CN104388841B - A kind of corrosion-resistant biological magnesium-base metal glass composite and preparation method thereof - Google Patents
A kind of corrosion-resistant biological magnesium-base metal glass composite and preparation method thereof Download PDFInfo
- Publication number
- CN104388841B CN104388841B CN201410543955.1A CN201410543955A CN104388841B CN 104388841 B CN104388841 B CN 104388841B CN 201410543955 A CN201410543955 A CN 201410543955A CN 104388841 B CN104388841 B CN 104388841B
- Authority
- CN
- China
- Prior art keywords
- base metal
- metal glass
- magnesium
- corrosion
- glass composite
- 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.)
- Active
Links
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of corrosion-resistant biological magnesium-base metal glass composite and preparation method thereof, the alloying component atomic percent expression formula of this composite is: Mga(Cu0.6Ag0.2Zn0.2)b(Gd0.7Y0.3)c, 70≤a≤85,10.8≤b≤21.6,4.2≤c≤8.4, a+b+c=100.Preparation method is as follows: first uses non-consumable arc furnace that high-melting-point constituent element melting is uniform under argon atmosphere, is prepared as intermediate alloy；Then intermediate alloy is put in crucible together with Mg, Zn element, use induction melting to become foundry alloy under argon shield；Again foundry alloy is put in quartz glass tube, under argon shield, use induction melting remelting, and make foundry alloy section bar by the casting of low pressure copper mold；Finally put into, by after foundry alloy section bar, the crucible that pretreatment is good, under argon shield, use induction melting be heated to complete molten condition and be incubated 10 minutes, implement rapid sequential solidification subsequently, form metal glass composite material.Magnesium-base metal glass composite full-size prepared by the present invention, up to 16mm, has corrosion resistance and the temperature-room type plasticity of excellence.
Description
Technical field
The invention belongs to metal-base composites technical field, a kind of corrosion-resistant biological magnesium-base metal glass is combined
Material and preparation method thereof.
Background technology
Magnesium-base metal glass (Mg-BMG) is the novel alloy of a kind of longrange disorder, has high intensity, low elastic modulus etc.
Unique mechanical property, and the decay resistance of excellence and good biocompatibility, thus become biodegradable material
One important development direction of material.But, owing to lacking dislocation, the work hardening mechanism such as twin, Mg-BMG is with height localization
Shear mode deform, its temperature-room type plasticity extreme difference, direct brittle fracture under tensile stress.This most seriously constrains Mg-BMG
Clinical practice as Biodegradable material, it is therefore necessary to solve the brittleness at room temperature problem of Mg-BMG.
For improving the brittleness at room temperature of BMG material, within 2000, U.S. Johnson research group first passage is at Zr-BMG alloy
System adds Nb alloy element, prepares the BMG composite of micron-scale β-Zr (Ti) solid solution phase plasticising, it is thus achieved that good
Good temperature-room type plasticity.Subsequently, scientific and technical personnel have developed a kind of Mg-BMG composite, and the room temperature compression strain before its fracture reaches
Arrive the 22%(patent No.: CN101418423).
But above-mentioned Mg-BMG composite Forming ability is relatively low, and critical dimension only has 6mm, it is difficult to meet the need of reality application
Want.Therefore, a kind of Mg-BMG composite with strong glass forming ability and toughness of exploitation and preparation method thereof is needed badly.
Summary of the invention
It is an object of the invention to provide a kind of Mg-BMG composite with strong glass forming ability and excellent toughness
And preparation method thereof.
The technical solution realizing the object of the invention is: a kind of corrosion-resistant biological magnesium-base metal glass composite, its
The alloying component atomic percent expression formula being characterised by described composite is: Mga(Cu0.6Ag0.2Zn0.2)b(Gd0.7Y0.3)c,
70≤a≤85,10.8≤b≤21.6,4.2≤c≤8.4, a+b+c=100.
A kind of corrosion-resistant biological magnesium-base metal glass composite material and preparation method thereof, it is characterised in that use rapid sequential solidification
Method, specifically includes following preparation process:
The first step: carry out proportioning according to the predetermined composition of composite, its alloying component atomic percent expression formula is: Mga
(Cu0.6Ag0.2Zn0.2)b(Gd0.7Y0.3)c, 70≤a≤85,10.8≤b≤21.6,4.2≤c≤8.4, a+b+c=100.First
Use non-consumable arc furnace that the high-melting-point constituent element meltings such as Cu, Ag, Gd, Y is uniform under argon atmosphere, be prepared as middle conjunction
Gold；Then intermediate alloy is put in crucible together with Mg, Zn element, use induction melting to become foundry alloy under argon shield；
Second step: put into by foundry alloy in quartz glass tube, uses induction melting remelting under argon shield, and by low
Foundry alloy section bar is made in pressure copper mold casting；
3rd step: put into the crucible that pretreatment is good by after foundry alloy section bar, under argon shield, uses induction melting to add
Heat is to complete molten condition and is incubated 10 minutes, implements rapid sequential solidification subsequently, forms metal glass composite material.
Compared with prior art, its remarkable advantage is the present invention: 1, designed and preparation technology by the composition of science, can
To obtain the large scale Mg-BMG composite of 16mm, and the volume first separating out magnesium sosoloid phase in composite can be at 30-
Can arbitrarily adjust in the range of 80%；2, Mg-BMG microstructure of composite is uniform, excellent in mechanical performance, also has good corrosion-resistant
Property and biocompatibility.
Accompanying drawing explanation
Fig. 1 is the preparation flow figure for corrosion-resistant biological magnesium-base metal glass composite.
Fig. 2 is corrosion-resistant biological magnesium-base metal glass composite macroscopic view sample, microstructure and XRD diffraction pattern.
Fig. 3 is that the polarization in the room temperature compression curve of corrosion-resistant biological magnesium-base metal glass composite and simulated body fluid is bent
Line.
Detailed description of the invention
Below in conjunction with the accompanying drawings the present invention is described in further detail
In conjunction with Fig. 1, a kind of corrosion-resistant biological magnesium-base metal glass composite of the present invention, its alloying component atomic percent
Expression formula is: Mga(Cu0.6Ag0.2Zn0.2)b(Gd0.7Y0.3)c, 70≤a≤85,10.8≤b≤21.6,4.2≤c≤8.4, a+b+
c =100。
A kind of corrosion-resistant biological magnesium-base metal glass composite of the present invention, its preparation method comprises the following steps:
The first step: choose purity and be more than 99.5% alloying element, carry out proportioning first in argon shield according to predetermined composition
Use non-consumable arc furnace that the high-melting-point constituent element meltings such as Cu, Ag, Gd, Y is uniform under atmosphere, be prepared as intermediate alloy；Then will
Intermediate alloy is put in crucible together with Mg, Zn element, uses induction melting to become foundry alloy under argon shield；
Second step: put into by foundry alloy in quartz glass tube, uses induction melting remelting under argon shield, and by low
Foundry alloy section bar is made in pressure copper mold casting；
3rd step: put into the crucible that pretreatment is good by after foundry alloy section bar, under argon shield, uses induction melting to add
Heat is to complete molten condition and is incubated 10 minutes, implements rapid sequential solidification subsequently, forms metal glass composite material.
The specific implementation process of the present invention is as follows:
(1) design of alloy:
First the alloy system (Mg-Cu-Ag-Gd) with good glass basis Forming ability is selected, and according to selecting mutually
Principle, designs the concrete alloying component that can form the Mg-BMG composite that Mg solid solution phase separates out, then adds appropriate conjunction
Alloying element Zn and Y, carries heavy alloyed glass forming ability further.
(2) foundry alloy melting:
According to the alloying component obtained by (1), first under argon atmosphere use non-consumable arc furnace by Cu, Ag,
The high-melting-point constituent element meltings such as Gd, Y are uniform, are prepared as intermediate alloy；Then intermediate alloy is put into crucible together with Mg, Zn element
In, use induction melting to become foundry alloy under argon shield；Again foundry alloy is put in quartz glass tube, adopt under argon shield
Use induction melting remelting, and make foundry alloy section bar by the casting of low pressure copper mold；
(3) rapid sequential solidification
Put into, by after foundry alloy section bar, the crucible that pretreatment is good, under argon shield, use induction melting to be heated to
Full-fusing state is also incubated 10 minutes, immerses the extremely strong Ga-In-Sn liquid of cooling capacity with the withdrawing rate of 3mm/s subsequently and closes
Jin Zhong, it is achieved rapid sequential solidifies, forms metal glass composite material.
(4) structure and performance characterization
Utilize the means such as XRD, OM that Mg-BMG composite carries out Microstructure characterization, mechanical property and corrosive nature table
Levy, to determine the composite microstructure with optimal combination property and corresponding alloying component thereof and preparation technology parameter.
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
(1) raw-material selection
The present invention prepares the purity such as table 1 of each metal constituent element that master alloy ingot is selected, and alloying component is Mg75
(Cu0.6Ag0.2Zn0.2)18.3(Gd0.7Y0.3)6.7(atomic percent).
Table 1 is prepared master alloy ingot and is selected the purity (%) of metal constituent element
| Alloying element | Mg | Cu | Ag | Zn | Gd | Y |
| Purity/% | 99.9 | 99.9 | 99.9 | 99.9 | 99.5 | 99.5 |
(2) preparation of foundry alloy section bar
First, under high-purity argon gas protective condition, found intermediate alloy with non-consumable arc-melting furnace and buckle ingot, its concrete journey
Sequence is as follows:
A, the surface mechanical grinding of refractory metal raw material Cu, Ag, Gd, Y is removed the oxide skin on surface after, according to setting
The composition proportion material counted is got the raw materials ready；According to the weight of every ingot about 80g, the material prepared is put into the water jacketed copper crucible of smelting furnace
In, cover bell and be evacuated to 2 × 10-3Pa；The high-purity argon gas (99.99%) of a certain amount of pressure, argon pressure model it is filled with in stove
Enclosing is 0.4 ~ 0.6MPa.
B, multi-pass melting intermediate alloy ingot: use non-consumable tungsten electrode by above-mentioned high-melting-point constituent element in function composite by electromagnetic stirring
Under melt together 3 times, the intermediate alloy button ingot being uniformly mixed.The electric current used during melting is 500 ~ 650A, electromagnetic agitation
The voltage used is 1 ~ 3V.
Uniform for electric arc melting intermediate alloy is crushed by second step, with low melting point constituent element Mg, Zn alloy raw material by being designed to
After dividing mixing, put in pretreated graphite crucible together, furnace chamber evacuation, it is re-filled with 0.06MPa argon as protection gas
Body, uses induction melting to make foundry alloy；
3rd step is put in quartz glass tube by broken for foundry alloy, uses induction melting remelting, and lead under argon shield
Cross the casting of low pressure copper mold and make foundry alloy section bar.
(3) rapid sequential solidification
The foundry alloy section bar of above-mentioned acquisition is put into the crucible that pretreatment is good, under argon shield, uses induction melting
It is heated to complete molten condition and is incubated 10 minutes, immersing, with the withdrawing rate of 3mm/s, the Ga-In-that cooling capacity is extremely strong subsequently
In Sn liquid alloy, it is achieved rapid sequential solidifies, form metal glass composite material.
(5) structure and performance characterization
Fig. 2 (a) is the Mg-BMG composite sample of a diameter of 16mm prepared by above-mentioned technique.Fig. 2 (b) is this sample
Micro-organization chart, it is seen that on glass basis, be uniform-distribution with the Mg solid solution phase that volume fraction is about 48%, and in sample
The casting flaw such as pore-free, shrinkage porosite.Fig. 2 (c) is the XRD figure spectrum of Mg-BMG composite, and it further demonstrate that this composite wood
Material is by glass basis and Mg solid solution phase two phase composition.
The room temperature compressive stress strain curve of the Fig. 3 (a) the Mg-BMG composite for preparing, it can be seen that composite wood
Yield strength and the plastic strain of material respectively reach 750MPa and 12%.Fig. 3 (b) is Mg-BMG composite and tradition AZ31 magnesium
Alloy electrochemical tests in simulated body fluid, it is seen that the corrosion potential of this composite is about-1.25V, is far above
The corrosion potential of-the 1.63V of AZ31 magnesium alloy, shows that this Mg-BMG composite has the corrosion resistance of excellence.
Above-mentioned it turns out that, compare existing magnesium alloy, magnesium-base metal glass and technique thereof, the Mg-BMG of present invention design
Composite has a strongest glass forming ability, and has prepared even tissue, Mg-BMG composite wood without casting flaw
Material, it is thus achieved that excellent mechanical performances and decay resistance.
Embodiment 2
Using method same as in Example 1, alloying component is Mg70(Cu0.6Ag0.2Zn0.2)21.6(Gd0.7Y0.3)8.4
(atomic percent), the withdrawing rate of rapid sequential solidification is 5mm/s.The 16mm diameter composite sample even tissue of preparation,
Glass basis is dispersed with the Mg solid solution phase that volume fraction is about 30%,.The mechanical properties of this composite and plasticity
Strain respectively reaches 820MPa and 7.5%, and the electrochemical corrosion potential in simulated body fluid is about-1.20V.
Embodiment 3
Using method same as in Example 1, alloying component is Mg80(Cu0.6Ag0.2Zn0.2)14.4(Gd0.7Y0.3)5.6 (former
Sub-percentage ratio), the withdrawing rate of rapid sequential solidification is 8mm/s.The composite sample even tissue of preparation, on glass basis
It is dispersed with the Mg solid solution phase that volume fraction is about 63%.Mechanical properties and the plastic strain of this composite respectively reach
700MPa and 14%, the electrochemical corrosion potential in simulated body fluid is about-1.32V.
Embodiment 4
Using method same as in Example 1, alloying component is Mg85(Cu0.6Ag0.2Zn0.2)10.8(Gd0.7Y0.3)4.2(former
Sub-percentage ratio), the withdrawing rate of rapid sequential solidification is 10mm/s.The composite sample even tissue of preparation, at glass basis
On be dispersed with the Mg solid solution phase that volume fraction is about 80%.
Claims (5)
1. a corrosion-resistant biological magnesium-base metal glass composite, it is characterised in that the alloying component atom of described composite
Percentage expression formula is: Mga(Cu0.6Ag0.2Zn0.2)b(Gd0.7Y0.3)c, 70≤a≤85,10.8≤b≤21.6,4.2≤c≤
8.4, a+b+c=100.
2. a corrosion-resistant biological magnesium-base metal glass composite material and preparation method thereof, it is characterised in that use rapid sequential solidification
Method, specifically includes following preparation process:
The first step: carry out proportioning according to the predetermined composition of composite, its alloying component atomic percent expression formula is: Mga
(Cu0.6Ag0.2Zn0.2)b(Gd0.7Y0.3)c, 70≤a≤85,10.8≤b≤21.6,4.2≤c≤8.4, a+b+c=100;First
Use non-consumable arc furnace that the high-melting-point constituent element meltings such as Cu, Ag, Gd, Y is uniform under argon atmosphere, be prepared as middle conjunction
Gold；Then intermediate alloy is put in crucible together with Mg, Zn element, use induction melting to become foundry alloy under argon shield；
Second step: put into by foundry alloy in quartz glass tube, uses induction melting remelting under argon shield, and by low pressure copper
Die cast makes foundry alloy section bar；
3rd step: put into the crucible that pretreatment is good by after foundry alloy section bar, under argon shield, uses induction melting to be heated to
Complete molten condition is also incubated 10 minutes, implements rapid sequential solidification subsequently, forms magnesium-base metal glass composite.
Corrosion-resistant biological magnesium-base metal glass composite material and preparation method thereof the most according to claim 2, it is characterised in that: the
The crucible that one step and the 3rd step are used is graphite crucible, and its purity is higher than 99.9%；The first step, second step and the 3rd step are adopted
Purity of argon higher than 99.9%, pressure is 0.06MPa；In 3rd step, the withdrawing rate of rapid sequential solidifying process controls
3-10mm/s。
Corrosion-resistant biological magnesium-base metal glass composite the most according to claim 1, it is characterised in that: magnesium-base metal glass
The full-size of glass composite reaches 16mm, and first precipitated phase is long period Mg solid solution phase, and its volume fraction is at 30-80% model
Can arbitrarily adjust in enclosing, and be evenly distributed on magnesium-base metal glass matrix；Bending of described magnesium-base metal glass composite
Take intensity more than 700MPa, room temperature compression plasticity >=8%.
Corrosion-resistant biological magnesium-base metal glass composite the most according to claim 1, it is characterised in that: magnesium-base metal glass
Glass composite electrochemical corrosion potential E in simulated body fluidP≥-1.2V。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410543955.1A CN104388841B (en) | 2014-10-15 | 2014-10-15 | A kind of corrosion-resistant biological magnesium-base metal glass composite and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410543955.1A CN104388841B (en) | 2014-10-15 | 2014-10-15 | A kind of corrosion-resistant biological magnesium-base metal glass composite and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104388841A CN104388841A (en) | 2015-03-04 |
| CN104388841B true CN104388841B (en) | 2016-08-24 |
Family
ID=52606797
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410543955.1A Active CN104388841B (en) | 2014-10-15 | 2014-10-15 | A kind of corrosion-resistant biological magnesium-base metal glass composite and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104388841B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110042327A (en) * | 2019-05-28 | 2019-07-23 | 北方民族大学 | A kind of a wide range of controllable Biological magnesium alloy of degradation rate |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1156596C (en) * | 2001-09-13 | 2004-07-07 | 中国科学院金属研究所 | Multicomponent magnesium-base amorphous alloy containing zinc element |
| KR100701029B1 (en) * | 2005-06-14 | 2007-03-29 | 연세대학교 산학협력단 | Magnesium Based Metallic Glasses with Enhanced Ductility |
| JP4602210B2 (en) * | 2005-09-27 | 2010-12-22 | 独立行政法人科学技術振興機構 | Magnesium-based metallic glass alloy-metal particle composite with ductility |
| CN102181809B (en) * | 2011-04-21 | 2013-06-19 | 南京理工大学 | Large-size metallic glass composite material with tensile ductility and preparation method thereof |
| CN103938125B (en) * | 2014-03-27 | 2016-08-17 | 同济大学 | A kind of degradable biological magnesium base amorphous alloy and preparation method thereof |
-
2014
- 2014-10-15 CN CN201410543955.1A patent/CN104388841B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN104388841A (en) | 2015-03-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102181809B (en) | Large-size metallic glass composite material with tensile ductility and preparation method thereof | |
| CN102925822B (en) | Metal glass composite material with high-oxygen content and preparation method thereof | |
| CN104152775B (en) | A kind of long-periodic structure strengthens magnesium alloy semisolid slurry and its preparation method | |
| CN104372225B (en) | Preparation method of cast-state Mg-Gd-Zn(-Zr) alloy with LPSO structure | |
| CN105543540A (en) | Copper chromium zirconium alloy and preparing method thereof | |
| CN106893951B (en) | Cu base bulk metallic glass composite material and preparation method | |
| CN108085549A (en) | A kind of method that ultrasonic wave auxiliary mechanical agitation prepares new magnesium-based composite material | |
| CN110669954A (en) | Preparation method of titanium niobium tantalum zirconium alloy | |
| CN101956148A (en) | Dual composite high strength and toughness block amorphous alloy and preparation method thereof | |
| CN102899592B (en) | Plastic zirconium-based metal glass and preparation method thereof | |
| CN104498797A (en) | High-strength casting magnesium alloy with low hot cracking tendency and preparation method for high-strength casting magnesium alloy | |
| CN101629252B (en) | Plastic bulk metallic glass in situ composite material and method for preparing same | |
| CN113502441A (en) | In-situ authigenic phase-reinforced magnesium-based amorphous composite material and preparation method thereof | |
| CN104264082B (en) | A kind of nitrogen-doping Strengthening and Toughening metal glass composite material and preparation method thereof | |
| CN102912259B (en) | Zirconium-based metal glass endogenic composite material and preparation method thereof | |
| CN107699745A (en) | A kind of composite inoculating hypoeutectic al-si alloy and preparation method thereof | |
| CN104328320A (en) | High-strength and high-plasticity magnesium alloy | |
| CN113106312B (en) | Degradable medical alloy and preparation method and application thereof | |
| CN104388841B (en) | A kind of corrosion-resistant biological magnesium-base metal glass composite and preparation method thereof | |
| CN106957986A (en) | A kind of high-ductility magnetostriction materials and preparation method thereof | |
| CN106636825A (en) | High-strength rare-earth magnesium alloy and preparation method thereof | |
| CN106756646B (en) | A kind of Strengthening and Toughening metal glass composite material and preparation method thereof | |
| CN102021359B (en) | Cu-Ni-Si alloy with high Ni and Si content and preparation method thereof | |
| CN101942618B (en) | Magnesium-based block metal glass composite material and preparation method thereof | |
| CN106636985B (en) | A kind of metal glass composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220114 Address after: No. 92, Xinqiao village, Taocun village, Jingqiao Town, Lishui District, Nanjing, Jiangsu 210008 Patentee after: NANJING BAOZUAN SPRING Co.,Ltd. Address before: 1 No. 211167 Jiangsu city of Nanjing province Jiangning Science Park Hongjing Road Patentee before: NANJING INSTITUTE OF TECHNOLOGY |
|
| TR01 | Transfer of patent right |