CN107815618A - A kind of amorphous Biological magnesium alloy and preparation method thereof - Google Patents

A kind of amorphous Biological magnesium alloy and preparation method thereof Download PDF

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Publication number
CN107815618A
CN107815618A CN201711017086.9A CN201711017086A CN107815618A CN 107815618 A CN107815618 A CN 107815618A CN 201711017086 A CN201711017086 A CN 201711017086A CN 107815618 A CN107815618 A CN 107815618A
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magnesium alloy
neodymium
amorphous
zinc
biological magnesium
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CN107815618B (en
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高成德
帅词俊
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Central South University
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Central South University
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C45/00—Amorphous alloys
    • C22C45/005—Amorphous alloys with Mg as the major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/11—Making amorphous alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/106—Coating with metal alloys or metal elements only

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials For Medical Uses (AREA)

Abstract

The present invention relates to a kind of amorphous Biological magnesium alloy and preparation method thereof, belongs to Biological magnesium alloy design and fabrication technology field.The amorphous Biological magnesium alloy includes following components by percentage to the quality：Magnesium 75 82%, zinc 15 20%, neodymium 3 5%.Its preparation method is：By design component with magnesium powder, zinc powder and neodymium powder is taken, under protective atmosphere, in 240 360r/min ball millings at least 2h, mixed-powder is obtained；Then under protective atmosphere, magnesium zinc neodymium amorphous Biological magnesium alloy is obtained using selective laser melting technique；During selective laser melting, the cooldown rate for controlling molten bath is 105‑1010K/s, it is 200 400W to control laser power, and sweep speed is 2 5m/s, and it is 50 μm to control spot diameter.The present invention prepares the Biological magnesium alloy with non crystalline structure with better simply step, improves the corrosion resistance of Biological magnesium alloy, promotes its application in tissue repair field.

Description

A kind of amorphous Biological magnesium alloy and preparation method thereof
Technical field
The present invention relates to a kind of amorphous Biological magnesium alloy and preparation method thereof, belong to Biological magnesium alloy design and fabrication technology Field.
Background technology
Biological magnesium alloy is considered as because of its natural degradability, the mechanical property of matching and good biocompatibility It is the bone renovating material of great potential.However, degradation rate of the standard biologic magnesium alloy in human body environment is too fast at present, make it The mechanical strength rapid decay after implanting, its structural support effect of premature loss；On the other hand, the too fast degraded of magnesium alloy Local ph rise is also resulted in, this is also unfavorable for new bone tissue growth.Therefore, the corrosion resistance for improving Biological magnesium alloy is to work as A preceding problem urgently to be resolved hurrily.
Amorphous magnesium alloy has the phase structure without crystal boundary, high uniformity, can be good at suppressing conventional magnesium alloy because of office Micro-cell corrosion caused by portion's chemical constituent difference, therefore show on Biological magnesium alloy corrosion resistance is improved huge excellent Gesture.In general, obtaining non crystalline structure needs specific alloy system and higher cooldown rate.Specifically, alloy body System usually requires three or more constituent element, and the atomic size difference between each constituent element is more than 10% and with the negative heat of mixing； And higher cooldown rate is disorderly arranged when the atom is kept liquid in alloy graining process, so as to promote non crystalline structure Formed.
Domestic and foreign scholars have carried out a series of researchs for magnesium base amorphous alloy system at present, obtain a variety of non-crystaline amorphous metals System, such as Mg58.5Cu30.5Y11、Mg65Ni20Nd15And Mg54Cu26.5Ag8.5Gd11Deng.But for the non-crystaline amorphous metal of Biological magnesium alloy Architectural study is seldom, containing a large amount of alloying elements with bio-toxicity in above-mentioned system, if will applied to tissue reparation Uncertain risk be present.Conventional preparation method includes die casting and quick quenching technique, and die casting is pressed after magnesium alloy is melted Enter in metal die cavity, using metal pattern heat conduction it is fast the characteristics of obtain than faster cooling velocity, so as to obtain amorphous magnesium alloy；It hurry up The method of quenching is to spray into the magnesium alloy of fusing in the less quartz glass tube of diameter, is put into quenching in water immediately and obtains amorphous magnesium conjunction Gold.But the size shape of die cavity can limit the size shape of contour alloy in die casting, and the cooling velocity of quick quenching technique is relatively low, Be not suitable for the weak magnesium alloy system of gamma transition ability.
The related record that amorphous Biological magnesium alloy is prepared using selective laser melting technique is yet there are no in the prior art.
The content of the invention
The problem of present invention can be poor for standard biologic corrosion resistance of magnesium alloy, the present invention propose that a kind of amorphous biology magnesium closes Gold and preparation method thereof, so as to improve its corrosion resistance.
A kind of amorphous Biological magnesium alloy of the present invention, by percentage to the quality including following components：
Magnesium 75-82%, preferably 77-80%, more preferably 78%；
Zinc 15-20%, preferably 17-19%, more preferably 19%；
Neodymium 3-5%, preferably 3-4%, more preferably 3%.
A kind of amorphous Biological magnesium alloy of the present invention, the amorphous Biological magnesium alloy surface also carries one layer of neodymia film.
A kind of preparation method of amorphous Biological magnesium alloy of the present invention, comprises the steps：
Step 1
Match somebody with somebody magnesium powder, zinc powder and the neodymium powder for taking particle size range to be 10-50 μm by design component, under protective atmosphere, in 240- 360r/min, it is preferably 360r/min, ball milling at least 2h, is preferably 3-4h, more preferably 4h, it is 10-50 μ to obtain particle diameter M mixed-powder；
Step 2
Using mixed-powder obtained by step 1 as raw material, under protective atmosphere, using selective laser melting technique obtain magnesium- Zinc-neodymium amorphous Biological magnesium alloy；During selective laser melting, the cooldown rate for controlling molten bath is 105-1010K/s, it is preferably 1010K/s, it is 200-500W, sweep speed 2-5m/s to control laser power, and it is 50 μm to control spot diameter.
A kind of preparation method of amorphous Biological magnesium alloy of the present invention, the protective atmosphere is high-purity argon gas.The high-purity argon Gas is the argon gas that purity is more than or equal to 99.999%.
The present invention quickly scans above-mentioned mixed-powder using selective laser melting technique and forms molten bath, and is received using laser Up to 10 in the range of second10K/s cooldown rate, no interface thermal conductivity and quick solidification are realized, so as to obtain magnesium-zinc-neodymium amorphous Biological magnesium alloy.
There is high uniformity and close with matrix on of the invention designed and preparation magnesium-zinc-neodymium amorphous Biological magnesium alloy surface With reference to neodymia film, can further improve the corrosion resistance of Biological magnesium alloy.The present invention, it is necessary to the use of strict control neodymium Amount, because thulium neodymium has very high activity, its reunion can be caused by adding the neodymium of too high amount, be closed so as to reduce magnesium Golden performance.If addition is too low, its corrosion resistance can not be ensured and ensure the non-crystallization degree of finished product.
Compared with prior art, advantage of the present invention is as follows：
(1) magnesium-zinc-neodymium alloy system developed can not only obtain amorphous Biological magnesium alloy, and with excellent Biocompatibility, it can be used in tissue reparation.
(2) present invention cleverly make use of selective laser melting technology to have the characteristics of high energy rapid cooling, appropriate big Under the synergy of atomic diameter (relative to Mg), the formation of Biological magnesium alloy non crystalline structure is promoted.
(3) the selective laser melting technology used in the present invention can be molded any multiple as a kind of increasing material manufacturing method The amorphous Biological magnesium alloy of miscellaneous shape.
(4) appropriate alloying element neodymium makes Biological magnesium alloy surface form high uniformity and the oxidation combined closely with matrix Neodymium film, the corrosion resistance of Biological magnesium alloy is further improved by passivation.
Embodiment
The embodiment of the present invention is illustrated below by two examples：
Embodiment 1
Magnesium, zinc and neodymium powder are used as raw material, by 78:19:3 mass ratio weighs 0.78g magnesium dusts, 0.19g zinc powders With 0.03g neodymium powder, the ball milling under the protection of 99.999% high-purity argon gas, drum's speed of rotation 360r/min, Ball-milling Time 4h, ball milling Dispersed magnesium-zinc-neodymium mixed-powder is obtained afterwards.In the protection of 99.999% high-purity argon gas, 50 μm of spot diameter, laser power 200W, sweep speed 5m/s process conditions under (cooldown rate in molten bath be 1010K/s), selective laser melting technique is utilized Magnesium-zinc-neodymium amorphous Biological magnesium alloy is prepared.
Thing mutually detects discovery, and prepared magnesium-zinc-neodymium alloy has the diffusing reflection peak of disperse, discloses its non crystalline structure；Electrification Credit analysis is found, compared to conventional magnesium-zinc-neodymium alloy, the corrosion electricity of magnesium-zinc-neodymium alloy of non crystalline structure in simulated body fluid Position is shuffled, the μ A/cm of corrosion electric current density 22；Observation corrosion surface is smooth under Electronic Speculum, and corrosion product is few, does not corrode significantly Hole；Find that magnesium-zinc-neodymium non-crystaline amorphous metal surface forms the neodymia passivating film of densification simultaneously, so as to improve its corrosion resistance. Corrosion rate 0.10mm/year, ultimate tensile strength 350MPa.
Embodiment 2
Magnesium, zinc and neodymium powder are used as raw material, by 80:17:3 mass ratio weighs 0.8g magnesium dusts, 0.17g zinc powders and 0.03g neodymium powder, the ball milling under the protection of 99.999% high-purity argon gas, drum's speed of rotation 300r/min, Ball-milling Time 2h, after ball milling Obtain dispersed magnesium-zinc-neodymium mixed-powder.In the protection of 99.999% high-purity argon gas, 50 μm of spot diameter, laser power 500W, sweep speed 3m/s process conditions under (cooldown rate in molten bath be 105K/s), selective laser melting technique is utilized Magnesium-zinc-neodymium amorphous Biological magnesium alloy is prepared.
Thing mutually detects discovery, and prepared magnesium-zinc-neodymium alloy has the diffusing reflection peak of disperse, discloses its non crystalline structure；Electrification Credit analysis is found, compared to conventional magnesium-zinc-neodymium alloy, the corrosion electricity of magnesium-zinc-neodymium alloy of non crystalline structure in simulated body fluid The μ A/cm of current density 72；It is smooth that corrosion surface is observed under Electronic Speculum；Find that magnesium-zinc-neodymium non-crystaline amorphous metal surface forms densification simultaneously Neodymia passivating film.Corrosion rate 0.17mm/year, ultimate tensile strength 320MPa.
Comparative example 1
Other conditions are consistent with embodiment 1, and difference is：By 80:19:1 mass ratio weighs 0.8g magnesium dusts, 0.19g zinc powders and 0.01g neodymium powder, obtain product, and discovery is mutually detected using thing obvious Mg, MgZn characteristic peak.Its institute The corrosion electric current density for obtaining product is 36.1 μ A/cm2, corrosion rate 1.66mm/year, ultimate tensile strength 212MPa.
Comparative example 2
Other conditions are consistent with embodiment 1, and difference is：(cooldown rate in molten bath is sweep speed 2m/s 104K/s), product is obtained, discovery is mutually detected using thing obvious Mg, MgZn characteristic peak.The corrosion current of its products obtained therefrom is close Spend for 26.8 μ A/cm2, corrosion rate 1.33mm/year, ultimate tensile strength 234MPa.
Comparative example 3
Other conditions are consistent with embodiment 1, and difference is：(cooldown rate in molten bath is sweep speed 0.1m/s 102K/s), product is obtained, discovery is mutually detected using thing there are obvious MgZn and MgZnNd characteristic peaks.The corrosion of its products obtained therefrom Current density is 28.4 μ A/cm2, corrosion rate 1.48mm/year, ultimate tensile strength 258MPa.
Can be seen that instant component and preparation technology by embodiment 1 and comparative example is an organic whole, when wherein When any one or several key parameters be not in the scope of the present invention, its significant effect declines.Pass through the embodiment of the present invention 1 Inherent contrast with embodiment 2 is found, preferred scheme of the invention, serves unexpected effect.

Claims (6)

  1. A kind of 1. amorphous Biological magnesium alloy, it is characterised in that；The amorphous Biological magnesium alloy includes following by percentage to the quality Component：
    Magnesium 75-82%；
    Zinc 15-20%；
    Neodymium 3-5%.
  2. A kind of 2. amorphous Biological magnesium alloy according to claim 1, it is characterised in that；The amorphous Biological magnesium alloy is with matter Amount percentages include following components：
    Magnesium 77-80%；
    Zinc 17-19%；
    Neodymium 3-4%.
  3. A kind of 3. amorphous Biological magnesium alloy according to claim 2, it is characterised in that；The amorphous Biological magnesium alloy is with matter Amount percentages include following components：
    Magnesium 78%；
    Zinc 19%；
    Neodymium 3%.
  4. A kind of 4. amorphous Biological magnesium alloy according to claim 1, it is characterised in that；The amorphous Biological magnesium alloy surface Also carry one layer of neodymia film.
  5. A kind of 5. preparation method of the amorphous Biological magnesium alloy as described in claim 1-4 any one, it is characterised in that；Including under State step：
    Step 1
    Match somebody with somebody magnesium powder, zinc powder and the neodymium powder for taking particle size range to be 10-50 μm by design component, under protective atmosphere, in 240-360r/ Min ball millings at least 2h, obtain the mixed-powder that particle diameter is 10-50 μm；
    Step 2
    Using mixed-powder obtained by step 1 as raw material, under protective atmosphere, using selective laser melting technique obtain magnesium-zinc- Neodymium amorphous Biological magnesium alloy；During selective laser melting, the cooldown rate for controlling molten bath is 105-1010K/s, control laser power For 200-500W, sweep speed 2-5m/s, it is 50 μm to control spot diameter.
  6. A kind of 6. preparation method of amorphous Biological magnesium alloy according to claim 5, it is characterised in that：The protective atmosphere For high-purity argon gas；The purity of the high-purity argon gas is more than or equal to 99.999%.
CN201711017086.9A 2017-10-26 2017-10-26 A kind of amorphous Biological magnesium alloy and preparation method thereof Expired - Fee Related CN107815618B (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109161766A (en) * 2018-09-21 2019-01-08 湘潭大学 A kind of Biological magnesium alloy and preparation method thereof of the layer of consolidation containing amorphous
CN110257731A (en) * 2019-06-28 2019-09-20 北京大学深圳研究院 Hypersorption Mg-Zn-Ag series non-crystalline state alloy and preparation method thereof
CN110257732A (en) * 2019-06-28 2019-09-20 北京大学深圳研究院 The medical embedded substrate of hypersorption Mg-Zn-Ag series non-crystalline state, preparation method and application
CN112575209A (en) * 2020-11-11 2021-03-30 西北工业大学 Amorphous preparation method based on crystalline phase-amorphous phase conversion
WO2021073404A1 (en) * 2019-10-15 2021-04-22 上海交通大学 Method for preparing high strength and toughness magnesium-rare earth alloy by means of selective laser melting additive manufacturing technology
CN116992794A (en) * 2023-09-27 2023-11-03 北京科技大学 Atomized amorphous powder yield calculation method and application

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109161766A (en) * 2018-09-21 2019-01-08 湘潭大学 A kind of Biological magnesium alloy and preparation method thereof of the layer of consolidation containing amorphous
CN109161766B (en) * 2018-09-21 2021-01-29 湘潭大学 Biological magnesium alloy containing amorphous fused layer and preparation method thereof
CN110257731A (en) * 2019-06-28 2019-09-20 北京大学深圳研究院 Hypersorption Mg-Zn-Ag series non-crystalline state alloy and preparation method thereof
CN110257732A (en) * 2019-06-28 2019-09-20 北京大学深圳研究院 The medical embedded substrate of hypersorption Mg-Zn-Ag series non-crystalline state, preparation method and application
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
WO2021073404A1 (en) * 2019-10-15 2021-04-22 上海交通大学 Method for preparing high strength and toughness magnesium-rare earth alloy by means of selective laser melting additive manufacturing technology
CN112575209A (en) * 2020-11-11 2021-03-30 西北工业大学 Amorphous preparation method based on crystalline phase-amorphous phase conversion
CN116992794A (en) * 2023-09-27 2023-11-03 北京科技大学 Atomized amorphous powder yield calculation method and application
CN116992794B (en) * 2023-09-27 2023-12-22 北京科技大学 Atomized amorphous powder yield calculation method and application

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