CN102605410A - Method for preparing bioactive composite film layer containing hydroxyapatite on titanium metal surface - Google Patents

Method for preparing bioactive composite film layer containing hydroxyapatite on titanium metal surface Download PDF

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CN102605410A
CN102605410A CN2012100763723A CN201210076372A CN102605410A CN 102605410 A CN102605410 A CN 102605410A CN 2012100763723 A CN2012100763723 A CN 2012100763723A CN 201210076372 A CN201210076372 A CN 201210076372A CN 102605410 A CN102605410 A CN 102605410A
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voltage
titanium metal
electrolytic solution
titanium
differential arc
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时惠英
马俊
王爱娟
蒋百灵
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Xian University of Technology
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Xian University of Technology
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Abstract

The invention provides a method for preparing a bioactive composite film layer containing hydroxyapatite on a titanium metal surface. The method comprises the following steps: preparing an electrolytic solution containing hydroxyapatite firstly; then applying voltage to the titanium metal through a power supply for low-voltage deposition and differential arc oxidation treatment, wherein at the low-voltage deposition stage: the voltage is controlled at 30V-120V and the deposition time is 5-20 minutes, and at the differential arc oxidation stage: the voltage is controlled at 450V-600V, the deposition time is 10 minutes and the frequency of the power supply is 200kHz, and the duty ratio is 10%; and growing a layer of HA (hydroxyapatite)-TiO2 composite ceramic layer on the surface of a titanium metal test sample after low-voltage deposition and differential arc oxidation. The method has the beneficial effects that the ceramic layer containing HA particles is prepared on the titanium test sample in the electrolyte solution, the process that the HA particles are deposited on the titanium metal test sample surface is simplified, and the content of HA in the film layer is changed through regulating the content of HA in the electrolyte solution or the deposition voltage and time.

Description

Surface of metal titanium prepares the method for the active composite film of hydroxyl apatite biological
Technical field
The invention belongs to titanium or titanium alloy implant surface treatment process technical field, relate to a kind of preparation titanium metal HA-TiO 2The method of composite film, concrete is, titanium or titanium alloy surface deposited hydroxyl apatite-titanium dioxide composite film layer, this rete is a kind of biological active materials, is mainly used in medical fields such as artificial skelecton, tooth.
Technical background
Titanium or titanium alloy has good biocompatibility and mechanical property as bio-medical material, is one of body implanting material of using always.But implant exists that biological activity is poor, bonding strength is low, and problem such as seriously corroded has limited further application clinically in physiological environment.
Mainly realize the bioactivation of surface of metal titanium at present, improve its bonding strength through surface coarsening through preparation bioactive coating and surface-treated.
Win 40350 (HA) is as typical bio-medical material, and its biological activity is high, is prone to form firm combining with osseous tissue; Therefore, preparation titanium base HA composite coating material can make it both have metallic substance HS and H.T., and good biological activity is arranged again; Implant and form direct chemical bond property between back and the osseous tissue and combine; It is stable in early days to help implant, and healing stage after the desmopyknosis has become the important content that bio-medical material is studied.
Adopt the composite coating material of method preparations such as vacuum plasma spray coating, laser deposition, electrophoretic deposition, ion enhanced sputtering, its result respectively has deficiency.Differential arc oxidization technique receives much concern in the biomaterial preparation in recent years; Document shows: through the titanium alloy surface of differential arc oxidation processing; Can obtain surface irregularity porous, inner compact layer and form the high firmness ceramic layer of metallurgical binding with matrix; And how HA is effectively introduced the focus that more becomes Recent study in the arc differential oxide ceramic layer, also be difficult point.Have the people to adopt differential arc oxidation or anodize to prepare the ceramic layer that is rich in the calcium phosphoric in the document, constant temperature soaks or through the synthetic processing of hydro-thermal, induces the formation of bone shape phosphatic rock in model fluid again; Some people then is after the differential arc oxidation pre-treatment, utilize electrophoretic deposition in its surface preparation the HA/TiO of about 15~20 μ m of one bed thickness 2Composite film.Though the employing aforesaid method can be prepared coarse and have certain bioactive surface, its complicated process of preparation, HA content is less in the rete, and subsequent handling also can cause the reduction of film-substrate cohesion.Therefore, seeking a kind of simple process at titanium or titanium alloy surface deposition HA coating is the key point of this technology large-scale application.
Summary of the invention
The purpose of this invention is to provide the method that a kind of surface of metal titanium prepares the active composite film of hydroxyl apatite biological, can be directly go out to cohere or coat HA particle, while to have kept the ceramic layer of film base bonding state preferably again in the titanium surface preparation.
The technical scheme that the present invention adopted is, surface of metal titanium prepares the method for the active composite film of hydroxyl apatite biological, and concrete operations are following:
Step 1, the preparation electrolytic solution
With concentration is that the phospho-glycerol calcium of 3~5g/L and lime acetate that concentration is 20~30g/L mix, and obtains mixture A, and the solvent among the mixture A is a zero(ppm) water; In mixture A, add sodium hydroxide again, regulating its PH is 11, obtains mixture B; Amount by 3g/L~12g/L adds Win 40350 in mixture B at last, promptly obtains electrolytic solution;
Step 2,
The titanium metal sample is put into the electrolytic solution that step 1 prepares; And titanium metal sample and positive source joined; Power cathode connects stainless steel plate, through power supply the titanium metal sample is applied voltage and carries out low pressure deposition and differential arc oxidation processing, and the corresponding relation of conduction time and voltage is:
The low pressure depositional phase: control voltage 30V~120V, depositing time 5~20min;
The differential arc oxidation stage: control voltage 450V~600V, depositing time 10min, the frequency of power supply is 200kHz, dutycycle is 10%;
After carrying out low pressure deposition and differential arc oxidation, can be at titanium metal specimen surface growth one deck HA-TiO 2Composite ceramic layer.
The invention has the beneficial effects as follows that the titanium metal sample prepares and contains HA particulate ceramic layer in electrolytic solution, simplified greatly in titanium metal specimen surface deposition HA particulate technology; Through content or deposition voltage and the time of HA in the adjustment electrolytic solution; Just can change the content of HA in the rete, this method is simple, and the membranous layer binding force of preparing is fine; Satisfy medical requirement fully, can solve the problem that this technology is difficult to large-scale application.
Description of drawings
Fig. 1 is preparation titanium metal HA-TiO 2The microarc oxidation equipment provided structural representation of composite film, among the figure, 1. electrolyzer, 2. titanium metal sample, 3. stainless steel cathode, 4. high voltage power supply, 5. system, 6. whisking appliance, 7. cooling system;
Fig. 2 is the graph of a relation of low pressure deposition voltage to HA content influence in the ceramic layer;
Fig. 3 is the graph of a relation of low pressure depositing treatment phase deposition time to HA content influence in the ceramic layer;
Fig. 4 is the graph of a relation of differential arc oxidation voltage to HA content influence in the ceramic layer;
Fig. 5 be in the electrolyte solution HA content to the graph of a relation of HA content influence in the ceramic layer;
Fig. 6 is that the ceramic layer surface topography SEM photo that in the electrolyte solution of different HA additions, prepares: Fig. 6-(a) is the ceramic layer surface scan photo that adds quantitative HA granules prepn in the original electrolytic solution by 3g/L; Fig. 6-(b) is the ceramic layer surface scan photo that adds quantitative HA granules prepn in the original electrolytic solution by 6g/L; Fig. 6-(c) is the ceramic layer surface scan photo that adds quantitative HA granules prepn in the original electrolytic solution by 9g/L; Fig. 6-(d) is the ceramic layer surface scan photo that adds quantitative HA granules prepn in the original electrolytic solution by 12g/L;
Fig. 7 is the HA-TiO through low pressure deposits and differential arc oxidation makes 2The cross section scanned photograph of composite ceramic layer;
Fig. 8 be surface treated implantation nail implant take out after 3 months in the living animal body after, implant the surface topography photo of nail, wherein Fig. 8-(a) is the photo that does not add the implantation nail that HA makes in the low pressure deposition process; Fig. 8-(b) is the photo that has added the implantation nail that HA makes in the low pressure deposition process.
Embodiment
The present invention provides a kind of surface of metal titanium to prepare the method for the active composite film of hydroxyl apatite biological, and concrete operations are following:
Step 1 is prepared electrolytic solution in oxidation trough
With concentration is that the phospho-glycerol calcium of 3~5g/L and lime acetate that concentration is 20~30g/L mix, and obtains mixture A, and the solvent in the mixed solution A is a zero(ppm) water; In mixture A, add sodium hydroxide again, regulating its PH is 11, obtains mixing solutions B; Amount by 3~12g/L adds Win 40350 in mixture B at last, promptly obtains electrolyte solution;
Step 2,
Earlier titanium metal sample (titanium or titanium alloy) is carried out surface treatment: the test button of at first polishing, clean oil removing to it then;
Titanium metal sample after will handling is again put into the electrolytic solution that step 1 prepares; And titanium metal sample and positive source joined; Power cathode connects stainless steel plate, through power supply the titanium metal sample is applied voltage and carries out low pressure deposition and differential arc oxidation processing, and the corresponding relation of conduction time and voltage is:
The low pressure depositional phase: control voltage 30V~120V, depositing time 5~20min;
The differential arc oxidation stage: control voltage 450V~600V, depositing time 10min, the frequency of power supply is 200kHz, dutycycle is 10%;
More than all be to carry out in microarc oxidation equipment provided to the processing of titanium metal sample as shown in Figure 1; Electrolyzer 1 is the splendid attire electrolytic solution, and titanium metal sample 2 is immersed in the electrolytic solution with stainless steel cathode 3, and the positive pole of high voltage power supply 4 connects the titanium metal sample; Negative pole connects the stainless steel plate negative electrode; System 5 is control high voltage power supply 4 output voltages and time, and whisking appliance 6 is to be used for accelerating electrolyte flow, makes reaction more steady; Cooling system 7 is to the electrolytic solution cooling, because can emit a large amount of heat in the differential arc oxidation process.
After carrying out low pressure deposition and differential arc oxidation, can be at titanium metal specimen surface growth one deck HA-TiO 2Composite ceramic layer.
Embodiment 1
Surface of metal titanium prepares the method for the active composite film of hydroxyl apatite biological, and concrete operations are following:
Step 1, in oxidation trough, prepare electrolytic solution:
With concentration is that the phospho-glycerol calcium of 4g/L and lime acetate that concentration is 25g/L mix, and obtains mixture A, and the solvent in the mixed solution A is a zero(ppm) water; In mixture A, add sodium hydroxide again, regulating its PH is 11, obtains mixing solutions B; Amount by 12g/L adds Win 40350 in mixture B at last, promptly obtains electrolyte solution;
Step 2,
Earlier pure titanium (purity 99.9%) is carried out surface treatment: polishing earlier, again it is cleaned oil removing;
Again the titanium metal sample is put into the electrolytic solution that step 1 prepares; And titanium metal sample and positive source joined; Stainless steel plate and power cathode join, and through power supply the titanium metal sample are applied voltage and carry out low pressure deposition and differential arc oxidation processing, and the corresponding relation of conduction time and voltage is:
The low pressure depositional phase: control voltage 120V, depositing time 20min;
The differential arc oxidation stage: control voltage 600V, depositing time 10min, supply frequency 200kHz, dutycycle is 10%;
After carrying out low pressure deposition and differential arc oxidation, can be at titanium metal specimen surface growth one deck HA-TiO 2Composite ceramic layer.
Through test, HA-TiO 2HA content in the composite ceramic layer is 13.6%.
Embodiment 2
Different with embodiment 1 is, only the control voltage of low pressure depositional phase is different, and voltage is 90V, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 10.3%.
Embodiment 3
Different with embodiment 1 is, only the control voltage of low pressure depositional phase is different, and voltage is 60V, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 9.8%.
Embodiment 4
Different with embodiment 1 is, only the control voltage of low pressure depositional phase is different, and voltage is 30V, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 9.2%.
From embodiment 1, embodiment 2, embodiment 3 and embodiment 4, can find; Like Fig. 2, under the identical situation of all the other conditions, along with the ascending variation of low pressure depositing treatment voltage; HA content also increases thereupon in the ceramic layer, and deposition voltage increases during for 120V the most obvious.
Embodiment 5
Different with embodiment 1 is, only the depositing time of low pressure depositional phase is different, and depositing time is 15min, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 12.3%.
Embodiment 6
Different with embodiment 1 is, only the depositing time of low pressure depositional phase is different, and depositing time is 10min, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 11.1%.
Embodiment 7
Different with embodiment 1 is, only the depositing time of low pressure depositional phase is different, and depositing time is 5min, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 8.7%.
By finding among embodiment 1, embodiment 5, embodiment 6 and the embodiment 7, as shown in Figure 3, under the identical situation of all the other conditions, along with the ascending variation of low pressure depositing treatment depositing time, HA content also increases thereupon in the ceramic layer.
Embodiment 8
Different with embodiment 1 is, only the control voltage in differential arc oxidation stage is different, and voltage is 550V, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 9.9%.
Embodiment 9
Different with embodiment 1 is, only the control voltage in differential arc oxidation stage is different, and voltage is 500V, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 9.2%.
Embodiment 10
Different with embodiment 1 is, only the control voltage in differential arc oxidation stage is different, and voltage is 450V, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 7.6%.
We can find from embodiment 1, embodiment 8, embodiment 9 and embodiment 10, and are as shown in Figure 4, and under the identical situation of all the other conditions, the content of HA increases with the increase of differential arc oxidation voltage in the ceramic layer.Hence one can see that, can improve the content of ceramic layer Win 40350 through the voltage that increases differential arc oxidation.
Embodiment 11
Different with embodiment 1 is, the amount that only in mixture B, adds Win 40350 is different, in original electrolytic solution, adds Win 40350 by the amount of 9g/L, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 10.4%.
Embodiment 12
Different with embodiment 1 is, the concentration that only in mixture B, adds Win 40350 is different, in original electrolytic solution, adds Win 40350 by the amount of 6g/L, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 9%.
Embodiment 13
Different with embodiment 1 is, the concentration that only in mixture B, adds Win 40350 is different, in original electrolytic solution, adds Win 40350 by the amount of 3g/L, and all the other are all identical with embodiment 1.
Through test, HA-TiO 2HA content in the composite ceramic layer is 6.5%.
From embodiment 1, embodiment 11, embodiment 12 and embodiment 13, can find; As shown in Figure 5; Increase along with HA content in the electrolytic solution; The content of HA also increases thereupon in the ceramic layer, explains that under the constant situation of other conditions the increase of the content of HA during HA content is with electrolytic solution in the ceramic layer increases.So, can improve specimen surface ceramic layer HA through the content that increases HA in the electrolytic solution, and in the electrolytic solution in HA content and the final ceramic layer HA content present proportional relationship.
Embodiment 1, embodiment 11, embodiment 12 and embodiment 13 resulting samples according to scanned photograph, are obtained Fig. 6, and this is the HA-TiO that the electrolytic solution of different HA content makes 2Composite film surface microscopic topographic SEM photo; Fig. 6-(a): original electrolytic solution+3gHA/L; Fig. 6-(b): original electrolytic solution+6gHA/L; Fig. 6-(c): original electrolytic solution+9gHA/L; Fig. 6-(d): original electrolytic solution+12gHA/L; As can be seen from the figure, Win 40350 (HA) is distributed in the ceramic layer with white granular, and along with the increase of adding HA content in the electrolytic solution, white particle quantity increases, and film surface discharge micropore size increases thereupon.The increase of HA content, the roughness change mostly helps biological tissue's growth in the above.
Embodiment 14
Surface of metal titanium prepares the method for the active composite film of hydroxyl apatite biological, and concrete operations are following:
Step 1, in oxidation trough, prepare electrolytic solution:
With concentration is that the phospho-glycerol calcium of 3g/L and lime acetate that concentration is 20g/L mix, and obtains mixture A, and the solvent in the mixed solution A is a zero(ppm) water; In mixture A, add sodium hydroxide again, regulating its PH is 11, obtains mixing solutions B; Amount by 3g/L adds Win 40350 in mixing solutions B at last, promptly obtains electrolytic solution;
Step 2,
Earlier pure titanium (purity 99.9%) is carried out surface treatment: polishing earlier, again it is cleaned oil removing;
Again the titanium metal sample is put into the electrolytic solution that step 1 prepares; And titanium metal sample and positive source joined; Power cathode connects stainless steel plate, through power supply the titanium metal sample is applied voltage and carries out low pressure deposition and differential arc oxidation processing, and the corresponding relation of conduction time and voltage is:
The low pressure depositional phase: control voltage 30V, depositing time 5min;
The differential arc oxidation stage: control voltage 450V, depositing time 10min, supply frequency 200kHz, dutycycle is 10%;
After carrying out low pressure deposition and differential arc oxidation, can be at titanium metal specimen surface growth one deck HA-TiO 2Composite ceramic layer.
Through test, HA-TiO 2HA content in the composite ceramic layer is 5.6%.
Embodiment 15
Surface of metal titanium prepares the method for the active composite film of hydroxyl apatite biological, and concrete operations are following:
Step 1, in oxidation trough, prepare electrolytic solution:
With concentration is that the phospho-glycerol calcium of 5g/L and lime acetate that concentration is 30g/L mix, and obtains mixture A, and the solvent in the mixed solution A is a zero(ppm) water; In mixture A, add sodium hydroxide again, regulating its PH is 11, obtains mixing solutions B; Amount by 12g/L adds Win 40350 in mixing solutions B at last, promptly obtains electrolytic solution;
Step 2,
Earlier titanium alloy (Ti-12Mo-6Zr-2Fe, model is TMZF) is carried out surface treatment: polishing earlier, again it is cleaned oil removing;
Again titanium alloy is put into the electrolytic solution that step 1 prepares; And titanium alloy sample and positive source joined; Power cathode connects stainless steel plate, through power supply titanium alloy is applied voltage and carries out low pressure deposition and differential arc oxidation processing, and the corresponding relation of conduction time and voltage is:
The low pressure depositional phase: control voltage 120V, depositing time 20min;
The differential arc oxidation stage: control voltage 500V, depositing time 10min, supply frequency 200kHz, dutycycle is 10%;
After carrying out low pressure deposition and differential arc oxidation, can be at titanium alloy specimen surface growth one deck HA-TiO 2Composite ceramic layer.
Through test, HA-TiO 2HA content in the composite ceramic layer is 6.2%.
Can find out by embodiment 14 and embodiment 15; The concentration of phospho-glycerol calcium and lime acetate is got the upper limit of concentration that sets respectively or is prescribed a time limit down in electrolytic solution; The ceramic layer HA content for preparing is all low than the HA content in the embodiment 1 prepared ceramic layer; Too high that the concentration of phospho-glycerol calcium and lime acetate can not be got in the electrolytic solution is described, can not be too low.Be that the concentration of 4g/L, lime acetate is that 25g/L is the best with the concentration of phospho-glycerol calcium during practical application.
Referring to Fig. 7, the sample of embodiment 1 gained is carried out the cross-section morphology analysis, the scanned photograph that obtains.From figure, can see; Be attached to the HA of specimen surface in the low pressure deposition process, in the differential arc oxidation process, be broken down by high-voltage, cause the fusing of matrix microcell and splash takes place; These molten state materials are met electrolytic solution and are solidified rapidly; The a part of HA that is deposited on sample surfaces is covered by among the coagulum, is present among the rete with a white group bunch shape, or sticks to the ceramic layer surface.
Referring to Fig. 8, be the implantation nail of handling through the inventive method, implant in the living animal body and to take out the surface topography photo that nail is implanted in the back in 3 months, wherein Fig. 8-(a) does not add the implantation nail photo that the electrolytic solution of HA makes; Fig. 8-(b) adds the implantation nail photo that the electrolytic solution of HA makes.Can see that implant the nail surface among Fig. 8-(a) and generated a part and have certain thickness cell tissue, the differential arc oxidation micropore is covered by a large amount of cell tissue, but the differential arc oxidation micropore still can be seen in the part; And Fig. 8-(b) the middle nail surface of implanting is covered by a large amount of cell tissue, surperficial existence that can't see micropore basically.Explain that containing HA particulate differential arc oxidization surface helps Oesteoblast growth, and combine good.This is because porous HA-TiO 2The composite film surface helps osteoblastic adhering to and the osseous tissue growth, and mechanical interlocking is provided; And the HA of some amount exists, and has improved combining of planting body and osseous tissue, thereby has made titanium metal have excellent biological compatibility and biological activity; Coat and stick to the inner and surperficial HA particle of ceramic layer simultaneously, can not cause the reduction of film substrate bond strength.

Claims (1)

1. surface of metal titanium prepares the method for the active composite film of hydroxyl apatite biological, it is characterized in that concrete operations are following:
Step 1, the preparation electrolytic solution
With concentration is that the phospho-glycerol calcium of 3~5g/L and lime acetate that concentration is 20~30g/L mix, and obtains mixture A, and the solvent among the mixture A is a zero(ppm) water; In mixture A, add sodium hydroxide again, regulating its PH is 11, obtains mixture B; Amount by 3g/L~12g/L adds Win 40350 in mixture B at last, promptly obtains electrolytic solution;
Step 2,
The titanium metal sample is put into the electrolytic solution that step 1 prepares; And titanium metal sample and positive source joined; Power cathode connects stainless steel plate, through power supply the titanium metal sample is applied voltage and carries out low pressure deposition and differential arc oxidation processing, and the corresponding relation of conduction time and voltage is:
The low pressure depositional phase: control voltage 30V~120V, depositing time 5~20min;
The differential arc oxidation stage: control voltage 450V~600V, depositing time 10min, the frequency of power supply is 200kHz, dutycycle is 10%;
After carrying out low pressure deposition and differential arc oxidation, can be at titanium metal specimen surface growth one deck HA-TiO 2Composite ceramic layer.
CN2012100763723A 2012-03-21 2012-03-21 Method for preparing bioactive composite film layer containing hydroxyapatite on titanium metal surface Pending CN102605410A (en)

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CN103898591A (en) * 2014-03-27 2014-07-02 昆明冶金研究院 Method for directly preparing hydroxyapatite-containing micro-arc oxidation ceramic film
CN104988558A (en) * 2015-08-08 2015-10-21 昆明冶金研究院 Method for preparing biological ceramic membrane layer on titanium alloy surface through graded combined oxidation in stages
CN110438541A (en) * 2019-09-12 2019-11-12 山东省科学院新材料研究所 A kind of particle doping type complex gradient differential arc oxidation coating and multi-stage preparation process, application
CN110528048A (en) * 2019-08-30 2019-12-03 广东省新材料研究所 A kind of titanium alloy implant Bio-surface active coating and preparation method thereof
CN112281199A (en) * 2020-10-05 2021-01-29 华中科技大学 Preparation and application of ultrasonic-assisted micro-arc oxidation composite film layer based on solution system

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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103898591A (en) * 2014-03-27 2014-07-02 昆明冶金研究院 Method for directly preparing hydroxyapatite-containing micro-arc oxidation ceramic film
CN104988558A (en) * 2015-08-08 2015-10-21 昆明冶金研究院 Method for preparing biological ceramic membrane layer on titanium alloy surface through graded combined oxidation in stages
CN104988558B (en) * 2015-08-08 2017-06-16 昆明冶金研究院 It is a kind of in the titanium alloy surface method that combined oxidation prepares bioceramic film layer stage by stage
CN110528048A (en) * 2019-08-30 2019-12-03 广东省新材料研究所 A kind of titanium alloy implant Bio-surface active coating and preparation method thereof
CN110438541A (en) * 2019-09-12 2019-11-12 山东省科学院新材料研究所 A kind of particle doping type complex gradient differential arc oxidation coating and multi-stage preparation process, application
CN110438541B (en) * 2019-09-12 2020-08-28 山东省科学院新材料研究所 Particle-doped composite gradient micro-arc oxidation coating, multistage preparation method and application
CN112281199A (en) * 2020-10-05 2021-01-29 华中科技大学 Preparation and application of ultrasonic-assisted micro-arc oxidation composite film layer based on solution system
CN112281199B (en) * 2020-10-05 2022-02-15 华中科技大学 Preparation and application of ultrasonic-assisted micro-arc oxidation composite film layer based on solution system

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Application publication date: 20120725