the invention
The problem that the present invention solves is the problem of the corrosion degradation excessive velocities of existing routine magnesium base alloy.
For solving the above problems, the present invention provides a kind of tough corrosion-resistant magnesium base composite material of medical high-strength, magnesium base composite material is made up of a-mg crystal phase and mg-ca-zn-y noncrystal substrate, wherein, described composite contains (atomic percent): calcium (ca) 5-15%, zinc (zn) 5-15%, re 1-5%, magnesium (mg) are surplus.
In a kind of concrete scheme, described re is yttrium.
In further scheme, the volume ratio of described noncrystal substrate accounts for the 30% ~ 70% of composite.
Invention additionally discloses the preparation method of the tough corrosion-resistant magnesium base composite material of medical high-strength, the method comprises the steps: s1, determines the composition of magnesium base composite material: calculates each constituent element quality according to composition design, described composite contains (atomic percent): calcium (ca) 5% ~ 15%, zinc (zn) 5% ~ 15%, re 1% ~ 5%, magnesium (mg) are surplus, carry out proportioning using high pure metal constituent element (>=99.95%)；S2, using high-melting-point constituent element prepare intermediate alloy ingot: high-melting-point constituent element (calcium and re) is melting into intermediate alloy ingot using water jacketed copper crucible non-consumable electric arc melting equipment; use electric arc melting under the protective atmosphere that ti air-breathing purifies, and the uniform intermediate alloy ingot of composition using electromagnetic agitation；S3, intermediate alloy ingot and low melting point constituent element are dried: remove the surface scale of low melting point constituent element (magnesium and zinc) and intermediate alloy ingot; it is then placed in being cleaned by ultrasonic in acetone soln; first put in the graphite crucible that prerinse was dried; place in medium frequency induction melting furnace; it is filled with protective gas, low melting point constituent element and intermediate alloy ingot are preheated to 473 ~ 573k in this furnace chamber and are incubated 5 hours and low melting point constituent element and intermediate alloy ingot are dried after the furnace chamber evacuation of this medium frequency induction melting furnace；S4, prepare magnesium base composite material: dried low melting point constituent element and intermediate alloy ingot are warming up to 923-1023k and obtain alloy melt; and adopt electromagnetic agitation 20 minutes; under protective atmosphere; by in the alloy melt injection mould after stirring, after cooling, obtain the tough corrosion-resistant magnesium base composite material of medical high-strength.
In a kind of concrete scheme, described mould is Hydrocooling metal die set.
In further scheme, cooldown rate in Hydrocooling metal die set for the alloy melt is 1 × 105~1×107k/s.
In further scheme, described protective gas is 99.0 ~ 99.5% argon and the sf of 0.5-1.0% for volumn concentration6Group composition mixed gas, described is the protective atmosphere that this mixed gas is constituted under the protective atmosphere that ti air-breathing purifies.
Compared with prior art, the invention has the advantages that
1st, because magnesium base composite material of the present invention includes re, re has higher solid solubility in magnesium, is remarkably improved the amorphous formation ability of alloy, and the percentage ratio of noncrystal substrate in magnesium base composite material is increased, thus, the magnesium base composite material corrosion degradation speed of the present invention is slow；Furthermore; magnesium base composite material of the present invention is made up of a-mg crystal phase and noncrystal substrate; corrosion focuses primarily upon the crystal phase as anode first; noncrystal substrate receives good protection; and the carrying out with corrosion; crystal phase dissolves substantially; expose more noncrystal substrates; corrosion galvanic couple disappears; piled up by the formed corrosion product of corrosion simultaneously and be conducive to skin covering of the surface to be formed in the surface of sample and repair; noncrystal substrate has good corrosion resistance, and therefore, the presence of crystal phase and noncrystal substrate makes the degradation speed of magnesium base composite material decline further.Further, since magnesium base composite material is not due to having dislocation movement by slip mechanism as cast alloy, its deformation is limited only in shear band, and its intensity improves 2-3 times.Also introduce amorphous phase and the crystalline phases with varying strength and elastic modelling quantity in composite, hinder the sliding of single shear band, promote generation and the sliding of many shear bands, be a kind of effective method improving alloy plasticity.So, the magnesium base composite material of the present invention also has the advantages that intensity is high and plasticity is good.
2nd, because the re of the present invention is yttrium, yttrium has higher solid solubility in magnesium alloy, is remarkably improved the volume fraction of amorphous phase in composite so that the corrosive power of magnesium base composite material is improved, so, degradation speed is slower.Meanwhile, yttrium corrosion potential is higher than magnesium elements, improves the corrosion potential of magnesium base composite material, carry heavy alloyed decay resistance after addition.
3rd, because, in above-mentioned magnesium base composite material, the volume ratio of noncrystal substrate accounts for the 30% ~ 70% of composite, so, degradation speed is slower than prior art it is generally the case that the higher degradation speed of noncrystal substrate fraction is slower.
4th, in above-mentioned preparation method; due to dried low melting point constituent element and intermediate alloy ingot being warming up to 923-1023k and obtaining alloy melt; and adopt electromagnetic agitation 20 minutes; under protective atmosphere; by in the alloy melt injection mould after stirring; the tough corrosion-resistant magnesium base composite material of medical high-strength is obtained, cooling makes the content of noncrystal substrate increase, the content of noncrystal substrate increases and makes degradation speed slack-off after cooling.When using water cooling mold, can make to contain more noncrystal substrates in magnesium base composite material.When cooldown rate is 1 × 105~1×107K/s, the content of noncrystal substrate can reach a% ~ 30%-70%, and now, the degradation speed of composite is the slowest.
Brief description
Fig. 1 is magnesium base composite material morphology figure；
Fig. 2 is the flow chart of the preparation method of the tough corrosion-resistant magnesium base composite material of medical high-strength of the present invention；
Fig. 3 is the xrd data of magnesium base composite material, in the xrd diffraction spectra of composite in addition to typical amorphous disperses peak, crystal diffraction peak also can be observed；
Fig. 4 is as-cast magnesium alloy, non-crystaline amorphous metal and composite materials property contrast, and experiment condition is: 2 × 4mm column sample, and experimental temperature is room temperature (25 degree), and compression strain speed is 1 × 10-4s-1；
Fig. 5 is as-cast magnesium alloy, non-crystaline amorphous metal and the contrast of composite corrosive nature.Experiment condition is: experimental temperature be body temperature (37 degree), corrosive liquid be hank simulated body fluid, concrete composition is: 8.0g/lnacl, 0.4 g/l kcl, 0.14 g/lcacl2,0.35
g/l nahco3,、1.0 g/lc6h6o6
(glucose)、0.2 g/l mgso4.7h2o、0.1 g/lkh2po4.h2O and 0.06 g/l na2hpo4.7h2o.
Specific embodiment
For describing the technology contents of the present invention, structural features, institute's reached purpose and effect in detail, below in conjunction with embodiment and coordinate accompanying drawing to be described in detail.
The magnesium base composite material of the present invention is made up of a-mg crystal phase and mg-ca-zn-y noncrystal substrate, and wherein, described composite contains (atomic percent): calcium (ca) 5-15%, zinc (zn) 5-15%, re 1-5%, magnesium (mg) are surplus.Because magnesium base composite material of the present invention includes re, re has higher solid solubility in magnesium, it is remarkably improved the amorphous formation ability of alloy and corrosion resistance and the percentage ratio of noncrystal substrate in magnesium base composite material is increased, thus, the magnesium base composite material corrosion degradation speed of the present invention is slow；Furthermore; magnesium base composite material of the present invention is made up of a-mg crystal phase and noncrystal substrate; corrosion focuses primarily upon the crystal phase as anode first; noncrystal substrate receives good protection; and the carrying out with corrosion; crystal phase dissolves substantially; expose more noncrystal substrates; corrosion galvanic couple disappears; piled up by the formed corrosion product of corrosion simultaneously and be conducive to skin covering of the surface to be formed in the surface of sample and repair; noncrystal substrate has good corrosion resistance, and therefore, the presence of crystal phase and noncrystal substrate makes the degradation speed of magnesium base composite material decline further.Further, since magnesium base composite material is not due to having dislocation movement by slip mechanism as cast alloy, its deformation is limited only in shear band, and its intensity improves 2-3 times.Also introduce amorphous phase and the crystalline phases with varying strength and elastic modelling quantity in composite, hinder the sliding of single shear band, promote generation and the sliding of many shear bands, be a kind of effective method improving alloy plasticity.So, the magnesium base composite material of the present invention also has the advantages that intensity is high and plasticity is good.
In a kind of specific embodiment, described re is yttrium, and yttrium has higher solid solubility in magnesium alloy, is remarkably improved the volume fraction of amorphous phase in composite so that the corrosive power of magnesium base composite material is improved, so, degradation speed is slower.Meanwhile, yttrium corrosion potential is higher than magnesium elements, improves the corrosion potential of magnesium base composite material, carry heavy alloyed decay resistance after addition.
In other implementations, the volume ratio of described noncrystal substrate accounts for composite 30% ~ 70%, and so, degradation speed is slower than prior art it is generally the case that the higher degradation speed of noncrystal substrate fraction is slower.Fig. 1 illustrates that the volume ratio of noncrystal substrate is the morphology figure of 60% composite of magnesium base composite material.The noncrystal substrate of in figure white tissues, Lycoperdon polymorphum Vitt needle-like be organized as crystal phase.
Refer to Fig. 2, the preparation method of the tough corrosion-resistant magnesium base composite material of medical high-strength of the present invention comprises the steps:
S1, determine the composition of magnesium base composite material: each constituent element quality is calculated according to composition design, described composite contains (atomic percent): calcium (ca) 5% ~ 15%, zinc (zn) 5% ~ 15%, re 1% ~ 5%, magnesium (mg) are surplus, carry out proportioning using high pure metal constituent element (>=99.95%)；
S2, using high-melting-point constituent element prepare intermediate alloy ingot: high-melting-point constituent element (calcium and re) is melting into intermediate alloy ingot using water jacketed copper crucible non-consumable electric arc melting equipment; use electric arc melting under the protective atmosphere that ti air-breathing purifies, and the uniform intermediate alloy ingot of composition using electromagnetic agitation；In this step, described protective gas is 99.0 ~ 99.5% argon and the sf of 0.5-1.0% for volumn concentration6Group composition mixed gas, described is the protective atmosphere that this mixed gas is constituted under the protective atmosphere that ti air-breathing purifies.It is therefore prevented that alloying element generates oxide volatilization with the oxygen haptoreaction of in the air under protection atmosphere, produce loss, reach the purpose reducing volatilization.
S3, intermediate alloy ingot and low melting point constituent element are dried: remove the surface scale of low melting point constituent element (magnesium and zinc) and intermediate alloy ingot; it is then placed in being cleaned by ultrasonic in acetone soln; first put in the graphite crucible that prerinse was dried; place in medium frequency induction melting furnace; it is filled with protective gas, low melting point constituent element and intermediate alloy ingot are preheated to 473 ~ 573k in this furnace chamber and are incubated 5-8 hour and low melting point constituent element and intermediate alloy ingot are dried after the furnace chamber evacuation of this medium frequency induction melting furnace；When temperature is less than 473k, the moisture that in alloy, intergranular incorporates cannot separate out, and does not reach the purpose of drying.When temperature is higher than 573k, alloy surface easily produces oxide, subtracts low-alloyed amorphous formation ability.The protective gas of this step such as step s2 is identical, will not be described here.
S4, prepare magnesium base composite material: dried low melting point constituent element and intermediate alloy ingot are warming up to 923 ~ 1023k and obtain alloy melt; and adopt electromagnetic agitation 20 minutes; under protective atmosphere; by in the alloy melt injection mould after stirring, after cooling, obtain the tough corrosion-resistant magnesium base composite material of medical high-strength.In this step, if temperature is less than 923k, do not reach the fusing point of alloy it is impossible to melting.If above 1023k, the boiling point of magnesium elements will be exceeded, magnesium elements can all volatilize consume.In this step, cooling makes the content of noncrystal substrate increase, and the content of noncrystal substrate increases and makes degradation speed slack-off.Better way is that described mould adopts water cooling mold, so, can make to contain more noncrystal substrates in magnesium base composite material.In addition, those skilled in the art find: the cooldown rate of water cooling mold also has an impact to the content of noncrystal substrate, when cooldown rate is 1 × 105~1×107K/s, the content of noncrystal substrate can reach a% ~ 30%-70%, and now, the degradation speed of composite is the slowest.
Below, enumerate several embodiments above-mentioned steps are described as follows:
Embodiment 1
(1) selection of raw material
The present invention prepares the purity such as table of each metal constituent element of magnesium base composite material selection: the formula of composite is mg75ca15zn5y5(atomic percent).
The purity (%) that master alloy ingot selects metal constituent element prepared by table 1
| Alloying element | mg | ca | y | zn |
| Purity/% | 99.95 | 99.99 | 99.99 | 99.99 |
(2) high-melting-point constituent element is utilized to prepare the intermediate alloy ingot melting of intermediate alloy ingot (also referred to as)
First under the conditions of ti air-breathing, protective atmosphere, found intermediate alloy ingot with non-consumable arc-melting furnace.The specific procedure of intermediate alloy ingot preparation is as follows:
The surface mechanical grinding of fusing point higher metal raw material ca, y is removed after the oxide skin on surface, the composition proportion material according to select/designing is got the raw materials ready；According to every ingot 80g about weight the material preparing is put in the water jacketed copper crucible in smelting furnace, cover bell and be evacuated to 5 × 10-3pa；It is filled with a certain amount of protective gas into stove.
Before founding master alloy ingot, the ti ingot melting 3 times of air-breathing will be used for.
Multi-pass molten alloy ingot: using non-consumable tungsten electrode, alloy pig is melted 3 times, and apply function composite by electromagnetic stirring, the intermediate alloy ingot being uniformly mixed.
(3), the drying of intermediate alloy ingot and low melting point constituent element
Ca-y intermediate alloy after scale removal is crushed by second step, puts in pretreated graphite crucible, put into furnace chamber evacuation, be filled with protective gas after mixing by design composition proportion with low melting point constituent element mg, zn, melting in induction furnace.And apply function composite by electromagnetic stirring, the intermediate alloy ingot being uniformly mixed.
(4), prepare magnesium base composite material (also referred to as formed product)
Under certain protective atmosphere, the aluminium alloy of melting is poured in water-cooled metal mould, after quick cooling, obtain required product.Cooldown rate is 1 × 105~1×107K/s, the shape physical dimension of product can be adjusted according to demand.
(5) structural characterization:
Using xrd, sem and dsc, Microstructure characterization is carried out to the composite of preparation.During technical maturity, this step can be omitted.
Fig. 2 is the magnesium base composite material morphology figure prepared.By crystal phase and amorphous organization, volume fraction is about 40%.
Fig. 3 analyzes for x-ray diffraction, and obtaining crystal phase through analysis is а-mg solid solution, and matrix phase is mg-ca-zn-y non-crystaline amorphous metal.
Fig. 4 is that as-cast magnesium alloy az31, non-crystaline amorphous metal and magnesium base composite material mechanical property contrast.Experiment condition is: sample is 2 × 4mm column sample, and experimental temperature is room temperature (25 DEG C), and compression strain speed is 1 × 10-4s-1.Mechanical experimental results show: prepared mg75ca15zn5y5Fracture of composite materials intensity, more than 1100mpa, is respectively increased 900 and 200mpa than as-cast magnesium alloy and non-crystaline amorphous metal, the compression plasticity of composite reaches 9%.
Fig. 5 is that as-cast magnesium alloy az31, non-crystaline amorphous metal and magnesium base composite material decay resistance contrast.Experiment condition is: experimental temperature is body temperature (37 degree), and corrosive liquid is hank simulated body fluid, and concrete composition is: .0 g/lnacl, 0.4 g/l kcl, 0.14 g/lcacl2、0.35 g/l nahco3、1.0
g/lc6h6o6(glucose)、0.2 g/l mgso4.7h2o, 0.1 g/lkh2po4.h2O and 0.06 g/l na2hpo4.7h2o.Corrosive nature test result shows: prepared mg75ca15zn5y5Composite corrosion electric current density is 0.091 ma/cm2, substantially less than as-cast magnesium alloy az31 alloy (1.326ma/cm2).
Fact proved, compared to as-cast magnesium alloy and non-crystaline amorphous metal, the decay resistance of magnesium base composite material significantly improves, and composite material exhibits go out substantially high intensity and plasticity simultaneously.
Embodiment 2
Using preparation method same as Example 1, alloying component is: mg75ca10zn10y5.
The anti-corrosion electric current density of composite is 0.125 ma/cm2, and fracture strength and plasticity are respectively 1050mpa, 6%.
Embodiment 3
Using preparation method same as Example 1, alloying component is: mg75ca5zn15y5
The anti-corrosion electric current density of composite is 0.085 ma/cm2, and fracture strength and plasticity are respectively 1150mpa, 12%.
Embodiment 4
Using preparation method same as Example 1, alloying component is: mg75ca12zn15y3
The anti-corrosion electric current density of composite is 0.115 ma/cm2, and fracture strength and plasticity are respectively 950mpa, 5%.
Embodiment 5
Using preparation method same as Example 1, alloying component is: mg75ca10zn12y3
The anti-corrosion electric current density of composite is 0.135 ma/cm2, and fracture strength and plasticity are respectively 980mpa, 7%.
Claims (4)
1. the preparation method of the tough corrosion-resistant magnesium base composite material of medical high-strength, is characterized in that: the method comprises the steps:
S1, determine the composition of magnesium base composite material: each constituent element quality is calculated according to composition design, described composite each component by atomic percent is: calcium ca5% ~ 15%, zinc zn5% ~ 15%, re 1% ~ 5%, magnesium mg are surplus, proportioning, tenor >=99.95% in described high pure metal constituent element are carried out using high pure metal constituent element；
S2, using high-melting-point constituent element prepare intermediate alloy ingot: calcium and re are melting into intermediate alloy ingot using water jacketed copper crucible non-consumable electric arc melting equipment; use electric arc melting under the protective atmosphere that ti air-breathing purifies, and adopt the uniform intermediate alloy ingot of electromagnetic agitation forming component；
S3, intermediate alloy ingot and low melting point constituent element are dried: remove the surface scale of demagging, zinc and intermediate alloy ingot; it is then placed in being cleaned by ultrasonic in acetone soln; first put in the graphite crucible that prerinse was dried; place in medium frequency induction melting furnace; it is filled with protective gas, low melting point constituent element and intermediate alloy ingot are preheated to 473 ~ 573k in this furnace chamber and are incubated 5 hours and low melting point constituent element and intermediate alloy ingot are dried after the furnace chamber evacuation of this medium frequency induction melting furnace；
S4, prepare magnesium base composite material: dried low melting point constituent element and intermediate alloy ingot are warming up to 923-1023k and obtain alloy melt; and adopt electromagnetic agitation 20 minutes; under protective atmosphere; by in the alloy melt injection mould after stirring, after cooling, obtain the tough corrosion-resistant magnesium base composite material of medical high-strength.
2. the preparation method of the tough corrosion-resistant magnesium base composite material of medical high-strength as claimed in claim 1, is characterized in that: described mould is Hydrocooling metal die set.
3. the preparation method of the tough corrosion-resistant magnesium base composite material of medical high-strength as claimed in claim 2, is characterized in that: cooldown rate in Hydrocooling metal die set for the alloy melt is 1 × 105~1×107k/s.
4. the preparation method of the tough corrosion-resistant magnesium base composite material of the medical high-strength as any one of claims 1 to 3, is characterized in that: described protective gas is 99.0 ~ 99.5% argon and the sf of 0.5-1.0% for volumn concentration6The mixed gas of composition, described is the protective atmosphere that this mixed gas is constituted under the protective atmosphere that ti air-breathing purifies.
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| CN106957999A (en) * | 2017-03-03 | 2017-07-18 | 上海理工大学 | A kind of magnesium zinc yttrium amorphous alloy material and preparation method thereof |
| CN109735753B (en) * | 2019-03-07 | 2021-02-23 | 山东融金粉末科技股份有限公司 | High-strength corrosion-resistant heat-resistant magnesium alloy material and preparation method thereof |
| CN109763045A (en) * | 2019-03-22 | 2019-05-17 | 鹤壁恒镁新材料科技有限公司 | Middle high-strength magnesium alloy and preparation method thereof |
| CN110257731B (en) * | 2019-06-28 | 2021-08-13 | 北京大学深圳研究院 | Full-absorption Mg-Zn-Ag amorphous alloy and preparation method thereof |
| CN110257732B (en) * | 2019-06-28 | 2021-07-13 | 北京大学深圳研究院 | Fully-absorbed Mg-Zn-Ag amorphous medical implant base material, and preparation method and application thereof |
| CN113265599B (en) * | 2021-05-17 | 2022-08-26 | 扬州大学 | Mg-Zn amorphous/nanocrystalline composite structure medical material and preparation method thereof |
| CN115519116A (en) * | 2022-10-21 | 2022-12-27 | 安徽智磁新材料科技有限公司 | High-biocompatibility magnesium-based amorphous alloy powder and preparation method thereof |
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| US5221376A (en) * | 1990-06-13 | 1993-06-22 | Tsuyoshi Masumoto | High strength magnesium-based alloys |
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| US5221376A (en) * | 1990-06-13 | 1993-06-22 | Tsuyoshi Masumoto | High strength magnesium-based alloys |
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| Title |
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| MgZnCa基非晶及其复合材料的制备、力学和腐蚀性能研究;魏怡芸;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20130315(第3期);第15页2.1引言，第73页6结论 * |
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