CN101709496B - Micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coating - Google Patents
Micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coating Download PDFInfo
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- CN101709496B CN101709496B CN200910227391XA CN200910227391A CN101709496B CN 101709496 B CN101709496 B CN 101709496B CN 200910227391X A CN200910227391X A CN 200910227391XA CN 200910227391 A CN200910227391 A CN 200910227391A CN 101709496 B CN101709496 B CN 101709496B
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Abstract
The invention discloses a micro-arc oxidation-electrodeposition preparation method of a magnesium-based bioactive coating. The preparation method comprises the following steps: putting a magnesium-based base material in micro-arc oxidation electrolyte after pretreatment to perform micro-arc oxidation reaction to obtain a micro-arc oxidation coating sample; then, putting the micro-arc oxidation coating sample in electrodeposition electrolyte to perform electrodeposition reaction; and after electrodeposition, taking the sample out, and washing and drying the sample. The micro-arc oxidation-electrodeposition preparation method has the advantages that a biologic coating prepared by the method has high binding property with a base material; and the entire biologic coating has excellent corrosion resistance, bioactivity and compatibility; moreover, the formed bioactive coating is a composite coating (comprising HA, OCP, Mg3(PO3)2 and MgO); and because the composite coating comprises OCP, problems that the degradation of pure HA is difficult are avoided and only an HA crust is left after the degradation of formed magnesium alloy can be avoided.
Description
Technical field
The invention belongs to the bio-medical material preparation field, relate to the material surface paint-on technique, be specifically related to a kind of micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coating.
Background technology
Hard tissue implanting material is the important component part of biomaterial, because its wide application, demand are big, has become the focus of various countries scientific worker development research; The bio-medical metallic substance, have good biomechanical property, processing characteristics and reliability, be clinical application load embedded material the most widely, be used for clinical human body hard tissue repairing at present and comprised medical stainless steel, cobalt-base alloy, titanium alloy and shape memory alloy etc. with metallic substance.But As time goes on, the expansion of metal inside-fixture range of application, the shortcoming of himself also exposes gradually, stress shielding, electrolytic corrosion, material fracture, second operation taking-up and patient's mental burden increase or the like, so the research of the biomaterial of degradable absorption becomes the international research forward position and the focus of current technical field of biological material.
Because magnesium not only has the good mechanical performance, and nontoxic, can progressively degrade in vivo by corrosion, thereby magnesium and alloy thereof have the degradable implantable bioartificial material of development potentiality to be subjected to people's favor day by day as a kind of utmost point human body.
Magnesium and alloy thereof mainly contain the advantage of the following aspects as bio-medical material: (1) has excellent biomechanical compatibility.The density of magnesium and magnesium alloy is 1.7g/cm
3Density minimum in all structured materials is with the Compact bone density (1.75g/cm of human body
3) very approaching, far below the density (4.47g/cm of Ti-6Al-4V
3), meet the requirement of desirable Steel Plate For Fixation Of Fracture; Magnesium and magnesium alloy have high specific tenacity and specific rigidity.The Young's modulus of magnesium and alloy thereof is about 45GPa, more near the Young's modulus (20GPa) of people's bone, can provide stable mechanical environment at the union of fracture initial stage, reduce stress force shelter reaction gradually, make fracture site bear the stress stimulation of increase gradually and even physiological level, thereby healing acceleration prevents local osteoporosis and refracture.(2) has good biological characteristics.Magnesium ion can promote the deposition of calcium, and magnesium can be used to strengthen the conductivity of bone, reduces bone premature aging, osteoporosis, soft tissue calcification etc.(3) has the absorbable and degradable characteristic.Magnesium has very low standard potential, thereby magnesium and alloy thereof can be degraded under the effect of people's body fluid gradually, the magnesium ion that generates can excrete by when injected organism tissue absorption on every side or by body fluid, so needn't take out after implanting, avoids second operation to patient's body misery and economical load.
Ren Yibin etc., Song Guangling etc. have studied the corrosion behavior of pure magnesium in physiological saline, artificial body fluid respectively, and Witte etc. have inquired into magnesium alloy corrosion behavior in animal body, think to be expected to it is developed into new bio medical degradable embedded material.But the erosion resistance of magnesium and alloy is relatively poor, erosion rate is faster in the physiological environment that particularly be lower than 11.5 in the pH value, Cl-exists, the intravital pH value of people is about 7.4, in postoperative body metabolism absorption process, may cause secondary acidosis in the human body, make the pH value of internal milieu be lower than 7.4, so magnesium alloy in vivo can accelerated corrosion as embedded material.Though magnesium is the major element of human body, absorbing excessive magnesium ion also is deleterious to human body.On the other hand, degradable biomaterial require material degradation speed and organize new life or healing rate between mate, the reparation of osseous tissue generally needed for 12～18 weeks, and magnesium alloy is because corrode the too fast due bearing capacity that causes losing in advance, simultaneously, corrode too fast meeting and cause a large amount of hydrogen in the subcutis of implant site to have little time the diffusion absorption, thereby produce phenomenons such as inflammation, necrosis.
Can magnesium alloy become degradable hard tissue implanting material, and the security of material and the control of degradation rate are two primary conditions.To investigate on the one hand the degraded corrosion of mg-based material under physiological environment to host's physiology each side and to the influence of skeletonization, be exactly the erosion resistance that improves magnesium by alloying and surface modification on the other hand, the speed of its degradation rate and osseous tissue healing is adapted, improve the biocompatibility of embedded material simultaneously by surface modification.
Bio-medical material has characteristics separately, each tool advantage when clinical application, and be the emphasis and the focus of bio-medical composition research and development with the composite system of and structure designed in conjunction with the differing materials advantage.Since the eighties in 20th century, cause various countries scholar's attention gradually at medical metal substrate surface structure calcium phosphate salt biological coating material.This mainly is based on the reason of two aspects: at first, calcium phosphate salt are as hydroxyapatite (HA, molecular formula Ca
10(PO
4)
6(OH)
2), octocalcium phosphate (OCP), tricalcium phosphate (Ca
3(PO
4)
2), calcium phosphate(acid) (CaHPO
42H
2O) etc., they are similar to the inorganic components of humans and animals osseous tissue, maybe can change the inorganic components of osseous tissue into, so when as the top layer of sclerous tissues's implant when body tissue contacts on every side, the danger that intoxicating (cause inflammation, stimulate, allergy etc.) can not arranged as metal implant and cause suddenling change, and near the growth of osseous tissue can also inducing, forms firm bone bonding, show the biological activity of excellence; Secondly, simple calcium phosphate salt crystal fragility is big, folding strength is low, should not be used to carry the reparation and the replacement of sclerous tissues, and metallic substance (as titanium, titanium alloy, stainless steel etc.) then can remedy calcium phosphate salt implant physical strength defect of insufficient.So calcium phosphate salt/metal bioplex system combines the advantage that the calcium phosphate salt biological activity is good and the metal physical strength is high, be to be used for the class ideal material that humans and animals sclerous tissues damage back is repaired or replaced.
Have at present directly by plasma spraying (Chinese application number: 03117835.9,200510021026.5,200710064147.7), electrochemical deposition method (Chinese application number: 200410071505.3,200810049023.6) prepare biological coating such as hydroxyapatite at Mg alloy surface.But plasma spraying is a linear process, be difficult on complex-shaped and surface irregularity matrix, obtain the uniform coating of thickness, simultaneously because thermal expansion coefficient difference, HA coating meeting stress in the spraying postcooling process is concentrated and is cracked, and the spraying process temperature is too high in addition easily makes the HA decomposition cause HA degree of crystallinity low.The HA coating that the Constant Electric Current deposition obtains and the bonding strength of matrix magnesium alloy are lower, are easy to come off in the process of implanting.All there is the problem of consistency and mechanical stability respectively in other single technology; Because some extreme treatment condition make that biological coating is inhomogeneous or decompose that coating and matrix mechanical property do not match, excessive as thermal expansivity, Young's modulus difference, easily cause stress concentration; Bonding strength is not enough between coating and the substrate, causes disbonding, and coating can not effectively be brought into play the function of combine closely substrate and cambium.Therefore research and development have the new bio coated material system of the active antistripping of good biological, corrosion prevention ability and novel preparation method with necessary.
Had at present the people by differential arc oxidation and hydrothermal treatment consists at the surface preparation HA of titanium alloy biological coating, and prepare calcium microcosmic salt bioactive coating also without report by differential arc oxidation in conjunction with electrodip process at Mg alloy surface.
Summary of the invention
Purpose of the present invention is intended to the deficiency at single preparation technology, and a kind of micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coating is provided.
The objective of the invention is to be achieved through the following technical solutions:
A kind of micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coating may further comprise the steps:
(1) pre-treatment body material: magnesium base substrate material surface is polished, cleaned up, standby; Can adopt preconditioning technique commonly used as well known to those skilled in the art to the pre-treatment of magnesium base base material, can specifically press following process operation among the present invention: use 100
#, 200
#, 400
#, 600
#, 800
#, 1000
#After the SiC abrasive paper for metallograph polished body material successively, it was acetone/dehydrated alcohol mixing solutions ultrasonic cleaning 5～15min of 1: 1 that body material is placed volume ratio, is used for removing impurity and grease on the body material, and it is standby to clean the back natural drying at room temperature;
(2) preparation differential arc oxidation electrolytic solution: the aqueous solution that differential arc oxidation electrolytic solution is made up of each composition of following concentration: Na
3PO
40.06～0.19mol/L, NaOH 0.025～0.075mol/L;
(3) differential arc oxidation: with the magnesium base base material handled well in the step (1) is anode, stainless steel substrates is a negative electrode, anode and negative electrode be immersed under stirring at room, carry out the reaction of continuous current differential arc oxidation in the electrolytic solution for preparing in the step (2), two interpole gaps, 5～15cm wherein, response voltage 100～400V, reaction current 0.5～3A, dutycycle 10～15%, positive frequencies 600～800Hz, reaction times 1～60min is with reaction differential arc oxidation sample wash, drying for standby later;
(4) preparation galvanic deposit electrolytic solution: the aqueous solution that galvanic deposit electrolytic solution is made up of each composition of following concentration: H
2PO
4 -0.0046～0.046mol/L, NaNO
30.041～0.112mol/L, Ca
2+0.008～0.08mol/L, regulator solution pH value is 4.0～7.0, and when regulating the pH value, those skilled in the art can select for use conventional soda acid to regulate, and preferred mass concentration is rare HNO of 1～12% among the present invention
3Or (CH
2OH)
3CNH
2
(5) galvanic deposit: the differential arc oxidation sample that will form in step (3) is as the electrodeposit reaction negative electrode, graphite flake is an anode, the electrolytic solution for preparing in the step (4) is heated to 50～100 ℃, negative electrode and anode be immersed in carry out the continuous current electrodeposit reaction in the electrolytic solution, two interpole gaps, 2～10cm wherein, depositing current density 1～100mA/cm
2, depositing time 1～90min;
(6) will take out flushing, dry getting final product through step (5) deposition sample later.
For the coating that differential arc oxidation is obtained contains calcium, for follow-up electrodeposit reaction provides the calcic substrate, on the basis of above-mentioned differential arc oxidation electrolyte prescription, can further be optimized for: also contain alkaline calcium salt 0.01～0.015mol/L in the differential arc oxidation electrolytic solution described in the step (2).
Described alkaline calcium salt is CaCO
3, Ca (OH)
2Or its combination.Differential arc oxidation electrolytic solution is prepared before or after above-mentioned optimization among the present invention, and the pH value of gained electrolytic solution is generally within 11～13.
In the galvanic deposit electrolytic solution of step (4), described H
2PO
4 -Be selected from NH
4H
2PO
4, NaH
2PO
4In a kind of or its combination, described Ca
2+Be selected from anhydrous nitric acid calcium Ca (NO
3)
2, four water-calcium nitrate Ca (NO
3)
24H
2O, calcium acetate Ca (CH
3COO)
2In a kind of or its combination.
Described bioactive coating is to contain hydroxyapatite (HA), octocalcium phosphate Ca
8H (PO
4)
65H
2O (being called for short OCP), trimagnesium phosphate Mg
3(PO
4)
2Bioactivity composite coating with magnesium oxide MgO.
In the step (3), stir speed (S.S.) is 20～50 rev/mins during differential arc oxidation.
In step (3) and the step (6), the samples dried temperature is 40～60 ℃.
Described magnesium base is pure magnesium or magnesium alloy.
Described magnesium alloy is Mg-Zn base, Mg-Al base, Mg-Mn base or Mg-Ca base alloy.
Among the present invention, described room temperature all is meant 25 ℃, all is water flushings during the flushing sample, preferably, and preferred deionized water or distilled water.
Compared with prior art, the present invention has the following advantages:
(1) differential arc oxidation and other surface treatment method of Mg alloy relatively, its over-all properties is more suitable for the surface treatment of magnesium alloy in the bio-medical environment, it has following advantage: erosion resistance, wear resistance are good; Form metallurgical binding, difficult drop-off with matrix; Can form uneven surface in the metallic surface helps scleroblast and adheres to; Compare with common anodic oxidation treatment, very little to the fatigue strength reduction of material;
(2) the differential arc oxidation rear surface has vesicular structure, the calcium microcosmic salt that galvanic deposit is formed is longer than in the hole, form pinning, between calcium microcosmic salt biological coating and differential arc oxidation layer, form mechanical chimeric interface structure, thereby improve the bonding properties between calcium microcosmic salt coating and the base material, make it than the original single bonding force height of being longer than smooth alloy surface;
(3) performance of differential arc oxidation layer makes to have the mechanical mechanics property of coupling more between compound coating and the base material between medical metal and calcium microcosmic salt pottery;
(4) utilize the corrosion protection of differential arc oxidation layer to improve the corrosion resistance nature of compound system, simultaneously the calcium microcosmic salt by galvanic deposit carries out half sealing of hole to the hole on differential of the arc surface again, further improve whole corrosion resistance of coating, the class bone characteristic of calcium microcosmic salt makes osteocyte be more prone in the growth on its surface in addition, thereby has improved whole biological activity and consistency.
(5) bioactive coating of the inventive method formation is compound coating (HA+OCP+Mg
3(PO
3)
2+ MgO), because the existence of OCP, avoided the problem of pure HA degraded difficulty in the compound coating, avoid forming the magnesium alloy degraded and finished the problem that the HA shell only is left in the back.
Description of drawings
The XRD figure spectrum of single differential arc oxidation (a), single galvanic deposit (b) and micro-arc oxidation-electrodeposition of the present invention (c) preparation coating among Fig. 1: the embodiment 1;
Single differential arc oxidation (a) and micro-arc oxidation-electrodeposition of the present invention among Fig. 2: the embodiment 1 (b, c) the typical SEM figure of preparation coating;
The typical EDS figure of single differential arc oxidation (a) and micro-arc oxidation-electrodeposition of the present invention (b) preparation coating among Fig. 3: the embodiment 1;
Delineation method testing coating bonding strength among Fig. 4: the embodiment 1: micro-arc oxidation-electrodeposition of the present invention prepares 0 grade of coating (a); 2 grades of single prepared by electrodeposition coatings (b);
Magnesium alloy substrate among Fig. 5: the embodiment 1 (1), single differential arc oxidation sample (2) and the polarization curve of micro-arc oxidation-electrodeposition sample of the present invention (3) in simulated body fluid;
The XRD figure spectrum of single differential arc oxidation (a) and micro-arc oxidation-electrodeposition of the present invention (b) preparation coating among Fig. 6: the embodiment 4;
Single differential arc oxidation (a) and micro-arc oxidation-electrodeposition of the present invention among Fig. 7: the embodiment 4 (b, c) the SEM figure of preparation coating;
The polarization curve of micro-arc oxidation-electrodeposition sample of the present invention in simulated body fluid among Fig. 8: the embodiment 4.
Embodiment
The invention will be further described below in conjunction with embodiment, and listed embodiment is being to implement under the prerequisite with the technical solution of the present invention all, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Method at Mg-2wt%Zn alloy surface differential arc oxidization-prepared by electrodeposition bioactive coating may further comprise the steps:
(1) pre-treatment body material: use 100
#, 200
#, 400
#, 600
#, 800
#, 1000
#After the SiC abrasive paper for metallograph polished body material successively, it was acetone/dehydrated alcohol mixing solutions ultrasonic cleaning 10min of 1: 1 that body material is placed volume ratio, is used for removing impurity and grease on the body material, and it is standby to clean the back natural drying at room temperature;
(2) preparation differential arc oxidation electrolytic solution: the aqueous solution that differential arc oxidation electrolytic solution is made up of each composition of following concentration: Na
3PO
40.1mol/L, NaOH 0.05mol/L;
(3) differential arc oxidation: with the magnesium base base material handled well in the step (1) is anode, stainless steel substrates is a negative electrode, anode and negative electrode be immersed under stirring at room (35 rev/mins), carry out the reaction of continuous current differential arc oxidation in the electrolytic solution for preparing in the step (2), two interpole gap 10cm wherein, (response voltage is not continuing to rise before the starting the arc response voltage 100～250V, begin the starting the arc after reaching striking voltage, this moment, voltage still rose along with coating is more and more thicker always, tend towards stability at last), reaction current 1A, dutycycle 10%, positive frequencies 800Hz, reaction times 30min, with reaction differential arc oxidation sample later with deionized water rinsing after 50 ℃ of following drying for standby;
(4) preparation galvanic deposit electrolytic solution: the aqueous solution that galvanic deposit electrolytic solution is made up of each composition of following concentration: NH
4H
2PO
40.01mol/L, NaNO
30.08mol/L, Ca (NO
3)
24H
2O 0.04mol/L is rare HNO of 7% with mass concentration
3Or (CH
2OH)
3CNH
2Regulator solution pH value is 5.0;
(5) galvanic deposit: the differential arc oxidation sample that will form in step (3) is as the electrodeposit reaction negative electrode, graphite flake is an anode, the electrolytic solution for preparing in the step (4) is heated to 80 ℃, negative electrode and anode be immersed in carry out the continuous current electrodeposit reaction in the electrolytic solution, two interpole gap 6cm wherein, depositing current density 1mA/cm
2, depositing time 30min;
(6) will take out through step (5) deposition sample later, after rinsing well with deionized water, dry getting final product under 50 ℃.
Be the advantage of explanation micro-arc oxidation-electrodeposition composite preparation process of the present invention, after base material is carried out pre-treatment, carry out controlled trial by following 2 kinds of conditions respectively in the present embodiment: 1, keep carrying out single differential arc oxidation controlled trial under the identical differential arc oxidation electrolytic solution of the present embodiment condition identical with the differential arc oxidation test parameter; 2, keep carrying out single galvanic deposit controlled trial under the identical galvanic deposit electrolytic solution of the present embodiment condition identical with the galvanic deposit test parameter.
Fig. 1 is the XRD figure spectrum of single differential arc oxidation (a), single galvanic deposit (b) and micro-arc oxidation-electrodeposition of the present invention (c) preparation coating: as can be seen, mainly comprise Mg in the coating by single differential arc oxidation formation from Fig. 1 (a)
3(PO
4)
2With two kinds of materials of MgO, from Fig. 1 (b), as can be seen, be mainly HA in the coating by single galvanic deposit formation, and Ca has also appearred in the material that can see except figure (a) and scheme to occur in (b) in Fig. 1 (c)
8H (PO
4)
65H
2The spectrum peak of O (OCP).
Fig. 2 is single differential arc oxidation (a) and micro-arc oxidation-electrodeposition (b of the present invention, c) the typical SEM figure of preparation coating: from Fig. 2 (a) as can be seen, the surface of coating has been covered with micropore, this micropore influences to some extent to the erosion resistance performance of integral body, the crystal growth that also forms for galvanic deposit simultaneously provides the place, at Fig. 2 (b, c) can see the growth morphology that carries out the top coat of galvanic deposit behind the differential arc oxidation in, from Fig. 2 (b, c) in as can be seen, numerous strip deposited crystal deposit in the differential arc oxidation substrate, and a large amount of settlings, the recess of micropore are arranged in the micropore of differential arc oxidation, illustrate that calcium microcosmic salt that galvanic deposit forms has carried out half sealing of hole to the micropore of differential arc oxidation, both improve whole corrosion resistance nature, kept micropore again, kept bigger area, help combination with implant, for growing into of cambium provides passage, improved the biocompatibility of implant, the growth in the hole has simultaneously also improved Bond Strength of Coating greatly.
Fig. 3 is the typical EDS figure of single differential arc oxidation (a) and micro-arc oxidation-electrodeposition of the present invention (b) preparation coating: shown mainly among Fig. 3 (a) that the coatingsurface in single differential arc oxidation preparation has only Mg, P, O, Na, Zn element, and mainly shown among Fig. 3 (b) and Mg, P, O, Na, Ca element in the coating of micro-arc oxidation-electrodeposition, have occurred, by a large amount of Ca elements having occurred in two kinds of method bonded coatings, illustrated that bioactive calcium microcosmic salt exists.
Fig. 4 is a delineation method testing coating bonding strength: micro-arc oxidation-electrodeposition of the present invention prepares coating 0 grade of (a) and 2 grades of single prepared by electrodeposition coatings (b): in the present invention by having the bonding strength of scratch method testing coating now, from Fig. 4 (a) as can be seen, it is level and smooth fully that the micro-arc oxidation-electrodeposition legal system is equipped with the cut edge of coating, none lattice comes off, can be decided to be 0 grade to this Bond Strength of Coating grade, and single Constant Electric Current is deposited on the infall of otch or along notching edge coating shedding is arranged in Fig. 4 (b), influenced cross cut area is greater than 5%, so be decided to be 2 grades.Explanation prepares Bond Strength of Coating by micro-arc oxidation-electrodeposition and improves greatly.Further, recording single galvanic deposit gained Bond Strength of Coating by existing shear tension test is 17～19Mpa, micro-arc oxidation-electrodeposition gained Bond Strength of Coating 60～80Mpa.
Fig. 5 is magnesium alloy substrate (1), single differential arc oxidation sample (2), micro-arc oxidation-electrodeposition of the present invention prepares the polarization curve of coating (3) in simulated body fluid: can know that by trial curve the corrosion resistance of magnesium alloy of seeing by after two kinds of modifications can all increase, wherein obtain material by micro-arc oxidation-electrodeposition and improve 146mV than matrix corrosion current potential, corrosion electric current density reduces about 2 orders of magnitude.The coating of whole polarization curve explanation micro-arc oxidation-electrodeposition preparation has improved whole corrosion resistance nature by half sealing of hole effect of differential arc oxidation and galvanic deposit, and is stronger more stable to the provide protection of matrix, reached design purpose.
In sum, the bioactive coating of micro-arc oxidation-electrodeposition complex method of the present invention preparation is better than the coating of single differential arc oxidation and single prepared by electrodeposition from structure, has also remedied the not high shortcoming of Bond Strength of Coating of single prepared by electrodeposition simultaneously.
Method at Mg-3wt%Al alloy surface differential arc oxidization-prepared by electrodeposition bioactive coating may further comprise the steps:
(1) pre-treatment body material: use 100
#, 200
#, 400
#, 600
#, 800
#, 1000
#After the SiC abrasive paper for metallograph polished body material successively, it was acetone/dehydrated alcohol mixing solutions ultrasonic cleaning 5min of 1: 1 that body material is placed volume ratio, is used for removing impurity and grease on the body material, and it is standby to clean the back natural drying at room temperature;
(2) preparation differential arc oxidation electrolytic solution: the aqueous solution that differential arc oxidation electrolytic solution is made up of each composition of following concentration: Na
3PO
40.06mol/L, NaOH 0.025mol/L;
(3) differential arc oxidation: with the magnesium base base material handled well in the step (1) is anode, stainless steel substrates is a negative electrode, anode and negative electrode be immersed under stirring at room (20 rev/mins), carry out the reaction of continuous current differential arc oxidation in the electrolytic solution for preparing in the step (2), two interpole gap 5cm wherein, response voltage 200～350V, reaction current 0.5A, dutycycle 12%, positive frequencies 600Hz, reaction times 60min is with reaction differential arc oxidation sample wash, drying for standby later;
(4) preparation galvanic deposit electrolytic solution: the aqueous solution that galvanic deposit electrolytic solution is made up of each composition of following concentration: NaH
2PO
40.0046mol/L, NaNO
30.041mol/L, anhydrous Ca (NO
3)
20.008mol/L, be rare HNO of 1% with mass concentration
3Or (CH
2OH)
3CNH
2Regulator solution pH value is 4.0;
(5) galvanic deposit: the differential arc oxidation sample that will form in step (3) is as the electrodeposit reaction negative electrode, graphite flake is an anode, the electrolytic solution for preparing in the step (4) is heated to 50 ℃, negative electrode and anode be immersed in carry out the continuous current electrodeposit reaction in the electrolytic solution, two interpole gap 2cm wherein, depositing current density 60mA/cm
2, depositing time 90min;
(6) will take out through step (5) deposition sample later, after rinsing well with deionized water, dry getting final product under 40 ℃.
Method at pure magnesium (99.99wt%) alloy surface differential arc oxidization-prepared by electrodeposition bioactive coating may further comprise the steps:
(1) pre-treatment body material: use 100
#, 200
#, 400
#, 600
#, 800
#, 1000
#After the SiC abrasive paper for metallograph polished body material successively, it was acetone/dehydrated alcohol mixing solutions ultrasonic cleaning 15min of 1: 1 that body material is placed volume ratio, is used for removing impurity and grease on the body material, and it is standby to clean the back natural drying at room temperature;
(2) preparation differential arc oxidation electrolytic solution: the aqueous solution that differential arc oxidation electrolytic solution is made up of each composition of following concentration: Na
3PO
40.19mol/L, NaOH 0.075mol/L;
(3) differential arc oxidation: with the magnesium base base material handled well in the step (1) is anode, stainless steel substrates is a negative electrode, anode and negative electrode be immersed under stirring at room (50 rev/mins), carry out the reaction of continuous current differential arc oxidation in the electrolytic solution for preparing in the step (2), two interpole gap 15cm wherein, response voltage 250～400V, reaction current 3A, dutycycle 15%, positive frequencies 700Hz, reaction times 1min is with reaction differential arc oxidation sample wash, drying for standby later;
(4) preparation galvanic deposit electrolytic solution: the aqueous solution that galvanic deposit electrolytic solution is made up of each composition of following concentration: NH
4H
2PO
40.046mol/L, NaNO
30.112mol/L, Ca (CH
3COO)
20.08mol/L, be rare HNO of 12% with mass concentration
3Or (CH
2OH)
3CNH
2Regulator solution pH value is 7.0;
(5) galvanic deposit: the differential arc oxidation sample that will form in step (3) is as the electrodeposit reaction negative electrode, graphite flake is an anode, the electrolytic solution for preparing in the step (4) is heated to 100 ℃, negative electrode and anode be immersed in carry out the continuous current electrodeposit reaction in the electrolytic solution, two interpole gap 10cm wherein, depositing current density 100mA/cm
2, depositing time 1min;
(6) will take out through step (5) deposition sample later, after rinsing well with deionized water, dry getting final product under 60 ℃.
Be with the difference of embodiment 1: the aqueous solution that the differential arc oxidation electrolytic solution in the step (2) is made up of each composition of following concentration: Na
3PO
40.1mol/L, NaOH 0.05mol/L, CaCO
30.013mol/L; In the step (4), in the galvanic deposit electrolytic solution with Ca (NO
3)
24H
2O and anhydrous Ca (NO
3)
2Combination replaced C a (NO
3)
24H
2O, and concentration is respectively Ca (NO
3)
24H
2O 0.01mol/L, anhydrous Ca (NO
3)
20.03mol/L.
Be the variation that illustrates that micro-arc oxidation-electrodeposition composite preparation process of the present invention is taken place after optimizing differential arc oxidation electrolytic solution, keeping carrying out single differential arc oxidation controlled trial under the identical differential arc oxidation electrolytic solution of the present embodiment condition identical with the differential arc oxidation test parameter equally in the present embodiment after base material is carried out pre-treatment, the result is as follows:
Fig. 6 is the XRD figure spectrum of (a) and micro-arc oxidation-electrodeposition of the present invention (b) preparation coating behind the single differential arc oxidation: from Fig. 6 (a) as can be seen, compare with Fig. 1 (a) of embodiment 1, had more CaP in the coating that the differential arc oxidation electrolytic solution after this optimizes generates
4O
11And CaH
2P
2O
5Two spectrum peaks, differential arc oxidation electrolytic solution optimization be described after, promoted the formation of calcium salt in the coating behind the differential arc oxidation really, and from Fig. 6 (b) as can be seen in the coating of micro-arc oxidation-electrodeposition included product consistent with embodiment 1.
Record in the present embodiment micro-arc oxidation-electrodeposition gained Bond Strength of Coating also within 60～80Mpa by existing shear tension test.
Fig. 7 is single differential arc oxidation (a) and micro-arc oxidation-electrodeposition (b of the present invention, c) preparation coating the SEM shape appearance figure: in Fig. 7 (a) as can be seen white point-like pattern appears in coatingsurface except meeting, similar with Fig. 2 (a) result of embodiment 1, be covered with micropore equally, at Fig. 7 (b, c) can find in that the coating of micro-arc oxidation-electrodeposition preparation is compared with embodiment 1 result and also be there is no considerable change except the tabular crystal that forms is slightly different with the strip crystal among the embodiment 1.
Fig. 8 is that micro-arc oxidation-electrodeposition prepares the polarization curve of sample in simulated body fluid: as can be seen from Figure 8 its corrosion resistance nature is compared also with matrix (Fig. 5 (1)) and is increased.
Be with the difference of embodiment 2: be base material with Mg-2.5wt%Ca; The aqueous solution that differential arc oxidation electrolytic solution in the step (2) is made up of each composition of following concentration: Na
3PO
40.06mol/L, NaOH0.025mol/L, Ca (OH)
20.01mol/L.
Be with the difference of embodiment 3: be base material with Mg-2wt%Mn; The aqueous solution that differential arc oxidation electrolytic solution in the step (2) is made up of each composition of following concentration: Na
3PO
40.06mol/L, NaOH0.025mol/L, CaCO
30.008mol/L, Ca (OH)
20.007mol/L; In the step (4), in the galvanic deposit electrolytic solution with NH
4H
2PO
4And NaH
2PO
4Combination replace NH
4H
2PO
4, and concentration is respectively NH
4H
2PO
40.02mol/L, NaH
2PO
40.026mol/L, with Ca (NO
3)
24H
2O, anhydrous Ca (NO
3)
2And Ca (CH
3COO)
2Combination replaced C a (CH
3COO)
2, and concentration is respectively Ca (NO
3)
24H
2O0.01mol/L, anhydrous Ca (NO
3)
20.03mol/L, Ca (CH
3COO)
20.04mol/L.
Claims (6)
1. the micro-arc oxidation-electrodeposition preparation method of a magnesium-based bioactive coating is characterized in that may further comprise the steps:
(1) pre-treatment body material: magnesium base substrate material surface is polished, cleaned up, standby;
(2) preparation differential arc oxidation electrolytic solution: the aqueous solution that differential arc oxidation electrolytic solution is made up of each composition of following concentration: Na
3PO
40.06～0.19mol/L, NaOH 0.025～0.075mol/L;
(3) differential arc oxidation: with the magnesium base base material handled well in the step (1) is anode, stainless steel substrates is a negative electrode, anode and negative electrode be immersed under stirring at room, carry out the reaction of continuous current differential arc oxidation in the electrolytic solution for preparing in the step (2), two interpole gaps, 5～15cm wherein, response voltage 100～400V, reaction current 0.5～3A, dutycycle 10～15%, positive frequencies 600～800Hz, reaction times 1～60min is with reaction differential arc oxidation sample wash, drying for standby later;
(4) preparation galvanic deposit electrolytic solution: the aqueous solution that galvanic deposit electrolytic solution is made up of each composition of following concentration: H
2PO
4 -0.0046～0.046mol/L, NaNO
30.041～0.112mol/L, Ca
2+0.008～0.08mol/L, regulator solution pH value is 4.0～7.0;
(5) galvanic deposit: the differential arc oxidation sample that will form in step (3) is as the electrodeposit reaction negative electrode, graphite flake is an anode, the electrolytic solution for preparing in the step (4) is heated to 50～100 ℃, negative electrode and anode be immersed in carry out the continuous current electrodeposit reaction in the electrolytic solution, two interpole gaps, 2～10cm wherein, depositing current density 1～100mA/cm
2, depositing time 1～90min;
(6) will take out flushing, dry getting final product through step (5) deposition sample later;
Wherein, described bioactive coating is to contain hydroxyapatite, octocalcium phosphate, trimagnesium phosphate and magnesian bioactivity composite coating; In the step (3), stir speed (S.S.) is 20～50 rev/mins during differential arc oxidation; In step (3) and the step (6), the samples dried temperature is 40～60 ℃.
2. the micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coating as claimed in claim 1 is characterized in that: also contain alkaline calcium salt 0.01～0.015mol/L in the differential arc oxidation electrolytic solution described in the step (2).
3. the micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coating as claimed in claim 2, it is characterized in that: described alkaline calcium salt is CaCO
3, Ca (OH)
2Or its combination.
4. as the micro-arc oxidation-electrodeposition preparation method of any described magnesium-based bioactive coating of claim 1～3, it is characterized in that: in the galvanic deposit electrolytic solution of step (4), described H
2PO
4 -Be selected from NH
4H
2PO
4, NaH
2PO
4In a kind of or its combination, described Ca
2+Be selected from anhydrous Ca (NO
3)
2, Ca (NO
3)
24H
2O, Ca (CH
3COO)
2In a kind of or its combination.
5. as the micro-arc oxidation-electrodeposition preparation method of any described magnesium-based bioactive coating of claim 1～3, it is characterized in that: described magnesium base is pure magnesium or magnesium alloy.
6. the micro-arc oxidation-electrodeposition preparation method of magnesium-based bioactive coating as claimed in claim 5 is characterized in that: described magnesium alloy is Mg-Zn base, Mg-Al base, Mg-Mn base or Mg-Ca base alloy.
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