CN106958014B - In the method for pure magnesium surface building hybrid inorganic-organic function and service coating - Google Patents

In the method for pure magnesium surface building hybrid inorganic-organic function and service coating Download PDF

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CN106958014B
CN106958014B CN201710221017.3A CN201710221017A CN106958014B CN 106958014 B CN106958014 B CN 106958014B CN 201710221017 A CN201710221017 A CN 201710221017A CN 106958014 B CN106958014 B CN 106958014B
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magnesium
solution
magnesium sheet
concentration
coating
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CN106958014A (en
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万国江
唐欣
张旋
张文泰
李薇
陈英奇
黄楠
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Southwest Jiaotong University
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    • 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
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Abstract

In the method for pure magnesium surface building hybrid inorganic-organic function and service coating, key step are as follows: A, magnesium sheet is polished, cleans, be dried in vacuo；B, magnesium sheet is put into the NaOH solution of 2-4mol/L, soaking 6-12h under the conditions of 50-60 DEG C；C, the plant acid solution for being 4-6g/L by concentration, adjusting PH with NaOH is 5-6；D, (the NH for being 0.1-0.2mol/L by concentration4)2TiF6The H that solution and concentration are 0.3-0.4mol/L3BO3Solution is respectively placed in 6-12h in 50-60 DEG C of water-bath；It is mixed to get mixed liquor in equal volume, then adjusts PH to 2.7-2.9 with HF；E, magnesium sheet is placed in 30-40min in the plant acid solution of C step；F, magnesium sheet is placed in 50-60 DEG C of heat preservation 40-60min in the mixed solution of D step, while with ultraviolet light magnesium sheet；G, it is primary that E, F step are repeated.The material that the method obtains, coating are well combined with substrate magnesium, and corrosion rate can be effectively reduced, and have good biocompatibility, the growth that can promote osteoblast, the characteristic with antibacterial and anti-inflammatory.

Description

In the method for pure magnesium surface building hybrid inorganic-organic function and service coating
Technical field
The present invention relates to a kind of methods in pure magnesium surface building hybrid inorganic-organic function and service coating.
Background technique
Magnesium alloy is a kind of ideal modern industry structural material.In recent years, magnesium and its alloy have obtained biology The highest attention of material circle, it has good mechanical property, and harmless, can be in human body gradually by corrosion The magnesium ion of degradation, generation can be absorbed by peripheral muscle tissue or be excreted by body fluid, need not be taken out after implanting. In addition, magnesium has good biological characteristics, magnesium ion can promote the deposition of calcium, and magnesium can be used for enhancing the conduction of bone Property, reduce bone aging, osteoporosis, soft tissue calciffication etc..Therefore, magnesium and its alloy are the biologies that there is development potentiality in a kind of pole Material has been known as being a kind of revolutionary metallic biomaterial in America and Europe.
However, the clinical implantation material needed and device allow for maintaining the several months long in vivo and keep enough strong Degree, until damaged tissues are fully recovered.Magnesium and its alloy implantation material can drop rapidly in the corrosive medium in human body containing chloride ion Solution is allowed to cannot to maintain time enough and premature failure (such as magnesium-based bracket just lost enabling capabilities in one month), Er Qieqi Pitting corrosion behavior is also possible to the induction serious inflammatory reaction of local organization.This too fast corrosion rate is that its anxious to be resolved is asked Topic and people once abandoned magnesium the main reason for medical instrument implantation Material Field is applied.In addition, being implanted into human body as foreign matter It is inevitable to generate biology rejection, admittedly it must assure that its good biocompatibility.It is current to be used to improve magnesium and its conjunction The technology of golden corrosion resistance is mainly process for modifying surface, significant effect.Magnesium and Magnesiumalloy surface modifying technology, mainly The coating that adhesive force is good is formed in metal surface, reduces even contact of the isolation base material with corrosive medium, and makes it not It is influenced by corrosive environment, to achieve the effect that reduce corrosion rate.In recent years, surface-coating technology achieved very big Development, such as anodizing technology, electrochemical deposition technique, chemical conversion technology, organic coat technology, they have many excellent Gesture, but there is also some factors to hinder their applications in terms of modification technology, such as catabolite complicates, it is feasible to operate Property and mechanical property be not good enough etc..
Summary of the invention
The present invention is intended to provide a kind of method in pure magnesium surface building hybrid inorganic-organic function and service coating, the party The magnesium-based biomaterial that method obtains, binding force is good between coating and substrate magnesium, and the corruption of magnesium-based biomaterial can be effectively reduced Rate is lost, and there is good biocompatibility, the growth that can promote osteoblast, the spy with antibacterial and anti-inflammatory response Property；Meanwhile the preparation condition of this method is mild, simple process is controllable.
The technical scheme adopted by the invention for realizing the object of the invention is, a kind of miscellaneous in pure magnesium surface building organic and inorganic Change the method for function and service coating, the specific steps are that:
A, magnesium sheet is polished with sand paper, then is cleaned by ultrasonic with deionized water, alcohol, pickling solution pickling, and be dried in vacuo；
B, the magnesium sheet for walking A is put into the NaOH solution of 2-4mol/L, soaking 6-12h under the conditions of 50-60 DEG C, to magnesium Piece carries out alkali activation processing；
C, the plant acid solution for being 4-6g/L by concentration, adjusting PH with NaOH is 5-6；
D, (the NH for being 0.1-0.2mol/L by concentration4)2TiF6The H that solution and concentration are 0.3-0.4mol/L3BO3Solution point It is not placed in 50-60 DEG C of water-bath and stands 6-12h；Then the two is mixed to get mixed liquor, mixed liquor HF tune in equal volume Save PH to 2.7-2.9；
E, magnesium sheet is placed in 30-40min in the plant acid solution of C step, its surface is made to obtain the organic layer rich in functional group；
F, magnesium sheet is placed in 50-60 DEG C of heat preservation 40-60min in the mixed solution of D step, while with ultraviolet light magnesium sheet；
G, the operation for repeating E, F step is primary, i.e., constructs hybrid inorganic-organic function and service coating in pure magnesium surface.
Mechanism of the invention is:
B step forms rich hydroxyl coating i.e. magnesium hydroxide coating on the surface of magnesium by activating to magnesium sheet alkali.
The magnesium sheet that alkali activates is placed in phytic acid by E step again to be impregnated, and the magnesium hydroxide of magnesium surface can be with the phosphorus in phytate molecule Acid reacts, and so that phytate molecule is fixed on the surface of magnesium, and expose a large amount of phosphate group in magnesium surface.Meanwhile in E step The magnesium ion and phytate molecule that magnesium surface is formed carry out chelation namely phytate molecule captures magnesium ion, and chelating forms equal Organic phytic acid coating of even densification
In D step, (NH4)2TiF6With H3BO3Complex reaction and dehydration condensation are carried out, mixed liquor becomes TiO2Deposit liquid；
The phosphate group of magnesium surface exposure is TiO in F step2Forming core site is provided, TiO is promoted2Forming core growth film forming, and The effect of ultraviolet light makes TiO2Film forms the surface of rich hydroxyl, improves the wetability of film surface, further promotes TiO2Film is heavy Product forms finer and close inorganic TiO2Coating；
Repeat the operation of E, F step, phytic acid and TiO2Mutual induction regulating controlling forming core, alternating deposit finally obtain organic (plant Acid)-inorganic (TiO2) hydridization hybrid coating.
Compared with prior art, the beneficial effects of the present invention are:
One, by alkali activate, magnesium surface formed magnesium hydroxide coating, magnesium hydroxide again with the phosphoric acid in phytate molecule It reacts, phytate molecule is made to be fixed on the surface of magnesium, meanwhile, the magnesium ion and phytate molecule that magnesium surface is formed carry out chelating work With, organic phytic acid coating of even compact is formed, so that binding force is good between coating and substrate magnesium of the invention, mechanical performance It is good；Coating is difficult to tilting of cracking, and falls off.
Two, the coating that the present invention obtains is hybrid coating, organic phytic acid and inorganic TiO2It is (covalent by powerful chemical key Key) it combines, rather than the hydrogen bond and Electrostatic Absorption that interaction force is weak.Phosphonyl group also participates in and promotes TiO in phytic acid2Shape Nucleus growth makes even compact inside hybrid coating, the corrosion rate of magnesium-based biomaterial can be effectively reduced.Depositing Ti O2Process In used ultraviolet irradiation, make TiO2Film forms the surface of rich hydroxyl, improves the wetability of film surface, further promotes TiO2It is thin Film deposition, forms finer and close inorganic TiO2Coating also greatly improves its corrosion resistance.
Three, phytate molecule itself is from nature, in addition TiO2Itself is nontoxic, thus the coating formed has well Biology performance.And by the TiO after ultraviolet irradiation2Surface is the surface of rich hydroxyl, the good hydrophilicity in surface, Also its biocompatibility (growth, antibacterial and the anti-inflammatory response that such as promote osteoblast) is made to be greatly improved.
Four, operation of the invention carries out in the liquid phase no more than 60 DEG C, and preparation condition is mild, and simple process can Control, use easy to spread.
Detailed description of the invention
Fig. 1 a is the obtained object (Mg-PA&TiO of embodiment 12- UV) SEM figure.
Fig. 1 b is the SEM figure of pure magnesium.
Fig. 2 a is the obtained object (Mg-PA&TiO of embodiment 12- UV) with the dynamic potential polarization curve of pure and beautiful (Mg).
Fig. 2 b is the obtained object (Mg-PA&TiO of embodiment 12- UV) with the electrochemical impedance spectroscopy of pure and beautiful (Mg).
Specific embodiment
Embodiment 1
A method of hybrid inorganic-organic function and service coating being constructed in pure magnesium surface, the specific steps are that:
A, magnesium sheet is polished with sand paper, then is cleaned by ultrasonic with deionized water, alcohol, pickling solution pickling, and be dried in vacuo；
B, the magnesium sheet for walking A is put into the NaOH solution of 3mol/L, soaking 12h under the conditions of 60 DEG C, is carried out to magnesium sheet Alkali is activated；
C, the plant acid solution for being 5g/L by concentration, adjusting PH with NaOH is 5.5；
D, (the NH for being 0.1mol/L by concentration4)2TiF6The H that solution and concentration are 0.3mol/L3BO3Solution is respectively placed in 60 DEG C water-bath in stand 12h；Then the two is mixed to get mixed liquor in equal volume, mixed liquor adjusts PH to 2.7 with HF；
E, magnesium sheet is placed in 40min in the plant acid solution of C step, its surface is made to obtain the organic layer rich in functional group；
F, magnesium sheet is placed in 50 DEG C of heat preservation 60min in the mixed solution of D step, while with ultraviolet light magnesium sheet；,
G, it is primary to repeat the operation that E is walked, F is walked, i.e., constructs hybrid inorganic-organic function and service coating in pure magnesium surface.
Embodiment 2
A, magnesium sheet is polished with sand paper, then is cleaned by ultrasonic with deionized water, alcohol, pickling solution pickling, and be dried in vacuo；
B, the magnesium sheet for walking A is put into the NaOH solution of 2mol/L, soaking 6h under the conditions of 50 DEG C, carries out alkali to magnesium sheet It is activated；
C, the plant acid solution for being 4g/L by concentration, adjusting PH with NaOH is 6；
D, (the NH for being 0.2mol/L by concentration4)2TiF6The H that solution and concentration are 0.4mol/L3BO3Solution is respectively placed in 50 DEG C water-bath in stand 6h；Then the two is mixed to get mixed liquor in equal volume, mixed liquor adjusts PH to 2.9 with HF；
E, magnesium sheet is placed in 30min in the plant acid solution of C step, its surface is made to obtain the organic layer rich in functional group；
F, magnesium sheet is placed in 60 DEG C of heat preservation 40min in the mixed solution of D step, while with ultraviolet light magnesium sheet；
G, it is primary to repeat the operation that E is walked, F is walked, i.e., constructs hybrid inorganic-organic function and service coating in pure magnesium surface.
Embodiment 3
A, magnesium sheet is polished with sand paper, then is cleaned by ultrasonic with deionized water, alcohol, pickling solution pickling, and be dried in vacuo；
B, the magnesium sheet for walking A is put into the NaOH solution of 4mol/L, soaking 9h under the conditions of 55 DEG C, carries out alkali to magnesium sheet It is activated；
C, the plant acid solution for being 6g/L by concentration, adjusting PH with NaOH is 5；
D, (the NH for being 0.15mol/L by concentration4)2TiF6The H that solution and concentration are 0.35mol/L3BO3Solution is respectively placed in 9h is stood in 55 DEG C of water-bath；Then the two is mixed to get mixed liquor in equal volume, mixed liquor adjusts PH to 2.8 with HF；
E, magnesium sheet is placed in 35min in the plant acid solution of C step, its surface is made to obtain the organic layer rich in functional group；
F, magnesium sheet is placed in 55 DEG C of heat preservation 50min in the mixed solution of D step, while with ultraviolet light magnesium sheet；；
G, it is primary to repeat the operation that E is walked, F is walked, i.e., constructs hybrid inorganic-organic function and service coating in pure magnesium surface.
Fig. 1 a is obtained object (the abbreviation Mg-PA&TiO in figure of embodiment 12- UV, wherein PA represents phytic acid, and UV represents ultraviolet Illumination) SEM figure, Fig. 1 b be pure magnesium (Mg) SEM figure.
From Fig. 1 a, Fig. 1 b it can be seen that compared with pure magnesium, by modified magnesium-based biomaterial (Mg-PA&TiO2- UV) surface is covered by the coating completely, embodies the induction and deposition effect of organic matter and the assistant depositing effect of light.
Fig. 2 a is obtained object (the abbreviation Mg-PA&TiO in figure of embodiment 12- UV, wherein PA represents phytic acid, and UV represents ultraviolet Illumination) with the dynamic potential polarization curve graph of pure and beautiful (Mg).
It can be seen that after magnesium surface obtains hybrid coating from Fig. 2 a, compared with pure magnesium, corrosion current at least declines An order of magnitude, corrosion potential increase to -1.35V from -1.7V, and corrosion resistance is significantly improved.
Fig. 2 b is obtained object (the abbreviation Mg-PA&TiO in figure of embodiment 12- UV, wherein PA represents phytic acid, and UV represents ultraviolet Illumination) with the electrochemical impedance spectroscopy of pure and beautiful (Mg).
It can be seen that embodiment 1 from Fig. 2 b the impedance arc of object be made and be significantly greater than pure and beautiful impedance arc.Illustrate the present invention Light assist hydridization hybrid coating, can effectively stop corrosion of the corrosive medium to magnesium-based bottom, to improve its corrosion resistance Energy.

Claims (1)

1. a kind of method in pure magnesium surface building hybrid inorganic-organic function and service coating, the specific steps are that:
A, magnesium sheet is polished with sand paper, then is cleaned by ultrasonic with deionized water, alcohol, pickling solution pickling, and be dried in vacuo；
B, the magnesium sheet for walking A is put into the NaOH solution of 2-4mol/L, soaking 6-12h under the conditions of 50-60 DEG C, to magnesium sheet into Row alkali is activated；
C, the plant acid solution for being 4-6g/L by concentration, adjusting PH with NaOH is 5-6；
D, (the NH for being 0.1-0.2mol/L by concentration4)2TiF6The H that solution and concentration are 0.3-0.4mol/L3BO3Solution is set respectively 6-12h is stood in 50-60 DEG C of water-bath；Then the two is mixed to get mixed liquor in equal volume, mixed liquor adjusts PH with HF To 2.7-2.9；
E, magnesium sheet is placed in 30-40min in the plant acid solution of C step, its surface is made to obtain the organic layer rich in functional group；
F, magnesium sheet is placed in 50-60 DEG C of heat preservation 40-60min in the mixed solution of D step, while with ultraviolet light magnesium sheet；
G, the operation for repeating E, F step is primary, i.e., constructs hybrid inorganic-organic function and service coating in pure magnesium surface.
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