CN101869726A - Mg-Zn-Sr alloy biomaterial of hydroxyapatite coating and preparation method thereof - Google Patents
Mg-Zn-Sr alloy biomaterial of hydroxyapatite coating and preparation method thereof Download PDFInfo
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- CN101869726A CN101869726A CN201010194231A CN201010194231A CN101869726A CN 101869726 A CN101869726 A CN 101869726A CN 201010194231 A CN201010194231 A CN 201010194231A CN 201010194231 A CN201010194231 A CN 201010194231A CN 101869726 A CN101869726 A CN 101869726A
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Abstract
The invention discloses an Mg-Zn-Sr alloy biomaterial of a hydroxyapatite coating, which belongs to the technical field of materials. The material consists of a magnesium alloy matrix and the hydroxyapatite coating, wherein the magnesium alloy matrix comprises the following components in percentage by weight: 2 to 6 percent of Zn, 0.5 to 2 percent of Sr and the balance of magnesium; the hydroxyapatite coating comprises the following components in percentage by weight: 1.8 to 5.4 percent of Zn, 0.45 to 1.8 percent of Sr, 5 to 14.95 percent of hydroxyapatite and the balance of magnesium; and the thickness of the hydroxyapatite coating is 0.1 to 0.3 micron. The HA biological coating is deposited on the alloy surface by a reasonable process; and close to the human skeleton, the biomaterial has high specific strength and specific stiffness, can be automatically degraded and absorbed by the human body, and does not produce long-term stimulation effect on an organism.
Description
Technical field
The invention belongs to the material technology field, particularly Mg-Zn-Sr alloy biomaterial of a kind of hydroxyapatite coating layer and preparation method thereof.
Background technology
At present, the clinical material that is used for the orthopaedics rehabilitation relates to traditional metal material (as rustless steel, vitallium, titanium alloy) and inorganic material and macromolecular material.There are problems such as intensity, rigidity and stability are lower in macromolecular material in clinical practice, there is obviously deficiency in treatment application to Compact bone, especially the fracture for the treatment of the heavy burden position, vertebral body, pelvis, long bone, refracture, malignant tumor infection and general metabolism disease patient etc.Inorganic material has been absorbed in mechanical compatibility in clinical practice relatively poor, and easily stress is concentrated and caused the predicament of material generation brittle fracture.
At present, the material of a large amount of bone fracture internal fixing device spares (screw, rod, spicule etc.) that use mainly is a traditional metal materials clinically, its usual way is the peg that has hammered into fixation at fracture, but has following shortcoming and problem: (1) stress-shielding effect.When the metal material implant into body, carefully knit because of the elastic modelling quantity of embedded material and human body bone and not match, can produce stress-shielding effect, can influence the growth of bone, produce osteoporosis, bone resorption or osteanabrosis etc., cause bone strength to reduce, it is slow to heal, and the secondary fracture easily takes place.(2) need second operation to take out.Traditional metal materials can not degraded in human body in the clinical practice, is being absorbed by the body, behind the rehabilitation certain hour, need carry out second operation takes out fixture, operation has certain risk, comprise that local infection, refracture, hurt in spirits, internal fixation are residual etc., produce complication rate and be up to 20%, increased patient's misery and financial burden greatly.(3) electrolytic etching, histocompatibility is poor.Electrolytic etching takes place in traditional metal materials easily in the human body environment, the metal ion of release can make body produce untoward reaction such as anaphylaxis and inflammation.(4) density of material and bone density differ greatly.Titanium alloy T i
6Al
4The density of V is 4.47g/cm
3, much larger than the about 175g/cm of people's bone density
3, rustless steel density is also very big, causes the uncomfortable reaction of Denging, and function of use is undesirable.(5) cost height.The cost height that resource is nervous relatively, preparation and processing cost height make embedded materials such as titanium alloy, rustless steel causes patient economy burden to increase the weight of.
Summary of the invention
At the existing clinical problem that is used on the orthopaedics material for rehabilitation therapy performance, the invention provides Mg-Zn-Sr alloy biomaterial of a kind of hydroxyapatite coating layer and preparation method thereof.
The Mg-Zn-Sr alloy biomaterial of hydroxyapatite coating layer of the present invention is made of magnesium alloy substrate and hydroxyapatite coating layer, and wherein the composition of magnesium alloy substrate is Zn2～6% by weight percentage, Sr0.5～2%, and surplus is a magnesium; The composition of hydroxyapatite coating layer is Zn1.8～5.4% by weight percentage, Sr0.45～1.8%, and hydroxyapatite 5～14.95%, surplus is a magnesium.
The thickness of described hydroxyapatite coating layer is 0.1～0.3 μ m.
The preparation method of above-mentioned alloy biomaterial is carried out according to the following steps:
1, smelt magnesium alloy, be cast into behind the ingot rollingly, ingot casting is carried out breaking down under 380 ± 10 ℃ of conditions, mill speed is 18～22m/min, and overall reduction is 10～20%; Roll in carrying out under 350 ± 10 ℃ of conditions then, mill speed is 14～16m/min, and overall reduction is 5～20%; Carry out finish to gauge again under 320 ± 10 ℃ of conditions, mill speed is 8～12m/min, and overall reduction is 2～5%; Obtain magnesium alloy substrate sheet material, its composition is Zn2～6% by weight percentage, Sr0.5～2%, and surplus is a magnesium.
The mechanical property of above-mentioned magnesium alloy substrate sheet material is: elastic modelling quantity 35～45Gpa, tensile strength 300～320MPa, percentage elongation 15～18%, hardness 60～65HV.
2, magnesium alloy substrate sheet material is placed 0.2～0.8vmol/L sodium hydroxide solution, heat treatment 120 ± 5min under 80 ± 2 ℃ of conditions.
3, the magnesium alloy substrate sheet material behind the heat treatment is placed contain Ca
2+And H
2PO
4 -Solution in, the pH value of regulator solution is 4.5～4.6, be anode then with graphite, magnesium alloy substrate sheet material is that cathodal closing carries out electrolysis, and electric current density is 0.02～0.03mA/cm during electrolysis, and solution temperature is 20～80 ℃ during electrolysis, electrolysis time is 60～120min, the hydroxyapatite that reaction is formed is deposited on the magnesium alloy substrate plate surface, is prepared into the Mg-Zn-Sr alloy biomaterial of hydroxyapatite coating layer, and reaction equation is
10Ca
2++6H
2PO
4 -+2OH
-＝Ca
10(PO
4)
6(OH)
2+6H
2
The mol ratio of the calcium ion of solution and phosphorus is Ca/P=1.3～1.5 in the above-mentioned cell reaction.
The present invention has designed the biomaterial as matrix alloy with Mg-Zn-Sr system, and by rational technology at its surface deposition HA biological coating.The magnesium alloy biological implantation material has following advantage: comprehensive mechanical properties such as the density of (1) magnesium, elastic modelling quantity are close with human skeleton, have higher specific strength and specific stiffness simultaneously, can effectively reduce stress-shielding effect; (2) magnesium alloy has degradable characteristic in the Human Physiology environment, can be degraded voluntarily, absorb by human body.Therefore, in a single day the bone fracture internal fixing device spare (screw, rod, spicule etc.) that adopts magnesium alloy to make is succeedd clinically and is used, and misery and the financial burden that promptly can avoid second operation that patient with bone fracture is caused are for patient with bone fracture brings glad tidings; (3) compatibility of magnesium and human body is fabulous.According to research, magnesium alloy can effectively prevent the repulsion of biological tissue, can not cause the loosening of implant and comes off.In addition, can not produce permanent stimulation to organism, can not cause biological bring out inflammation and cytometaplasia, and dissolved magnesium ion is the element of needed by human (the indispensable element of nervous system especially just, everyone every day required Mg amount of being grown up surpasses 350mg), and be of value to the growth of the metabolism and the osseous tissue of human body; (4) compare with the traditional metal materials of present clinical practice, as titanium alloy, rustless steel, cobalt alloy etc., magnesium resource is abundant, and cheap, particularly China's magnesium resource accounts for 1/2 of world saving, and the advantage of market development is more obvious.But magnesium alloy is too fast in the intravital corrosion rate of people, and both uncontrollable its corrosion produces Mg
2+Speed, human body is worked the mischief; Can be unfavorable for wound healing because of corroding the too fast quick decline that causes the fixture mechanical property again.
Mg-Zn-Sr is choosing mainly based on the following aspects of biomaterial matrix alloy composition: the composition of plurality of enzymes in (1) Zn:Zn wide participation body is relevant with the activity of 300 plurality of enzymes in the body.Be used in addition regulating and control must or the metalloprotein of the metabolic a lot of non-enzymes of non-essential element and other melts combine biopolymers in merit contain Zn.Lack Zn in the body and can make dna replication dna slow, biosynthesis block, protein synthesis is suppressed.In addition, Zn to add power also useful to the mechanical property and the corrosion resistance of magnesium alloy, contain a spot of Zn in the alloy and can not only play the solution strengthening effect, also can make be solid-solubilized in matrix α mutually in the content of Zn improve, the current potential of matrix is suitably increased, promoted the enhancing of alloy corrosion resistance energy.Zn also helps to form passivating film at Mg alloy surface, and weakens the adverse effect of impurity such as Fe, Ni to the alloy corrosive nature; (2) Sr:Sr is the important component part of skeleton and tooth, can promote the formation of skeleton development and osteoid, regulates calcium metabolism.Discovering in recent years, Sr is essential and not replaceable in the fetal development of many Molluscas (as sea hare, squid, Gourde(G) clam etc.).Osteoporosis may be due to Ca, the Sr metabolism disorder, and stable Sr chemical compound has therapeutical effect to osteoporosis.Studies show that low dosage Sr salt can reduce bone resorption, keep higher bone formation rate, promote synthetic, the metabolism of bone.At present, Sr has been used in the treatment of osteoporosis, is listed in one of osteoporotic three big new treatment measures.Germany Laves company produced be suitable for osteoporosis, fracture and callus formation disfunction contain Sr medicine Stronticol.Aspect the mechanical property that improves alloy, Sr is one of important alloying element for magnesium alloy, the interpolation of Sr is the tissue of refinement magnesium alloy effectively, improve the casting properties of magnesium alloy, improve room temperature and pyritous mechanical property, improved the croop property of magnesium alloy, the Sr element can also improve the corrosion resistance of magnesium alloy to a certain extent.Though the cost of Sr is higher relatively, Sr can improve the casting manufacturability of alloy, adds a spot of Sr and can satisfy large batch of die casting production, thereby production cost is reduced.In a word, Mg-Zn-Sr is that the selection of alloy is based on the trace element that Zn, Sr are needed by human body, and mechanical property and the corrosion resistance to alloy is all useful simultaneously.
Using HA (hydroxyapatite) is because of its constituent, structure and character are consistent with the inanimate matter in the body bone tissue as coating material, and nontoxic, no carcinogenesis, with sclerotin good binding and excellent biocompatibility is arranged.Studies show that HA can form strong synosteosis with natural bone,, can produce bone matrix collagen,, promote the formation of osseous tissue along with further mineralising in case cell attachment stretches.But its fracture toughness is poor, elastic modelling quantity is low and degradation speed wait for drawbacks limit slowly HA use separately as biomaterial, it uses the hard tissue repair only be confined to not be subjected to load region.In conjunction with the characteristics of Mg-Zn-Sr alloy and HA, for reaching the purpose of maximizing favourable factors and minimizing unfavourable ones, adopt electrodeposition process to prepare the HA coating at the Mg-Zn-Sr alloy surface, both slowed down the magnesium alloy corrosion rate, avoided the mechanical property defect of insufficient of HA again.
Adopt electrochemical deposition method to prepare HA (hydroxyapatite) and carries out under cryogenic conditions, so there is not thermal stress issues in matrix and coating interface, phase transformation and the embrittlement of having avoided pyrolytic coating to cause help strengthening matrix and are coated with the interlayer bond strength.The elastic modelling quantity and the human skeleton of the Mg-Zn-Sr degradable biomaterial of electro-deposition HA coating preparation are close behind surperficial alkali heat treatment, have higher specific strength and specific stiffness simultaneously, can effectively reduce stress-shielding effect; With human body fabulous biocompatibility is arranged, can effectively prevent the repulsion of biological tissue, can not cause the loosening of implant and come off.In addition, can not produce permanent stimulation to organism, can not cause biological bring out inflammation and cytometaplasia, and the dissolved magnesium ion element of needed by human (the indispensable element of nervous system especially) just, be of value to growth to the metabolism and the osseous tissue of human body; In the Human Physiology environment, have degradability,, can avoid the misery of second operation and reduce medical expense as the embedded material of degradability.
Description of drawings
Fig. 1 is the metallographic structure photo figure of the magnesium alloy substrate sheet material in the embodiment of the invention 1.
Fig. 2 is the hydroxyapatite coating layer SEM shape appearance figure of product in the embodiment of the invention 1.
Fig. 3 is the hydroxyapatite EDS energy spectrum analysis figure of product in the embodiment of the invention 1.
Fig. 4 is the hydroxyapatite XRD material phase analysis figure of product in the embodiment of the invention 1.
The specific embodiment
The milling train that adopts in the embodiment of the invention is Φ 300 type milling trains.
Embodiment 1
Smelt magnesium alloy, be cast into behind the ingot rollingly, milling method is: ingot casting is carried out breaking down under 380 ± 10 ℃ of conditions, mill speed is 18m/min, and overall reduction is 10%; Roll in carrying out under 350 ± 10 ℃ of conditions then, mill speed is 14m/min, and overall reduction is 5%; Carry out finish to gauge again under 320 ± 10 ℃ of conditions, mill speed is 8m/min, and overall reduction is 2%; Obtain magnesium alloy substrate sheet material, its composition is Zn2% by weight percentage, Sr0.5%, and surplus is a magnesium.The mechanical property of magnesium alloy substrate sheet material is: elastic modelling quantity 35Gpa, tensile strength 300MPa, percentage elongation 15%, hardness 65HV; The metallographic structure photo as shown in Figure 1.
Magnesium alloy substrate sheet material is placed the 0.2mol/L sodium hydroxide solution, heat treatment 115min under 80 ± 2 ℃ of conditions.
Magnesium alloy substrate sheet material behind the heat treatment placed contain Ca
2+And H
2PO
4 -Solution in, the mol ratio of calcium ion and phosphorus is Ca/P=1.3 in the solution; The pH value of regulator solution is 4.5, is anode then with graphite, and magnesium alloy substrate sheet material is that cathodal closing carries out electrolysis, and electric current density is 0.02mA/cm
2Solution temperature is 20 ℃ during electrolysis, electrolysis time is 120min, the hydroxyapatite that reaction is formed is deposited on the magnesium alloy substrate plate surface, is prepared into the Mg-Zn-Sr alloy biomaterial of hydroxyapatite coating layer, and the thickness of hydroxyapatite coating layer is 0.1 μ m, composition is Zn1.8% by weight percentage, Sr0.45%, hydroxyapatite 5%, surplus is a magnesium; The surface hydroxyapatite coating layer SEM pattern as shown in Figure 2, the EDS energy spectrum analysis as shown in Figure 3, XRD material phase analysis figure is as shown in Figure 4.
Smelt magnesium alloy, be cast into behind the ingot rollingly, milling method is: ingot casting is carried out breaking down under 380 ± 10 ℃ of conditions, mill speed is 20m/min, and overall reduction is 15%; Roll in carrying out under 350 ± 10 ℃ of conditions then, mill speed is 15m/min, and overall reduction is 10%; Carry out finish to gauge again under 320 ± 10 ℃ of conditions, mill speed is 10m/min, and overall reduction is 3%; Obtain magnesium alloy substrate sheet material, its composition is Zn3% by weight percentage, Sr1%, and surplus is a magnesium.The mechanical property of magnesium alloy substrate sheet material is: elastic modelling quantity 40Gpa, tensile strength 305MPa, percentage elongation 16%, hardness 60HV.
Magnesium alloy substrate sheet material is placed the 0.4vmol/L sodium hydroxide solution, heat treatment 120min under 80 ± 2 ℃ of conditions.
Magnesium alloy substrate sheet material behind the heat treatment placed contain Ca
2+And H
2PO
4 -Solution in, the mol ratio of calcium ion and phosphorus is Ca/P=1.4 in the solution; The pH value of regulator solution is 4.6, is anode then with graphite, and magnesium alloy substrate sheet material is that cathodal closing carries out electrolysis, and electric current density is 0.03mA/cm
2Solution temperature is 40 ℃ during electrolysis, electrolysis time is 100min, the hydroxyapatite that reaction is formed is deposited on the magnesium alloy substrate plate surface, is prepared into the Mg-Zn-Sr alloy biomaterial of hydroxyapatite coating layer, and hydroxyapatite coating layer thickness is 0.2 μ m, composition is Zn2.5% by weight percentage, Sr0.9%, hydroxyapatite 8.2%, surplus is a magnesium.
Embodiment 3
Smelt magnesium alloy, be cast into behind the ingot rollingly, milling method is: ingot casting is carried out breaking down under 380 ± 10 ℃ of conditions, mill speed is 22m/min, and overall reduction is 20%; Roll in carrying out under 350 ± 10 ℃ of conditions then, mill speed is 16m/min, and overall reduction is 15%; Carry out finish to gauge again under 320 ± 10 ℃ of conditions, mill speed is 12m/min, and overall reduction is 4%; Obtain magnesium alloy substrate sheet material, its composition is Zn4% by weight percentage, Sr1.5%, and surplus is a magnesium.The mechanical property of magnesium alloy substrate sheet material is: elastic modelling quantity 45Gpa, tensile strength 310MPa, percentage elongation 17%, hardness 63HV.
Magnesium alloy substrate sheet material is placed the 0.6mol/L sodium hydroxide solution, heat treatment 125min under 80 ± 2 ℃ of conditions.
Magnesium alloy substrate sheet material behind the heat treatment placed contain Ca
2+And H
2PO
4 -Solution in, the mol ratio of calcium ion and phosphorus is Ca/P=1.5 in the solution; The pH value of regulator solution is 4.5, is anode then with graphite, and magnesium alloy substrate sheet material is that cathodal closing carries out electrolysis, and electric current density is 0.02mA/cm
2Solution temperature is 60 ℃ during electrolysis, electrolysis time is 80min, the hydroxyapatite that reaction is formed is deposited on the magnesium alloy substrate plate surface, is prepared into the Mg-Zn-Sr alloy biomaterial of hydroxyapatite coating layer, and hydroxyapatite coating layer thickness is 0.3 μ m, composition is Zn3.7% by weight percentage, Sr1.4%, hydroxyapatite 11.3%, surplus is a magnesium.
Smelt magnesium alloy, be cast into behind the ingot rollingly, milling method is: ingot casting is carried out breaking down under 380 ± 10 ℃ of conditions, mill speed is 20m/min, and overall reduction is 15%; Roll in carrying out under 350 ± 10 ℃ of conditions then, mill speed is 15m/min, and overall reduction is 18%; Carry out finish to gauge again under 320 ± 10 ℃ of conditions, mill speed is 10m/min, and overall reduction is 5%; Obtain magnesium alloy substrate sheet material, its composition is Zn6% by weight percentage, Sr2%, and surplus is a magnesium.The mechanical property of magnesium alloy substrate sheet material is: elastic modelling quantity 40Gpa, tensile strength 320MPa, percentage elongation 18%, hardness 61HV.
Magnesium alloy substrate sheet material is placed the 0.8vmol/L sodium hydroxide solution, heat treatment 120min under 80 ± 2 ℃ of conditions.
Magnesium alloy substrate sheet material behind the heat treatment placed contain Ca
2+And H
2PO
4 -Solution in, the mol ratio of calcium ion and phosphorus is Ca/P=1.4 in the solution; The pH value of regulator solution is 4.6, is anode then with graphite, and magnesium alloy substrate sheet material is that cathodal closing carries out electrolysis, and electric current density is 0.03mA/cm
2Solution temperature is 80 ℃ during electrolysis, electrolysis time is 60, the hydroxyapatite that reaction is formed is deposited on the magnesium alloy substrate plate surface, is prepared into the Mg-Zn-Sr alloy biomaterial of hydroxyapatite coating layer, and hydroxyapatite coating layer thickness is 0.2 μ m, composition is Zn5.4% by weight percentage, S r1.8%, hydroxyapatite 14.95%, surplus is a magnesium.
Claims (4)
1. the Mg-Zn-Sr alloy biomaterial of a hydroxyapatite coating layer is characterized in that this material is made of magnesium alloy substrate and hydroxyapatite coating layer, and wherein the composition of magnesium alloy substrate is Zn2～6% by weight percentage, Sr0.5～2%, and surplus is a magnesium; The composition of hydroxyapatite coating layer is Zn1.8～5.4% by weight percentage, Sr0.45～1.8%, and hydroxyapatite 5～14.95%, surplus is a magnesium; The thickness of hydroxyapatite coating layer is 0.1～0.3 μ m.
2. the preparation method of the Mg-Zn-Sr alloy biomaterial of the described a kind of hydroxyapatite coating layer of claim 1 is characterized in that carrying out according to the following steps:
(1) smelt magnesium alloy, be cast into behind the ingot rollingly, ingot casting is carried out breaking down under 380 ± 10 ℃ of conditions, mill speed is 18～22m/min, and overall reduction is 10～20%; Roll in carrying out under 350 ± 10 ℃ of conditions then, mill speed is 14～16m/min, and overall reduction is 5～20%; Carry out finish to gauge again under 320 ± 10 ℃ of conditions, mill speed is 8～12m/min, and overall reduction is 2～5%; Obtain magnesium alloy substrate sheet material, its composition is Zn2～6% by weight percentage, Sr0.5～2%, and surplus is a magnesium;
(2) magnesium alloy substrate sheet material is placed 0.2～0.8vmol/L sodium hydroxide solution, heat treatment 120 ± 5min under 80 ± 2 ℃ of conditions;
(3) the magnesium alloy substrate sheet material behind the heat treatment is placed contain Ca
2+And H
2PO
4 -Solution in, the pH value of regulator solution is 4.5～4.6, is anode then with graphite, magnesium alloy substrate sheet material is that cathodal closing carries out electrolysis, electric current density is 0.02～0.03mA/cm during electrolysis
2, solution temperature is 20～80 ℃ during electrolysis, and electrolysis time is 60～120min, and the hydroxyapatite that reaction is formed is deposited on the magnesium alloy substrate plate surface, is prepared into the Mg-Zn-Sr alloy biomaterial of hydroxyapatite coating layer.
3. the preparation method of the Mg-Zn-Sr alloy biomaterial of a kind of hydroxyapatite coating layer according to claim 2, elastic modelling quantity 35～the 45Gpa that it is characterized in that the magnesium alloy substrate sheet material of acquisition in the step (1), tensile strength 300～320MPa, percentage elongation 15～18%, hardness 60～65HV.
4. the preparation method of the Mg-Zn-Sr alloy biomaterial of a kind of hydroxyapatite coating layer according to claim 2 is characterized in that the described Ca of containing
2+And H
2PO
4 -Solution in the mol ratio of calcium ion and phosphorus be Ca/P=1.3～1.5.
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| CN102220551A (en) * | 2011-05-27 | 2011-10-19 | 华南理工大学 | Method for plasma spraying of Ca-P bioactive coating on surface of magnesium alloy |
| CN102978495A (en) * | 2012-12-13 | 2013-03-20 | 北京大学 | Mg-Sr-Zn alloy and preparation method thereof |
| CN103014465A (en) * | 2012-12-18 | 2013-04-03 | 江苏康欣医疗设备有限公司 | Uniformly degradable orthopedic implant magnesium alloy material |
| CN103184380A (en) * | 2013-03-29 | 2013-07-03 | 江苏康欣医疗设备有限公司 | Biodegradable Mg-Gd-Zn-Ag-Zr series magnesium alloy and preparation method thereof |
| CN103725942A (en) * | 2013-12-31 | 2014-04-16 | 重庆大学 | Mg-Zn-Sr-Ca system magnesium alloy and preparation method thereof |
| CN106756925A (en) * | 2016-12-22 | 2017-05-31 | 武汉科技大学 | A kind of argentum-carried hydroxylapatite coating of magnesium alloy or magnesium surface and preparation method thereof |
| CN108286003A (en) * | 2018-03-12 | 2018-07-17 | 王甲林 | A kind of orthopaedics implantation magnesium alloy materials and preparation method |
| CN108411173A (en) * | 2018-03-29 | 2018-08-17 | 江苏理工学院 | A kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys and preparation method thereof |
| CN109161955A (en) * | 2018-11-07 | 2019-01-08 | 吉林大学 | A kind of electro-deposition preparation method of medical magnesium alloy surface hydroxyapatite and graphene oxide composite biological coating |
| US10246763B2 (en) * | 2012-08-24 | 2019-04-02 | The Regents Of The University Of California | Magnesium-zinc-strontium alloys for medical implants and devices |
| CN110819865A (en) * | 2019-12-05 | 2020-02-21 | 中南林业科技大学 | Preparation method of Nb-Ta-Ti-Si biomedical composite material with surface activity |
| CN114086011A (en) * | 2021-10-25 | 2022-02-25 | 江苏理工学院 | Preparation method of component gradient magnesium-based implant material with controllable degradation |
| CN116005053A (en) * | 2023-01-18 | 2023-04-25 | 中国医学科学院北京协和医院 | Mg-Sr-Zn magnesium alloy with bone immunoregulation function and preparation method and application thereof |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102220551A (en) * | 2011-05-27 | 2011-10-19 | 华南理工大学 | Method for plasma spraying of Ca-P bioactive coating on surface of magnesium alloy |
| US10246763B2 (en) * | 2012-08-24 | 2019-04-02 | The Regents Of The University Of California | Magnesium-zinc-strontium alloys for medical implants and devices |
| CN102978495A (en) * | 2012-12-13 | 2013-03-20 | 北京大学 | Mg-Sr-Zn alloy and preparation method thereof |
| CN103014465A (en) * | 2012-12-18 | 2013-04-03 | 江苏康欣医疗设备有限公司 | Uniformly degradable orthopedic implant magnesium alloy material |
| CN103014465B (en) * | 2012-12-18 | 2014-11-19 | 江苏康尚医疗器械有限公司 | Uniformly degradable orthopedic implant magnesium alloy material |
| CN103184380A (en) * | 2013-03-29 | 2013-07-03 | 江苏康欣医疗设备有限公司 | Biodegradable Mg-Gd-Zn-Ag-Zr series magnesium alloy and preparation method thereof |
| CN103184380B (en) * | 2013-03-29 | 2016-05-04 | 江苏康欣医疗设备有限公司 | Biodegradable Mg-Gd-Zn-Sr-Zr series magnesium alloy and preparation method thereof |
| CN103725942A (en) * | 2013-12-31 | 2014-04-16 | 重庆大学 | Mg-Zn-Sr-Ca system magnesium alloy and preparation method thereof |
| CN106756925A (en) * | 2016-12-22 | 2017-05-31 | 武汉科技大学 | A kind of argentum-carried hydroxylapatite coating of magnesium alloy or magnesium surface and preparation method thereof |
| CN108286003A (en) * | 2018-03-12 | 2018-07-17 | 王甲林 | A kind of orthopaedics implantation magnesium alloy materials and preparation method |
| CN108411173A (en) * | 2018-03-29 | 2018-08-17 | 江苏理工学院 | A kind of bio-medical Mg-Sn-Zn-Sr magnesium alloys and preparation method thereof |
| CN109161955A (en) * | 2018-11-07 | 2019-01-08 | 吉林大学 | A kind of electro-deposition preparation method of medical magnesium alloy surface hydroxyapatite and graphene oxide composite biological coating |
| CN110819865A (en) * | 2019-12-05 | 2020-02-21 | 中南林业科技大学 | Preparation method of Nb-Ta-Ti-Si biomedical composite material with surface activity |
| CN110819865B (en) * | 2019-12-05 | 2021-04-09 | 中南林业科技大学 | Preparation method of Nb-Ta-Ti-Si biomedical composite material with surface activity |
| CN114086011A (en) * | 2021-10-25 | 2022-02-25 | 江苏理工学院 | Preparation method of component gradient magnesium-based implant material with controllable degradation |
| CN114086011B (en) * | 2021-10-25 | 2022-07-08 | 江苏理工学院 | Preparation method of component gradient magnesium-based implant material with controllable degradation |
| CN116005053A (en) * | 2023-01-18 | 2023-04-25 | 中国医学科学院北京协和医院 | Mg-Sr-Zn magnesium alloy with bone immunoregulation function and preparation method and application thereof |
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