CN108796491B - It is a kind of with highly corrosion resistant and surface-functionalized magnesium-base metal conversion coating and preparation method thereof - Google Patents
It is a kind of with highly corrosion resistant and surface-functionalized magnesium-base metal conversion coating and preparation method thereof Download PDFInfo
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- CN108796491B CN108796491B CN201810731286.9A CN201810731286A CN108796491B CN 108796491 B CN108796491 B CN 108796491B CN 201810731286 A CN201810731286 A CN 201810731286A CN 108796491 B CN108796491 B CN 108796491B
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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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- 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
- C23C22/06—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 acidic solutions with pH less than 6
- C23C22/48—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 acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/57—Treatment of magnesium or alloys based thereon
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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
- C23C22/60—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 alkaline aqueous solutions with pH greater than 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
- C23C22/05—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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Abstract
The invention discloses a kind of with highly corrosion resistant and surface-functionalized magnesium-base metal conversion coating and preparation method thereof.Method includes the following steps: (1) pre-processes magnesium alloy base material；(2) pretreated magnesium alloy is placed in poly- positive electricity electrolyte solution, after reacting 1~30min, takes out and cleaned with deionized water；(3) products therefrom in step (2) is placed in the mixed solution of polyphenolic substance and poly- negative electrolyte, after reacting 1~30min, takes out and cleaned with deionized water；(4) using step (3) products therefrom as substrate, step (2)~(3) are repeated described process 10~100 times, and dry with nitrogen, obtains conversion coating.The method of the present invention is easy to operate, at low cost, and universality is wide, is suitable for the area researches such as magnesium-based intravascular stent and bone immobilizing material.
Description
Technical field
The invention belongs to field of medical materials, and in particular to a kind of with highly corrosion resistant and surface-functionalized magnesium-based gold
Belong to conversion coating and preparation method thereof, can be used for magnesium-based degradable orthopedic implanting material and degradable magnesium base alloy intravascular stent material
The study on the modification of material.
Background technique
It is compared with metal materials such as traditional biological medical stainless steel, titanium alloys, magnesium-base metal material has good biology
The many advantages such as compatibility, mechanical performance, biodegradable, low cause bolt, low inflammatory reaction are widely studied expectation application
In blood stent material, orthopaedics repair materials etc..Although degradable magnesium alloy has the advantages that its uniqueness, but its particularly pertinent is asked
Topic is that degradation rate is too fast, and degradation finishes substantially in three months.At the same time, although degradable magnesium alloy material
Expect the physical and chemical performance and biocompatibility already close to even better than inert metal material, but long service is in moist life
It manages in environment, the too fast degradation rate of magnesium alloy is easy to cause implantation material to lose stress support effect too early.Magnesium alloy is in vivo
Gas-evolving electrodes occur, body tissue local pH increases, and is unfavorable for the growth of surrounding tissue.
Method currently used for improving corrosion resistance of magnesium alloy energy mainly has block modified (alloying and microstructure tune
It is whole) and surface modification.Wherein block is modified mainly by mixing a small amount of microelement such as Zn, Ca, Mn etc. in magnesium metal,
The modes such as the crystal phase structure of adjustable metal and grain size effectively improve the mechanical performance and corrosion resistance of alloy, should
The defects of alloy of method preparation has good biocompatibility, excessive but there are costs, and repeatability is not high.Surface changes
Property is current Magnesiumalloy surface modifying most efficient method, can take into account the control and describing property of biology of Corrosion Behaviors of Magnesium Alloys.At present
Developing a kind of good corrosion resistance and the magnesium alloy conversion coating of surface good biocompatibility of having both is still degradable magnesium-based
Metallic stent material problem urgently to be resolved.
Common Magnesiumalloy surface modifying coating is non-covalent bond effect, is had outer vulnerable to environment pH, temperature, salt ion etc.
The influence of portion's factor leads to burst drug release, breakdown of coating, accelerated corrosion, the service life for shortening implantation material.
Summary of the invention
For above-mentioned deficiency in the prior art, the present invention provides a kind of with highly corrosion resistant and surface-functionalized magnesium
Base Metal conversion coating and preparation method thereof, can effectively solve existing magnesium-based conversion coating vulnerable to wet environment influences corrosion rate
It is too fast, the problem of leading to stress fracture and influence surrounding tissue growth.
To achieve the above object, the technical solution adopted by the present invention to solve the technical problems is:
It is a kind of with highly corrosion resistant and the preparation method of surface-functionalized magnesium-base metal conversion coating, including following step
It is rapid:
(1) magnesium alloy base material is pre-processed；
(2) pretreated magnesium alloy is placed in 0.01~1mM, in the poly- positive electricity electrolyte solution that pH value is 4~10, in 4
After~37 DEG C of 1~30min of reaction, takes out and cleaned 3~5 times with deionized water；
(3) products therefrom in step (2) is placed in 0.01~20mM, the polyphenolic substance and poly- yin that pH value is 5.5~8.5
In the mixed solution of electrolyte, after 4~37 DEG C of 1~30min of reaction, takes out and cleaned 3~5 times with deionized water；Wherein, institute
The molar ratio for stating polyphenolic substance and poly- negative electrolyte is 1~2:1~2；
(4) using step (3) products therefrom as substrate, step (2)~(3) are repeated described process 10~100 times, and uses nitrogen
It is dry, obtain conversion coating.
Further, magnesium alloy is pure magnesium, magnesium rare earth-based alloy, new bio medical magnesium alloy or magnalium in step (1)
It is alloy.
Wherein, magnesium rare earth-based alloy is AZ31 magnesium alloy, AZ91 magnesium alloy or WE43 magnesium alloy.
Wherein, new bio medical magnesium alloy is AE21 magnesium alloy, Mg-Mn-Zn alloy or Mg-Si alloy.
Further, in step (2) gather sun electrolyte be poly-L-Lysine hydrobromate, polyallylamine hydrochloride,
Poly-L-arginine hydrochloride, polyethyleneimine, chitosan, poly- hexyl purple nitrile or gentamicin and kanamycin sulfate.
Further, the molar ratio of polyphenolic substance and poly- negative electrolyte is 1:1 in step (3).
Further, polyphenolic substance is epicatechin, epigallocatechin, epigallocatechin in step (3)
Gallate, L-Epicatechin gallate, gallic acid, resveratrol, vitamin B2, tanshinone, chromocor compound, ginger
Flavine or tannic acid.
Further, in step (3) gather yin electrolyte be heparin, Heparan sulfate, hyaluronic acid, chondroitin sulfate,
Collagen, glucan, keratan sulfate, polyacrylic acid, kayexalate salt, sodium alginate, polyglutamic acid or deoxidation
Ribonucleic acid.
Further, gathering positive electrolyte concentration is 0.01~1mM, pH value 7.4；The concentration of the mixed solution is
0.001~20mM, pH value 7.2.
What the above method was prepared has highly corrosion resistant and surface-functionalized magnesium-base metal conversion coating.
Of the invention is effective are as follows:
1, since polyphenolic substance can pass through hydrogen bond, π-π effect and part with poly- positive electrolyte, poly- negative electrolyte
Covalent bond effect forms stable polymer coating, and the present invention makes poly- positive electricity solution by LBL self-assembly philosophy and technique as a result,
Matter, polyphenol/poly- negative pentalyte form the cross-linked network coating of dense uniform on magnesium alloy materials surface, are prepared
Conversion coating is strong with substrate caking power, and has preferable resistance to corrosion.
2, containing a large amount of ortho position phenolic hydroxyl group in the molecular structure of polyphenolic substance, the magnesium that can be generated with bracket corrosion,
Chelation occurs for zinc, manganese plasma, and the such metal ion corroded is assisted effectively to convert deposition on mg-based material surface,
Coating can be effectively avoided further to be corroded.
3, polyphenolic substance especially tea polyphenolic compounds can protect blood vessel endothelium due to its good oxidation resistance
Cell is from oxidativestress damage, and in mg-based material degradation process, the polyphenol metal complex with antioxygenic property is free
Release, can maintain normal redox equilibrium in local vascular in a certain range；Meanwhile polyphenolic substance inherently has
There is preferable biocompatibility, and using the building of plant polyphenol intervention organic transformation layer, not only can effectively improve coating
Whole resistance to corrosion, while a variety of functional groups can be introduced, conducive to the fixation of subsequent load medicine and biomolecule.
4, the coating prepared needed for the present invention is usually less than 100nm, gained coating uniform, and raw material needed for prepares coating is put into
Seldom, raw material incorporation is easy to regulate and control, and the coating being prepared can be modified in surfaces of various materials, subtracts with traditional
Slow corrosion resistant coating technology is compared, and easy to operate, cost is relatively low, and universality is wide.
Detailed description of the invention
Fig. 1 be conversion coating prepared by the present invention atomic force microscope (Atomic Force Microscope,
AFM) testing result figure；
Fig. 2 is the anticoagulation function detection figure with conversion coating prepared by the present invention.
Specific embodiment
A specific embodiment of the invention is described below, in order to facilitate understanding by those skilled in the art this hair
It is bright, it should be apparent that the present invention is not limited to the ranges of specific embodiment, for those skilled in the art,
As long as various change is in the spirit and scope of the present invention that the attached claims limit and determine, these variations are aobvious and easy
See, all are using the innovation and creation of present inventive concept in the column of protection.
Embodiment 1
It is a kind of with highly corrosion resistant and the preparation method of surface-functionalized magnesium-base metal conversion coating, including following step
It is rapid:
(1) the pure magnesium material modified to needs is polished, is cleaned, is dried；
(2) step (1) products therefrom is placed in concentration for 0.01mM, in the polyethylenimine solution that pH value is 7.4, in 4
DEG C reaction 2min, then take out, and cleaned 3 times with deionized water；
(3) step (2) products therefrom is placed in concentration is 0.2mM, the epicatechin and Heparan sulfate that pH value is 7.5
Mixed solution in, in 10 DEG C of reaction 5min, then take out, and cleaned 3 times with deionized water；Wherein, epicatechin and sulfuric acid
The molar ratio of heparan is 1:2；
(4) using step (3) products therefrom as substrate, step (2)~(3) are repeated described process 60 times, and dry with nitrogen,
Then it saves and the conversion coating with corrosion resistance can be obtained in a vacuum drying oven.
Embodiment 2
It is a kind of with highly corrosion resistant and the preparation method of surface-functionalized magnesium-base metal conversion coating, including following step
It is rapid:
(1) the magnesium manganese alloy for needing modification is polished, cleaned and is dried；
(2) step (1) products therefrom is placed in concentration for 0.01mM, in the poly- hexyl purple nitrile solution that pH value is 7.5, in 5
DEG C reaction 2min, then take out, and cleaned 3 times with deionized water；
(3) step (2) products therefrom is placed in concentration is 0.02mM, the epigallocatechin galla turcica that pH value is 7.8
In the mixed solution of acid esters and dermatan sulfate, in 15 DEG C of reaction 5min, then take out, and cleaned 3 times with deionized water；Its
In, the molar ratio of Epigallo-catechin gallate (EGCG) and dermatan sulfate is 1:1；
(4) using step (3) products therefrom as substrate, step (2)~(3) are repeated described process 3 times, and dry with nitrogen,
Then it saves and the conversion coating with corrosion resistance can be obtained in a vacuum drying oven.
Embodiment 3
It is a kind of with highly corrosion resistant and the preparation method of surface-functionalized magnesium-base metal conversion coating, including following step
It is rapid:
(1) the WE43 magnesium alloy for needing modification is polished, cleaned and is dried；
(2) step (1) products therefrom is placed in concentration for 0.01mM, in the chitosan solution that pH value is 7.4, instead in 5 DEG C
2min is answered, is then taken out, and is cleaned 3 times with deionized water；
(3) by step (2) products therefrom be placed in concentration be 0.05mM, pH value be 7.2 L-Epicatechin gallate with
In the mixed solution of chondroitin sulfate, in 10 DEG C of reaction 5min, then take out, and cleaned 3 times with deionized water；Wherein, table
The molar ratio of catechin gallate and chondroitin sulfate is 1.5:2；
(4) using step (3) products therefrom as substrate, step (2)~(3) are repeated described process 5 times, and dry with nitrogen,
Then it saves and the conversion coating with corrosion resistance can be obtained in a vacuum drying oven.
Embodiment 4
It is a kind of with highly corrosion resistant and the preparation method of surface-functionalized magnesium-base metal conversion coating, including following step
It is rapid:
(1) the WE43 magnesium alloy for needing modification is polished, cleaned and is dried, it is spare；
(2) step (1) products therefrom is placed in concentration for 0.05mM, in the poly- hexyl purple nitrile solution that pH value is 7.6, in 5
DEG C reaction 2min, then take out, and cleaned 3 times with deionized water；
(3) step (2) products therefrom is placed in concentration is 0.4mM, the mixing of gallic acid and glucan that pH value is 7.4
In solution, in 20 DEG C of reaction 5min, then take out, and cleaned 3 times with deionized water；Wherein, gallic acid and glucan rub
You are than being 2:1；
(4) using step (3) products therefrom as substrate, step (2)~(3) are repeated described process 20 times, and dry with nitrogen,
Then it saves and the conversion coating with corrosion resistance can be obtained in a vacuum drying oven.
Embodiment 5
It is a kind of with highly corrosion resistant and the preparation method of surface-functionalized magnesium-base metal conversion coating, including following step
It is rapid:
(1) the WE43 magnesium alloy for needing modification is polished, cleaned and is dried；
(2) step (1) products therefrom is placed in concentration is 0.02mM, the poly-L-arginine HCI solution that pH value is 7.4
In, in 4 DEG C of reaction 1min, then take out, and cleaned 3 times with deionized water；
(3) step (2) products therefrom is placed in concentration is 0.002mM, the theaflavin and polystyrolsulfon acid that pH value is 7.4
In the mixed solution of sodium salt, in 10 DEG C of reaction 5min, then take out, and cleaned 3 times with deionized water；Wherein, theaflavin and poly-
The molar ratio of styrene sulfonic acid sodium salt is 1:1；
(4) using step (3) products therefrom as substrate, step (2)~(3) are repeated described process 5 times, and dry with nitrogen,
Then it saves and the conversion coating with corrosion resistance can be obtained in a vacuum drying oven.
Embodiment 6
It is a kind of with highly corrosion resistant and the preparation method of surface-functionalized magnesium-base metal conversion coating, including following step
It is rapid:
(1) the magnesium manganese alloy for needing modification is polished, cleaned and is dried；
(2) step (1) products therefrom is placed in concentration is 0.01mM, the diallyl dimethyl chlorination that pH value is 7.6
In ammonium salt solution, in 4 DEG C of reaction 1min, then take out, and cleaned 3 times with deionized water；
(3) step (2) products therefrom is placed in concentration is 0.002mM, the epigallocatechin and poly- third that pH value is 7.4
In the mixed solution of olefin(e) acid, in 10 DEG C of reaction 5min, then take out, and cleaned 3 times with deionized water；Wherein, epigallocatechin gallate
The molar ratio of theine and polyacrylic acid is 1:1；
(4) using step (3) products therefrom as substrate, step (2)~(3) are repeated described process 5 times, and dry with nitrogen,
Then it saves and the conversion coating with corrosion resistance can be obtained in a vacuum drying oven.
Embodiment 7
It is a kind of with highly corrosion resistant and the preparation method of surface-functionalized magnesium-base metal conversion coating, including following step
It is rapid:
(1) the AZ31 magnesium alloy for needing modification is polished, cleaned and is dried；
(2) step (1) products therefrom is placed in concentration for 0.02mM, in the polyethylenimine solution that pH value is 7.8, in 4
DEG C reaction 1min, then take out, and cleaned 3 times with deionized water；
(3) step (2) products therefrom is placed in concentration is 0.001mM, the mixed solution of EGCG and heparin that pH value is 7.2
In, in 10 DEG C of reaction 5min, then take out, and cleaned 3 times with deionized water；Wherein, the molar ratio of EGCG and heparin is 1:1；
(4) using step (3) products therefrom as substrate, step (2)~(3) are repeated described process 5 times, and dry with nitrogen,
Then it saves and the conversion coating with corrosion resistance can be obtained in a vacuum drying oven.
Embodiment 8
It is a kind of with highly corrosion resistant and the preparation method of surface-functionalized magnesium-base metal conversion coating, including following step
It is rapid:
(1) the AZ31 magnesium alloy for needing modification is polished, cleaned and is dried, it is spare；
(2) step (1) products therefrom is placed in concentration for 0.01mM, in the chitosan solution that pH value is 7.4, instead in 4 DEG C
1min is answered, is then taken out, and is cleaned 3 times with deionized water；
(3) step (2) products therefrom is placed in concentration is 0.001mM, tannic acid that pH value is 7.2 and hyaluronic acid it is mixed
It closes in solution, in 10 DEG C of reaction 5min, then takes out, and cleaned 3 times with deionized water；Wherein, tannic acid and hyaluronic acid
Molar ratio is 1:1；
(4) using step (3) products therefrom as substrate, step (2)~(3) are repeated described process 5 times, and dry with nitrogen,
Then it saves and the conversion coating with corrosion resistance can be obtained in a vacuum drying oven.
Detection
Atomic force microscope (AFM) detection and anticoagulant property are carried out to the conversion coating that embodiment 7 is prepared respectively
It can detect, test map is shown in Fig. 1 and Fig. 2 respectively.
It can be seen from figure 1 that the conversion coating forms cross-linked network compact texture, pass through extreme condition and long-term PBS
Middle immersion test finds that there is the figure layer good resistance to extreme condition to destroy and long-term stability.
As can be seen from Figure 2, conversion coating sample surfaces illustrate the conversion coating almost without there is the enrichment of blood platelet
Stick with good antiplatelet and anticoagulant functions；Moreover, the polyphenolic substance in the conversion coating has super hydrophilic function
Can, the aggregation of protein on the surface of the material in blood can be effectively prevented, in addition, the heparin molecule in conversion coating can be with
The activation and destruction of ingredient in effectively preventing blood.
The experiment of PBS aqueous solution long period of soaking is carried out to the conversion coating that embodiment 7 is prepared, detailed process is as follows:
The unmodified magnesium alloy face of silicone rubber seal, the coat side that only exposure was modified are used first；It is 1cm's by four diameters
Magnesium alloy sample is put into the device of homemade measurement hydrogen, addition 400ml PBS solution, sealing device, every under the conditions of 37 DEG C
The amounts of hydrogen of measurement sample release in 12 hours, reads volume, discharges the corrosion rate of the speed response of hydrogen magnesium alloy；Pass through
Above-mentioned detection discovery, hydrogen rate of release is very low, shows the conversion coating that the present invention is prepared, and has excellent corrosion resistant
Corrosion energy.
The conversion coating and conventional coatings progress extreme condition electro-chemical test that embodiment 7 is prepared respectively, tool
Body process is as follows:
The conversion coating and conventional coatings progress extreme condition electro-chemical test that embodiment 7 is prepared respectively, tool
Body process is as follows:
First by the sample back side, copper sheet sanding and polishing, then copper sheet and sample cohesive are got up with conductive silver glue, with silicon rubber
Glue gets up sample sealing backside, and solidification is used for the test of chemical property overnight；Electro-chemical test PBS under the conditions of 37 DEG C is molten
In liquid, and detect the impedance value and corrosion current size of the conversion coating；It is found by detection, what the present invention was prepared
Conversion coating, impedance value are significantly larger than conventional coatings, meanwhile, corrosion current is also far below conventional coatings, shows the present invention
The conversion coating being prepared has excellent corrosion resistance.
Claims (8)
1. a kind of with highly corrosion resistant and the preparation method of surface-functionalized magnesium-base metal conversion coating, which is characterized in that
The following steps are included:
(1) magnesium alloy base material is pre-processed；
(2) pretreated magnesium alloy is placed in 0.01~1mM, in the poly- positive electricity electrolyte solution that pH value is 4~10, in 4~37
DEG C reaction 1~30min after, take out simultaneously cleaned 3~5 times with deionized water；
(3) products therefrom in step (2) is placed in 0.01~20mM, the polyphenolic substance and poly- negative electricity solution that pH value is 5.5~8.5
In the mixed solution of matter, after 4~37 DEG C of 1~30min of reaction, takes out and cleaned 3~5 times with deionized water；Wherein, described more
The molar ratio of phenolic compounds and poly- negative electrolyte is 1~2:1~2；
(4) using step (3) products therefrom as substrate, step (2)~(3) are repeated described process 10~100 times, and dry with nitrogen
It is dry, obtain conversion coating.
2. according to claim 1 with the preparation side of highly corrosion resistant and surface-functionalized magnesium-base metal conversion coating
Method, which is characterized in that magnesium alloy described in step (1) is pure magnesium, magnesium rare earth-based alloy, new bio medical magnesium alloy or magnalium
It is alloy.
3. according to claim 1 with the preparation side of highly corrosion resistant and surface-functionalized magnesium-base metal conversion coating
Method, which is characterized in that described in step (2) gather sun electrolyte be poly-L-Lysine hydrobromate, polyallylamine hydrochloride,
Poly-L-arginine hydrochloride, polyethyleneimine, chitosan or poly- hexyl purple nitrile.
4. according to claim 1 with the preparation side of highly corrosion resistant and surface-functionalized magnesium-base metal conversion coating
Method, which is characterized in that the molar ratio of polyphenolic substance described in step (3) and poly- negative electrolyte is 1:1.
5. having the preparations of highly corrosion resistant and surface-functionalized magnesium-base metal conversion coating according to claim 1 or described in 4
Method, which is characterized in that the polyphenolic substance is epicatechin, epigallocatechin, epigallocatechin galla turcica
Acid esters, L-Epicatechin gallate, gallic acid, resveratrol, vitamin B2, tanshinone, chromocor compound, curcumin or
Tannic acid.
6. having the preparations of highly corrosion resistant and surface-functionalized magnesium-base metal conversion coating according to claim 1 or described in 4
Method, which is characterized in that the poly- negative electrolyte is heparin, Heparan sulfate, hyaluronic acid, chondroitin sulfate, collagen egg
White, glucan, keratan sulfate, polyacrylic acid, kayexalate salt, sodium alginate, polyglutamic acid or deoxyribose core
Acid.
7. according to claim 1 with the preparation side of highly corrosion resistant and surface-functionalized magnesium-base metal conversion coating
Method, which is characterized in that the poly- positive electrolyte concentration is 0.01~1mM, pH value 7.4；The concentration of the mixed solution is
0.001~20mM, pH value 7.2.
8. any one of claim 1~7 the method is prepared golden with highly corrosion resistant and surface-functionalized magnesium-based
Belong to conversion coating.
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| CN104195535A (en) * | 2014-08-12 | 2014-12-10 | 西南交通大学 | Modification method for improving corrosion resistance and surface functionalization of biomedical magnesium-based metal material |
| CN109055926A (en) * | 2018-07-05 | 2018-12-21 | 四川大学 | A kind of magnesium-base metal material conversion film and preparation method thereof |
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