CN107267973B - A method of metal-organic framework composite coating is constructed in magnesium based metal - Google Patents
A method of metal-organic framework composite coating is constructed in magnesium based metal Download PDFInfo
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- CN107267973B CN107267973B CN201710321932.XA CN201710321932A CN107267973B CN 107267973 B CN107267973 B CN 107267973B CN 201710321932 A CN201710321932 A CN 201710321932A CN 107267973 B CN107267973 B CN 107267973B
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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 method of metal-organic framework composite coating being constructed in magnesium based metal, step is main are as follows: A, by magnesium sheet metal sanding and polishing, then be cleaned by ultrasonic, then it is dried in vacuo；B, magnesium sheet is put into 2-4mol/L, 55-65 DEG C of NaOH solution and impregnates 10-14h, the magnesium sheet metal after obtaining alkali activation；C, configuration concentration is the 1-hydroxy ethylidene-1,1-diphosphonic acid solution of 0.4-0.6g/L, then adjusts pH to 7-8；D, deionized water and dehydrated alcohol are configured to mixed solvent by 0.8-1.2: 1 volume ratio, then zirconium ion is dissolved in mixed solvent, obtain the zirconium ion solution of concentration 0.8-1.2mmol/L；E, the magnesium sheet for walking B is put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C is walked, and 8-12h is impregnated under the conditions of 55-65 DEG C；F, magnesium sheet is deposited into 10-30s in zirconium ion solution；G, magnesium sheet is deposited into 3-5min in 1-hydroxy ethylidene-1,1-diphosphonic acid solution；H, operation 4-6 times of F, G step is repeated；To obtain the final product.The coating film-substrate cohesion of this method preparation is good, and coating is thin and compact, can control the corrosion rate of magnesium well, and its osseo-compatible is good.
Description
Technical field
The present invention relates to a kind of methods in magnesium based metal building coating.
Background technique
Magnesium can be degraded and corroding in vivo, and intermediate corrosion product can be reacted by chloride ion to be absorbed or be metabolized as
There are absorb in body fluid or by macrophage for the form of magnesium ion.Meanwhile magnesium also has close to the appropriate mechanical strong of cortex bone
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
Implantation material can have been stimulated the formation of new bone by wide coverage, this is especially advantageous for union again.In short, magnesium metal is as new one
The medical metal material in generation can exempt from after completing its function because it is with good biodegradability as inner implantation material
Except second operation, field of orthopaedics more and more attention has been paid to.
Implantation material and device clinically allows for maintaining the several months long in vivo and keeps enough intensity, so
And due to the lower standard electrode potential of magnesium and higher chemical activity, by physiological environment when making magnesium as implantation material
Corrosive medium attack keep corrosion rate too fast, so as to make magnesium-based be implanted into material premature failure, and in fast degradation process
In, generate excessive alkaline Mg (OH)2, local pH is increased, hemolysis rate is caused to increase, inflammatory reaction, and tissue is delayed to be cured
The problems such as conjunction, in addition generating bubble hydrogen in corrosion process also will affect the adherency and growth of cell.For these problems, to magnesium gold
Category, which is modified, just seems necessary.
In recent years, surface modification is carried out to magnesium also to have been greatly developed, mainly construct in magnesium metal material surface
Coating reduces even isolation matrix and contacts with corrosive medium, to achieve the purpose that control magnesium corrosion.In surface modifying method,
Such as: anode/differential arc oxidization technique, electrochemical deposition, chemical conversion technology, they have many advantages, but apparent scarce
Point hampers their development, such as: energy consumption is big, at high cost, film performance is poor, preparation process is complicated.Existing surface
It is to construct single coating 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 to be obtained after organic solvent, organic solvent evaporation by macromolecule dissolution, is deposited on magnesium based metal by physical bond mode.
The polymeric coating layer of building is often inhomogenous, aggregation and multiple cracks.And the modified magnesium metal of polymeric coating layer is as plant
Enter material, since polymeric coating layer film-substrate cohesion is poor, frequently can lead to disbonding accelerates magnesium metal erosion, to make to plant
Enter object premature failure.In addition the macromolecule degraded often inhibits cell adherence, leads to local inflammation and delays organization healing.
Summary of the invention
Goal of the invention of the invention is to provide a kind of side in magnesium based metal building metal-organic framework composite coating
The coating of method, this method preparation has better film-substrate cohesion, and coating is relatively thin and even compact, can control the corruption of magnesium well
Rate is lost, and its osseo-compatible is good, osteoblast 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 multiple in magnesium based metal building metal-organic framework
The method for closing coating, the steps include:
A, by magnesium sheet metal carborundum paper sanding and polishing, then deionized water, dehydrated alcohol, acetone, pickling are successively used
Liquid is cleaned by ultrasonic, and is then dried in vacuo；
B, the magnesium sheet metal that A is walked is put into 2-4mol/L, 55-65 DEG C of NaOH solution and impregnates 10-14h, obtained
Magnesium sheet metal after alkali activation；
C, configuration concentration is 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution of 0.4-0.6g/L, then adjusts its pH to 7- with NaOH
8；
D, deionized water and dehydrated alcohol are configured to mixed solvent by 0.8-1.2: 1 volume ratio, then by ZrOCl2·
8H2O is dissolved in mixed solvent, obtains the zirconium ion solution of concentration 0.8-1.2mmol/L；
E, the magnesium sheet metal after activating the alkali that B is walked is put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C is walked, 55-
8-12h is impregnated under the conditions of 65 DEG C；
F, magnesium sheet metal is deposited into 10-30s in the zirconium ion solution that D is walked；
G, magnesium sheet metal is deposited into 3-5min in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution that C is walked；
H, operation 4-6 times of F, G step is repeated；Magnesium sheet metal is finally put into vacuum oven drying, i.e., in magnesium metal watch
Construct metal-organic framework composite coating in face.
Mechanism of the invention is:
B step makes to form rich hydroxyl surface, to be subsequent organic phospho acid by carrying out alkali activating pretreatment to magnesium sheet metal
Molecule covalent grafting provides a large amount of binding sites.
The magnesium sheet of alkali activating pretreatment is impregnated 8- in 55-65 DEG C 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution by E step
12h, the hydroxyl reaction of phosphonyl group and magnesium surface in 1-hydroxy ethylidene-1,1-diphosphonic acid, makes 1-hydroxy ethylidene-1,1-diphosphonic acid by covalently fixing
Mode be grafted on magnesium surface formed good combination power subcoat.
Magnesium sheet metal is deposited 10-30s in zirconium ion solution by F step；It is deposited in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution
3-5min；The phosphonyl group of zirconium ion and coating surface chelating, forms metal (zirconium)-organic (1-hydroxy ethylene-1,1-diphosphonic of coordinate bond
Acid) the netted coating of skeleton.Magnesium sheet metal is impregnated 3-5min, coating table in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution again by G step
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.Zirconium ion and hydroxy ethylidene two are formed in magnesium based metal after multiple alternating deposit
The metal-organic framework composite coating that phosphonic acids sufficiently chelates.
Compared with prior art, the beneficial effects of the present invention are:
One, the 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) that uses of the present invention is a kind of green, bio-safety, environment amenable band
There are two the small organic molecule of phosphonyl group, chemical structure is similar to cell membrane phospholipid bilayer, ensure 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 that uses of the present invention and zirconium oxide can also promote the increment and differentiation of osteoblast.Therefore, prepared by the present invention
Coating has preferable biocompatibility, can advantageously promote the increment and differentiation of osteoblast.
Two, the present invention constructs 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, metal (zirconium)-organic (1-hydroxy ethylidene-1,1-diphosphonic acid) skeleton three-dimensional is obtained
Netted coating makes coating stable, uniform, densification；So as to reduce the corrosion of magnesium metal base body, by alternate frequency and impregnate molten
The adjusting of liquid concentration can conveniently, effectively control the corrosion rate of magnesium matrix.
Three, alkali activating pretreatment is carried out to magnesium sheet, so that forming the magnesium hydroxide layer for being rich in hydroxyl, hydroxyl in sample surfaces
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, increases the stability of coating, to effectively control the corrosion of magnesium.
Four, technique of the invention is liquid deposition, and maximum temperature is only 55-65 DEG C, preparation method mild condition, technique
It is simple controllable.
Detailed description of the invention
Fig. 1 a is the stereoscan photograph of magnesium based metal；
Fig. 1 b is the stereoscan photograph of coating prepared by the embodiment of the present invention 3；
Fig. 2 a is the dynamic potential polarization of the coating (Mg-OH HEDP+Zr) of pure magnesium (Mg) and the preparation of the embodiment of the present invention 3
Curve；
Fig. 2 b is pure magnesium (Mg) and coating (Mg-OH@HEDP+Zr) electrochemical impedance spectroscopy prepared by the embodiment of the present invention 3；
Fig. 3 a is the fluorescence micrograph after pure magnesium (Mg) surface seeding osteoblast 6 hours；
Fig. 3 b is the fluorescence after coating (Mg-OH@HEDP+Zr) prepared by the embodiment of the present invention 3 is inoculated with osteoblast 6 hours
Microphoto.
Specific embodiment
Embodiment 1
A method of metal-organic framework composite coating being constructed in magnesium based metal, the steps include:
A, by magnesium sheet metal carborundum paper sanding and polishing, then deionized water, dehydrated alcohol, acetone, pickling are successively used
Liquid is cleaned by ultrasonic, and is then dried in vacuo；
B, the magnesium sheet metal that A is walked is put into 2mol/L, impregnates 14h in 65 DEG C of NaOH solution, after obtaining alkali activation
Magnesium sheet metal；
C, configuration concentration is 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution of 0.4g/L, then adjusts its pH to 8 with NaOH；
D, deionized water and dehydrated alcohol are configured to mixed solvent by 1.0: 1 volume ratio, then by ZrOCl2·8H2O is molten
Solution obtains the zirconium ion solution of concentration 0.8mmol/L in mixed solvent；
E, the magnesium sheet metal after activating the alkali that B is walked is put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C is walked, and 65 DEG C
Under the conditions of impregnate 12h；
F, magnesium sheet is deposited into 30s in the zirconium ion solution that D is walked；
G, magnesium sheet is deposited into 5min in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution that C is walked；
H, operation 4 times of F, G step are repeated；Magnesium sheet metal is finally put into vacuum oven drying, i.e., in magnesium based metal
Construct metal-organic framework composite coating.
Embodiment 2
A method of metal-organic framework composite coating being constructed in magnesium based metal, the steps include:
A, by magnesium sheet metal carborundum paper sanding and polishing, then deionized water, dehydrated alcohol, acetone, pickling are successively used
Liquid is cleaned by ultrasonic, and is then dried in vacuo；
B, the magnesium sheet metal that A is walked is put into 4mol/L, impregnates 10h in 55 DEG C of NaOH solution, after obtaining alkali activation
Magnesium sheet metal；
C, configuration concentration is 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution of 0.6g/L, then adjusts its pH to 7 with NaOH；
D, deionized water and dehydrated alcohol are configured to mixed solvent by 1.2: 1 volume ratio, then by ZrOCl2·8H2O is molten
Solution obtains the zirconium ion solution of concentration 1.2mmol/L in mixed solvent；
E, the magnesium sheet metal after activating the alkali that B is walked is put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C is walked, and 55 DEG C
Under the conditions of impregnate 8h；
F, magnesium sheet is deposited into 10s in the zirconium ion solution that D is walked；
G, magnesium sheet is deposited into 3min in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution that C is walked；
H, operation 6 times of F, G step are repeated；Magnesium sheet metal is finally put into vacuum oven drying, i.e., in magnesium based metal
Construct metal-organic framework composite coating.
Embodiment 3
A method of metal-organic framework composite coating being constructed in magnesium based metal, the steps include:
A, by magnesium sheet metal carborundum paper sanding and polishing, then deionized water, dehydrated alcohol, acetone, pickling are successively used
Liquid is cleaned by ultrasonic, and is then dried in vacuo；
B, the magnesium sheet metal that A is walked is put into 3mol/L, impregnates 12h in 60 DEG C of NaOH solution, after obtaining alkali activation
Magnesium sheet metal；
C, configuration concentration is 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution of 0.5g/L, then adjusts its pH to 7.5 with NaOH；
D, deionized water and dehydrated alcohol are configured to mixed solvent by 0.8: 1 volume ratio, then by ZrOCl2·8H2O is molten
Solution obtains the zirconium ion solution of concentration 1.0mmol/L in mixed solvent；
E, the magnesium sheet metal after activating the alkali that B is walked is put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C is walked, and 60 DEG C
Under the conditions of impregnate 10h；
F, magnesium sheet is deposited into 20s in the zirconium ion solution that D is walked；
G, magnesium sheet is deposited into 4min in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution that C is walked；
H, operation 5 times of F, G step are repeated；Magnesium sheet metal is finally put into vacuum oven drying, 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 preparation 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 being 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 is the dynamic potential polarization curve of the coating (Mg-OH@HEDP+Zr) of pure magnesium (Mg) and this example preparation.
It can be seen that compared with pure magnesium from the dynamic potential polarization curve of Fig. 2 a, it is multiple to form metal-organic framework in magnesium surface
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 is the electrochemical impedance spectroscopy of the coating (Mg-OH@HEDP+Zr) of pure magnesium (Mg) and this example preparation.
From the electrochemical impedance spectroscopy of Fig. 2 b it can be seen that the impedance ring of the metal-organic framework coating of modified formation is bright
The aobvious impedance ring greater than pure magnesium.Therefore, it is analyzed from aerodynamic point, the present invention is in the organic bone of metal-that magnesium based metal constructs
Frame compound coat, which can effectively reduce, even obstructs electrolyte to the Corrosive attack of magnesium matrix, to improve magnesium-based biology material
The corrosion resistance of material.
Fig. 3 a, Fig. 3 b be respectively pure magnesium (Mg) and this example preparation coating (Mg-OH@HEDP+Zr) surface seeding skeletonization it is thin
Fluorescence micrograph after born of the same parents 6 hours.
As can be seen that the osteoblast of the modified magnesium based metal of the present invention is obviously 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) skeleton coating that the present invention is formed in magnesium-based biomaterial surface
Osteoblast can be promoted to rise in value, there is preferable biocompatibility.
Claims (1)
1. a kind of method in magnesium based metal building metal-organic framework composite coating, the steps include:
A, by magnesium sheet metal carborundum paper sanding and polishing, then successively with deionized water, dehydrated alcohol, acetone, pickling solution into
Row ultrasonic cleaning, is then dried in vacuo；
B, the magnesium sheet metal that A is walked is put into 2-4mol/L, 55-65 DEG C of NaOH solution and impregnates 10-14h, it is living to obtain alkali
Magnesium sheet metal after change；
C, configuration concentration is 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution of 0.4-0.6g/L, then adjusts its pH to 7-8 with NaOH；
D, deionized water and dehydrated alcohol are configured to mixed solvent by 0.8-1.2: 1 volume ratio, then by ZrOCl2·8H2O is molten
Solution obtains the zirconium ion solution of concentration 0.8-1.2mmol/L in mixed solvent；
E, the magnesium sheet metal after activating the alkali that B is walked is put into the 1-hydroxy ethylidene-1,1-diphosphonic acid solution that C is walked, and 55-65 DEG C
Under the conditions of impregnate 8-12h；
F, magnesium sheet metal is deposited into 10-30s in the zirconium ion solution that D is walked；
G, magnesium sheet metal is deposited into 3-5min in 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) solution that C is walked；
H, operation 4-6 times of F, G step is repeated；Magnesium sheet metal is finally put into vacuum oven drying, i.e., in magnesium based metal structure
Build out metal-organic framework composite coating.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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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| 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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