CN109675120A - A kind of preparation method and application of medical magnesium-base metal stress corrosion resistant self-repair function coating - Google Patents

A kind of preparation method and application of medical magnesium-base metal stress corrosion resistant self-repair function coating Download PDF

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CN109675120A
CN109675120A CN201811480461.8A CN201811480461A CN109675120A CN 109675120 A CN109675120 A CN 109675120A CN 201811480461 A CN201811480461 A CN 201811480461A CN 109675120 A CN109675120 A CN 109675120A
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base metal
medical magnesium
magnesium
coating
stress corrosion
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CN109675120B (en
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陈连喜
王小健
李卫
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Jinan University
University of Jinan
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Jinan University
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Abstract

The invention discloses the preparation methods and application of a kind of medical magnesium-base metal stress corrosion resistant self-repair function coating.This method is using medical magnesium-base metal as matrix, first carry out pretreatment removal processing residual and surface adjunct, it is then placed in progress hydroxylating processing in sodium hydroxide solution, then corrosion inhibiter is coated in matrix surface, it is thermally treated to be formed by curing with stress corrosion resistant self-repair function coating；Wherein, corrosion inhibiter includes three kinds of silane coupling agent, phytic acid and graphene oxide ingredients.The process of preparing of coating of the present invention is simple, it is easily operated, the anchoring strength of coating obtained is good, biocompatibility is good, there is self-reparing capability in physiological environment, it can be improved the corrosion resistance of magnesium alloy and inhibit Sensitivity of Stress Corrosion, it therefore, can be using the magnesium-base metal obtained for having protective coating as medical embedded property device material applying clinical aspect.

Description

A kind of preparation method of medical magnesium-base metal stress corrosion resistant self-repair function coating with Using
Technical field
The invention belongs to Implantable Medical Device field, in particular to a kind of medical magnesium-base metal stress corrosion resistant selfreparing The preparation method and application of functional coating.
Background technique
Traditional biological medical metal material, because it is with excellent corrosion resistance, stable mechanical property and obtained wide General application, such as stainless steel, titanium alloy and cochrome.However in these traditional inert metal material instrument longer-term persistence bodies, The problems such as may cause chronic inflammation, advanced stage stent thrombosis and anticoagulant drug need to be taken for a long time；Simultaneously for interim solid in vivo Fixed or support implantation material, need to take out after organization healing through second operation, this will bring secondary injury and doctor to patient Treat burden.Biological medical degradable magnesium alloy good biocompatibility and can be dropped in vivo because with higher mechanical property The characteristics such as solution become the hot spot that interventional medicine engineering field researchs and develops in worldwide.Its catabolite magnesium ion (Mg2+) It is adjustable cardiovascular activity, participates in human metabolism, can be used for reducing hypertension, treatment acute myocardial infarction AMI and prevention of arterial Atherosis, and bone tissue can be promoted to form and induce bone tissue regeneration.Therefore, medical magnesium alloy is in biological medical degradable Material Field has received widespread attention and quite with important application prospects.
However, magnesium alloy degradation rate too fast in physiological environment seriously limits its clinical application.The standard of magnesium is rotten It is low (- 2.37V) to lose current potential, is easy to water reaction and generates hydrogen and loose magnesium hydroxide (Mg (OH)2) the corrosion product beds of precipitation.Together When physiological solution in chloride ion (Cl-) the soluble magnesium chloride (MgCl of generation can be reacted with magnesium hydroxide2) and hydroxyl (OH-) Ion.The quick raising of the accumulation of hydrogen, magnesium ion concentration and pH value easily leads to implantation surrounding materials tissue and is inflamed and feels Dye, delays the healing of tissue.It is used as interior fixed bone plate and angiocarpy bracket material, in clinical operation implantation process, material simultaneously Material need to carry out certain plastic deformation to be bonded fracture site or support cardiovascular organization, will also carry certain biotic stress. Classical evaluation magnesium alloy degradation rate, it is general using technologies such as corrosion immersion and electro-chemical tests, and ignore in plastic deformation The influence of stress (i.e. residual stress) and biotic stress to corrosion behavior.The collective effect of stress and internal corrosive environment will be made Stress degradation occurs at implant, serious person causes implant failure fracture, i.e. stress corrosion fracture, this is that one kind takes than expected Use as a servant the catastrophic failure fracture mode of time limit earlier.In chloride ion-containing (Cl-) in physiological environment, magnesium alloy is more quick to stress corrosion Sense.Therefore, it not only needs to control the degradation rate of medical magnesium alloy, while to inhibit stress corrosion inclination, could push medical Magnesium alloy degradation behavior is controllable.
There are many inorganic (such as differential arc oxidation (MAO), calcium phosphor coating and hydroxyapatite coating layers) and organic is (such as Polylactic acid, l-lactic acid (PLLA) and poly lactide-glycolide acid (PLGA) coating) surface modified coat, it is applied to Improve the corrosion resistance of magnesium alloy.Surface modified coat is equivalent to one layer of physical barriers protective layer, prevents solution and magnesium alloy Substrate contact reaction, to reduce corrosion rate.But differential arc oxidation and calcium phosphor coating, although medical magnesium can be greatly improved The corrosion resistance of alloy, but due to belonging to inorganic ceramic type coating, when matrix is in stress or deforms, coating will be produced Raw crackle peels off；Organic matter coating and magnesium alloy substrate always exist interface cohesion problem, seriously affect coating combination Intensity and stability.Defect existing for these modified coatings or deficiency, and due to matrix strain or stress under, coating Crack initiation, extension and part and matrix leafing occurs, coating can not also lean on itself or biomineralization to repair defect, raw More serious Local electrochemical corrosion reaction can be occurred by these defects and magnesium alloy substrate by managing solution, cause Corrosion Behaviors of Magnesium Alloys Rate is not controlled rationally.Therefore, a kind of corrosion-resistant finishes with self-repair function need be developed to control medical magnesium Degradation in Base Metal body.
However, existing most of coatings, as one layer of physical shielding layer, effective inhibition anode that cannot be permanent is molten Solution type stress corrosion fracture mechanism, the hydrogen caused for a small amount of hydrogen that corrosion reaction generates cause stress corrosion fracture rejection ability It is extremely limited.Moreover, most coatings are applied to structural timber field, coating composition may contain toxic or cause Cancer substance is no longer applicable in as bio-medical modified coating.
To sum up, it is implanted into material for the medical magnesium alloy that need to be plastically deformed, needs to develop new medical and reviews one's lessons by oneself overcoating Layer realizes the bonds well and holiday of coating by chemical bonds using the excellent coating composition of biological safety Self-regeneration to realize its corrosion protection or physical shielding recovery of performance, and incline for stress corrosion existing for medical magnesium alloy To, by inhibiting anodic solution and reducing the source that hydrogen causes hydrogen in stress corrosion fracture, thus realize existing coating mechanical strength and The multiple reparation such as adhesion property and coating stress corrosion resistant function, stable protection is provided for medical magnesium-base metal.
Summary of the invention
The primary purpose of the present invention is that the shortcomings that overcoming the prior art and insufficient, provide that a kind of medical magnesium-base metal is anti-to answer The preparation method of power corrosion self-repair function coating.
Another object of the present invention is to provide the medical magnesium-base metal stress corrosion resistants that the method is prepared to review one's lessons by oneself Multiple functional coating.
A further object of the present invention is to provide the systems of the medical magnesium-base metal stress corrosion resistant self-repair function coating The application of Preparation Method.
The purpose of the invention is achieved by the following technical solution: a kind of medical magnesium-base metal stress corrosion resistant self-repair function The preparation method of coating is to apply corrosion inhibiter (silane coupling agent, phytic acid and graphene oxide) using medical magnesium-base metal as matrix Matrix surface is overlayed on, it is thermally treated to be formed by curing with stress corrosion resistant self-repair function coating；Specifically comprise the following steps:
(1) medical magnesium-base metal is pre-processed, removal processing residual and surface adjunct obtain pretreated doctor Use magnesium-base metal；
(2) pretreated medical magnesium-base metal is soaked in 1~5mol/L obtained in step (1) sodium hydroxide is molten Hydroxylating processing is carried out in liquid, is then washed, and hydroxylating is obtained treated medical magnesium-base metal；
(3) 1. by silane coupling agent, phytic acid [C6H6(H2PO4)6] and graphene oxide be added in solvent, ultrasonic agitation is equal It is even, and pH value is adjusted to 6~10, obtain corrosion inhibiter A (coatings mixed solution)；Then corrosion inhibiter A is coated to step (2) surface of treated the medical magnesium-base metal of hydroxylating obtained in is washed, vacuum drying, then places it in 80~120 DEG C Under the conditions of carry out curing process, obtain medical magnesium-base metal stress corrosion resistant self-repair function coating；
Either:
2. silane coupling agent is added in solvent, ultrasonic agitation uniformly, and adjusts pH value to 6~10, obtains corrosion inhibiter B (solution of silane)；Phytic acid and graphene oxide are added in solvent, ultrasonic agitation uniformly, and adjusts pH value to 6~10, obtains Corrosion inhibiter C (mixed solution of phytic acid and graphene oxide)；Then corrosion inhibiter B is coated to hydroxylating obtained in step (2) The surface of treated medical magnesium-base metal is washed, vacuum drying, then carries out curing process under the conditions of being placed in 80~120 DEG C, is obtained Medical magnesium-base metal after to silane pretreatment；Corrosion inhibiter C is finally coated to the medical magnesium-base metal after silane pretreatment Surface, washing, after vacuum drying, carries out curing process under the conditions of placing it in 80~120 DEG C, obtains that medical magnesium-base metal is anti-to answer Power corrodes self-repair function coating.
Medical magnesium-base metal described in step (1) is degradable magnesium-base metal；Preferably WE43 magnesium alloy, ZK40 magnesium Alloy, AZ31 magnesium alloy or Mg-1Zn-1Ca magnesium alloy.
Pretreatment described in step (1) is realized preferably by following steps: medical magnesium-base metal polished with sand paper, And it is rinsed with deionized water；It is then placed in acetone and/or dehydrated alcohol and is cleaned by ultrasonic, and rinsed with deionized water；Again with acid Washing lotion or alkali wash water cleaning, and be cleaned by ultrasonic with deionized water；It is finally dried in vacuo, is pre-processed under the conditions of 60 ± 5 DEG C Medical magnesium-base metal afterwards.
Described is successively to be polished with the sand paper of 400#, 800#, 1200#, 1500# and 2000# with sand paper polishing.
The sand paper is preferably silicon carbide silicon carbide paper.
The time being cleaned by ultrasonic in acetone that is put into is 10~15 minutes；Preferably 10 minutes.
The time being cleaned by ultrasonic in dehydrated alcohol that is put into is 10~15 minutes；Preferably 10 minutes.
The pickling solution is the mixed solution that acetic acid and neutral sodium-salt are mixed to get.
The neutral sodium-salt is sodium chloride or sodium nitrate.
The concentration of acetic acid is 160~240mg/mL (preferably 200mg/mL) in the mixed solution, neutral sodium-salt Concentration is 40~60mg/mL (preferably 60mg/mL).
The time cleaned with pickling solution or alkali wash water is 0.5~1 minute.
The alkali wash water is sodium hydroxide and the mixed solution that alkaline sodium salt is mixed to get.
The alkaline sodium salt is tertiary sodium phosphate, sodium carbonate or sodium bicarbonate.
The concentration of sodium hydroxide is 20~40mg/mL (preferably 20mg/mL) in the mixed solution, alkaline sodium salt Concentration is 10~20mg/mL (preferably 10mg/mL).
The time being cleaned by ultrasonic with deionized water is 10~15 minutes；Preferably 10 minutes.
The vacuum drying temperature is preferably 60 DEG C.
Water described in step (2) and (3) is preferably deionized water.
The condition of the processing of hydroxylating described in step (2) are as follows: 50~80 DEG C are handled 0.5~2 hour；Preferably 50~80 DEG C processing 1~2 hour；More preferably 50~80 DEG C are handled 1.5~2 hours；Hydroxylating processing is that magnesium-base metal is impregnated hydrogen-oxygen Change and obtains a large amount of the basic hydroxide group (- OH in surface in sodium solution-), the introducing of surface hydroxyl is conducive to follow-up coating ingredient and magnesium-based The chemical bonds of metal.
The concentration of sodium hydroxide solution described in step (2) is preferably 2~5mol/L；More preferably 3~5mol/L.
Step (3) 1. and 2. described in solvent be mixed solvent that water and ethyl alcohol are mixed to get；Preferably by such as the following group It is grouped as: 5~20% (v/v) water and 80~95% (v/v) ethyl alcohol；It is more preferably grouped as by following group: 5~15% (v/v) Water and 85~95% (v/v) ethyl alcohol.
The water is preferably deionized water.
Step (3) 1. and 2. described in silane coupling agent be methyltrimethoxysilane (MS), γ-(2,3- epoxies third Oxygroup) propyl trimethoxy silicane, methyltriethoxysilane (MTES), ethyl orthosilicate silane (TEOS) and 3- aminopropyl Trimethoxy silane (NH2(CH2)3Si(OCH3)3At least one of, APTES)；Preferably 3- aminopropyl trimethoxy silicon Alkane.
Step (3) 1. and 2. described in the average diameter of graphene oxide be 0.5~3 μm, average height 0.55~ 1.2nm。
Step (3) 1. described in corrosion inhibiter A in the concentration of silane coupling agent be 4~20mg/mL, the concentration of phytic acid is 2 ~20mg/mL, the concentration of graphene oxide are 0.5~5mg/mL；The concentration of silane coupling agent is preferably in the corrosion inhibiter A 4~8mg/mL, the concentration of phytic acid are preferably 12~20mg/mL, and the concentration of graphene oxide is preferably 0.5~1mg/mL.
Step (3) 1. described in corrosion inhibiter A obtained preferably by following method: silane coupling agent is added to solvent In, ultrasonic agitation is uniform；Then phytic acid is added, ultrasonic agitation is uniform；Graphene oxide is added, ultrasonic agitation uniformly, and is adjusted PH value is saved to 6~10, obtains corrosion inhibiter A (coatings mixed solution).
Addition silane coupling agent, phytic acid and the time of graphene oxide stirring is 30~60 minutes；Preferably 40~60 minutes.
Step (3) 1. and 2. described in adjusting pH value be to be adjusted using acetic acid and ammonium hydroxide；Preferably using acetic acid and Ammonium hydroxide adjusts pH value to 8.
Step (3) 1. and 2. described in the temperature of ultrasonic agitation be preferably 25~35 DEG C.
Step (3) 1. described in ultrasonic agitation time be 90~200 minutes；Preferably 100~200 minutes；It is more excellent It is selected as 120~180 minutes.
Step (3) 2. described in corrosion inhibiter B in silane coupling agent concentration be 4~20mg/mL；Preferably 4mg/mL.
Step (3) 2. described in obtain corrosion inhibiter B needed for mixing time be preferably 30~60 minutes；Preferably 40~ 60 minutes.
Step (3) 2. described in corrosion inhibiter C in phytic acid concentration be 2~20mg/mL (preferably 20mg/mL), oxidation The concentration of graphene is 0.5~5mg/mL (preferably 0.5mg/mL).
Step (3) 2. described in obtain corrosion inhibiter C needed for mixing time be preferably 60~120 minutes.
Step (3) 2. described in corrosion inhibiter C obtained preferably by following method: phytic acid is added in solvent, surpass Sound stirs evenly；Then graphene oxide is added, ultrasonic agitation uniformly, and adjusts pH value to 6~10, obtains corrosion inhibiter C (phytic acid With the mixed solution of graphene oxide).
The time of the addition phytic acid and graphene oxide stirring is 30~60 minutes；Preferably 40~60 minutes.
Step (3) 1. and 2. described in applied to one of extraction, spin-coating method and hydro-thermal method；Preferably extract Method.
The extraction is achieved by the steps of: by treated the medical magnesium-based of hydroxylating obtained in step (2) Metal is put into corrosion inhibiter A, B or C, is impregnated 2~4 hours under the conditions of 25 DEG C.
The time of the immersion is preferably 4 hours.
The spin-coating method is achieved by the steps of: corrosion inhibiter A, B or C are spun to hydroxyl obtained in step (2) Change treated medical magnesium-base metal surface, each spin coating with a thickness of 1~2.5 μm, repeat 2~3 times.
The spin coating preferably carries out spin coating using desk-top sol evenning machine.
The hydro-thermal method is achieved by the steps of: by treated the medical magnesium-based of hydroxylating obtained in step (2) Metal is put into corrosion inhibiter A, B or C, is heated to 150~200 DEG C, keeps the temperature 3~6 hours.
The condition of the hydro-thermal method processing is preferred are as follows: 180 DEG C keep the temperature 3 hours.
Step (3) 1. and 2. described in time of curing process be 0.5~2 hour；Preferably 1~1.5 hour.
Step (3) 1. and 2. described in vacuum drying condition are as follows: 30 DEG C drying 24 hours.
A kind of medical magnesium-base metal stress corrosion resistant self-repair function coating, is prepared by method described in any of the above embodiments It obtains.
The thickness of the medical magnesium-base metal stress corrosion resistant self-repair function coating is preferably 4~9 μm.
The preparation method of the medical magnesium-base metal stress corrosion resistant self-repair function coating is preparing bio-medical gold Belong to the application in material.
Design principle of the present invention is as follows:
Traditional medical magnesium alloy surface modified coating, such as inorganic (such as differential arc oxidation (MAO), calcium phosphor coating and hydroxyl Apatite coating) and organic (such as polylactic acid, l-lactic acid (PLLA) and poly lactide-glycolide acid (PLGA) painting Layer) surface modified coat, the degradation rate of magnesium alloy can be substantially improved.However for medical embedded material, medical magnesium alloy exists The plastic deformation occurred in implantation process to surface covering will cause mechanical-physical destroy or damage, coating will crack or with Matrix leafing reduces the bond strength, stability and physical shielding protective value of coating.Also, as carrying Biological Strength It is implanted into material, magnesium alloy has very big stress corrosion fracture sensibility, and existing coating in the physiological environment of chloride ion-containing This respect design is considered less.
As Implantable Medical Device, biocompatibility and safety for material itself have very big requirement.If Meter prepares surface self-repairing functional coating, selects, is avoided using with bio-toxicity or carcinogenic substance in coating composition.And And it coated substance energy degradation in vivo or is excreted by urinary system.
From phytic acid as cereal crops extract, medical and health and food processing are widely used to, from biological effect From the point of view of angle, can be used as the antioxidant of Nantural non-toxic, have it is anti-oxidant with prevent lipid peroxidation injury effect, to changing Mercy myocardial ischemia has certain therapeutic effect.Furthermore the aggregation of blood platelet also can be effectively suppressed in phytic acid, reduces cardiovascular disease incidence Danger prevents the oxidative damage of DNA, prevention and inhibition tumor promotion and cancer, as anti-tumor drug.Phytic acid can also pass through kidney It is dirty to excrete.Also, phytic acid has very strong sequestering power, can form chelate with magnesium ion, calcium ion, be deposited in coating Defect or cracks, to play certain self-repair function.It is acted on by chelating, phytic acid can be with metal ion (such as Mg2+, Ca2+ Deng) in one layer of fine and close unimolecule protective film of metal surface generation, to effectively control the corrosion resistance of matrix, and end official It can group-PO4H2Be conducive to the raising of substrate surface bioactivity, there is good biocompatibility.But simple phytic acid converts film layer There are a large amount of micro-cracks, improve to the corrosion resistance of magnesium alloy limited.
Silane coupling agent is as a kind of economy, and effectively, corrosion-inhibiting coating environmental-friendly, non-hazardous to human body has been applied successfully In magnesium alloy.It is generally made of inorganic and organic two classes group, and chemical formula is generally R '-(CH2)n-Si-X3, R ' is organic official It can roll into a ball, (CH2)nFor linking group, X is hydrolyzable groups such as chlorine, alkoxy, acyloxy, amino etc..It is generally acknowledged that silane passes through Itself hydrolysis, dehydrating condensation, hydrogen bond attachment and heat cure dehydration, in metal surface formation-Si-O-Me key, the silanol of hydrolysis can With metal surface excess silanol group formation-Si-O-Si- reticular structure, to form one layer of organosilicon with corrosion resistance Coating, and improve matrix/coating interface binding force.Pass through hydrolyzable silane group (- OCH3), silanol is generated, thus Formation-Si-O-Si- or-Si-O-Mg network is concentrated, increases the coating degree of cross linking, to play certain self-repair function.However, Silane treatment magnesium alloy is in aqueous solution, it is also possible to itself hydrolysis occur, so as to cause the failure of silane conversion film, need into one Walk modification.
Graphene oxide (GO) has the characteristics such as high length-diameter ratio, strong heating conduction and excellent mechanical performance, it is considered to be Enhance the ideal nano material of coating performance.Moreover, there are a large amount of oxygen-containing groups (to deposit in plane on graphene oxide basic plane There are carbonyls and carboxyl in epoxy group and hydroxyl, edge), these functional groups can become modified reaction site, Ke Yijin One step improves the dispersibility and compatibility of graphene oxide, to achieve the purpose that improve its corrosion resistance.Graphene oxide warp After macromolecular (such as chitosan, polyethylene glycol, dextran, peroxidase and albumen) is surface modified, only show Low-down cellulotoxic effect, and biodegrade can occur by way of enzymatic oxidation, it can be used as coating corrosion inhibiter and company Connect agent enhancing coating corrosion resistance and self-reparing capability.In addition, graphene oxide can be reacted with H, c h bond is generated, magnesium is reduced Alloy base material reacts the hydrogen (Mg+2H generated with water2O=Mg (OH)2+H2), inhibit hydrogen to the unfavorable shadow of magnesium alloy to a certain degree It rings, improves magnesium alloy stress corrosion resistant.But since graphene oxide and metallic matrix binding force are poor, tend not to stable deposit In metal base surface, so being added in coating generally as coating corrosion inhibiter or bridging agent, to improve the corrosion-resistant of coating Performance and stability.
Meanwhile three kinds of silane, phytic acid and the graphene oxide ingredients used in the present invention, it is mainly used in medical instrument neck Domain.By integrating the different function of three kinds of coating compositions, to just be able to achieve of the present invention with stress corrosion resistant and oneself The coating of repair function.
The present invention has the following advantages and effects with respect to the prior art:
(1) the purpose of the invention is to medical magnesium alloy provide the good physical shielding layer of one layer of biocompatibility with It prevents from corroding, with the self-repair function in physiological environment, realize because in medical magnesium alloy implantation process, plastic deformation is made At surface covering destruction or micro-crack, and have inhibit magnesium alloy stress corrosion inclination ability.The self-repair function applies Layer includes degradable magnesium Base Metal matrix and coatings.Wherein: the medical magnesium-base metal include degradable pure magnesium and Magnesium alloy, and hydroxylating processing, the matrix as coating are carried out in advance；The self-repair function coating by silane coupling agent, Three kinds of corrosion inhibiter of phytic acid and graphene oxide are mixed with, and are coated in substrate surface, heat treatment for solidification, which is formed, has anti-answer Power corrodes self-repair function coating.
(2) present invention pre-processes magnesium-base metal using hydroxylating, for medical magnesium-base metal in implantation process, because of outside Mechanical damage or implantation material plasticity deformation, cause surface covering to form micro-crack or local defect.The present invention is with chemical bonded refractory The good combination of coating and matrix and the self-repair function of coating are realized in conjunction, chelation reaction and amide reaction, are realized in physiology Long-term corrosion-resistant stability in corrosive environment；It is anti-to improve to realize that coating inhales hydrogen and corrosion inhibitive function by addition graphene oxide Stress corrosion performance；And the effective protection coating production with good biocompatibility.
(3) present invention is to realize the stress corrosion resistant and self-repair function of coating, good using biocompatibility and can The ingredient degraded in vivo, coating include three kinds of silane coupling agent, phytic acid and graphene oxide ingredients；Certainly using coating method preparation Repair function coating；Air drying, curing process obtains stress corrosion resistant self-repair function coating in constant-temperature vacuum case.
(4) present invention considers medical magnesium alloy implantation material in clinical medical, and the plastic deformation and magnesium of generation are closed Stress corrosion inclination existing for gold is proposed to be improved the corrosion resistance of magnesium alloy using self-repair function coating and inhibits stress rotten Lose sensibility.
(5) magnesium-base metal of the invention is as medical embedded property device material, using good biocompatibility and can review one's lessons by oneself Material is as coating material.
(6) process of preparing of coating of the present invention is simple, easily operated, and the anchoring strength of coating obtained is good, biofacies Capacitive is excellent, has self-reparing capability in physiological environment, can be improved and effectively stablizes protection.
Detailed description of the invention
Fig. 1 is the surface surface sweeping electron microscope of the self-repair function coating prepared in embodiment 1.
Fig. 2 is the self-regeneration in embodiment 1 with coating, and corrosion tendency gradually decreases, be expressed as corrosion potential by The schematic diagram gradually shuffled.
Fig. 3 is that coatings before and after the processing answer by the aerial slow strain rate tension stress of magnesium alloy in embodiment 1 Varied curve figure (i.e. coating influences magnesium alloy substrates tensile mechanical properties).
Fig. 4 is that magnesium alloy compares the slow strain in air and simulated body fluid to coatings before and after the processing in embodiment 1 Rate tensile stress-strain curve diagram.
Fig. 5 is stress corrosion resistant coatings and phytic acid+silane coating sample dynamic potential polarization curve in comparative example 1 With slow strain rate test stress-strain curve diagram；Wherein, figure a is stress corrosion resistant coatings and phytic acid+silane The dynamic potential polarization curve of coating sample；Scheming b is stress corrosion resistant coatings and the slow strain of phytic acid+silane coating sample Rate tensile tests stress-strain diagram.
Fig. 6 is stress corrosion resistant coatings and graphene oxide+silane coating sample potentiodynamic polarization in comparative example 2 Curve and open circuit potential curve graph；Wherein, figure a is stress corrosion resistant coatings and graphene oxide+silane coating sample Dynamic potential polarization curve；Scheming b is stress corrosion resistant coatings and graphene oxide+silane coating sample open circuit potential Curve.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto. Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method and apparatus；Unless It illustrates, raw materials of the present invention, reagent can pass through commercially available acquisition.Hydroxide involved in the embodiment of the present invention Sodium, dehydrated alcohol, acetone, acetic acid, ammonium hydroxide are the chemical pure and above purity.
1, magnesium-base metal substrate is preferably extruded Magnesium Alloy substrate in the present invention, has good mechanical mechanics property, Steps are as follows for magnesium alloy pretreated in embodiment:
A) the advanced line of magnesium-base metal sample is cut, then successively with 400#, 800#, 1200#, 1500# and 2000# The polishing of silicon carbide silicon carbide paper mechanical grinding；
B) magnesium alloy after sanding and polishing is first washed with deionized water, then is cleaned by ultrasonic with analysis pure acetone, then wash, It is cleaned by ultrasonic again with dehydrated alcohol；
C) magnesium alloy substrate after cleaning is subjected to pickling with pickling solution or carries out alkali cleaning oil removing with alkali wash water, located at room temperature Reason 0.5~1 minute；Wherein, pickling solution is acetic acid and neutral sodium-salt mixed solution, can be the pure acetic acid of 200mg/mL concentration with The blend solution of the neutral sodium-salts such as the sodium chloride or sodium nitrate of 60mg/mL concentration；Alkali wash water is that sodium hydroxide and alkaline sodium salt are mixed Solution is closed, can be the blending of the alkaline sodium salts such as the pure cerium hydroxide sodium of 20mg/mL concentration and the pure phosphoric acid trisodium of 10mg/mL concentration Solution.
D) to pickling or alkali cleaning, treated magnesium alloy progress deionized water ultrasonic cleaning 10~15 minutes again, deionized water It rinses, the 60 DEG C of dryings of last vacuum oven are spare.
2,3- TSL 8330 (NH in the embodiment of the present invention2(CH2)3Si(OCH3)3, APTES, 98% matter Measure score) and phytic acid (C6H6(H2PO4)6, 70% mass fraction) and it is purchased from Aladdin Chinese companies；Graphene oxide is purchased from Chinese section Chengdu organic chemistry Co., Ltd, institute, purity are greater than 99%, and average diameter is 0.5~3 μm, and average height 0.55~ 1.2nm.Simulated body fluid is SBF simulated body fluid (sterile, to be purchased from LEAGENE company).
Embodiment 1
Selecting commercially available As-extruded WE43 magnesium alloy is substrate, prepares stress corrosion resistant in the Mg alloy surface and reviews one's lessons by oneself coating Process is as follows:
(1) it pre-processes: magnesium alloy (is carbonized with the polishing of the sand paper of 400#, 800#, 1200#, 1500# and 2000# respectively The polishing of silicon silicon carbide paper mechanical grinding), then rinsed with deionized water, it is then placed in acetone and is cleaned by ultrasonic 10 minutes, then spend Ionized water rinses, then carries out pickling 0.5 minute with the mixed solution of final concentration of 200mg/mL acetic acid and 60mg/mL sodium nitrate, Then it is cleaned by ultrasonic 10 minutes with deionized water, deionized water is rinsed, 60 DEG C of dryings of vacuum oven, for use.
(2) hydroxylating is handled: magnesium alloy obtained in step (1) is soaked in 50 DEG C of the sodium hydroxide solution of 5mol/L In 2 hours, carry out hydroxylating processing, obtain a large amount of basic hydroxide group in surface, then rinsed with deionized water.
(3) prepare coatings mixed solution: the solvent in coatings mixed solution is using 10% (volume point Number) deionized water and 90% (volume fraction) analyze straight alcohol；By 0.6g 3- TSL 8330,1.6g phytic acid It is respectively added slowly in the above-mentioned solvent of 100mL with 0.1g graphene oxide, every kind of ingredient ensures that former ingredient is mixed before being added It closes uniformly, using ultrasonic agitation, being kept stirring temperature is 25 DEG C, and it is 60 minutes that mixing time, which is added, in every kind of ingredient, is stirred in total Time is 180 minutes.Ammonium hydroxide and acetic acid is used to adjust mixed solution pH as 8 to get coatings mixed solution.
(4) prepare coatings: by hydroxylating obtained in step (2), treated that magnesium alloy is put into step (3) In obtained coatings mixed solution, after 25 DEG C of room temperature are impregnated 4 hours, proposed using 1mm/ minutes speed, and spend Ionized water rinses, and is subsequently placed in 30 DEG C drying 24 hours in vacuum oven.
(5) curing process: will extract sample obtained in step (4), be put into vacuum oven, vacuumize, 100 DEG C of dryings Curing process 1 hour, obtain stress corrosion resistant self-repair function coating sample (coating layer thickness is 4~8 μm).
It is standardized on coating with blade by stress corrosion resistant self-repair function coating (Fig. 1) prepared in the present embodiment Tool marks are placed in 37 DEG C of simulated body fluid, and distribution is taken out after impregnating 4 days and 7 days, and the observation of surface sweeping Electronic Speculum and shooting are in different reparations Time scratch area modification of surface morphology, discovery are obviously repaired at scratch when reaching 7 days repair time, are showed (Fig. 2) is gradually shuffled for the corrosion potential of coating sample.
It is tested by slow strain rate tension, using 10-6s-1Strain rate, obtain with/without coatings handle magnesium Alloy sample, in air with the stress corrosion fracture sensitivity tests result in simulated body fluid corrosive environment (without place The uncoated WE43 magnesium alloy of reason is control).Stress strain curve is found out from air, and the stress of magnesium alloy is answered after coating modified Varied curve is not much different with uncoated material, it is less to illustrate that coating influences magnesium alloy substrates tensile mechanical properties, such as Fig. 3).It is right Than the stress strain curve (such as Fig. 4) in air and simulated body fluid, the results showed that, by its stress of the modified sample of coatings Strain curve is substantially better than without the bare metal magnesium alloy materials modified by surface, illustrates that magnesium closes after coatings are handled Golden stress corrosion inclination is significantly lower than bare metal magnesium alloy, that is to say, that coatings significantly improve medical magnesium alloy and exist Stress corrosion resistant in physiological solution environment.
Embodiment 2
Selecting commercially available ZK40 magnesium alloy is substrate, prepares stress corrosion resistant in the Mg alloy surface and reviews one's lessons by oneself the process of coating such as Under:
(1) it pre-processes: magnesium alloy (is carbonized with the polishing of the sand paper of 400#, 800#, 1200#, 1500# and 2000# respectively The polishing of silicon silicon carbide paper mechanical grinding), then rinsed with deionized water, it is then placed in acetone and is cleaned by ultrasonic 10 minutes, then spend Ionized water rinses, then carries out pickling 0.5 minute with the mixed solution of 200mg/mL acetic acid and 60mg/mL sodium nitrate, then spends Ionized water is cleaned by ultrasonic 10 minutes, and deionized water is rinsed, 60 DEG C of dryings of vacuum oven, for use.
(2) hydroxylating is handled: magnesium alloy obtained in step (1) is soaked in 80 DEG C of the sodium hydroxide solution of 3mol/L In 1.5 hours, carry out hydroxylating processing, obtain a large amount of basic hydroxide group in surface, then rinsed with deionized water.
(3) prepare coatings mixed solution: the solvent in coatings mixed solution is using 5% (volume fraction) Deionized water and 95% (volume fraction) analyze straight alcohol.By 0.4g 3- TSL 8330,1.2g phytic acid and 60mg graphene oxide is respectively added slowly in the above-mentioned solvent of 100mL, and every kind of ingredient ensures that former ingredient mixes before being added Uniformly, using ultrasonic agitation, being kept stirring temperature is 35 DEG C, and it is 40 minutes, when stirring in total that mixing time, which is added, in every kind of ingredient Between be 120 minutes.Ammonium hydroxide and acetic acid is used to adjust mixed solution pH as 8 to get coatings mixed solution.
(4) coatings are prepared: will using desk-top sol evenning machine by coatings mixed solution obtained in step (3) Coatings mixed solution is spin-coated on sample (hydroxylating obtained in step (2) treated magnesium alloy) surface, is repeated 3 times Spin coating, each spin coating are rinsed with a thickness of 1~2.5 μm, then with deionized water, and it is small to be subsequently placed in 30 DEG C of dryings 24 in vacuum oven When.
(5) curing process: by the magnesium alloy sample after spin coating obtained in step (4), being put into vacuum oven, takes out true Sky, 120 DEG C of dry solidifications are handled 1 hour, obtain stress corrosion resistant self-repair function coating sample (coating layer thickness is 3~7 μm).
By stress corrosion resistant self-repair function coating prepared in the present embodiment, with blade on coating standardized tool marks, It is placed in 37 DEG C of simulated body fluid, distribution is taken out after impregnating 4 days and 7 days, and the observation of surface sweeping Electronic Speculum and shooting are in different repair times Scratch area modification of surface morphology, it is as a result same as Example 1.It is tested by slow strain rate tension, using 10-6s-1Strain Rate, obtain with/without coatings handle magnesium alloy sample, in air with the stress corrosion in simulated body fluid corrosive environment Fracture-sensitive test result, it is as a result same as Example 1.
Embodiment 3
Selecting commercially available AZ31 magnesium alloy is substrate, prepares stress corrosion resistant in the Mg alloy surface and reviews one's lessons by oneself the process of coating such as Under:
(1) it pre-processes: magnesium alloy (is carbonized with the polishing of the sand paper of 400#, 800#, 1200#, 1500# and 2000# respectively The polishing of silicon silicon carbide paper mechanical grinding), then rinsed with deionized water, it is then placed in acetone and is cleaned by ultrasonic 10 minutes, then spend Ionized water rinses, then carries out pickling 0.5 minute with the mixed solution of final concentration of 200mg/mL acetic acid and 60mg/mL sodium nitrate, Then it is cleaned by ultrasonic 10 minutes with deionized water, deionized water is rinsed, 60 DEG C of dryings of vacuum oven, for use.
(2) hydroxylating is handled: magnesium alloy obtained in step (1) is soaked in 80 DEG C of the sodium hydroxide solution of 3mol/L In 1.5 hours, carry out hydroxylating processing, obtain a large amount of basic hydroxide group in surface, then rinsed with deionized water.
(3) prepare coatings mixed solution: the solvent in coatings mixed solution is using 15% (volume point Number) deionized water and 85% (volume fraction) analyze straight alcohol.By 0.8g 3- TSL 8330,2g phytic acid and 50mg graphene oxide is respectively added slowly in the above-mentioned solvent of 100mL, and every kind of ingredient ensures that former ingredient mixes before being added Uniformly, using ultrasonic agitation, being kept stirring temperature is 30 DEG C, and it is 50 minutes, when stirring in total that mixing time, which is added, in every kind of ingredient Between be 150 minutes.Ammonium hydroxide and acetic acid is used to adjust mixed solution pH as 8 to get coatings mixed solution.
(4) prepare coatings: by hydroxylating obtained in step (2), treated that magnesium alloy is put into fills selfreparing In the reaction kettle of coating mixed solution, it is heated to 180 DEG C and maintains 3 hours, taken out after cooling.It is rinsed using deionized water, then It is placed in a vacuum drying oven 30 DEG C of dryings 24 hours.
(5) curing process: by sample obtained in step (4), being put into vacuum oven, vacuumize, 80 DEG C of dry solidifications Processing 1.5 hours obtains stress corrosion resistant self-repair function coating sample (coating layer thickness is 5~8 μm).
By stress corrosion resistant self-repair function coating prepared in the present embodiment, with blade on coating standardized tool marks, It is placed in 37 DEG C of simulated body fluid, distribution is taken out after impregnating 4 days and 7 days, and the observation of surface sweeping Electronic Speculum and shooting are in different repair times Scratch area modification of surface morphology, it is as a result same as Example 1.It is tested by slow strain rate tension, using 10-6s-1Strain Rate, obtain with/without coatings handle magnesium alloy sample, in air with the stress corrosion in simulated body fluid corrosive environment Fracture-sensitive test result, it is as a result same as Example 1.
Embodiment 4
Selection Mg-1Zn-1Ca magnesium alloy is substrate, prepares the process that stress corrosion resistant reviews one's lessons by oneself coating in the Mg alloy surface It is as follows:
(1) it pre-processes: magnesium alloy (is carbonized with the polishing of the sand paper of 400#, 800#, 1200#, 1500# and 2000# respectively The polishing of silicon silicon carbide paper mechanical grinding), then rinsed with deionized water, it is then placed in acetone and is cleaned by ultrasonic 10 minutes, then spend Ionized water rinses, then carries out pickling 0.5 minute with the mixed solution of final concentration of 200mg/mL acetic acid and 60mg/mL sodium nitrate, Then it is cleaned by ultrasonic 10 minutes with deionized water, deionized water is rinsed, 60 DEG C of dryings of vacuum oven, for use.
(2) hydroxylating is handled: magnesium alloy obtained in step (1) is soaked in 50 DEG C of the sodium hydroxide solution of 4mol/L In 2 hours, carry out hydroxylating processing, obtain a large amount of basic hydroxide group in surface, then rinsed with deionized water.
(3) mixed solution needed for preparing coatings: solvent uses 15% (volume in coatings mixed solution Score) deionized water and 85% (volume fraction) analyze straight alcohol.200mL solvent is divided into two equal portions: by 0.8g 3- aminopropan Base trimethoxy silane is added thereto in a 100mL solvent, prepares solution of silane；Again by 2g phytic acid and 50mg graphite oxide Alkene is added separately in other portion 100mL solvent, and every kind of ingredient ensures that former ingredient is uniformly mixed before being added.Using ultrasound Two kinds of solution are stirred, being kept stirring temperature is 30 DEG C, and it is 50 minutes that mixing time, which is added, in every kind of ingredient, and mixing time is in total 150 minutes.Use ammonium hydroxide and acetic acid to adjust two kinds of mixed solution pH as 8, be distributed solution of silane and phytic acid add graphene oxide Mixed solution.
(4) silane pretreatment: by hydroxylating obtained in step (2), treated that magnesium alloy is put into step (3) obtains Solution of silane in, at 25 DEG C of room temperature, after impregnating 4 hours, by the taking-up of 1mm/ minutes speed.And rinsed again with deionized water, very 30 DEG C drying 24 hours, place into vacuum oven, vacuumize in empty drying box, 100 DEG C of dry solidifications handle 1 hour to get To silane pretreatment sample.
(5) it prepares coatings/curing process: by silane pretreatment sample obtained in step (4), being put into step (3) in phytic acid obtained in and graphene oxide mixed solution, at 25 DEG C of room temperature, after impregnating 4 hours, by 1mm/ minutes speed It takes out.And rinsed again with deionized water, 30 DEG C drying 24 hours, place into vacuum oven, vacuumize in vacuum oven, and 80 DEG C dry solidification is handled 1.5 hours, is obtained stress corrosion resistant self-repair function coating sample (coating layer thickness is 5~9 μm).
By stress corrosion resistant self-repair function coating prepared in the present embodiment, with blade on coating standardized tool marks, It is placed in 37 DEG C of simulated body fluid, distribution is taken out after impregnating 4 days and 7 days, and the observation of surface sweeping Electronic Speculum and shooting are in different repair times Scratch area modification of surface morphology, it is as a result same as Example 1.It is tested by slow strain rate tension, using 10-6s-1Strain Rate, obtain with/without coatings handle magnesium alloy sample, in air with the stress corrosion in simulated body fluid corrosive environment Fracture-sensitive test result, it is as a result same as Example 1.
Comparative example 1
Selecting commercially available AZ31 magnesium alloy is substrate, prepares phytic acid+silane coating and this method respectively in the Mg alloy surface The stress corrosion resistant of invention reviews one's lessons by oneself coating, and process is as follows:
(1) it pre-processes: magnesium alloy (is carbonized with the polishing of the sand paper of 400#, 800#, 1200#, 1500# and 2000# respectively The polishing of silicon silicon carbide paper mechanical grinding), then rinsed with deionized water, it is then placed in acetone and is cleaned by ultrasonic 10 minutes, then spend Ionized water rinses, then carries out pickling 0.5 minute with the mixed solution of final concentration of 200mg/mL acetic acid and 60mg/mL sodium nitrate, Then it is cleaned by ultrasonic 10 minutes with deionized water, deionized water is rinsed, 60 DEG C of dryings of vacuum oven, for use.
(2) hydroxylating is handled: magnesium alloy obtained in step (1) is soaked in 60 DEG C of the sodium hydroxide solution of 5mol/L In 1 hour, carry out hydroxylating processing, obtain a large amount of basic hydroxide group in surface, then rinsed with deionized water.
(3) phytic acid+solution of silane and stress corrosion resistant coatings mixed solution are prepared: phytic acid+silane coating and anti- The solvent of stress corrosion coatings all uses 15% (volume fraction) deionized water and 85% (volume fraction) to analyze pure second Alcohol.200mL solvent is divided into two equal portions: 0.6g 3- TSL 8330 and 1.5g phytic acid are added separately to it In middle portion 100mL solvent, phytic acid+silane mixture solution is prepared.0.6g 3- TSL 8330,1.5g are planted Acid and 80mg graphene oxide are added separately in other portion 100mL solvent, and every kind of ingredient ensures former ingredient before being added It is uniformly mixed, prepares stress corrosion resistant coatings mixed solution.Using two kinds of solution of ultrasonic agitation, being kept stirring temperature is 30 DEG C, it is 50 minutes that mixing time, which is added, in every kind of ingredient, and mixing time is respectively 100 and 150 minutes in total.Using ammonium hydroxide and vinegar It is 8 that acid, which adjusts two kinds of mixed solution pH, obtains phytic acid+solution of silane and stress corrosion resistant coatings mixed solution respectively.
(4) prepares coating: by hydroxylating obtained in step (2), treated that magnesium alloy sample is respectively put into step (3) Obtained in phytic acid+solution of silane and stress corrosion resistant coatings mixed solution, all use 25 DEG C of room temperature, it is small to impregnate 4 Shi Hou is taken out by 1mm/ minutes speed, and is rinsed with deionized water, and it is small to be subsequently placed in 30 DEG C of dryings 24 in vacuum oven When, vacuum oven is placed into, is vacuumized, 100 DEG C of dry solidifications handle 1 hour and handle sample to get to phytic acid+silane coating With stress corrosion resistant self-repair function coating sample；Wherein, phytic acid+silane coating with a thickness of 4~7 μm, review one's lessons by oneself by stress corrosion resistant Multiple functional coating is with a thickness of 4~8 μm.
By phytic acid+silane coating and stress corrosion resistant self-repair function coating sample prepared in this comparative example, use The difference of electro-chemical test corrosion resistance and anti-stress corrosion performance between the two, such as Fig. 5.It can be seen from Fig. 5a that anti- Its corrosion electric current density of stress corrosion coatings is lower than phytic acid+silane coating an order of magnitude, from Fig. 5 b slow strain rate In tension test, tensile strength and elongation after fracture improve 20.5% and 49.13% relative to phytic acid+silane coating sample. Illustrate that its corrosion resistance of stress corrosion resistant coatings prepared by the present invention and stress corrosion resistant ability are significantly higher than to be free of Phytic acid+silane coating of graphene oxide.
Comparative example 2
Select commercially available ZK40 magnesium alloy be substrate, the Mg alloy surface prepare respectively silane+graphite oxide ene coatings and The stress corrosion resistant of present method invention reviews one's lessons by oneself coating, and process is as follows:
(1) it pre-processes: magnesium alloy (is carbonized with the polishing of the sand paper of 400#, 800#, 1200#, 1500# and 2000# respectively The polishing of silicon silicon carbide paper mechanical grinding), then rinsed with deionized water, it is then placed in acetone and is cleaned by ultrasonic 10 minutes, then spend Ionized water rinses, then carries out pickling 0.5 minute with the mixed solution of final concentration of 200mg/mL acetic acid and 60mg/mL sodium nitrate, Then it is cleaned by ultrasonic 10 minutes with deionized water, deionized water is rinsed, 60 DEG C of dryings of vacuum oven, for use.
(2) hydroxylating is handled: magnesium alloy obtained in step (1) is soaked in 70 DEG C of the sodium hydroxide solution of 4mol/L In 40 minutes, carry out hydroxylating processing, obtain a large amount of basic hydroxide group in surface, then rinsed with deionized water.
(3) silane+graphene oxide solution and stress corrosion resistant coatings mixed solution: silane+oxidation stone are prepared The solvent of black ene coatings and stress corrosion resistant coatings all uses 10% (volume fraction) deionized water and 90% (volume point Number) analysis straight alcohol.200mL solvent is divided into two equal portions: 0.6g 3- TSL 8330 and 100mg are aoxidized Graphene is added separately in a copy of it 100mL solvent, prepares silane+graphene oxide mixed solution.By 0.6g 3- amino Propyl trimethoxy silicane, 1.5g phytic acid and 100mg graphene oxide are added separately in other portion 100mL solvent, and every kind Ingredient ensures that former ingredient is uniformly mixed before being added, prepare stress corrosion resistant coatings mixed solution.It is stirred using ultrasound Two kinds of solution are mixed, being kept stirring temperature is 30 DEG C, and it is 50 minutes that mixing time, which is added, in every kind of ingredient, and mixing time is respectively in total 100 and 150 minutes.Using ammonium hydroxide and acetic acid to adjust two kinds of mixed solution pH is 8, respectively acquisition silane+graphene oxide solution With stress corrosion resistant coatings mixed solution.
(4) coatings are prepared: using treated the magnesium alloy sample of hydroxylating obtained in step (2) as substrate, Spin-coating method prepares coating.Silane+graphene oxide solution obtained in step (3) and stress corrosion resistant coatings are mixed Mixing liquid is spin-coated on specimen surface by solution, desk-top sol evenning machine, is repeated 3 times spin coating, then rinsed with deionized water, is subsequently placed in 30 DEG C drying 24 hours in vacuum oven.Vacuum oven is placed into, is vacuumized, 100 DEG C of dry solidifications handle 1 hour, i.e., Obtain silane+graphene oxide coating treatment sample and stress corrosion resistant self-repair function coating sample；Wherein, silane+oxidation stone Black ene coatings are 4~7 μm with a thickness of 3~6 μm and stress corrosion resistant self-repair function coating layer thickness.
By silane+graphite oxide ene coatings and stress corrosion resistant self-repair function coating examination prepared in this comparative example Sample, using the electro-chemical test difference between corrosion resistance and coatings ability, such as Fig. 6 between the two.From Fig. 6 a As can be seen that its corrosion electric current density of stress corrosion resistant coatings is significantly lower than silane+graphite oxide ene coatings, from Fig. 6 b In open circuit potential test, its corrosion potential of stress corrosion resistant coatings is gradually shuffled, and indicates the self-regeneration of coating, and silicon Alkane+graphite oxide ene coatings open circuit potential is not shuffled substantially, illustrates that its self-reparing capability is weaker.Synthesis obtains, of the invention Its corrosion resistance of the stress corrosion resistant coatings of preparation and self-reparing capability are significantly higher than silane+graphene oxide and apply Layer.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of preparation method of medical magnesium-base metal stress corrosion resistant self-repair function coating, which is characterized in that including as follows Step:
(1) medical magnesium-base metal is pre-processed, removal processing residual and surface adjunct obtain pretreated medical magnesium Base Metal；
(2) pretreated medical magnesium-base metal obtained in step (1) is soaked in the sodium hydroxide solution of 1~5mol/L Hydroxylating processing is carried out, is then washed, hydroxylating is obtained treated medical magnesium-base metal；
(3) 1. silane coupling agent, phytic acid and graphene oxide are added in solvent, ultrasonic agitation uniformly, and adjusts pH value to 6 ~10, obtain corrosion inhibiter A；Then corrosion inhibiter A is coated to hydroxylating obtained in step (2) treated medical magnesium-base metal Surface, wash, vacuum drying then carries out curing process under the conditions of placing it in 80~120 DEG C, and it is anti-to obtain medical magnesium-base metal Stress corrosion self-repair function coating；
Either:
2. silane coupling agent is added in solvent, ultrasonic agitation uniformly, and adjusts pH value to 6~10, obtains corrosion inhibiter B；It will Phytic acid and graphene oxide are added in solvent, and ultrasonic agitation uniformly, and adjusts pH value to 6~10, obtain corrosion inhibiter C；Then Corrosion inhibiter B is coated to hydroxylating obtained in step (2) treated the surface of medical magnesium-base metal, is washed, vacuum drying, Curing process is carried out under the conditions of being placed in 80~120 DEG C again, the medical magnesium-base metal after obtaining silane pretreatment；Finally by corrosion inhibiter C is coated to the surface of the medical magnesium-base metal after silane pretreatment, and washing after vacuum drying, places it in 80~120 DEG C of conditions Lower carry out curing process obtains medical magnesium-base metal stress corrosion resistant self-repair function coating.
2. the preparation method of medical magnesium-base metal stress corrosion resistant self-repair function coating according to claim 1, special Sign is:
Step (3) 1. and 2. described in silane coupling agent be methyltrimethoxysilane, γ-(2,3- glycidoxy) propyl In trimethoxy silane, methyltriethoxysilane, ethyl orthosilicate silane and 3- TSL 8330 at least It is a kind of；
Step (3) 1. and 2. described in solvent be mixed solvent that water and ethyl alcohol are mixed to get.
3. the preparation method of medical magnesium-base metal stress corrosion resistant self-repair function coating according to claim 2, special Sign is:
Step (3) 1. and 2. described in silane coupling agent be 3- TSL 8330；
Step (3) 1. and 2. described in solvent be grouped as by following group: 5~20% (v/v) water and 80~95% (v/v) second Alcohol.
4. the preparation method of medical magnesium-base metal stress corrosion resistant self-repair function coating according to claim 1, special Sign is:
The concentration of sodium hydroxide solution described in step (2) is 2~5mol/L；
Step (3) 1. described in corrosion inhibiter A in the concentration of silane coupling agent be 4~20mg/mL, the concentration of phytic acid is 2~ 20mg/mL, the concentration of graphene oxide are 0.5~5mg/mL；
Step (3) 2. described in corrosion inhibiter B in silane coupling agent concentration be 4~20mg/mL；
Step (3) 2. described in corrosion inhibiter C in the concentration of phytic acid be 2~20mg/mL, the concentration of graphene oxide is 0.5~ 5mg/mL。
5. the preparation method of medical magnesium-base metal stress corrosion resistant self-repair function coating according to claim 1, special Sign is that pretreatment described in step (1) is achieved by the steps of:
Medical magnesium-base metal is polished with sand paper, and is rinsed with deionized water；It is then placed in acetone and/or dehydrated alcohol ultrasonic Cleaning, and rinsed with deionized water；It is cleaned with pickling solution or alkali wash water, and is cleaned by ultrasonic with deionized water again；Finally 60 ± 5 It is dried in vacuo under the conditions of DEG C, obtains pretreated medical magnesium-base metal；
Described is successively to be polished with the sand paper of 400#, 800#, 1200#, 1500# and 2000# with sand paper polishing；
The time being cleaned by ultrasonic in acetone that is put into is 10~15 minutes；
The time being cleaned by ultrasonic in dehydrated alcohol that is put into is 10~15 minutes；
The pickling solution is the mixed solution that acetic acid and neutral sodium-salt are mixed to get；The neutral sodium-salt is sodium chloride or nitre Sour sodium；The concentration of acetic acid is 160~240mg/mL in the mixed solution, and the concentration of neutral sodium-salt is 40~60mg/mL；
The time cleaned with pickling solution or alkali wash water is 0.5~1 minute；
The alkali wash water is sodium hydroxide and the mixed solution that alkaline sodium salt is mixed to get；The alkaline sodium salt is tricresyl phosphate Sodium, sodium carbonate or sodium bicarbonate；In the mixed solution concentration of sodium hydroxide be 20~40mg/mL, alkaline sodium salt it is dense Degree is 10~20mg/mL；
The time being cleaned by ultrasonic with deionized water is 10~15 minutes.
6. the preparation method of medical magnesium-base metal stress corrosion resistant self-repair function coating according to claim 1, special Sign is:
Step (3) 1. and 2. described in applied to one of extraction, spin-coating method and hydro-thermal method；
The extraction is achieved by the steps of: by treated the medical magnesium-base metal of hydroxylating obtained in step (2) It is put into corrosion inhibiter A, B or C, is impregnated 2~4 hours under the conditions of 25 DEG C；
The spin-coating method is achieved by the steps of: corrosion inhibiter A, B or C are spun at hydroxylating obtained in step (2) Medical magnesium-base metal surface after reason, each spin coating with a thickness of 1~2.5 μm, repeat 2~3 times；
The hydro-thermal method is achieved by the steps of: by treated the medical magnesium-base metal of hydroxylating obtained in step (2) It is put into corrosion inhibiter A, B or C, is heated to 150~200 DEG C, keep the temperature 3~6 hours.
7. the preparation method of medical magnesium-base metal stress corrosion resistant self-repair function coating according to claim 1, special Sign is,
Medical magnesium-base metal described in step (1) is WE43 magnesium alloy, ZK40 magnesium alloy, AZ31 magnesium alloy or Mg-1Zn-1Ca Magnesium alloy；
Step (3) 1. and 2. described in the average diameter of graphene oxide be 0.5~3 μm, 0.55~1.2nm of average height；
Step (3) 1. and 2. described in adjusting pH value be that pH value is adjusted to 8 using acetic acid and ammonium hydroxide.
8. the preparation method of medical magnesium-base metal stress corrosion resistant self-repair function coating according to claim 1, special Sign is:
The condition of the processing of hydroxylating described in step (2) are as follows: 50~80 DEG C are handled 0.5~2 hour；
Step (3) 1. and 2. described in the temperature of ultrasonic agitation be 25~35 DEG C；
Step (3) 1. described in ultrasonic agitation time be 90~200 minutes；
Step (3) 2. described in obtain corrosion inhibiter B needed for mixing time be 30~60 minutes；
Step (3) 2. described in obtain corrosion inhibiter C needed for mixing time be 60~120 minutes；
Step (3) 1. and 2. described in time of curing process be 0.5~2 hour；
Step (3) 1. and 2. described in vacuum drying condition are as follows: 30 DEG C drying 24 hours.
9. a kind of medical magnesium-base metal stress corrosion resistant self-repair function coating, it is characterised in that: pass through claim 1~8 times Method described in one is prepared.
10. the preparation method of medical magnesium-base metal stress corrosion resistant self-repair function coating according to any one of claims 1 to 8 Preparing the application in biomedical metallic material.
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