CN107267973A - A kind of method for building metal organic framework composite coating in magnesium based metal - Google Patents
A kind of method for building metal organic framework composite coating in magnesium based metal Download PDFInfo
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- CN107267973A CN107267973A CN201710321932.XA CN201710321932A CN107267973A CN 107267973 A CN107267973 A CN 107267973A CN 201710321932 A CN201710321932 A CN 201710321932A CN 107267973 A CN107267973 A CN 107267973A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/73—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals characterised by the process
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/68—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous solutions with pH between 6 and 8
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/78—Pretreatment of the material to be coated
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Abstract
A kind of method for building metal organic framework composite coating in magnesium based metal, its step is mainly：A, by magnesium sheet metal sanding and polishing, then be cleaned by ultrasonic, be then dried in vacuo；B, magnesium sheet is put into 2 4mol/L, 55 65 DEG C of NaOH solution and soaks 10 14h, obtain the magnesium sheet metal after alkali activation；C, configuration concentration are 0.4 0.6g/L 1-hydroxy ethylidene-1,1-diphosphonic acid solution, then adjust pH to 78；D, deionized water and absolute ethyl alcohol by 0.8 1.2: 1 volume ratio be configured to mixed solvent, then zirconium ion is dissolved in mixed solvent, obtain the 1.2mmol/L of concentration 0.8 zirconium ion solution；E, the magnesium sheet for obtaining B steps are put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C steps are obtained, and 8 12h are soaked under the conditions of 55 65 DEG C；F, magnesium sheet deposited into 10 30s in zirconium ion solution；G, magnesium sheet deposited into 3 5min in 1-hydroxy ethylidene-1,1-diphosphonic acid solution；The operation of H, repeatedly F, G step 46 times；Produce.Coating film-substrate cohesion prepared by this method is good, and coating is thin and compact, and the corrosion rate of magnesium can be controlled well, and its osseo-compatible is good.
Description
Technical field
The present invention relates to a kind of method for building coating in magnesium based metal.
Background technology
Magnesium can be degraded by corroding in vivo, and middle corrosion product can be absorbed or be metabolized as by chlorion reaction
The form of magnesium ion exists in body fluid or absorbed by macrophage.Meanwhile, magnesium also has the appropriate machinery close to cortex bone strong
Degree, can solve the problems, such as the poor healing or refracture of fracture site by reducing stress shielding.In addition, it is often more important that magnesium
Implant can be stimulated the formation of new bone by wide coverage, and this is especially advantageous for union again.In a word, magnesium metal is used as new one
The medical metal material in generation, because it has good biodegradability, can exempt from as inner implantation material after its function is completed
Except second operation, increasingly attracted attention in field of orthopaedics.
Implantation material and device clinically allows for maintaining the several months long in vivo and keeps enough intensity, so
And, due to the relatively low standard electrode potential of magnesium and higher chemism, make magnesium as implantation material when by physiological environment
Corrosive medium attack make corrosion rate too fast, so as to make magnesium-based be implanted into material premature failure, and in fast degradation process
In, produce excessive alkaline Mg (OH)2, local pH is raised, causes hemolysis rate to increase, inflammatory reaction, and delay tissue to be cured
The problems such as conjunction, will also the adhesion and growth of cell be influenceed by producing bubble hydrogen in corrosion process in addition.For these problems, to magnesium gold
Category, which is modified, just seems necessary.
In recent years, surface modification is carried out to magnesium and has also obtained very big development, mainly built in magnesium metal material surface
Coating, reduces even isolation matrix and is contacted with corrosive medium, so as to reach the purpose of control magnesium corrosion.In surface modifying method,
Such as：Anode/differential arc oxidization technique, electrochemical deposition, chemical conversion technology etc., they have many advantages, but obvious scarce
Point hampers their development, such as：Energy resource consumption is big, cost is high, film performance is poor, preparation technology is complicated etc..Existing surface
It is that single coating is built in magnesium based metal mostly in modified method, has often only taken into account reduction magnesium metal erosion speed
Rate, and have ignored the modified magnesium biocompatible metal in surface.It is very thick as polymeric coating layer to reach tens microns, mainly
It is, in being obtained after organic solvent, organic solvent evaporation, magnesium based metal to be deposited on by physical bond mode by macromolecule dissolution.
The polymeric coating layer of structure is often heterogeneity, aggregation and multiple crackses.And the modified magnesium metal of polymeric coating layer is used as plant
Enter material, because polymeric coating layer film-substrate cohesion is poor, frequently can lead to disbonding accelerates magnesium metal erosion, so that planting
Enter thing premature failure.The macromolecule degraded in addition often suppresses cell adherence, causes local inflammation and delays organization healing.
The content of the invention
The goal of the invention of the present invention is to provide a kind of side that metal-organic framework composite coating is built in magnesium based metal
Method, coating prepared by this method has a more preferable film-substrate cohesion, and coating is relatively thin and even compact, and the corruption of magnesium can be controlled well
Speed is lost, and its osseo-compatible is good, and Gegenbaur's cell can be promoted to rise in value and break up.
The technical scheme adopted by the invention for realizing the object of the invention is to build metal-organic framework in magnesium based metal to answer
The method for closing coating, its step is：
A, by magnesium sheet metal carborundum paper sanding and polishing, then successively use deionized water, absolute ethyl alcohol, acetone, pickling
Liquid is cleaned by ultrasonic, and is then dried in vacuo；
B, the magnesium sheet metal for obtaining A steps are put into 2-4mol/L, 55-65 DEG C of NaOH solution and soak 10-14h, obtain
Magnesium sheet metal after alkali activation；
C, configuration concentration are 0.4-0.6g/L 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution, then adjust with NaOH its pH to 7-
8；
D, deionized water and absolute ethyl alcohol by 0.8-1.2: 1 volume ratio be configured to mixed solvent, then by ZrOCl2·
8H2O is dissolved in mixed solvent, obtains concentration 0.8-1.2mmol/L zirconium ion solution；
E, the magnesium sheet metal walked B after obtained alkali activation are put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C steps are obtained, 55-
8-12h is soaked under the conditions of 65 DEG C；
F, magnesium sheet metal deposited into 10-30s in the zirconium ion solution that D is walked；
G, magnesium sheet metal deposited into 3-5min in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution that C is walked；
The operation of H, repeatedly F, G step 4-6 times；Magnesium sheet metal finally is put into vacuum drying chamber to dry, i.e., in magnesium metal watch
Construct metal-organic framework composite coating in face.
The present invention mechanism be：
B steps make to form rich hydroxyl surface by carrying out alkali activating pretreatment to magnesium sheet metal, so as to be follow-up organic phospho acid
Molecule covalent grafting provides a large amount of binding sites.
The magnesium sheet of alkali activating pretreatment is soaked 8- by E steps in 55-65 DEG C 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution
The hydroxyl reaction of phosphonyl group and magnesium surface in 12h, 1-hydroxy ethylidene-1,1-diphosphonic acid, makes 1-hydroxy ethylidene-1,1-diphosphonic acid by covalently fixing
Mode be grafted on magnesium surface formation good combination power subcoat.
Magnesium sheet metal is deposited 10-30s by F steps in zirconium ion solution；Deposited in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution
3-5min；The phosphonyl group chelating of zirconium ion and coating surface, forms metal (zirconium)-organic (1-hydroxy ethylene-1,1-diphosphonic of coordinate bond
Acid) the netted coating of skeleton.Magnesium sheet metal is soaked 3-5min, coating table by G steps in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution again
Phosphonyl group chelating of the zirconium ion in face again and in 1-hydroxy ethylidene-1,1-diphosphonic acid, forms organic (1-hydroxy ethylene-1,1-diphosphonic of coordinate bond
Acid)-metal (zirconium) skeleton composite coating.I.e. in magnesium based metal formation zirconium ion and hydroxy ethylidene two after multiple alternating deposit
The metal-organic framework composite coating that phosphonic acids is fully chelated.
Compared with prior art, the beneficial effects of the invention are as follows：
First, the 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) that the present invention is used is a kind of green, bio-safety, environment amenable band
There is the organic molecule of two phosphonyl groups, chemical constitution is similar to cell membrane phospholipid bilayer, it is ensured that the biology of coating
Compatibility.1-hydroxy ethylidene-1,1-diphosphonic acid and energy and Mg2+、Zr4+Metal ion-chelant forms the stable one-dimensional network knot to three-dimensional
Structure.Meanwhile, the zirconium and zirconium oxide that the present invention is used can also promote the increment and differentiation of Gegenbaur's cell.Therefore, prepared by the present invention
Coating, with preferable biocompatibility, can advantageously promote the increment and differentiation of Gegenbaur's cell.
2nd, the present invention builds metal-organic framework composite coating using the mode of liquid phase alternating deposit.Zirconium ion in coating
With 1-hydroxy ethylidene-1,1-diphosphonic acid alternating, mutually abundant chelating, the three-dimensional of metal (zirconium)-organic (1-hydroxy ethylidene-1,1-diphosphonic acid) skeleton is obtained
Netted coating, makes coating stable, uniform, densification；It is molten by alternate frequency and immersion so as to reduce the corrosion of magnesium metal base body
The regulation of liquid concentration, you can the corrosion rate of convenient, effective control magnesium matrix.
3rd, alkali activating pretreatment is carried out to magnesium sheet so that in magnesium hydroxide layer of the sample surfaces formation rich in hydroxyl, hydroxyl
The phosphonyl group and hydroxyl of ethylene-diphosphonic acid make 1-hydroxy ethylidene-1,1-diphosphonic acid covalently be fixed on magnesium surface by covalent bond, make coating
It is well bonded with matrix, adds the stability of coating, so as to effectively controls the corrosion of magnesium.
4th, technique of the invention is liquid deposition, and maximum temperature is only 55-65 DEG C, its preparation method mild condition, technique
It is simple controllable.
Brief description of the drawings
Fig. 1 a are the stereoscan photographs of magnesium based metal；
Fig. 1 b are the stereoscan photographs of coating prepared by the embodiment of the present invention 3；
Fig. 2 a are the dynamic potential polarizations of coating (Mg-OH HEDP+Zr) prepared by pure magnesium (Mg) and the embodiment of the present invention 3
Curve；
Fig. 2 b are coating (Mg-OH@HEDP+Zr) electrochemical impedance spectroscopies prepared by pure magnesium (Mg) and the embodiment of the present invention 3；
Fig. 3 a are fluorescence micrograph of pure magnesium (Mg) the surface seeding Gegenbaur's cell after 6 hours；
Fig. 3 b are that coating (Mg-OH@HEDP+Zr) prepared by the embodiment of the present invention 3 is inoculated with fluorescence of the Gegenbaur's cell after 6 hours
Microphoto.
Embodiment
Embodiment 1
A kind of method for building metal-organic framework composite coating in magnesium based metal, its step is：
A, by magnesium sheet metal carborundum paper sanding and polishing, then successively use deionized water, absolute ethyl alcohol, acetone, pickling
Liquid is cleaned by ultrasonic, and is then dried in vacuo；
B, the magnesium sheet metal for obtaining A steps are put into 2mol/L, 65 DEG C of NaOH solution and soak 14h, obtain after alkali activation
Magnesium sheet metal；
C, configuration concentration are 0.4g/L 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution, then adjust with NaOH its pH to 8；
D, deionized water and absolute ethyl alcohol by 1.0: 1 volume ratio be configured to mixed solvent, then by ZrOCl2·8H2O is molten
Solution obtains concentration 0.8mmol/L zirconium ion solution in mixed solvent；
E, the magnesium sheet metal walked B after obtained alkali activation are put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C steps are obtained, 65 DEG C
Under the conditions of soak 12h；
F, magnesium sheet deposited into 30s in the zirconium ion solution that D is walked；
G, magnesium sheet deposited into 5min in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution that C is walked；
The operation of H, repeatedly F, G step 4 times；Magnesium sheet metal finally is put into vacuum drying chamber to dry, i.e., in magnesium based metal
Construct metal-organic framework composite coating.
Embodiment 2
A kind of method for building metal-organic framework composite coating in magnesium based metal, its step is：
A, by magnesium sheet metal carborundum paper sanding and polishing, then successively use deionized water, absolute ethyl alcohol, acetone, pickling
Liquid is cleaned by ultrasonic, and is then dried in vacuo；
B, the magnesium sheet metal for obtaining A steps are put into 4mol/L, 55 DEG C of NaOH solution and soak 10h, obtain after alkali activation
Magnesium sheet metal；
C, configuration concentration are 0.6g/L 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution, then adjust with NaOH its pH to 7；
D, deionized water and absolute ethyl alcohol by 1.2: 1 volume ratio be configured to mixed solvent, then by ZrOCl2·8H2O is molten
Solution obtains concentration 1.2mmol/L zirconium ion solution in mixed solvent；
E, the magnesium sheet metal walked B after obtained alkali activation are put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C steps are obtained, 55 DEG C
Under the conditions of soak 8h；
F, magnesium sheet deposited into 10s in the zirconium ion solution that D is walked；
G, magnesium sheet deposited into 3min in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution that C is walked；
The operation of H, repeatedly F, G step 6 times；Magnesium sheet metal finally is put into vacuum drying chamber to dry, i.e., in magnesium based metal
Construct metal-organic framework composite coating.
Embodiment 3
A kind of method for building metal-organic framework composite coating in magnesium based metal, its step is：
A, by magnesium sheet metal carborundum paper sanding and polishing, then successively use deionized water, absolute ethyl alcohol, acetone, pickling
Liquid is cleaned by ultrasonic, and is then dried in vacuo；
B, the magnesium sheet metal for obtaining A steps are put into 3mol/L, 60 DEG C of NaOH solution and soak 12h, obtain after alkali activation
Magnesium sheet metal；
C, configuration concentration are 0.5g/L 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution, then adjust with NaOH its pH to 7.5；
D, deionized water and absolute ethyl alcohol by 0.8: 1 volume ratio be configured to mixed solvent, then by ZrOCl2·8H2O is molten
Solution obtains concentration 1.0mmol/L zirconium ion solution in mixed solvent；
E, the magnesium sheet metal walked B after obtained alkali activation are put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C steps are obtained, 60 DEG C
Under the conditions of soak 10h；
F, magnesium sheet deposited into 20s in the zirconium ion solution that D is walked；
G, magnesium sheet deposited into 4min in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution that C is walked；
The operation of H, repeatedly F, G step 5 times；Magnesium sheet metal finally is put into vacuum drying chamber to dry, i.e., in magnesium based metal
Construct metal-organic framework composite coating.
Fig. 1 a, Fig. 1 b be respectively pure magnesium (Mg) and this example prepare coating (Mg-OH@HEDP+Zr, OH represent hydroxyl in figure,
HEDPD represents 1-hydroxy ethylidene-1,1-diphosphonic acid, and Zr represents the zirconium ion added) scanning electron microscope image on surface.
From Fig. 1 a, Fig. 1 b, it is apparent that comparing with pure magnesium, the modified magnesium based metal coated of the present invention is complete
Covering, and the more uniform densification in surface.
Fig. 2 a are the dynamic potential polarization curves of coating (Mg-OH@HEDP+Zr) prepared by pure magnesium (Mg) and this example.
It can be seen that and compared with pure magnesium from Fig. 2 a dynamic potential polarization curve, answered in magnesium surface formation metal-organic framework
The corrosion potential for closing the sample of coating is significantly raised, and corrosion current density at least reduces two orders of magnitude.
Fig. 2 b are the electrochemical impedance spectroscopies of coating (Mg-OH@HEDP+Zr) prepared by pure magnesium (Mg) and this example.
It can be seen that from Fig. 2 b electrochemical impedance spectroscopy：The impedance ring of the metal-organic framework coating of modified formation is bright
The aobvious impedance ring more than pure magnesium.Therefore, analyzed from aerodynamic point, metal-organic bone that the present invention is built in magnesium based metal
Frame compound coat can effectively reduce or even obstruct Corrosive attack of the electrolyte to magnesium matrix, so as to improve the biological material of magnesium-based
The corrosion resistance of material.
Fig. 3 a, Fig. 3 b are that coating (Mg-OH@HEDP+Zr) surface seeding skeletonization prepared by pure magnesium (Mg) and this example is thin respectively
Fluorescence micrograph of the born of the same parents after 6 hours.
As can be seen that the Gegenbaur's cell of the modified magnesium based metal of the present invention is substantially than pure magnesium table from Fig. 3 a, Fig. 3 b
Face is more, illustrates metal (zirconium)-organic (1-hydroxy ethylidene-1,1-diphosphonic acid) the skeleton coating of the present invention in the formation of magnesium-based biomaterial surface
Gegenbaur's cell can be promoted to rise in value, there is preferable biocompatibility.
Claims (1)
1. a kind of method for building metal-organic framework composite coating in magnesium based metal, its step is：
A, entered with deionized water, absolute ethyl alcohol, acetone, pickle by magnesium sheet metal carborundum paper sanding and polishing, then successively
Row is cleaned by ultrasonic, and is then dried in vacuo；
B, the magnesium sheet metal for obtaining A steps are put into 2-4mol/L, 55-65 DEG C of NaOH solution and soak 10-14h, obtain alkali work
Magnesium sheet metal after change；
C, configuration concentration are 0.4-0.6g/L 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution, then adjust with NaOH its pH to 7-8；
D, deionized water and absolute ethyl alcohol by 0.8-1.2: 1 volume ratio be configured to mixed solvent, then by ZrOCl2·8H2O is molten
Solution obtains concentration 0.8-1.2mmol/L zirconium ion solution in mixed solvent；
E, the magnesium sheet metal walked B after obtained alkali activation are put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C steps are obtained, 55-65 DEG C
Under the conditions of soak 8-12h；
F, magnesium sheet metal deposited into 10-30s in the zirconium ion solution that D is walked；
G, magnesium sheet metal deposited into 3-5min in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution that C is walked；
The operation of H, repeatedly F, G step 4-6 times；Magnesium sheet metal finally is put into vacuum drying chamber to dry, i.e., in magnesium based metal structure
Build out metal-organic framework composite coating.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110137435A (en) * | 2019-05-13 | 2019-08-16 | 天津大学 | Magnesium metal cathode preparation method containing fast ionic transport interface |
| CN112522703A (en) * | 2020-10-10 | 2021-03-19 | 桂林理工大学 | Fluorine-free super-hydrophobic Zn-MOF composite coating on surface of magnesium alloy and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5447218B2 (en) * | 2009-07-06 | 2014-03-19 | 新日鐵住金株式会社 | Surface-treated plated steel sheet and surface treatment liquid |
| CN106011815A (en) * | 2016-06-07 | 2016-10-12 | 西南交通大学 | Preparation method for hybrid composite coating used for magnesium-based biological material surface medication |
| CN106086842A (en) * | 2016-08-25 | 2016-11-09 | 济南御麟化工科技有限公司 | A kind of metal surface high biological compatibility coating and preparation method |
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2017
- 2017-05-09 CN CN201710321932.XA patent/CN107267973B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5447218B2 (en) * | 2009-07-06 | 2014-03-19 | 新日鐵住金株式会社 | Surface-treated plated steel sheet and surface treatment liquid |
| CN106011815A (en) * | 2016-06-07 | 2016-10-12 | 西南交通大学 | Preparation method for hybrid composite coating used for magnesium-based biological material surface medication |
| CN106086842A (en) * | 2016-08-25 | 2016-11-09 | 济南御麟化工科技有限公司 | A kind of metal surface high biological compatibility coating and preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110137435A (en) * | 2019-05-13 | 2019-08-16 | 天津大学 | Magnesium metal cathode preparation method containing fast ionic transport interface |
| CN112522703A (en) * | 2020-10-10 | 2021-03-19 | 桂林理工大学 | Fluorine-free super-hydrophobic Zn-MOF composite coating on surface of magnesium alloy and preparation method thereof |
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| CN107267973B (en) | 2019-07-19 |
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