CN102978494A - Mg-Ge magnesium alloy and preparation method thereof - Google Patents
Mg-Ge magnesium alloy and preparation method thereof Download PDFInfo
- Publication number
- CN102978494A CN102978494A CN2012105393737A CN201210539373A CN102978494A CN 102978494 A CN102978494 A CN 102978494A CN 2012105393737 A CN2012105393737 A CN 2012105393737A CN 201210539373 A CN201210539373 A CN 201210539373A CN 102978494 A CN102978494 A CN 102978494A
- Authority
- CN
- China
- Prior art keywords
- magnesium alloy
- trace element
- percentage composition
- quality percentage
- alloy
- 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.)
- Granted
Links
Images
Landscapes
- Powder Metallurgy (AREA)
- Materials For Medical Uses (AREA)
Abstract
The invention discloses an Mg-Ge magnesium alloy and a preparation method thereof. The magnesium alloy comprises Mg and Ge; and the content of Ge in the magnesium alloy is 0-5 wt%, but is not zero. The preparation method of the magnesium alloy comprises the following steps: mixing the Mg, Ge, Ca, Zn and microelements in any of the following modes 1)-6) to obtain a mixture: 1) Mg and Ge; 2) Mg, Ge and Ca; 3) Mg, Ge and Zn; 4) Mg, Ge and microelements; 5) Mg, Ge, Ca and microelements; and 6) Mg, Ge, Zn and microelements; and carrying out vacuum smelting on the mixture or sintering the mixture, and cooling to obtain the magnesium alloy. In order to improve the characteristics of low mechanical properties and poor corrosion resistance in the traditional medical magnesium alloy, the biodegradable and bioabsorbable Mg-Ge-(Ca, Zn) alloy disclosed by the invention adopts Ge, Ca and Zn with favorable biocompatibility as alloying elements, and combines the composition design and preparation technique, thereby implementing the regulation and control on the mechanical properties and corrosion resistance of the magnesium alloy.
Description
Technical field
The present invention relates to a kind of Mg-Ge series magnesium alloy and preparation method thereof, belong to medical magnesium alloy material and preparation method thereof field.
Background technology
At present, the biomedical metallic material of widespread use mainly comprises 316L, 317L, 304V stainless steel, Co-Cr-Mo alloy, pure titanium, Ti-6Al-4V, TiNi alloy etc. clinically.The implant that these materials are prepared from possesses good mechanical property, corrosion resistance nature and excellent biocompatibility, is usually used to clinically substitute damaged tissue or auxiliary trauma repair in the body.In being used to substitute body, it during damaged tissue, require implant can keep for a long time in vivo constitutionally stable state.And in most of the cases, people to implant and support in vivo the demand of the function that provides all be temporary transient.Because these materials all are inert materials, can not degrade voluntarily in vivo, therefore need second operation to take out, increased medical expense and patient's risk.In addition, implant is retained in the body for a long time can bring the negative impact that can not expect, and for example, the intravascular stent of inserting for a long time in the body can cause inflammation and vascellum endometrial hyperplasia, and then causes vascular restenosis.
Meanwhile, its Young's modulus of these biomedical metallic materials and the osseous tissue of current widespread use extremely do not match, thereby cause " stress shielding " effect.Such consequence is that freshman bone tissue is produced and the stimulation of plasticity weakens, and makes the stability decreases of implant.
Magnesium is a kind of special light metal, and its density is 1.74g/cm
3, with people's bone density (1.8-2.1g/cm
3) approach.Compare with other metal implant materials, its Young's modulus and compression yield strength are closer to normal bone tissues.Magnesium is the second important positively charged ion in the human body, and content is only second to potassium.Magnesium normal contents in human body is 25 grams, and half is present in the bone.In addition, magnesium is indispensable in the human normal metabolic processes.Magnesium ion between 0.7-1.05mmol/L, keeps its concentration stabilize by kidney and small intestine at the fluctuation of concentration of extracellular fluid.The main drawback of magnesium in engineering is used is low erosion resistance, but this shortcoming has become its advantage of using as biomaterial: magnesium can be degraded in vivo soluble nontoxic oxide compound and harmless from intestinal tissue, excrete external.Therefore, as novel biological medical degradable material, magnesium and magnesium alloy possess good mechanical property, corrodible degradation property and biocompatibility, have a good application prospect.
Trace element germanium plays an important role in human life's process, and is closely related with HUMAN HEALTH.Germanium is distributed widely in each histoorgan of human body, many enzymes in the body such as guanidine propylhomoserin enzyme, cellular oxidation enzyme, carbonic anhydride enzyme and pallium, grey matter composition all contain germanium, also contain germanium in the subcellular components such as cell walls, plastosome, lysosome and the intercellular substance matrix.The grownup almost all by gastrointestinal absorption, enters blood circulation from the average germanium 0.4-3.7mg that takes in such as drinking-water, food every day.Germanium does not have selectivity to each tissue after entering human body, and is most of via kidney discharge from urine in 4-7d usually without cumulative effect, also has part germanium directly to excrete from the form of digestive tube with ight soil.Experimental results demonstrate that the multi-functional such as that germanium has is antitumor, anti-inflammatory and immunomodulatory, antiviral, anti-oxidant, anti-ageing, reducing blood-fat is a kind of trace element with good health protection effect.From the materialogy angle, germanium in magnesium matrix with middle phase Mg
2The form of Ge exists.The interpolation of element Ge is crystal grain thinning effectively, improves mechanical property and the corrosion resistance nature of magnesium alloy.
Calcium is a kind of essential element, also is the abundantest magnanimity metallic element of content in the human body, and content is only second to C, H, O, N.Become the interior calcium contents of human body to be about 1200g in the normal situation, wherein about 99% is present in bone and the tooth, and mainly the form with hydroxyapatite crystal exists, and keeps bone and tooth and has hard structure and support.About 1% calcium often is present in the outer liquid of soft tissue cells and the blood with ionic condition free or combination in addition, is referred to as miscible calcium pool.Calcium plays an important role in the various physiology and chemistry processes of body.From the materialogy angle, calcium is crystal grain thinning significantly, thereby improves plasticity and the intensity of magnesium alloy, also can reduce the microbattery effect of magnesium alloy, improves the corrosion resistance of magnesium alloy.
Zinc is the essential trace element of human body.Zinc in the body almost all is the Zn that is attached to cell protein
2+Form exists, it is to the high-affinity of electronics, so that it very easily reacts with amino acid side chain, and form crosslinked in polypeptide or between polypeptide, change tertiary protein structure and function, therefore zinc is brought into play keying action in Growth of Cells and atomization, ZD detrimentally affect is outstanding shows immunity system.On the metallurgy, the maximum solid solution degree of zinc in magnesium is 6.2%, is a kind of effective alloy element except aluminium, has the effect of solution strengthening and ageing strengthening.Can significantly improve the magnesium alloy room temperature strength, improve the erosion resistance of magnesium alloy.
Summary of the invention
The purpose of this invention is to provide a kind of Mg-Ge series magnesium alloy and preparation method thereof, Mg-Ge series magnesium alloy provided by the invention has good biocompatibility and corrosion resistance nature, and can satisfy the requirement of mechanical property, can be used as medical embedded material.
A kind of Mg-Ge series magnesium alloy provided by the present invention, described magnesium alloy comprises Mg and Ge;
By weight percentage, in the described magnesium alloy, the content of Ge can be 0 ~ 5%, but non-vanishing, and magnesium alloy provided by the invention can be dense structure or vesicular structure.
In the above-mentioned magnesium alloy, described magnesium alloy also comprises Ca, and the quality percentage composition of described Ca can be 0 ~ 2%, but non-vanishing.
In the above-mentioned magnesium alloy, described magnesium alloy also comprises Zn, and the quality percentage composition of described Zn can be 0 ~ 2%, but non-vanishing.
In the above-mentioned magnesium alloy, described magnesium alloy also comprises trace element, and described trace element is at least a in manganese, zirconium, tin, rare earth and the yttrium;
In the described magnesium alloy, the quality percentage composition of described trace element can be 0 ~ 2%, but non-vanishing and 2%.
In the above-mentioned magnesium alloy, in the described magnesium alloy, the quality percentage composition of manganese is not more than 1.5%, the quality percentage composition of zirconium is not more than 1%, the quality percentage composition of tin is not more than 2%, and the quality percentage composition of rare earth is not more than 2%, and the quality percentage composition of yttrium is not more than 1%.
The concrete composition of above-mentioned magnesium alloy can be: be comprised of Ge and magnesium, the quality percentage composition of Ge is 1.5% ~ 3%, and surplus is magnesium, specifically can be magnesium or 3% Ge and the magnesium of surplus of magnesium, 2.5% Ge and the surplus of 1.5% Ge and surplus; Be comprised of Ge, magnesium and Ca, the quality percentage composition of Ge is that the quality percentage composition of 1.5%, Ca is 0.2% ~ 1.5% and the magnesium of surplus, specifically can be 0.2% Ca, 1.5% Ge and the magnesium of surplus, the magnesium of 1.5% Ca, 1.5% Ge and surplus; Be comprised of Ge, magnesium and Zn, the quality percentage composition of Ge is that the quality percentage composition of 2.5%, Zn is 1.5% and the magnesium of surplus.
The invention provides the preparation method of above-mentioned magnesium alloy, comprise the steps: described Mg, Ge, Ca, Zn and trace element according to following 1) ~ 6) in any mode be mixed to get mixture:
1) Mg and Ge;
2) Mg, Ge and Ca;
3) Mg, Ge and Zn;
4) Mg, Ge and trace element;
5) Mg, Ge, Ca and trace element;
5) Mg, Ge, Zn and trace element;
At CO
2And SF
6Under the atmosphere protection, described mixture is carried out melting, namely obtain described magnesium alloy after the cooling, be dense structure.
Among the above-mentioned preparation method, the temperature of described melting can be 650 ~ 800 ℃, and described smelting time can be 2 ~ 8h, such as melting under 800 ℃ condition 5 hours.
Among the above-mentioned preparation method, described method also comprises the step of described magnesium alloy being carried out mechanical workout; Described mechanical workout comprises rolling and/or the rapid solidification step;
Described rolling comprising the steps: carried out solution treatment with described magnesium alloy, as 300 ~ 500 ℃ of lower solution treatment 2 ~ 20 hours, then successively through roughing, in roll and finish rolling, as carry out roughing under 400 ~ 500 ℃, reduction in pass is 10 ~ 15%; In to roll temperature be 350 ~ 400 ℃, reduction in pass 30 ~ 60%; 200 ~ 350 ℃ of final rolling temperatures, reduction in pass 5 ~ 10%;
Described rapid solidification comprises the steps: to adopt high vacuum fast quenching system to make rapid coagulation band under the protection of Ar gas, wherein feeding quantity is 2 ~ 8g, induction heating power is 3 ~ 7kW, nozzle and roller spacing are 0.8mm, spraying pressure is 0.05 ~ 0.2MPa, roller speed is 500 ~ 5000r/min, nozzle slot size 1film * 8mm * 6mm; Then strip is broken into Powdered, 200 ~ 350 ℃ of vacuum hotpressing 1 ~ 24h, making Mg-Sr-Zn is the alloy extrusion billet, then in 200 ~ 400 ℃ of scopes the extruding, extrusion ratio is 10 ~ 60.
The present invention also provides the preparation method of another kind of above-mentioned magnesium alloy, comprises the steps: described Mg, Ge, Ca, Zn and trace element according to following 1) ~ 6) in any mode be mixed to get mixture:
1) Mg and Ge;
2) Mg, Ge and Ca;
3) Mg, Ge and Zn;
4) Mg, Ge and trace element;
5) Mg, Ge, Ca and trace element;
5) Mg, Ge, Zn and trace element;
Described mixture is carried out sintering, then namely obtain described magnesium alloy through cooling, this magnesium alloy is vesicular structure;
Describedly be sintered to following any method: element powders mixed-sintering method, prealloy powder sintering process and self propagating high temperature synthesis method.
Described element powders mixed-sintering method comprises the steps: to carry out sintering in Ar gas protective atmosphere; after being warming up to 200 ~ 500 ℃ with the speed of 2 ~ 4 ℃/min; then the speed with 30 ℃/min is warming up to 650 ~ 800 ℃; carried out sintering 1 ~ 12 hour; then the cold cooling of stove obtains the magnesium alloy of vesicular structure, after being warming up at a slow speed 300 ℃ with 2 ℃/min; then be rapidly heated to 700 ℃ with 30 ℃/min, then under this temperature, keep 4h.
Described prealloy powder sintering process comprises the steps: described mixture placed under 300 ~ 600 ℃ the condition and heat-treated 10 ~ 12 hours, obtains the magnesium alloy of vesicular structure.
Described self propagating high temperature synthesis method comprises the steps: under protection of inert gas, gaseous tension 1 * 10
3-1 * 10
5Pa, lighting described mixture under 200 ~ 700 ℃, to carry out self propagating high temperature synthetic, obtains the magnesium alloy of vesicular structure.
In the above-mentioned method, for the degradable that improves the inventive method preparation absorbs Mg-Ge-(Ca, Zn) corrosion resistance nature of serial medical magnesium alloy, described method also comprises to the step of the surface-coated degradable ceramic coating of described magnesium alloy;
The material of described degradable ceramic coating is one or more the arbitrary combination in hydroxyapatite, strontium containing hydroxyapatite, fluoridated hydroxyapatite, type alpha tricalcium phosphate, bata-tricalcium phosphate and phosphoric acid oxygen four calcium.
Among the above-mentioned preparation method, the thickness of described degradable ceramic coating can be 0.01 ~ 5mm;
Apply described degradable ceramic coating by plasma spraying, galvanic deposit or differential arc oxidation method;
The used plasma gas master of described plasma spraying degradable ceramic coating gas: Ar 30-100scfh, inferior gas: H
25-20scfh, spraying current: 400 ~ 800A, spray voltage: 40 ~ 80V, spray distance 100 ~ 500mm.
Described galvanic deposit degradable ceramic coating is take described magnesium alloy as negative electrode, and in the electrolytic solution of the material for preparing the degradable ceramic coating, current density is 0.5 ~ 30mA/cm
2, temperature is 25 ~ 85 ℃, behind processing 10 ~ 60min, cleaning-drying gets final product.
The method of described differential arc oxidation be with described magnesium alloy in the electrolytic solution of the material of preparation degradable ceramic coating, oxidation 5 ~ 30min under 200 ~ 500V condition.
The present invention has following beneficial effect:
Degradable provided by the invention absorbs Mg-Ge-(Ca, Zn) series alloy, the characteristics that mechanical property is lower, corrosion resistance nature is relatively poor that generally have in order to improve the conventional medical magnesium alloy, select the good germanium of biocompatibility, calcium, zinc as alloy element, by Composition Design and preparation technology's combination, realized the mechanical property of magnesium alloy and the regulation and control of corrosion resistance nature.
Description of drawings
Fig. 1 is Mg-Ge-(Ca, the Zn of embodiment 1 and embodiment 2 preparations) the metallographic microstructure figure of alloy material.
Fig. 2 is Mg-Ge-(Ca, the Zn of embodiment 1 and embodiment 2 preparations) the room temperature tensile performance curve of alloy.
Fig. 3 is Mg-Ge-(Ca, the Zn of embodiment 1 and embodiment 2 preparations) alloy carries out the corrosive nature curve that electrochemical test obtains in human simulation body fluid.
Fig. 4 is Mg-Ge-(Ca, Zn in embodiment 1 and embodiment 2 preparations) cultivate 1,3 and 5 day in the alloy material vat liquor after the cell survival rate of MG63 and MC-3T3, wherein Fig. 4 (a) and Fig. 4 (b) are respectively the cell survival rate of MG63 and MC-3T3.
Embodiment
Employed experimental technique is ordinary method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Embodiment 1, preparation as cast condition Mg-Ge-(Ca, Zn) alloy
Test raw material adopts pure Mg(99.9wt.%), Ge powder (99.9wt.%), Ca powder (99.8wt.%) and Zn powder (99.8wt.%).
Cooperate mixture according to following component with proportioning respectively:
(a) Mg of Ge 1.5% and surplus; (b) Mg of Ge 2.5% and surplus; (c) Mg of Ge 3% and surplus; (d) Mg of Ge 1.5%, Ca 0.2% and surplus; (e) Mg of Ge 1.5%, Zn 1.5% and surplus, above-mentioned surplus refers to be supplemented to quality to 100%.
Then the component with said ratio places mortar to carry out hand mix, then in the batch mixing instrument with the rotating speed mixing 5min of 2000rpm.Then mixed powder is placed plumbago crucible, at CO
2And SF
6Carry out melting 5h under the atmosphere protection condition; temperature is 700 ℃; then melt is poured in the mould that is preheating in advance 200 ℃; obtain as-cast magnesium alloy: Mg-1.5Ge; Mg-2.5Ge, Mg-3Ge, Mg-1.5Ge-0.2Ca and Mg-1.5Ge-1.5Ca; its micro-organization chart is followed successively by Fig. 1 (a), Fig. 1 (b), Fig. 1 (c), Fig. 1 (d) and Fig. 1 (e) as shown in Figure 1.
Can be learnt that by Fig. 1 the grain-size of magnesium alloy reduces gradually with the increase of Ge constituent content, behind the interpolation Ca element, the grain-size of alloy increases to some extent, and the interpolation of Zn element has significantly reduced the grain-size of material.
Attitude Mg-Ge-(Ca, Zn are rolled in embodiment 2, preparation) alloy
At first prepare the Mg-Ge alloy cast ingot of as cast condition according to the step among the embodiment 1; The Mg-Ge alloy cast ingot is processed into the 5mm heavy-gauge sheeting, sand papering is to no significant defect, in 400 ℃ of lower solution treatment 3 hours, be rolled, carry out successively roughing, in roll and finish rolling: under 450 ℃, carry out roughing, reduction in pass is 10%, roll in carrying out under 400 ℃, reduction in pass is 50%, carries out roughing under 350 ℃, reduction in pass is 10%, finally is rolled down to 2mm thickness plate.
Present embodiment obtains rolling attitude magnesium alloy: Mg-1.5Ge, Mg-2.5Ge, and Mg-3Ge, its microstructure is followed successively by Fig. 1 (f), Fig. 1 (g) and Fig. 1 (h) as shown in Figure 1, can be learnt by this figure, and through after rolling, each alloy grain size all decreases.
Mg-Ge-(Ca, Zn with embodiment 1 and embodiment 2 preparations) alloy is according to the standby stretching sample of ASTM-E8-04 Elongation test standard system, the SiC sand papering is to 2000#, adopt the general purpose material tensile testing machine at room temperature to carry out tension test, draw speed is 1mm/min.
Mg-Ge-(Ca, the Zn of the present invention preparation) alloy the room temperature tensile performance as shown in Figure 2, can be learnt that by Fig. 2 with the increase of Ge content, tensile strength and the unit elongation of material all increase.The interpolation of Zn element has improved intensity and the unit elongation of material simultaneously, and has added alloy strength and all to some extent decline of unit elongation of Ca element.With respect to cast alloy, yield strength and the tensile strength of rolling attitude alloy all are significantly improved, and unit elongation then descends to some extent.
Mg-Ge-(Ca, Zn with embodiment 1 and embodiment 2 preparations) alloy wire is cut into 10 * 10 * 2mm
3Block sample, be polished to 2000# with sand papering.Then in 37 ℃ Hank ' s simulated body fluid, carry out electrochemical test.
Mg-Ge-(Ca, the Zn of the present invention preparation) alloy corrosion potential-corrosion current curve as shown in Figure 3, can be learnt that by this figure the corrosion resistance nature of rolling rear alloy obviously improves, show as corrosion potential and raise, corrosion current descends.With respect to binary Mg-Ge alloy, the interpolation of Ca and Zn element has also effectively improved the corrosion resistance nature of material.
Adopting the method among the embodiment 4 to prepare test sample, is 1.25cm according to surface-area/vat liquor volume ratio behind the uv irradiating sterilization 2h
2Ml
-1The standby vat liquor of standard system (sample after will sterilizing is immersed in the MEM substratum that does not contain serum, after 72 hours, taking out substratum carries out centrifugal, the supernatant liquor that obtains is vat liquor), adopt human osteosarcoma cell MG63 and mouse bone-forming cell MC-3T3 to estimate Mg-Ge-(Ca, Zn that the present invention obtains) cytotoxicity of alloy.
With cell in vat liquor, cultivate respectively behind 1d, 3d and the 5d cell survival rate as shown in Figure 4, can be learnt that by this figure the cytotoxicity of rolling rear alloy is apparently higher than cast alloy.With the prolongation of cell incubation time in vat liquor, the survival rate of MG63 cell shows as to some extent and descends, but still keeps higher cell survival rate after 5 days except rolling attitude Mg-3Ge, and its cytotoxicity still is in the safety range; The survival rate of MC-3T3 cell prolongs without considerable change with incubation time, still keeps the survival rate more than 100% after 5 days, shows that the alloy vat liquor has the effect that promotes growth to the MC-3T3 cell.
Be 99.95% with pure Mg(purity), pure Ge(purity is 99.9%) and pure Zn(purity be 99.999%), pure Ca(purity is 99.9%), be Ge:Zn=2.5:1.5 in mass ratio, magnesium is surplus, Ge:Ca=1.5:0.2, magnesium is that surplus mixes, be pressed into base, sintering in vacuum sintering furnace (vacuum tightness is 0.5atm), the step of concrete sintering is: after being warming up at a slow speed 300 ℃ with 2 ℃/min, then be rapidly heated to 700 ℃ with 30 ℃/min, then under this temperature, keep 4h, last, the cold cooling of stove obtains the Mg-Ge-(Ca of vesicular structure with the element powders mixed-sintering method, Zn) alloy.
Claims (10)
1. Mg-Ge series magnesium alloy, it is characterized in that: described magnesium alloy comprises Mg and Ge;
By weight percentage, in the described magnesium alloy, the content of Ge is 0 ~ 5%, but non-vanishing.
2. magnesium alloy according to claim 1, it is characterized in that: described magnesium alloy also comprises Ca, the quality percentage composition of described Ca is 0 ~ 2%, but non-vanishing.
3. magnesium alloy according to claim 1, it is characterized in that: described magnesium alloy also comprises Zn, the quality percentage composition of described Zn is 0 ~ 2%, but non-vanishing.
4. each described magnesium alloy according to claim 1-3, it is characterized in that: described magnesium alloy also comprises trace element, described trace element is at least a in manganese, zirconium, tin, rare earth and the yttrium;
In the described magnesium alloy, the quality percentage composition of described trace element is 0 ~ 2%, but non-vanishing and 2%.
5. magnesium alloy according to claim 4, it is characterized in that: in the described magnesium alloy, the quality percentage composition of manganese is not more than 1.5%, the quality percentage composition of zirconium is not more than 1%, the quality percentage composition of tin is not more than 2%, the quality percentage composition of rare earth is not more than 2%, and the quality percentage composition of yttrium is not more than 1%.
6. the preparation method of each described magnesium alloy among the claim 1-5 comprises the steps: described Mg, Ge, Ca, Zn and trace element according to following 1) ~ 6) in any mode be mixed to get mixture:
1) Mg and Ge;
2) Mg, Ge and Ca;
3) Mg, Ge and Zn;
4) Mg, Ge and trace element;
5) Mg, Ge, Ca and trace element;
5) Mg, Ge, Zn and trace element;
At CO
2And SF
6Under the atmosphere protection, described mixture is carried out melting, namely obtain described magnesium alloy after the cooling.
7. method according to claim 6, it is characterized in that: described method also comprises the step of described magnesium alloy being carried out mechanical workout; Described mechanical workout comprises rolling and/or the rapid solidification step;
Described rolling comprising the steps: carried out solution treatment with described magnesium alloy, then successively through roughing, in roll and finish rolling.
8. the preparation method of each described magnesium alloy among the claim 1-5 comprises the steps: described Mg, Ge, Ca, Zn and trace element according to following 1) ~ 6) in any mode be mixed to get mixture:
1) Mg and Ge;
2) Mg, Ge and Ca;
3) Mg, Ge and Zn;
4) Mg, Ge and trace element;
5) Mg, Ge, Ca and trace element;
5) Mg, Ge, Zn and trace element;
Described mixture is carried out sintering, then namely obtain described magnesium alloy through cooling;
Describedly be sintered to following any method: element powders mixed-sintering method, prealloy powder sintering process and self propagating high temperature synthesis method.
9. each described method according to claim 6-8 is characterized in that: described method also comprises to the step of the surface-coated degradable ceramic coating of described magnesium alloy;
The material of described degradable ceramic coating is one or more the arbitrary combination in hydroxyapatite, strontium containing hydroxyapatite, fluoridated hydroxyapatite, type alpha tricalcium phosphate, bata-tricalcium phosphate and phosphoric acid oxygen four calcium;
The thickness of described degradable ceramic coating is 0.01 ~ 5mm;
Apply described degradable ceramic coating by plasma spraying, galvanic deposit or differential arc oxidation method.
10. the application of each described Mg-Ge series magnesium alloy in the preparation medical implant among the claim 1-5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210539373.7A CN102978494B (en) | 2012-12-13 | 2012-12-13 | Mg-Ge magnesium alloy and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210539373.7A CN102978494B (en) | 2012-12-13 | 2012-12-13 | Mg-Ge magnesium alloy and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102978494A true CN102978494A (en) | 2013-03-20 |
| CN102978494B CN102978494B (en) | 2015-06-10 |
Family
ID=47852828
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210539373.7A Active CN102978494B (en) | 2012-12-13 | 2012-12-13 | Mg-Ge magnesium alloy and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102978494B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104046870A (en) * | 2014-07-09 | 2014-09-17 | 北京汽车股份有限公司 | High-elasticity-modulus magnesium alloy and preparation method thereof |
| CN106756860A (en) * | 2016-12-20 | 2017-05-31 | 薛亚红 | For Anticorrosion method for neodymium iron boron ferrite |
| CN109966568A (en) * | 2019-04-11 | 2019-07-05 | 湘潭大学 | A kind of Zn-Ge-X ternary bio-medical material and preparation method thereof |
| CN109972007A (en) * | 2019-03-20 | 2019-07-05 | 北京科技大学 | A kind of anastomosis staple material and preparation method thereof of biology degradable in vivo Mg-Zn-Ca-M |
| WO2020083387A1 (en) * | 2018-10-26 | 2020-04-30 | 宝山钢铁股份有限公司 | High-strength and corrosion-resistant magnesium alloy material and method for fabricating same |
| US10711330B2 (en) | 2017-10-24 | 2020-07-14 | GM Global Technology Operations LLC | Corrosion-resistant magnesium-aluminum alloys including germanium |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665669A (en) * | 1992-08-25 | 1994-03-08 | Honda Motor Co Ltd | Heat resistant mg alloy and its production |
| CN102552973A (en) * | 2012-02-17 | 2012-07-11 | 浙江海圣医疗器械有限公司 | Medical degradable and absorbable Mg-Sr-Ca series magnesium alloy implant and preparation method thereof |
| CN102813966A (en) * | 2012-08-29 | 2012-12-12 | 哈尔滨工程大学 | Medical degradable magnesium alloy bone-fixing screw |
-
2012
- 2012-12-13 CN CN201210539373.7A patent/CN102978494B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0665669A (en) * | 1992-08-25 | 1994-03-08 | Honda Motor Co Ltd | Heat resistant mg alloy and its production |
| CN102552973A (en) * | 2012-02-17 | 2012-07-11 | 浙江海圣医疗器械有限公司 | Medical degradable and absorbable Mg-Sr-Ca series magnesium alloy implant and preparation method thereof |
| CN102813966A (en) * | 2012-08-29 | 2012-12-12 | 哈尔滨工程大学 | Medical degradable magnesium alloy bone-fixing screw |
Non-Patent Citations (1)
| Title |
|---|
| 刘红宾: "基于合金化改善镁合金强/韧性的研究", 《《中国博士学位论文全文数据库 (电子期刊)工程科技I辑》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104046870A (en) * | 2014-07-09 | 2014-09-17 | 北京汽车股份有限公司 | High-elasticity-modulus magnesium alloy and preparation method thereof |
| CN106756860A (en) * | 2016-12-20 | 2017-05-31 | 薛亚红 | For Anticorrosion method for neodymium iron boron ferrite |
| US10711330B2 (en) | 2017-10-24 | 2020-07-14 | GM Global Technology Operations LLC | Corrosion-resistant magnesium-aluminum alloys including germanium |
| WO2020083387A1 (en) * | 2018-10-26 | 2020-04-30 | 宝山钢铁股份有限公司 | High-strength and corrosion-resistant magnesium alloy material and method for fabricating same |
| CN111101039A (en) * | 2018-10-26 | 2020-05-05 | 宝山钢铁股份有限公司 | High-strength corrosion-resistant magnesium alloy material and manufacturing method thereof |
| KR20210028682A (en) * | 2018-10-26 | 2021-03-12 | 바오샨 아이론 앤 스틸 유한공사 | High-strength and corrosion-resistant magnesium alloy material and its manufacturing method |
| US20210189527A1 (en) * | 2018-10-26 | 2021-06-24 | Baoshan Iron & Steel Co., Ltd. | High-strength and corrosion-resistant magnesium alloy material and method for fabricating same |
| KR102573665B1 (en) * | 2018-10-26 | 2023-09-04 | 바오샨 아이론 앤 스틸 유한공사 | High-strength and corrosion-resistant magnesium alloy material and manufacturing method thereof |
| CN109972007A (en) * | 2019-03-20 | 2019-07-05 | 北京科技大学 | A kind of anastomosis staple material and preparation method thereof of biology degradable in vivo Mg-Zn-Ca-M |
| CN109966568A (en) * | 2019-04-11 | 2019-07-05 | 湘潭大学 | A kind of Zn-Ge-X ternary bio-medical material and preparation method thereof |
| CN109966568B (en) * | 2019-04-11 | 2021-08-06 | 湘潭大学 | Zn-Ge-X ternary biomedical material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102978494B (en) | 2015-06-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102978494B (en) | Mg-Ge magnesium alloy and preparation method thereof | |
| CN109972007B (en) | Anastomosis nail material capable of degrading Mg-Zn-Ca-M in organism and preparation method thereof | |
| JP6431957B2 (en) | Biodegradable metal alloy | |
| CN101015711B (en) | Medical implantation material capable of by degraded by body fluid and its preparing process | |
| CN106890356B (en) | Degradable zinc-based alloy implant material and preparation method and application thereof | |
| CN102552973A (en) | Medical degradable and absorbable Mg-Sr-Ca series magnesium alloy implant and preparation method thereof | |
| CN102978495A (en) | Mg-Sr-Zn alloy and preparation method thereof | |
| CN101899600B (en) | Osteopathic magnesium alloy interstitial implant material and preparation method thereof | |
| WO2017084363A1 (en) | Medical degradable zn-cu-x alloy material and preparation method thereof | |
| CN101837145B (en) | High-toughness corrosion-resistant magnesium alloy implanted material capable of being degraded in organism | |
| CN104762542B (en) | Biomedical degradable absorption Mg-Sr-Cu alloy material, preparation method and application | |
| CN100368028C (en) | Bio-absorbable Mg-Zn two-elements magnesium alloy material | |
| CN1792383A (en) | Bio-absorbable Mg-Zn-Ca three-elements magnesium alloy material | |
| CN104120320B (en) | A kind of degradable magnesium-rare earth biomaterial for medical purpose and preparation method | |
| CN105986146B (en) | A kind of degradable medical is metal material embedded and preparation method thereof | |
| CN102433477A (en) | Biomedical Mg-Sn-Zn-Mn magnesium alloy and preparation method thereof | |
| CN111155013B (en) | Medical three-dimensional printing alloy material and preparation method thereof | |
| CN104451303A (en) | Biomedical magnesium alloy and preparation method and application of biomedical magnesium alloy wire | |
| CN101550510A (en) | High intensity degradable biological medical magnesium alloy and preparation method thereof | |
| WO2020042745A1 (en) | Mg-zn-sn series magnesium alloy with controllable degradation rate, preparation method and application thereof | |
| CN102258806B (en) | Degradable magnesium-base biomedical material for implantation in orthopaedics, and preparation method thereof | |
| CN103184380B (en) | Biodegradable Mg-Gd-Zn-Sr-Zr series magnesium alloy and preparation method thereof | |
| CN100372574C (en) | Multi-elements magnesium alloy contg. Mg-Zn-Ca-Fe of bio-absorbable type | |
| CN111334688A (en) | Zn-RE series zinc alloy and preparation method and application thereof | |
| CN105803254B (en) | A kind of preparation method of bulk titanium copper calcium biomaterial |
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 |