CN109045351A - A kind of magnesium alloy based on surface treatment and fibroin albumen connection method - Google Patents

A kind of magnesium alloy based on surface treatment and fibroin albumen connection method Download PDF

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CN109045351A
CN109045351A CN201810667795.XA CN201810667795A CN109045351A CN 109045351 A CN109045351 A CN 109045351A CN 201810667795 A CN201810667795 A CN 201810667795A CN 109045351 A CN109045351 A CN 109045351A
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magnesium alloy
fibroin albumen
surface treatment
connection method
fibroin
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CN109045351B (en
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王晨曦
戚晓芸
孙亚汝
鲁添
王岩松
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Harbin Institute of Technology
Harbin Engineering University
Harbin Medical University
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Harbin Institute of Technology
Harbin Medical University
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    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/02Inorganic materials
    • A61L27/04Metals or alloys
    • A61L27/06Titanium or titanium alloys
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/14Macromolecular materials
    • A61L27/22Polypeptides or derivatives thereof, e.g. degradation products
    • A61L27/227Other specific proteins or polypeptides not covered by A61L27/222, A61L27/225 or A61L27/24
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L27/00Materials for grafts or prostheses or for coating grafts or prostheses
    • A61L27/50Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
    • A61L27/58Materials at least partially resorbable by the body
    • CCHEMISTRY; METALLURGY
    • C23COATING 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F3/00Brightening metals by chemical means
    • C23F3/02Light metals
    • C23F3/03Light metals with acidic solutions
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61LMETHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
    • A61L2420/00Materials or methods for coatings medical devices
    • A61L2420/02Methods for coating medical devices

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Animal Behavior & Ethology (AREA)
  • Transplantation (AREA)
  • Veterinary Medicine (AREA)
  • Public Health (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Epidemiology (AREA)
  • Dermatology (AREA)
  • Medicinal Chemistry (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Materials For Medical Uses (AREA)
  • Prostheses (AREA)

Abstract

The invention discloses a kind of magnesium alloy based on surface treatment and fibroin albumen connection method, shown method realizes the connection between magnesium alloy and fibroin albumen according to the following steps: Mg alloy surface mechanical polishing → magnesium alloy surface chemical polishing and cleaning → Mg alloy surface plasma or short-wavelength light processing → silk fibroin protein solution are coated on Mg alloy surface → drying process.The present invention is not in the case where introducing bio-toxicity substance and not changing Properties of Magnesium Alloy, realize the firm connection of fibroin albumen and magnesium alloy, effectively slow down magnesium alloy degradation rate, has great advantage in numerous Magnesiumalloy surface modifyings and using having in the method for silane coupling agent connection fibroin albumen and magnesium alloy.

Description

A kind of magnesium alloy based on surface treatment and fibroin albumen connection method
Technical field
The invention belongs to biomedical material technologies, are related to the connection method of a kind of magnesium alloy and fibroin albumen, tool Body is related to a kind of law temperature joining method between the magnesium alloy and fibroin albumen being surface-treated based on plasma or short-wavelength light.
Background technique
Medical magnesium alloy is known as third generation bio-medical material as degradable medical material.This kind of new medical metal Material abandons the traditional thought that people usually use metal implant material as bio-inert material, and dexterously utilizes magnesium-based The characteristic of corrosion (degradation) easily occurs in human body environment for metal material (pure magnesium and magnesium alloy) to realize metal implant in body It inside gradually degrades until the clinical medicine purpose finally to disappear.Magnesium alloy materials are as degradable hard tissue implanting material with Ceramics, the calcium sulfate for starting clinical application are compared with polylactic acid with very big advantage: the catabolite biology of magnesium alloy first It is compatible, apparent negative interaction will not be generated to human body, and the magnesium ion of micro release is beneficial to tissue growth;Secondly conduct can drop Solve hard tissue implanting material, magnesium alloy mechanical property can preferably meet the requirement as orthopedic implanting material, especially its compared with Low springform (about 42GPa) and stainless steel (189 ~ 205 GPa), titanium alloy (105 ~ 117 GPa) and Co-Cr (230 GPa) alloy is compared, and with people's bone more close to (2 ~ 20GPa), can greatly reduce stress-shielding effect.But magnesium alloy exists It is mainly that degradation rate is too fast in applying upper problem, it is difficult to achieve effective control.Existing many method of modifying such as alkali heat-treatment, Heat treatment and anodic oxidation and the methods of differential arc oxidation and ion implanting, but can't effectively solve that degradation speed is too fast to ask Topic.Using APTES(3- aminopropyl triethoxysilane) etc. silane coupling agents realize organic-biological macromolecular material fibroin egg It is white to be connect with magnesium alloy chemical, fibroin albumen coat can effectively slow down implantation magnesium alloy degradation, but introduce APTES It will appear after placing a period of time with potential cytotoxicity, and fibroin albumen coating and magnesium alloy composite construction to organism Different degrees of cracking influences the controllability to magnesium alloy degradation rate.Therefore, magnesium alloy is realized using biological non-toxicity method With being reliably connected for effectively delaying magnesium alloy degradation rate, expanding magnesium alloy in bio-medical material for fibroin albumen coating The application in field has important research meaning.
Summary of the invention
For the existing method of modifying of magnesium alloy and the existing and fibroin albumen connection method problem, the present invention is provided A kind of magnesium alloy based on surface treatment and fibroin albumen connection method are closed not introducing bio-toxicity substance and not changing magnesium In the case where golden performance, realizes the firm connection of fibroin albumen and magnesium alloy, effectively slow down magnesium alloy degradation rate, in numerous magnesium Have in the method for alloy surface modifying and use silane coupling agent connection fibroin albumen and magnesium alloy and has great advantage.
The purpose of the present invention is what is be achieved through the following technical solutions:
A kind of magnesium alloy based on surface treatment and fibroin albumen connection method, as shown in Figure 1, realizing that magnesium closes according to the following steps Connection between gold and fibroin albumen: Mg alloy surface mechanical polishing → magnesium alloy surface chemical polishing and cleaning → magnesium alloy table Surface plasma or short-wavelength light processing → silk fibroin protein solution are coated on Mg alloy surface → drying process, specific implementation step It is as follows:
Step 1: it by Mg alloy surface sand paper machinery polishing treatment, is subsequently placed in deionized water and cleans;
Step 2: being placed in 15 ~ 30s in the mixed liquor of nitric acid and sulfuric acid for the magnesium alloy after mechanical polishing and carry out chemical polishing, with It is successively cleaned with ethyl alcohol and deionized water, is then dried afterwards;
Step 3: by 0.5 ~ 1.5min of corona treatment or the short-wavelength light used for magnesium alloy irradiation 10 ~ 20 after overpickling min;
Step 4: silk fibroin protein solution is coated into the Mg alloy surface to after processing, and is dried;
Step 5: the fibroin albumen after drying-magnesium alloy sample is soaked in 6 ~ 12h in methanol solution, so that fibroin albumen water Dissolubility structure changes to structure not soluble in water, completes the connection of fibroin albumen and magnesium alloy.
In the present invention, the magnesium alloy is magnesium-based biomedical alloy.
In the present invention, successively mechanical polishing is handled for 100 mesh of the Mg alloy surface, 240 mesh, 600 mesh, 800 mesh sand paper.
In the present invention, each sand paper bruting process is 3 ~ 5 min in the mechanical polishing process.
In the present invention, the volume ratio of the nitric acid and sulfuric acid is 8:1.
In the present invention, the deionized water and ethyl alcohol have ultrasonic wave added when cleaning, and scavenging period is 5 ~ 15 min.
In the present invention, the plasma is oxygen plasma, and short-wavelength light wavelength is 100 ~ 400 nm.
In the present invention, the drying in the step 2 and step 4 is carried out in 60 DEG C of constant temperature damp heat box, when dry Between be 1 h.
In the present invention, drying at room temperature is taken when fibroin albumen structure changes in the step 5.
In the present invention, the mass concentration of the silk fibroin protein solution is 1 ~ 10%.
In the present invention, the volumetric concentration of the methanol solution is 80%.
The principle of the present invention is as follows:
Micron mastoid process is formed in Mg alloy surface first by the way of mechanical polishing, is increased and the contact of fibroin albumen coat Then area obtains clean surface by chemical polishing removal oxide on surface and pollutant, then uses plasma or shortwave Long light handles Mg alloy surface, makes surface with hydroxyl, and hydroxyl is reacted with the fibroin albumen organo-functional group of coating, does After dry and magnesium alloy forms secured connection.
Compared with the prior art, the present invention has the advantage that
1, in method of the invention temperature be no more than 60 DEG C, without pressurization, no complex operations step can be realized fibroin albumen with Magnesium alloy is reliably connected.
2, method of the invention will not change magnesium alloy property, will not influence subsequent applications.
3, the present invention can be realized being directly connected to for fibroin albumen coat magnesium alloy, without middle layer.
4, equipment needed for the present invention is simple, connection procedure safe and convenient, and the connection period is short, does not introduce toxic substance.
5, fibroin albumen-magnesium alloy composite construction after method of the invention connection is strong compared to other connection methods connection Degree is high, period of storage is long.
Detailed description of the invention
Fig. 1 is Joining Technology flow chart of the invention.
Fig. 2 is the nano impress image that fibroin albumen coats sample, in figure: a is to do the connection of middle layer using APTES to try Sample, b are the connection sample of plasma treated surface, and c is the connection sample that short-wavelength light handles surface.
Fig. 3 is that the fibroin albumen after room temperature storage 30 days coats Sample Image, and in figure: a is to do middle layer using APTES Sample is connected, b is the connection sample of plasma treated surface, and c is the connection sample that short-wavelength light handles surface.
Fig. 4 is Mg alloy surface contact angle image, in figure: a is unprocessed magnesium alloy sample, and b is the magnesium for having APTES layers Alloy sample, c are corona treatment magnesium alloy sample, and d is that short wavelength handles magnesium alloy sample.
Fig. 5 is fibroin albumen-magnesium alloy composite construction surface chart as in figure: a is the examination of plasma treated connection Sample, b are to handle latter linked sample through short-wavelength light, and 1 is fibroin albumen, and 2 be magnesium alloy.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawing, and however, it is not limited to this, all to this Inventive technique scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered Within the protection scope of the present invention.
Embodiment 1:
A kind of using plasma processing Mg alloy surface is present embodiments provided to realize between magnesium alloy and fibroin albumen The method of law temperature joining, specific implementation step are as follows:
(1) it mechanically polishes: diameter is used into 100 mesh, 240 mesh, 600 mesh, 800 mesh for 10 mm, with a thickness of the magnesium alloy of 2 mm respectively Sand paper successively polish, observe be put into ultrasonic wave added cleaning 10 in deionized water after surface texture is uniform under an optical microscope It is taken out after min.
(2) chemical polishing: configuration volumetric concentration is the mixed solution of 8% nitric acid and 1% sulfuric acid, after then cleaning the first step Magnesium alloy be put into 20 s in acid solution, then successively clean 10 min through ultrasonic wave added with ethyl alcohol and deionized water, passed through after taking-up 60 DEG C of damp and hot dryings of constant temperature.
(3) plasma surface treatment: the magnesium alloy after drying is placed in plasma chamber, oxygen plasma treatment 1 It is taken out after min.
(4) fibroin albumen coats: 3 g fibroin albumen freeze-dried powders are dissolved in 3 mL deionized waters to obtain fibroin albumen molten Then liquid uniformly coats silk fibroin protein solution to plasma-treated Mg alloy surface;It is damp and hot in 60 DEG C of constant temperature Dry 1 h in drying box.
(5) fibroin albumen structure changes: after the fibroin albumen of redrying-magnesium alloy composite construction is taken out, being put into body 5 h are impregnated in the methanol that product concentration is 80%, room temperature is dried after taking-up.
It is as shown in Figure 2 b according to sample surfaces made from the present embodiment the method and nano impress result, it is used with Fig. 2 a APTES is high as sample sample bonding strength compared to known to of middle layer, and magnesium alloy surface layer fibroin albumen coating continuity is good.
Fig. 3 b was fibroin albumen-magnesium alloy composite construction room temperature storage of using plasma processing method connection after 30 days As a result, with Fig. 3 a using APTES as middle layer sample fibroin albumen coating rupture compared with, using plasma handle Method fibroin albumen coating and magnesium alloy connection reliability are higher.
Fig. 4 c is plasma-treated Mg alloy surface contact angle image, with the untreated Mg alloy surface of Fig. 4 a And the Mg alloy surface that Fig. 4 b is handled through APTES is compared, it is plasma-treated after Mg alloy surface contact angle occur very Reduce to big degree, almost become total hydrophilic, it is possible thereby to prove plasma-treated Mg alloy surface hydroxyl value later Amount increases, and is the basis for generating fibroin albumen and magnesium alloy and being reliably connected.
Fig. 5 a is plasma treated fibroin albumen and magnesium alloy linkage interface figure, it can be seen that fibroin albumen with Magnesium alloy is completely embedded, and interface is without cavity.
Embodiment 2:
Present embodiments provide it is a kind of using short-wavelength light irradiation Mg alloy surface to realizing between magnesium alloy and fibroin albumen The method of law temperature joining, specific implementation step are as follows:
(1) it mechanically polishes: diameter is used into 100 mesh, 240 mesh, 600 mesh, 800 mesh for 10 mm, with a thickness of the magnesium alloy of 2 mm respectively Sand paper successively polish, observe be put into ultrasonic wave added cleaning 10 in deionized water after surface texture is uniform under an optical microscope It is taken out after min.
(2) chemical polishing: configuration volumetric concentration is the mixed solution of 8% nitric acid and 1% sulfuric acid, after then cleaning the first step Magnesium alloy be put into 20 s in acid solution, then successively clean 10 min through ultrasonic wave added with ethyl alcohol and deionized water, passed through after taking-up 60 DEG C of damp and hot dryings of constant temperature.
(3) short-wavelength light surface is irradiated: the magnesium alloy after dry is placed in short-wavelength light device, is 172 nm's through wavelength Short-wavelength light takes out after irradiating 15 min.
(4) fibroin albumen coats: 3 g fibroin albumen freeze-dried powders are dissolved in 3 mL deionized waters to obtain fibroin albumen molten Then liquid uniformly coats silk fibroin protein solution to plasma-treated Mg alloy surface;It is damp and hot in 60 DEG C of constant temperature Dry 1 h in drying box.
(5) fibroin albumen structure changes: after the fibroin albumen of redrying-magnesium alloy composite construction takes out, being put into volume 5 h are impregnated in the methanol that concentration is 80%, room temperature is dried after taking-up.
It is as shown in Figure 2 c according to sample surfaces made from the present embodiment the method and nano impress result, it is used with Fig. 2 a APTES is high as sample sample bonding strength compared to known to of middle layer, and magnesium alloy surface layer fibroin albumen coating continuity is good.
After Fig. 3 c is the fibroin albumen-magnesium alloy composite construction room temperature storage 30 days connected using short-wavelength light processing method As a result, with Fig. 3 a using APTES as middle layer sample fibroin albumen coating rupture compared with, handled using short-wavelength light Method fibroin albumen coating and magnesium alloy connection reliability are higher.
Fig. 4 d is the Mg alloy surface contact angle image handled through short-wavelength light, with the untreated Mg alloy surface of Fig. 4 a And the Mg alloy surface that Fig. 4 b is handled through APTES is compared, the Mg alloy surface contact angle after short-wavelength light is processed occurs very Reduce to big degree, almost become total hydrophilic, it is possible thereby to prove the Mg alloy surface hydroxyl value after short-wavelength light is processed Amount increases, and is the basis for generating fibroin albumen and magnesium alloy and being reliably connected.
Fig. 5 b is through short-wavelength light treated fibroin albumen and magnesium alloy linkage interface figure, it can be seen that fibroin albumen with Magnesium alloy is completely embedded, and interface is without cavity.

Claims (10)

1. a kind of magnesium alloy based on surface treatment and fibroin albumen connection method, it is characterised in that the method specific implementation step It is rapid as follows:
Step 1: it by Mg alloy surface sand paper machinery polishing treatment, is subsequently placed in deionized water and cleans;
Step 2: being placed in 15 ~ 30s in the mixed liquor of nitric acid and sulfuric acid for the magnesium alloy after mechanical polishing and carry out chemical polishing, with It is successively cleaned with ethyl alcohol and deionized water, is then dried afterwards;
Step 3: by 0.5 ~ 1.5min of corona treatment or the short-wavelength light used for magnesium alloy irradiation 10 ~ 20 after overpickling min;
Step 4: silk fibroin protein solution is coated into the Mg alloy surface to after processing, and is dried;
Step 5: fibroin albumen-magnesium alloy sample after will be dried is soaked in 6 ~ 12h in methanol solution, completes fibroin albumen With the connection of magnesium alloy.
2. the magnesium alloy according to claim 1 based on surface treatment and fibroin albumen connection method, it is characterised in that institute Stating magnesium alloy is magnesium-based biomedical alloy.
3. the magnesium alloy according to claim 1 based on surface treatment and fibroin albumen connection method, it is characterised in that institute Stating 100 mesh of Mg alloy surface, 240 mesh, 600 mesh, 800 mesh sand paper, successively mechanical polishing is handled.
4. the magnesium alloy according to claim 3 based on surface treatment and fibroin albumen connection method, it is characterised in that institute Stating each sand paper bruting process in mechanical polishing process is 3 ~ 5 min.
5. the magnesium alloy according to claim 1 based on surface treatment and fibroin albumen connection method, it is characterised in that institute The volume ratio for stating nitric acid and sulfuric acid is 8:1.
6. the magnesium alloy according to claim 1 based on surface treatment and fibroin albumen connection method, it is characterised in that institute There is ultrasonic wave added when stating deionized water and ethyl alcohol cleaning, scavenging period is 5 ~ 15 min.
7. the magnesium alloy according to claim 1 based on surface treatment and fibroin albumen connection method, it is characterised in that institute Stating plasma is oxygen plasma, and short-wavelength light wavelength is 100 ~ 400 nm.
8. the magnesium alloy according to claim 1 based on surface treatment and fibroin albumen connection method, it is characterised in that institute It states the drying in step 2 and step 4 to carry out in 60 DEG C of constant temperature damp heat box, drying time is 1 h.
9. the magnesium alloy according to claim 1 based on surface treatment and fibroin albumen connection method, it is characterised in that institute The mass concentration for stating silk fibroin protein solution is 1 ~ 10%.
10. the magnesium alloy according to claim 1 based on surface treatment and fibroin albumen connection method, it is characterised in that institute The volumetric concentration for stating methanol solution is 80%.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110327307A (en) * 2019-06-26 2019-10-15 浙江大学 A kind of preparation method and product of medicine carrying fibroin nano-microcapsule
CN111991619A (en) * 2020-07-30 2020-11-27 九魁(苏州)医疗科技有限公司 Medical intervention polylactic acid degradable catheter and preparation method thereof
CN112675362A (en) * 2020-12-24 2021-04-20 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of personalized magnesium alloy bracket for bone repair and product thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101264339A (en) * 2007-03-14 2008-09-17 北京奥精医药科技有限公司 Magnesium alloy bone surgery internal fixation and implantation material
KR20130076387A (en) * 2011-12-28 2013-07-08 재단법인 포항산업과학연구원 Surface treatments method of magnesium alloy
CN104083802A (en) * 2014-07-23 2014-10-08 江苏大学 Method for improving binding strength of medical bio-coating on surface of medical magnesium alloy
CN106492270A (en) * 2016-11-28 2017-03-15 哈尔滨工业大学 A kind of method for connecting between magnesium alloy and fibroin albumen
CN106512082A (en) * 2016-11-28 2017-03-22 哈尔滨医科大学 Composite structure capable of retarding magnesium-alloy degradation under coating by silk fibroin

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101264339A (en) * 2007-03-14 2008-09-17 北京奥精医药科技有限公司 Magnesium alloy bone surgery internal fixation and implantation material
KR20130076387A (en) * 2011-12-28 2013-07-08 재단법인 포항산업과학연구원 Surface treatments method of magnesium alloy
CN104083802A (en) * 2014-07-23 2014-10-08 江苏大学 Method for improving binding strength of medical bio-coating on surface of medical magnesium alloy
CN106492270A (en) * 2016-11-28 2017-03-15 哈尔滨工业大学 A kind of method for connecting between magnesium alloy and fibroin albumen
CN106512082A (en) * 2016-11-28 2017-03-22 哈尔滨医科大学 Composite structure capable of retarding magnesium-alloy degradation under coating by silk fibroin

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110327307A (en) * 2019-06-26 2019-10-15 浙江大学 A kind of preparation method and product of medicine carrying fibroin nano-microcapsule
CN111991619A (en) * 2020-07-30 2020-11-27 九魁(苏州)医疗科技有限公司 Medical intervention polylactic acid degradable catheter and preparation method thereof
CN112675362A (en) * 2020-12-24 2021-04-20 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of personalized magnesium alloy bracket for bone repair and product thereof

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