CN107815618B - 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

Info

Publication number
CN107815618B
CN107815618B CN201711017086.9A CN201711017086A CN107815618B CN 107815618 B CN107815618 B CN 107815618B CN 201711017086 A CN201711017086 A CN 201711017086A CN 107815618 B CN107815618 B CN 107815618B
Authority
CN
China
Prior art keywords
magnesium alloy
neodymium
amorphous
zinc
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201711017086.9A
Other languages
Chinese (zh)
Other versions
CN107815618A (en
Inventor
高成德
帅词俊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Central South University
Original Assignee
Central South University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Central South University filed Critical Central South University
Priority to CN201711017086.9A priority Critical patent/CN107815618B/en
Publication of CN107815618A publication Critical patent/CN107815618A/en
Application granted granted Critical
Publication of CN107815618B publication Critical patent/CN107815618B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • 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 alloys and preparation method thereof, belong 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%.Preparation method are as follows: by design component with magnesium powder, zinc powder and neodymium powder is taken, under protective atmosphere, in 240-360r/min ball milling at least 2h, obtain mixed-powder；Then under protective atmosphere, magnesium-zinc-neodymium amorphous Biological magnesium alloy is obtained using selective laser melting technique；When selective laser melting, the cooling rate for controlling molten bath is 105‑1010K/s, control laser power are 200-400W, sweep speed 2-5m/s, and control spot diameter is 50 μm.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 it in the 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 alloys and preparation method thereof, belong to Biological magnesium alloy design and fabrication technology Field.
Background technique
Biological magnesium alloy is considered because of its natural degradability, matched mechanical property 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 degradation of magnesium alloy Local ph raising 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.
Phase structure of the amorphous magnesium alloy with no crystal boundary, high uniformity, can be good at inhibiting conventional magnesium alloy because of office Micro-cell corrosion caused by portion chemical constituent difference, therefore show on improving Biological magnesium alloy corrosion resistance huge excellent Gesture.In general, obtaining non crystalline structure needs specific alloy system and higher cooling rate.Specifically, alloy body System usually requires three or more constituent element, and the atomic size difference between each constituent element is greater than 10% and has the negative heat of mixing； And higher cooling rate is disorderly arranged when atom can be made to keep liquid in alloy graining process, to promote non crystalline structure It is formed.
Domestic and foreign scholars have carried out a series of researchs for magnesium base amorphous alloy system at present, obtain a variety of amorphous alloys System, such as Mg58.5Cu30.5Y11、Mg65Ni20Nd15And Mg54Cu26.5Ag8.5Gd11Deng.But it is directed to the amorphous alloy of Biological magnesium alloy Architectural study is seldom, will if being applied to tissue reparation containing a large amount of alloying elements with bio-toxicity in above-mentioned system There are uncertain risks.Common preparation method includes die casting and quick quenching technique, and die casting is pressed after melting magnesium alloy Enter in metal die cavity, is obtained using the thermally conductive fast feature of metal mold than faster cooling velocity, to obtain amorphous magnesium alloy；Fastly The method of quenching is that the magnesium alloy that will be melted sprays into the lesser quartz glass tube of diameter, and quenching obtains amorphous magnesium conjunction into the water immediately Gold.However the size shape of die cavity will limit the size shape of contour alloy in die casting, and the cooling velocity of quick quenching technique is lower, Be not suitable for the weak magnesium alloy system of gamma transition ability.
It yet there are no the related record that amorphous Biological magnesium alloy is prepared using selective laser melting technique in the prior art.
Summary of the invention
The present invention problem poor for standard biologic corrosion resistance of magnesium alloy energy, the present invention propose that a kind of amorphous biology magnesium closes Gold and preparation method thereof, to improve its corrosion resistance.
A kind of amorphous Biological magnesium alloy of the present invention, includes following components by percentage to the quality:
Magnesium 75-82%, preferably 77-80%, further preferably 78%；
Zinc 15-20%, preferably 17-19%, further preferably 19%；
Neodymium 3-5%, preferably 3-4%, further preferably 3%.
A kind of amorphous Biological magnesium alloy of the present invention, amorphous Biological magnesium alloy surface also has one layer of neodymia film.
A kind of preparation method of amorphous Biological magnesium alloy of the present invention, includes the following steps:
Step 1
Match 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, preferably 360r/min, ball milling at least 2h, preferably 3-4h, further preferably 4h, obtaining partial size is 10-50 μ The mixed-powder of m；
Step 2
Using mixed-powder obtained by step 1 as raw material, under protective atmosphere, magnesium-is obtained using selective laser melting technique Zinc-neodymium amorphous Biological magnesium alloy；When selective laser melting, the cooling rate for controlling molten bath is 105-1010K/s, it is preferably 1010K/s, control laser power are 200-500W, sweep speed 2-5m/s, and control spot diameter is 50 μm.
A kind of preparation method of amorphous Biological magnesium alloy of the present invention, the protective atmosphere are 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 second range10The cooling rate of K/s is realized without interface thermal conductivity and quick solidification, to obtain magnesium-zinc-neodymium amorphous Biological magnesium alloy.
There is high uniformity and close with matrix on magnesium-zinc-neodymium amorphous Biological magnesium alloy surface that is of the invention designed and preparing In conjunction with neodymia film, the corrosion resistance of Biological magnesium alloy can be further increased.The present invention, it is necessary to the use of strict control neodymium Amount, because thulium neodymium has very high activity, the neodymium for adding too high amount will lead to its reunion, to reduce magnesium conjunction Golden performance.If additive amount is too low, it not can guarantee its corrosion resistance and guarantee 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 have excellent Biocompatibility can be used in tissue reparation.
(2) selective laser melting technology, which is cleverly utilized, in the present invention has the characteristics that high energy rapid cooling, suitable big Under the synergistic effect 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 form any multiple as a kind of increasing material manufacturing method The amorphous Biological magnesium alloy of miscellaneous shape.
(4) oxidation that suitable alloying element neodymium makes Biological magnesium alloy surface form high uniformity and combines closely with matrix Neodymium film further increases the corrosion resistance of Biological magnesium alloy by passivation.
Specific embodiment
A specific embodiment of the invention is illustrated below by two examples:
Embodiment 1
It uses magnesium, zinc and neodymium powder for raw material, weighs 0.78g magnesium dust, 0.19g zinc powder by the mass ratio of 78:19:3 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 Evenly 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, scanning speed 5m/s process conditions under (cooling rate in molten bath be 1010K/s), selective laser melting technique is utilized Magnesium-zinc-neodymium amorphous Biological magnesium alloy is prepared.
Object mutually detects discovery, and prepared magnesium-zinc-neodymium alloy has the diffusing reflection peak of disperse, discloses its non crystalline structure；Electrification Credit analysis discovery, compared to conventional magnesium-zinc-neodymium alloy, corrosion electricity of the magnesium-zinc-neodymium alloy of non crystalline structure in simulated body fluid Position is shuffled, 2 μ A/cm of corrosion electric current density2；Observation corrosion surface is smooth under Electronic Speculum, and corrosion product is few, does not corrode significantly Hole；Find that magnesium-zinc-neodymium amorphous alloy surface forms fine and close neodymia passivating film simultaneously, to improve its corrosion resistance. Corrosion rate 0.10mm/year, ultimate tensile strength 350MPa.
Embodiment 2
Use magnesium, zinc and neodymium powder for raw material, by 80:17:3 mass ratio weigh 0.8g magnesium dust, 0.17g zinc powder 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 evenly dispersed magnesium-zinc-neodymium mixed-powder.In the protection of 99.999% high-purity argon gas, 50 μm of spot diameter, laser power 500W, scanning speed 3m/s process conditions under (cooling rate in molten bath be 105K/s), selective laser melting technique is utilized Magnesium-zinc-neodymium amorphous Biological magnesium alloy is prepared.
Object mutually detects discovery, and prepared magnesium-zinc-neodymium alloy has the diffusing reflection peak of disperse, discloses its non crystalline structure；Electrification Credit analysis discovery, compared to conventional magnesium-zinc-neodymium alloy, corrosion electricity of the magnesium-zinc-neodymium alloy of non crystalline structure in simulated body fluid 7 μ A/cm of current density2；It is smooth that corrosion surface is observed under Electronic Speculum；Find that magnesium-zinc-neodymium amorphous alloy 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, the difference is that: 0.8g magnesium dust is weighed by the mass ratio of 80:19:1, 0.19g zinc powder and 0.01g neodymium powder, obtain product, and discovery is mutually detected using object apparent 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, the difference is that: (cooling rate in molten bath is scanning speed 2m/s 104K/s), product is obtained, discovery is mutually detected using object apparent Mg, MgZn characteristic peak.The corrosion current of its products obtained therefrom is close Degree is 26.8 μ A/cm2, corrosion rate 1.33mm/year, ultimate tensile strength 234MPa.
Comparative example 3
Other conditions are consistent with embodiment 1, the difference is that: (cooling rate in molten bath is scanning speed 0.1m/s 102K/s), product is obtained, discovery is mutually detected using object apparent MgZn and MgZnNd characteristic peak.The corrosion of its products obtained therefrom Current density is 28.4 μ A/cm2, corrosion rate 1.48mm/year, ultimate tensile strength 258MPa.
It can be seen that instant component by embodiment 1 and comparative example and preparation process be an organic whole, when wherein When any one or several key parameters be not in the scope of the present invention, significant effect decline.Through the embodiment of the present invention 1 With the inherent comparison discovery of embodiment 2, preferred embodiment of the invention plays unexpected effect.

Claims (5)

1. a kind of 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%；
The amorphous Biological magnesium alloy is prepared by following step:
Step 1
Match 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 milling at least 2h obtains the mixed-powder that partial size is 10-50 μm；
Step 2
Using mixed-powder obtained by step 1 as raw material, under protective atmosphere, magnesium-zinc-is obtained using selective laser melting technique Neodymium amorphous Biological magnesium alloy；When selective laser melting, the cooling rate for controlling molten bath is 105-1010K/s controls laser power For 200-500W, sweep speed 2-5m/s, controlling spot diameter is 50 μm.
2. a kind of amorphous Biological magnesium alloy according to claim 1, it is characterised in that；The amorphous Biological magnesium alloy is with matter Measuring percentages includes following components:
Magnesium 77-80%；
Zinc 17-19%；
Neodymium 3-4%.
3. a kind of amorphous Biological magnesium alloy according to claim 2, it is characterised in that；The amorphous Biological magnesium alloy is with matter Measuring percentages includes following components:
Magnesium 78%；
Zinc 19%；
Neodymium 3%.
4. a kind of amorphous Biological magnesium alloy according to claim 1, it is characterised in that；Amorphous Biological magnesium alloy surface Also have one layer of neodymia film.
5. a kind of amorphous Biological magnesium alloy according to claim 1, it is characterised in that: the protective atmosphere is 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)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711017086.9A CN107815618B (en) 2017-10-26 2017-10-26 A kind of amorphous Biological magnesium alloy and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711017086.9A CN107815618B (en) 2017-10-26 2017-10-26 A kind of amorphous Biological magnesium alloy and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107815618A CN107815618A (en) 2018-03-20
CN107815618B true CN107815618B (en) 2019-04-19

Family

ID=61604126

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711017086.9A Expired - Fee Related CN107815618B (en) 2017-10-26 2017-10-26 A kind of amorphous Biological magnesium alloy and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107815618B (en)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109161766B (en) * 2018-09-21 2021-01-29 湘潭大学 Biological magnesium alloy containing amorphous fused layer 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
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
CN110681869B (en) * 2019-10-15 2021-08-03 上海交通大学 Method for preparing high-strength and high-toughness magnesium rare earth alloy by 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
CN116992794B (en) * 2023-09-27 2023-12-22 北京科技大学 Atomized amorphous powder yield calculation method and application

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2911267B2 (en) * 1991-09-06 1999-06-23 健 増本 High strength amorphous magnesium alloy and method for producing the same
CN105671391B (en) * 2016-01-19 2020-08-04 周倩 Fully-degradable magnesium alloy and preparation method thereof

Also Published As

Publication number Publication date
CN107815618A (en) 2018-03-20

Similar Documents

Publication Publication Date Title
CN107815618B (en) A kind of amorphous Biological magnesium alloy and preparation method thereof
CN108486433B (en) Al-Mg-Sc-Zr series aluminum alloy composition for selective laser melting technology and preparation method of formed part
CN107096923A (en) The preparation method of the high-melting-point high-entropy alloy spherical powder manufactured based on laser gain material
CN107747019B (en) A kind of high entropy high temperature alloy of Ni-Co-Cr-Al-W-Ta-Mo system and preparation method thereof
WO2019029031A1 (en) Additive manufacturing method for lead-free environmentally-friendly high-strength brass alloy
CN109023013B (en) Preparation method of corrosion-resistant high-strength AlCoCrFeNi-Cu high-entropy alloy
JP7132751B2 (en) Cu-based alloy powder
CN105950945B (en) A kind of high intensity high-entropy alloy NbMoTaWVCr and preparation method thereof
CN107513642A (en) Co-based alloy powder and its preparation method and application
CN105543747A (en) Preparation method of material increase manufactured nickel-based high-temperature alloy reserved with Laves phase
CN107363262A (en) A kind of preparation method and application of high-purity compact spherical titanium zirconium alloy powder
CN109161766B (en) Biological magnesium alloy containing amorphous fused layer and preparation method thereof
CN108486408A (en) A kind of low elastic modulus dental filling beta titanium alloy and its manufacturing method
CN105033249A (en) Preparation method of titanium and titanium alloy wires or powder for 3D printing
CN108977693B (en) A kind of recrystallization high-strength titanium alloy and preparation method thereof
CN113073274B (en) Novel method for preparing double-phase ultra-fine grain high-entropy alloy
US11987870B2 (en) Cu-based alloy powder
CN109926582B (en) Preparation method of medical titanium-niobium alloy product
CN105562680B (en) The method that a kind of high-entropy alloy powder and hot pressed sintering prepare high-entropy alloy coating
JP2019516017A (en) BCC materials of titanium, aluminum, niobium, vanadium and molybdenum, and products produced therefrom
CN108034874B (en) One kind magnesium-rare earth containing molybdenum-rhenium and preparation method thereof
Tan et al. Direct Metal Deposition of Satellited Ti‐15Mo: Microstructure and Mechanical Properties
CN107630150B (en) A kind of preparation method of the enhanced CuNiSi alloy of timeliness
Li et al. The microstructure tailoring and property improving of directed energy deposited Al-Zn-Mg-Cu alloy modified with various Si and ZrO2 contents
CN103789709A (en) Centimeter-sized Zr-based bulk amorphous alloy, and preparation and application methods thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20190419

Termination date: 20191026

CF01 Termination of patent right due to non-payment of annual fee