CN103526261A - Preparation method of zinc-containing micro-arc oxidation electrolyte and zinc-containing biological ceramic membrane - Google Patents
Preparation method of zinc-containing micro-arc oxidation electrolyte and zinc-containing biological ceramic membrane Download PDFInfo
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Abstract
The invention relates to a method for preparing a zinc-containing biological ceramic membrane on the surface of titanium or magnesium metal through a micro-arc oxidation technology. The method comprises the steps of preparing soluble zinc and calcium-containing electrolyte, and implementing plasma pulse high energy electro discharge treatment in the prepared zinc and calcium electrolyte by taking the titanium or magnesium metal as an anode and taking stainless steel as a cathode through control on pulse voltage, frequency, duty ratio and other micro-arc oxidation parameters, thus generating the zinc and calcium-containing ceramic membrane with bioactivity on the surface of the titanium or magnesium metal. The biological membrane not only is degradable in a human body but also has functions of resisting bacteria, promoting cell growth and the like. The formation of the biological ceramic membrane can remarkably improve biocompatibility and bioactivity of titanium or magnesium metal in a living body, and can effectively overcome shortcomings of titanium or magnesium metal as a biomedical material. The raw materials adopted by the method are environment-friendly, and are free from toxicity and pollution; according to the method, the preparation process is simple, the operation is convenient, the production efficiency is high and the membrane is applicable to industrial production.
Description
Technical field
The present invention relates to a kind of novel method of preparing bioactive ceramics film at titanium alloy and Mg alloy surface, this bioactive ceramics film not only has the good mechanical property of metallic substance, the low wearing and tearing of stupalith, corrosion resistant advantage, and make body material by 'inertia', become " activity " material in vivo.Be specially adapted to the surface modification of hard tissue repair or replacement material (as artificial prosthesis, Steel Plate For Fixation Of Fracture etc.), can effectively improve the problem that exists in the titanium alloy use procedure of using clinically at present (as infected, joint loosening etc. in early days) and magnesium alloy and not mate a difficult problem of being obstructed in clinical application because of degradation rate and bone reparation speed.
Background technology
As tissue repair and alternative biomaterial, at medical field, there is very important status, especially at orthopaedics, orthopedics, decorative sursery, Stomatological Department and neurocranial surgery, bringing into play especially extremely important effect, as the reparation of fracture, the displacement of joint prosthesis etc.Fast development along with economic society, the sclerous tissues's damage being caused by wound, infection or tumour etc. is increasing, the raising of living standards of the people simultaneously, people are more and more higher to the requirement of hard tissue repair and equivalent material, and these factors force researchist to seek outward appearance and the more superior biomaterial of performance.
Infection is biomaterial graft failure major cause in vivo, also be the biggest problem of the puzzlement doctor of Clinical Surgery, this is wherein both relevant with the misoperation in operation, also change with embedded material position local environment, affect microbial growth, increased the possibility that bacterium infects, therefore, if itself has had anti-microbial activity biomaterial, not only can reduce planting body inflammation occurs, improve the biological activity of embedded material, shorten bone healing time, enter postoperative organization healing, improve the success ratio of operation, alleviate the burden of patient on spirit and material, and effectively overcome the series of problems that antibiotic a large amount of use causes.
Zine ion active antibacterial mechanism: bacterium is conventionally electronegative, the zine ion of positively charged can dissociate out gradually, while arriving cytolemma, by coulombic force, the two mortise, zine ion permeates cell membranes, enter cell, react with the sulfydryl in cell, make protein denaturation, thereby cell is lost division growth ability and death; Zine ion can also destroy microorganisms electric transmission system, respiratory system and transport of substances system; After thalline is killed, zine ion out contacts with other bacterium colonies by sedimentation equilibrium is free again, carries out new round killing bacteria, goes round and begins again.So, in the antimicrobial products such as adhesive bandage, added very early zinc oxide as anti-biotic material and wound astringent matter abroad, and obtained good result.
Calcium constituent is one of important Body composition, generally always with calcium ion form, exists, and calcium ion is the indispensable ion of the every physiological activity of body.It is for the membrane potential that maintains cytolemma, nerve conduction, and the contraction of muscle and diastolic function, the synthetic of the activity of regulatory enzyme and neurotransmitter and hormone all plays an important role with discharging etc.Calcium is very large at people's in-vivo content, and the overwhelming majority is all in existence and bone and tooth, and because the inorganic components in osseous tissue is mainly calcium phosphate salt, and calcium, phosphonium ion play a very important role in the metabolism of osseous tissue.Therefore, scholars expect to carry out bio-modification by calcium, phosphonium ion are incorporated into biomaterial surface.
Tradition hard tissue substituting and internal fixation material as stainless steel and other metal materials wear resistance and biocompatibility poor, easily aging, and Young's modulus is large, easily produces " stress shielding ", causes osteoporosis and fracture delayed union, has limited its clinical application; And the macromolecular materials such as poly(lactic acid) due to physical strength and abrasion resistance properties poor, be difficult to bear larger heavy burden; The wear resisting property that stupalith is as good in although silicon carbide ceramics has, mechanical property itself is too poor, is easy to chippingly, in the making of artificial joint prosthesis, is difficult to obtain widespread use.Titanium or titanium alloy is one of most widely used embedded material clinically at present, its relative density is little, physical strength is high, corrosion-resistant and anti-fatigue performance is good, but titanium and alloy material thereof are " biologically inert " material, biological activity is poor, to lack bone inductive effect, do not exist strong chemical to be combined with surrounding tissue be field of planting one of unsolved difficult problem always, many problems in implant into body, have also been brought, as fracture delayed union, Aseptic Loosening etc.
Magnesium and alloy material thereof are in density, Young's modulus, physical strength aspect and human skeleton are extremely approaching, there is the unrivaled high-performance of other biological material, the more important thing is, magnesium and alloy material thereof have degradability, if be applied to clinical, by the problem of avoiding current orthopaedics implant to need second operation to take out, greatly alleviated patient's misery, Ye Wei family and society have alleviated burden simultaneously, it is a kind of ideal biomaterial, but magnesium alloy degradation speed in the physiological environment of human body is too fast, degradation speed does not mate with speed of fracture union..By in its surface modification being the focus of studying at present.
In view of traditional biological surface treatment technology of material exists the bonding strength of coating and matrix low as plasma spraying and electrochemical deposition etc., the problems such as coating uniformity and the more difficult control of stability, and differential arc oxidization technique has high-efficiency environment friendly, easy to operate, coatings and substrate bonding strength is high, can by high temperature sintering and discharge breakdown effect, form the advantages such as porous ceramics coated material that contain required function element at coatingsurface, therefore the present invention mainly adopts differential arc oxidization technique to process titanium alloy and magnesium alloy, effectively improve the bonding strength of coatings and substrate, obtain the titanium with efficient bio-active and anti-microbial property simultaneously, magnesium antibiotic bioactive anti-bacteria ceramic film.
In view of traditional differential arc oxidation electrolytic solution contains hazardous and noxious substances mostly, can not be absorbed in vivo, can cause environmental pollution, the problem such as expensive.Develop a kind of nontoxic, can degradation in vivo, safety non-toxic after absorption of human body, and environmental protection, free of contamination electrolytic solution be current differential arc oxidization technique urgent problem, Zinc Gluconate, calglucon are a kind of have nutritive value, compounds absorbed by the body.Zine ion has effect antibiotic and promotion tissue growth, and in human body, synthetic and activation and the zinc of plurality of enzymes is closely related.Calcium ion has the multiple biological activitys such as blood coagulation, participates in action potential, the Muscle contraction of cell, maintains acid base equilibrium in body, and both are abundant at people's in-vivo content, are bringing into play extremely important effect in maintaining the vital movement of body.
Summary of the invention
Poor with magnesium alloy biocompatibility and the biological activity with potential potential applicability in clinical practice for overcoming the titanium alloy using clinically at present, wear-resisting and corrosion resistance nature is not good, without shortcomings such as antibiotic bioactives, the present invention proposes and a kind ofly at hard tissue repair and replacement material titanium alloy and Mg alloy surface preparation, there is the method for multiple bioactive ceramics film and the electrolytic solution using thereof.
The object of the invention is in view of traditional hard tissue substituting and internal fixation material as stainless steel and other metal materials wear resistance and biocompatibility poor, easily aging, and Young's modulus is large, easily produces " stress shielding ", causes osteoporosis and fracture delayed union; And the macromolecular materials such as poly(lactic acid) due to physical strength and abrasion resistance properties poor, be difficult to bear larger heavy burden; The wear resisting property that stupalith is as good in although silicon carbide ceramics has; but the mechanical property of itself is too poor; be easy to chipping; and titanium and alloy material thereof are " biologically inert " material; there is the problems such as biological activity and biocompatibility be poor, as fracture delayed union, Aseptic Loosening etc.; In view of in traditional biological process for treating surface, exist biological activity element bonding strength low simultaneously, equipment and complex procedures, expensive, the shortcoming that environmental pollution is heavy.
For addressing the above problem, in the present invention, adopt differential arc oxidization technique to carry out modification to the titanium alloy of routine clinical use and the Mg alloy surface with potential source biomolecule application prospect, at titanium alloy and Mg alloy surface preparation, there is the multiple bioactive porous bio-ceramic films such as antibiotic, this bioceramic film can make up titanium alloy biological activity and the poor shortcoming of bone inducibility of clinical application, also can effectively improve the corrosion resisting property of magnesium alloy.The degradation speed of magnesium alloy and the healing rate of fracture are matched.This bioceramic film can be applicable to the surface modification of bone fracture plate, screw, the damaged packing material of artificial prosthesis and sclerous tissues.
Technical scheme of the present invention: take titanium alloy and magnesium alloy as matrix, the electrolytic solution that utilization contains Zinc Gluconate and calglucon, adopt differential arc oxidization technique to carry out surface modification to titanium alloy and magnesium alloy, in its Surface Creation porous and be rich in broad-spectrum antimicrobial antiseptic elements zinc and the bioactive ceramics film of biological activity element calcium, phosphorus.
This invention has following feature.
(1) propose a kind ofly at titanium alloy and Mg alloy surface, to pass through differential arc oxidization technique, prepared multiple bioactive bioceramic films such as having antibiotic and the growth of promotion histocyte concurrently, this bioceramic film can be applicable to joint prosthesis, the surface modification of the biomaterials such as bone fracture plate, screw or sclerous tissues's replacement and reparation.
(2) propose a kind of differential arc oxidation electrolytic solution, this electrolytic solution is mainly comprised of Zinc Gluconate and calglucon etc., is the compound of body supplementing energy, is easily absorbed by the body, and safety non-toxic, is the compound using as electrolytic solution first.
(3) the bioactive ceramics film that utilizes the method to prepare at titanium alloy and Mg alloy surface, dense structure by surperficial vesicular structure and deep layer forms, and rete and metallic matrix mortise, not only kept metallic substance mechanical property and the low wearing and tearing of stupalith well, corrosion resistant advantage, and porous surface and the ceramic membrane that is rich in biological activity element have overcome the matrix metal material feature of 'inertia' in vivo greatly.
The present invention includes following steps.
The pre-treatment of step 1, sample: the pre-treatment of described sample comprises oil removing, grinding and buffing.
Oil removing: the capable cleaning of sample after line being cut by alkali lye; Titanium alloy and magnesium alloy sample are immersed in 5-10% sodium hydroxide solution, soak after 15-20 minute and take out, with tap water, rinse to remove the sodium hydroxide solution of remained on surface.
Polishing: titanium alloy and magnesium alloy sample after surface degreasing are polished; Use successively the sand papering of 200#, 400#, 600#, 800#, 1000#, 1500#, 2000#.
Polishing: the titanium alloy after surface finish and magnesium alloy sample carry out polishing, makes the smooth finish of specimen surface reach Ra and is less than 0.8.
Step 2, cleaning: first the sample having polished puts into the beaker that fills acetone, by ultrasonic cleaning after 30 minutes, putting into the beaker that fills dehydrated alcohol, by ultrasonic cleaning 30 minutes, finally pass through deionized water ultrasonic cleaning 30 minutes, put into 60 ℃ of oven for drying, obtain pretreated sample.
Step 3, differential arc oxidation: titanium alloy and magnesium alloy are carried out to differential arc oxidation processing, concrete grammar: pretreated sample is immersed in differential arc oxidation electrolytic solution completely, usings titanium alloy and magnesium alloy as anode, using be greater than sample stainless steel as negative electrode; The voltage of differential arc oxidation is pulsed voltage; In differential arc oxidation process, by agitator, electrolytic solution is stirred, and by condenser, control the temperature of electrolytic solution, in whole differential arc oxidation process, control the temperature of electrolytic solution below 25 ℃; Processing parameter in differential arc oxidation process is: current density is 3-6A/dm
2, dutycycle is 10-30, and frequency is 500-800Hz, and oxidization time is 2-30min, anode cathode separation 30-60mm.
The invention allows for a kind of electrolytic solution for the preparation of described titanium alloy ceramic coating formed by micro-arc oxidation method, by Zinc Gluconate, calglucon, sodium phosphate, sodium hydroxide and Trisodium Citrate, formed, wherein their content is: Zinc Gluconate is 3-6g/L, and calglucon is 3-6g/L, sodium phosphate 3-5g/L, sodium hydroxide 3-6g/L Trisodium Citrate is 1-2g/L, all the other are deionized water, described Zinc Gluconate, calglucon, sodium phosphate, sodium hydroxide and Trisodium Citrate are analytical pure.
The invention allows for a kind of electrolytic solution for the preparation of described magnesium alloy differential arc oxidation ceramic membrane method, Zinc Gluconate, calglucon, sodium phosphate, sodium hydroxide and EDTA, consist of, wherein their content is: Zinc Gluconate is 2-5g/L, and calglucon is 2-4g/L, sodium phosphate 3-6g/L, sodium hydroxide 3-6g/L, EDTA is 1-2g/L, all the other are deionized water, described Zinc Gluconate, calglucon, sodium phosphate, sodium hydroxide and EDTA are analytical pure.
Differential arc oxidation electrolytic solution in the present invention has following characteristics.
(1) Zinc Gluconate and calglucon are soluble compound, are to supplement on the market at present the common compound of the required zinc element of body and calcium constituent, can be absorbed by the body, and safety non-toxic; Containing environmentally harmful material, be environmental protection electrolytic solution, to environment without any pollution.
(2) ceramic membrane that utilizes this electrolytic solution to prepare at titanium alloy and Mg alloy surface contains broad-spectrum antimicrobial element zinc, can reduce material and implant the risk that the bacterium that causes infects, and improves the success ratio of operation.
(3) ceramic membrane that utilizes this electrolytic solution to prepare at titanium alloy and Mg alloy surface contains biologically actived calcium and phosphoric, can improve the biological activity of titanium alloy and magnesium alloy, aspect the biocompatibility of shortening healing time and raising prosthese and osseous tissue, play an important role.
The preparation of electrolytic solution.
Titanium alloy: required deionized water is divided into three parts, Zinc Gluconate dissolves a, calglucon dissolves a, sodium phosphate, sodium hydroxide and Trisodium Citrate dissolve a, treat described Zinc Gluconate, calglucon, sodium phosphate, after sodium hydroxide and Trisodium Citrate dissolve respectively completely, stirring and evenly mixing.
Magnesium alloy: required deionized water is divided into three parts, and Zinc Gluconate dissolves a, and calglucon dissolves a, sodium phosphate, sodium hydroxide and EDTA dissolve a, treat described Zinc Gluconate, calglucon, sodium phosphate, after sodium hydroxide and EDTA dissolve respectively completely, stirring and evenly mixing.
Embodiment
Embodiment 1.
The present embodiment is by differential arc oxidization technique, at titanium alloy surface, to prepare the method for bioceramic film, and handled titanium alloy is TC4 titanium alloy, and sample is processed to the disk of 25mm * 1mm, and the concrete steps of the present embodiment are.
The surface preparation of step 1, titanium sample: the pre-treatment of described sample comprises oil removing, polishing, polishing.
Oil removing: the capable cleaning of sample after line being cut by alkali lye; Titanium alloy sample is immersed in 5-10% sodium hydroxide solution, soak after 15-20 minute and take out, with tap water, rinse to remove the sodium hydroxide solution of remained on surface.
Polishing: the titanium alloy sample after surface degreasing is polished; Use successively the sand papering of 200#, 400#, 600#, 800#, 1000#, 1500#, 2000#.
Polishing: the titanium alloy sample after surface finish carries out polishing, makes the smooth finish of specimen surface reach Ra and is less than 0.8.
Step 2, cleaning: first the sample having polished puts into the beaker that fills acetone, by ultrasonic cleaning after 30 minutes, putting into the beaker that fills dehydrated alcohol, by ultrasonic cleaning 30 minutes, finally pass through deionized water ultrasonic cleaning 30 minutes, put into 60 ℃ of oven for drying, obtain pretreated sample.
Step 3, differential arc oxidation: titanium alloy is carried out to differential arc oxidation processing, specifically: utilize micro drill to bore a diameter for 2mm circular hole on titanium alloy sample top, in drill hole, fix the titanium wire of 2.0mm, tighten in case contact position has space to occur electricity sparking; Pretreated titanium alloy sample is immersed in differential arc oxidation electrolytic solution, usings titanium alloy as anode, using be greater than sample stainless steel substrates as negative electrode; The voltage of differential arc oxidation is pulsed voltage; In differential arc oxidation process, by agitator, electrolytic solution is stirred, and by condenser, control the temperature of electrolytic solution, in whole differential arc oxidation process, control the temperature of electrolytic solution below 25 ℃; Processing parameter in differential arc oxidation process is: current density is 6A/dm
2, dutycycle is 30%, and frequency is 600Hz, and oxidization time is 10min, anode cathode separation 60mm; At specimen surface, form the fine and close ceramic coating uniformly of one deck; With tap water, clean the ceramic coating obtain, after removing the residual electrolytic solution on this ceramic coating surface, dry up, obtain the sample after differential arc oxidation.
The invention allows for a kind of electrolytic solution for the preparation of described titanium alloy differential arc oxidation biological ceramics membrane method, by Zinc Gluconate, Trisodium Citrate, sodium phosphate and sodium hydroxide, formed, wherein their content is: Zinc Gluconate is 5g/, sodium phosphate 5g/L, sodium hydroxide 6g/L, Trisodium Citrate 2g/L, all the other are deionized water; Described Zinc Gluconate, Trisodium Citrate, sodium phosphate and sodium hydroxide are analytical pure.
The preparation of differential arc oxidation electrolytic solution: get 1L deionized water, weigh the required main ionogen of experiment, then 1L distilled water is divided in two beakers, in one, add ionogen Zinc Gluconate, in one, add ionogen sodium phosphate, sodium hydroxide and Trisodium Citrate, be placed in magnetic stirring apparatus and stir respectively, until ionogen dissolves completely and is uniformly dispersed, after by phosphoric acid sodium, the solution of sodium hydroxide and Trisodium Citrate is poured in the solution that contains calglucon, be placed on magnetic stirring apparatus and stir, until after two solution fully mix, the electrolytic solution configuring is put into electrolyzer and carry out differential arc oxidation.
Embodiment 2.
The present embodiment is by differential arc oxidization technique, at titanium alloy surface, to prepare the method for bioceramic film, and handled titanium alloy is TC4 titanium alloy, and sample is processed to the disk of 25mm x 1mm.The concrete steps of the present embodiment are.
The surface preparation of step 1, titanium sample: the pre-treatment of described sample comprises oil removing, polishing, polishing.
Oil removing: the capable cleaning of sample after line being cut by alkali lye; Titanium alloy sample is immersed in 5-10% sodium hydroxide solution, soak after 15-20 minute and take out, with tap water, rinse to remove the sodium hydroxide solution of remained on surface.
Polishing: the titanium alloy sample after surface degreasing is polished; Use successively the sand papering of 200#, 400#, 600#, 800#, 1000#, 1500#, 2000#.
Polishing: the titanium alloy sample after surface finish carries out mechanical polishing, makes the smooth finish of specimen surface reach Ra and is less than 0.8.
Step 2, cleaning: first the sample having polished puts into the beaker that fills acetone, by ultrasonic cleaning after 30 minutes, putting into the beaker that fills dehydrated alcohol, by ultrasonic cleaning 30 minutes, finally pass through deionized water ultrasonic cleaning 30 minutes, put into 60 ℃ of oven for drying, obtain pretreated sample.
Step 3, differential arc oxidation: titanium alloy is carried out to differential arc oxidation processing, specifically: utilize micro drill to bore a 2mm circular hole on titanium alloy sample top, in drill hole, fix the titanium wire of 2.0mm, tighten in case contact position has space to occur electricity sparking; Pretreated titanium alloy sample is immersed in differential arc oxidation electrolytic solution, usings titanium alloy as anode, using be greater than sample stainless steel substrates as negative electrode; The voltage of differential arc oxidation is pulsed voltage; In differential arc oxidation process, by agitator, electrolytic solution is stirred, and by condenser, control the temperature of electrolytic solution, in whole differential arc oxidation process, control the temperature of electrolytic solution below 25 ℃; Processing parameter in differential arc oxidation process is: current density is 6A/dm
2, dutycycle is 30%, and frequency is 600Hz, and oxidization time is 10min, anode cathode separation 60mm; At specimen surface, form the fine and close ceramic coating uniformly of one deck; With tap water, clean the ceramic coating obtain, after removing the residual electrolytic solution on this ceramic coating surface, dry up, obtain the sample after differential arc oxidation.
The invention allows for a kind of electrolytic solution for the preparation of described titanium alloy differential arc oxidation biological ceramics membrane method, by Zinc Gluconate, calglucon, Trisodium Citrate, sodium phosphate and sodium hydroxide, formed, wherein their content is: Zinc Gluconate is 3g/L, calglucon is 3g/L, sodium phosphate 5g/L, sodium hydroxide 6g/L, Trisodium Citrate 2g/L, all the other are deionized water, and described Zinc Gluconate, calglucon, Trisodium Citrate, sodium phosphate and sodium hydroxide are analytical pure.
The preparation of differential arc oxidation electrolytic solution: get 1L deionized water, weigh the required main ionogen of experiment, then 1L distilled water is divided in three beakers, in one, add ionogen Zinc Gluconate, in one, add ionogen calglucon, in last, add ionogen sodium phosphate, sodium hydroxide and Trisodium Citrate, be placed in magnetic stirring apparatus and stir respectively, until ionogen dissolves completely and is uniformly dispersed, after three kinds of solution are mixed, be placed on magnetic stirring apparatus and stir, until after two solution fully mix, the electrolytic solution configuring is put into electrolyzer and carry out differential arc oxidation.
Embodiment 3.
The present embodiment is by differential arc oxidization technique, at Mg alloy surface, to prepare the method for bioceramic film.Handled magnesium alloy is AZ91 magnesium alloy, and sample is processed to the disk of 35mm * 1mm.The concrete steps of the present embodiment are.
The surface preparation of step 1, magnesium alloy sample: the pre-treatment of described sample comprises oil removing, polishing, polishing.
Oil removing: the capable cleaning of sample after line being cut by alkali lye; Magnesium alloy sample is immersed in 5-10% sodium hydroxide solution, soak after 15-20 minute and take out, with tap water, rinse to remove the sodium hydroxide solution of remained on surface.
Polishing: the magnesium alloy sample after surface degreasing is polished; Use successively the sand papering of 200#, 400#, 600#, 800#, 1000#, 1500#, 2000#.
Polishing: the magnesium alloy sample after surface finish carries out mechanical polishing, makes the smooth finish of specimen surface reach Ra and is less than 0.8.
Step 2, cleaning: first the sample having polished puts into the beaker that fills acetone, by ultrasonic cleaning after 30 minutes, putting into the beaker that fills dehydrated alcohol, by ultrasonic cleaning 30 minutes, finally pass through deionized water ultrasonic cleaning 30 minutes, put into 60 ℃ of oven for drying, obtain pretreated sample.
Step 3, differential arc oxidation: magnesium alloy is carried out to differential arc oxidation processing, specifically: utilize micro drill on magnesium alloy sample top, to bore a diameter 2mm circular hole, in drill hole, fix the magnesium line of 2.0mm, tighten in case contact position has space to occur electricity sparking; Pretreated titanium alloy sample is immersed in differential arc oxidation electrolytic solution, usings magnesium alloy as anode, using be greater than sample stainless steel substrates as negative electrode; The voltage of differential arc oxidation is pulsed voltage; In differential arc oxidation process, by agitator, electrolytic solution is stirred, and by condenser, control the temperature of electrolytic solution, in whole differential arc oxidation process, control the temperature of electrolytic solution below 25 ℃; Processing parameter in differential arc oxidation process is: current density is 6A/dm2, and dutycycle is 30%, and frequency is 600Hz, and oxidization time is 10min, anode cathode separation 60mm.; At specimen surface, form the fine and close ceramic coating uniformly of one deck; With tap water, clean the ceramic coating obtain, after removing the residual electrolytic solution on this ceramic coating surface, dry up, obtain the sample after differential arc oxidation.
The invention allows for a kind of electrolytic solution for the preparation of described magnesium alloy differential arc oxidation biological ceramics membrane method, by Zinc Gluconate, sodium phosphate, sodium hydroxide and EDTA, formed, wherein their content is: Zinc Gluconate is 3g/, sodium phosphate is 5g/L, sodium hydroxide is 6g/L, EDTA is 2g/L, and all the other are deionized water, and described Zinc Gluconate, sodium phosphate, sodium hydroxide and EDTA are analytical pure.
The preparation of differential arc oxidation electrolytic solution: get 1L deionized water, weigh the required main ionogen of experiment, then 1L distilled water is divided in two beakers, in one, add ionogen Zinc Gluconate, in one, add ionogen sodium phosphate, sodium hydroxide and EDTA, be placed in magnetic stirring apparatus and stir respectively, until ionogen dissolves completely and is uniformly dispersed, after by the two mixing, be placed on magnetic stirring apparatus and stir, until after two solution fully mix, the electrolytic solution configuring is put into electrolyzer and carry out differential arc oxidation.
Embodiment 4.
The present embodiment is by differential arc oxidization technique, at Mg alloy surface, to prepare the method for bioceramic film.Handled magnesium alloy is AZ91 magnesium alloy, and sample is processed to the disk of 35mm * 1mm.The concrete steps of the present embodiment are.
The surface preparation of step 1, magnesium alloy sample: the pre-treatment of described sample comprises oil removing, polishing, polishing.
Oil removing: the capable cleaning of sample after line being cut by alkali lye; Magnesium alloy sample is immersed in 5-10% sodium hydroxide solution, soak after 15-20 minute and take out, with tap water, rinse to remove the sodium hydroxide solution of remained on surface.
Polishing: the magnesium alloy sample after surface degreasing is polished; Use successively the sand papering of 200#, 400#, 600#, 800#, 1000#, 1500#, 2000#.
Polishing: the magnesium alloy sample after surface finish carries out mechanical polishing, makes the smooth finish of specimen surface reach Ra and is less than 0.8.
Step 2, cleaning: first the sample having polished puts into the beaker that fills acetone, by ultrasonic cleaning after 30 minutes, putting into the beaker that fills dehydrated alcohol, by ultrasonic cleaning 30 minutes, finally pass through deionized water ultrasonic cleaning 30 minutes, put into 60 ℃ of oven for drying, obtain pretreated sample.
Step 3, differential arc oxidation: magnesium alloy is carried out to differential arc oxidation processing, specifically: utilize micro drill on magnesium alloy sample top, to bore a diameter 2mm circular hole, in drill hole, fix the magnesium line of 2.0mm, tighten in case contact position has space to occur electricity sparking; Pretreated titanium alloy sample is immersed in differential arc oxidation electrolytic solution, usings titanium alloy as anode, using be greater than sample stainless steel substrates as negative electrode; The voltage of differential arc oxidation is pulsed voltage; In differential arc oxidation process, by agitator, electrolytic solution is stirred, and by condenser, control the temperature of electrolytic solution, in whole differential arc oxidation process, control the temperature of electrolytic solution below 25 ℃; Processing parameter in differential arc oxidation process is: current density is 6A/dm
2, dutycycle is 30%, and frequency is 600Hz, and oxidization time is 10min, anode cathode separation 60mm; At specimen surface, form the fine and close ceramic coating uniformly of one deck; With tap water, clean the ceramic coating obtain, after removing the residual electrolytic solution on this ceramic coating surface, dry up, obtain the sample after differential arc oxidation.
The invention allows for a kind of electrolytic solution for the preparation of described titanium alloy differential arc oxidation biological ceramics membrane method, by Zinc Gluconate, calglucon, sodium phosphate, sodium hydroxide and EDTA, formed, wherein their content is: Zinc Gluconate is 3g/L, calglucon is 2g/L, sodium phosphate is 4g/L, and sodium hydroxide is 6g/L, and EDTA is 2g/L, all the other are deionized water, and described Zinc Gluconate, calglucon, sodium phosphate, sodium hydroxide and EDTA are analytical pure.
The preparation of differential arc oxidation electrolytic solution: get 1L deionized water, weigh the required main ionogen of experiment, then 1L distilled water is divided in three beakers, in one, add ionogen Zinc Gluconate, in one, add ionogen calglucon, in last, add ionogen sodium phosphate, sodium hydroxide and EDTA, be placed in magnetic stirring apparatus and stir respectively, until ionogen dissolves completely and is uniformly dispersed, after three is mixed, be placed on magnetic stirring apparatus and stir, until after two solution fully mix, the electrolytic solution configuring is put into electrolyzer and carry out differential arc oxidation.
Claims (6)
1. proposition is a kind of passes through differential arc oxidization technique at titanium alloy and Mg alloy surface, preparation has multiple bioactive bioceramic film concurrently, this bioceramic film can be applicable to joint prosthesis, the surface modification of sclerous tissues's replacements such as the outer volume repair materials of bone fracture plate, oral cavity and jaw face and repair materials, is characterized in that:
(1) electrolytic solution of this utilization is mainly comprised of Zinc Gluconate and calglucon etc., is the compound of body supplementing energy, is easily absorbed by the body, and safety non-toxic, is the compound using as differential arc oxidation electrolytic solution first;
(2) bioceramic film that utilizes differential arc oxidization technique to prepare, the bonding strength of titanium alloy bioceramic film and matrix is between 15MPa-25MPa; The bonding strength of magnesium alloy bioceramic film and matrix is between 8MPa-15MPa, and the bonding strength of this ceramic membrane, far above common coating, is one of feature of the tool incentive of this technology;
(3) this bioactive ceramics film, is comprised of surperficial vesicular structure and inner dense structure, the vesicular structure of its mesexine, the porosity of titanium alloy ceramic membrane surface between 15%-30%, aperture can regulate and control within the scope of 1 μ m-20 μ m; Fabrication of ceramic coat of magnesium alloy surface porosity factor between 10%-20%, aperture can regulate and control within the scope of 0.5 μ m-20 μ m, hole connectivity is good, be beneficial to histiocytic growing into, the thickness of rete can regulate and control between 10-30 μ m, can effectively stop the invasion of corroding ion in body fluid;
(4) the method is prepared the ceramic membrane containing biological activity element at titanium alloy and the Mg alloy surface of good mechanical performance, metallic substance mechanical property and the low wearing and tearing of stupalith well, corrosion resistant advantage have not only been kept, the more important thing is, vesicular structure and the introducing of being rich in bioactive element have overcome the matrix metal material feature of 'inertia' in vivo greatly;
(5) the porous bio-ceramic film containing elements such as zinc, calcium and phosphorus of preparing by differential arc oxidization technique, can effectively overcome the titanium alloy of current routine clinical use because implanting and take out caused infection, also can improve the joint that causes because titanium alloy biocompatibility the is poor complication such as loosening, fracture delayed union or disunion in early days, can improve the magnesium alloy problem that solidity to corrosion is poor under physiological environment, degradation rate is fast simultaneously;
(6) this bioactive ceramics film has degradability in human body, and degraded product is mainly zine ion and calcium ion, can be absorbed completely by human body, both can bring into play corresponding multiple biological activity, can supplement again the necessary trace element of body;
(7) this bioceramic film can be by the ratio of regulation and control correlation technique parameter (as voltage, time etc.) and each composition of electrolytic solution, regulates and controls the content of life elements in the structure (as the thickness of rete, porosity etc.) of ceramic film and rete;
(8) preparation of this bioactive ceramics film adopts differential arc oxidization technique, and required equipment is simple, safe and convenient to use; Material source is abundant, production efficiency is high; To environment nontoxic pollution-free, it is a kind of environmental protection treatment technology;
Bioactive ceramics film according to claim 1, is characterized in that: (1) body material is selected respectively titanium alloy and the magnesium alloy of good mechanical properties; (2) preparation of bioceramic film adopts differential arc oxidization technique; (3) electrolytic solution is comprised of biological absorbable compound Zinc Gluconate and calglucon etc.
2. bioactive ceramics film according to claim 1, is characterized in that comprising the following steps:
The surface preparation of step 1, titanium matrix and magnesium alloy comprises oil removing, grinding and buffing: oil removing: titanium alloy and magnesium alloy after by 5-10% sodium hydroxide solution, line being cut clean; Polishing: the titanium alloy after surface degreasing and the polishing of the magnesium alloy sample property entered; Use successively the sand papering of 200#, 400#, 600#, 800#, 1000#, 1500#, 2000#, 3000#; Polishing: titanium alloy and magnesium alloy sample that above-mentioned polishing is good carry out mechanical polishing, make specimen surface smooth finish reach Ra and are less than 0.8.
3. step 2, cleaning: first the titanium alloy having polished and magnesium alloy sample put into the beaker that fills acetone, by ultrasonic cleaning after 30 minutes, putting into the beaker that fills dehydrated alcohol, by ultrasonic cleaning 30 minutes, finally pass through deionized water ultrasonic cleaning 20 minutes, 60 ℃ of oven for drying, obtain pretreated titanium alloy and magnesium alloy sample.
4. biological activity anti-bacteria ceramic film according to claim 1, is characterized in that: titanium alloy differential arc oxidation basic electrolyte system is comprised of Zinc Gluconate, calglucon, Trisodium Citrate, sodium phosphate and sodium hydroxide; Magnesium alloy differential arc oxidation basic electrolyte system is comprised of Zinc Gluconate, calglucon, EDTA, sodium phosphate and sodium hydroxide.
5. biological activity anti-bacteria ceramic film according to claim 1, is characterized in that differential arc oxidation voltage is 200V-350V, and pulse-repetition is 500Hz-800Hz, oxidization time 2min-30min, and dutycycle is 10%-30%, anode cathode separation 30mm-60mm.
6. titanium alloy according to claim 1 and magnesium alloy bioactive ceramics film can be used for sclerous tissues's tissue replacement and the repair materials such as artificial prosthesis, bone fracture plate, skull and dental prosthetic material.
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| US20200214822A1 (en) * | 2017-09-30 | 2020-07-09 | Lifetech Scientific (Shenzhen) Co., Ltd | Implantable device |
| CN108486634A (en) * | 2018-04-20 | 2018-09-04 | 黄智慧 | A kind of preparation method of corrosion resistant type Mg alloy surface ceramic membrane materials |
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| EP3816327A1 (en) | 2019-06-25 | 2021-05-05 | Politechnika Slaska | The formation method of porous antibacterial coatings on titanium and titanium alloys surface |
| CN110685000A (en) * | 2019-11-11 | 2020-01-14 | 北京大学深圳研究生院 | High-corrosion-resistance coating, preparation method, electrolyte and application thereof |
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