CN106637183A - Preparing method for composite coating integrating photocatalysis and protection performance of magnesium alloy surface - Google Patents

Preparing method for composite coating integrating photocatalysis and protection performance of magnesium alloy surface Download PDF

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CN106637183A
CN106637183A CN201610987262.0A CN201610987262A CN106637183A CN 106637183 A CN106637183 A CN 106637183A CN 201610987262 A CN201610987262 A CN 201610987262A CN 106637183 A CN106637183 A CN 106637183A
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coating
magnesium alloy
oxide layer
magnesium
photocatalysis
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杨巍
陈建
姚小飞
吕煜昆
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Xian University of Technology
Xian Technological University
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Xian Technological University
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    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00Coating starting from inorganic powder
    • C23C24/08Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • C23C24/085Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/087Coating with metal alloys or metal elements only
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/024Anodisation under pulsed or modulated current or potential
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02Anodisation
    • C25D11/26Anodisation of refractory metals or alloys based thereon

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Ceramic Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
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Abstract

The invention discloses a composite coating integrating photocatalysis and wear resistance of a magnesium alloy surface. The composite coating is composed of a cold spraying Ti coating located on the surface of a magnesium alloy matrix and a titanium oxide layer located on the surface of the Ti coating and prepared through micro-arc oxidation. The cold spraying technology is adopted in the Ti coating so that the Ti coating with the rough surface characteristic is formed on the surface of the magnesium alloy matrix, wherein the thickness of the Ti coating ranges from 100 microns to 300 microns. Micro-arc oxidation is used for preparing the titanium oxide layer with vanadium and tin or without doping of other metal elements, and the titanium oxide layer having photocatalytic activity is obtained through regulation on the electrolyte composition and technological parameters, wherein the thickness of the titanium oxide layer ranges from 6 microns to 20 microns. Compared with an existing magnesium alloy micro-arc oxide layer and a titanium surface micro-arc oxide layer, the composite coating is a film layer having more excellent corrosion-resisting and wear-resisting performance and photocatalytic performance, beneficial modification on the surface of the magnesium alloy matrix can be achieved, application of magnesium alloys in the photocatalytic field is promoted, and the technology can be popularized to modification of surfaces of aluminum alloys.

Description

Mg alloy surface has the preparation method of composite coating of photocatalysis and barrier propterty concurrently
Technical field
The present invention relates to metal surface has the technical field of protection and functional coating concurrently, and in particular to a kind of Mg alloy surface Have the composite coating and preparation method of photocatalysis and barrier propterty concurrently.
Background technology
Magnesium alloy has little density, specific strength and specific stiffness height, good stability of the dimension, electromagnetic wave shielding good and good Many advantages, such as damping property, under the dual-pressure of current energy and environment, have become domestic and international high performance light alloy material Research and development focus.China's magnesium resource enriches, and the country has formed the high-tech sectors such as Aero-Space and automobile, five metals, bathroom, letter The wide application demand situation that the productions such as breath product are proposed with manufacturing enterprise to magnesium alloy materials, carries out magnesium alloy materials with application The correlative study of technology seems particularly urgent and important.Currently, around Magnesiumalloy surface modifying coating technology of preparing develop and Its performance characterization, domestic and international researcher has carried out more research, and chemical composition coating, anodic oxidation, micro- is emerged in succession Arc is aoxidized(MAO), plating, thermal spraying, the kinds of surface modified coating technology such as laser surface modification and vapour deposition, to reach To the purpose for improving surfacecti proteon performance with make it have a certain functional characteristic.
MAO technologies are a kind of can simply to construct ceramic oxides porous membrane structure in alloy surfaces such as magnesium, aluminium, titaniums Technology, can be formed in situ ceramic layer in the MgO membrane structure that Mg alloy surface is prepared with matrix is metallurgical binding, Mg alloy surface And improve the performance of matrix, but surface ceramii layer loose structure and its own yet suffer from relatively low electrode potential and cause to prevent Shield limited capacity.
, used as a kind of relatively new face coat technology of preparing, it is with well-known heat spraying method not for cold spray technique Together, very low with coating's air hole ratio, the thermic load very little of matrix material and coating, material oxidation is few, eliminates in coating and crystallizes Change uneven phenomenon, be adapted to the light-alloy surface modification treatments such as aluminium, magnesium.
The above analysis, differential arc oxidization technique can be formed in situ ceramic layer and improve the property of matrix in Mg alloy surface Can, but surface ceramii layer loose structure and ceramic oxides film itself yet suffer from relatively low electrode potential and cause protection Limited capacity.If in the cold spraying Ti coating of the previously prepared hundreds of microns of thickness in magnesium-based surface, and differential of the arc oxygen is prepared as base Change film layer, obtain cold spraying Ti+ differential arc oxidation composite coatings, the differential arc oxidation of magnesium-based surface titanium is capable of achieving, due to titanium-based micro-arc Oxide layer has the performance more excellent compared with magnesium-based differential arc oxidation layer, and hundred micron-sized cold spraying T layers, so as to realize to magnesium The significantly improvement of matrix barrier propterty.Meanwhile, cold spraying titanium layer surface has substantial amounts of concavo-convex different structure, after differential arc oxidation Prepared composite coating(Internal layer is cold spraying Ti layers, and top layer is TiO2Layer)Surface is conducive to big specific surface area Improve the photocatalysis performance of composite coating.
The content of the invention
The technical purpose of the present invention is difficult to have function and barrier propterty concurrently for existing Magnesiumalloy surface modifying coating It is not enough, there is provided a kind of Mg alloy surface has composite coating of photocatalysis and corrosion-resisting wear-proof and preparation method thereof, the composite coating concurrently With photocatalytic activity, while and with preferable corrosion-resisting wear-proof performance.
The present invention realize technical scheme that above-mentioned technical purpose adopted for:A kind of Mg alloy surface has photocatalysis concurrently and resists The composite coating of abrasion, by the cold spraying Ti coating positioned at magnesium alloy matrix surface, and positioned at the differential of the arc of the Ti coating surfaces Oxidation prepares titanium oxide layer composition;The Ti coating is to utilize cold spray technique, forms magnesium alloy matrix surface and has coarse table Region feature, thickness are 100~300 μm of Ti coating;Differential arc oxidation is prepared containing vanadium, oxygen stanniferous or without other metallic element doping Change titanium layer, and by regulating and controlling electrolyte composition and technological parameter, obtain and there is photocatalytic activity, thickness is 6~20 μm of oxygen Change titanium layer.
Preferably, the thickness of described cold spraying Ti coating is 150~200 μm, described titanium oxide layer thickness is 8 ~10 μm.
Present invention also offers a kind of above-mentioned Mg alloy surface has photocatalysis concurrently with the composite coating of corrosion-resisting wear-proof performance Preparation method, specifically includes following steps:
Step 1:Ti powder particles used by cold spraying preparation Ti coating are a diameter of 5 ~ 28 μm, the powder feeding gas based on nitrogen, nitrogen For technical grade purity nitrogen, 600 ~ 900 DEG C are heated to, 1 ~ 5 Mpa is reached by air compressor, Ti powder is sprayed on into magnesium-based body surface Face, in cold spray process, nozzle is held in 10 ~ 30 mm with the distance of matrix, and it is 10 ~ 50 mm/s to walk rifle speed, is closed in magnesium Gold surface prepares 100~300 μm of Ti coating.
Step 2:Magnesium alloy substrate is cleaned by ultrasonic Jing after step 1 process, is removed and dried after the impurity that T coating surfaces contain It is dry;
Step 3:Chemical reagent is selected according to the matching principle of magnesium alloy differential arc oxidation electrolyte, silicate differential arc oxidation is prepared Electrolyte;
Step 4:Using DC pulse mao power source, energy and oxidization time are exported by adjusting pulse, make cold spraying The top layer Ti atoms of Ti coating are formed in situ the titanium oxide layer that thickness is 5~40 μm.
Preferably, in the step 3, ammonium metavanadate or sodium stannate are added in electrolyte, so as to obtain preparing V or The electrolyte of the MAO layers of Sn doping, detailed process is:Add 10g/L ammonium metavanadates or 15g/L in 30g/L silicic acid sodium based solutions Sodium stannate, stirring is dissolved each other, and in described step 4, the pulse output voltage of DC pulse mao power source is 300~ 450V, frequency is 300~600 Hz, and dutycycle is 5~20%, and oxidization time is 3~10 min.
Compared with prior art, the present invention is drawn on its surface based on magnesium alloy materials first with cold spray technique Enter the Ti coating that thickness is 100~300 μm, then prepare the oxidation that thickness is 6-20 μm in the transition zone surface by micro-arc oxidation Titanium layer, so as to realize that Mg alloy surface has the composite coating of photocatalysis and anti-corrosion abrasion-resistant concurrently, the coating and magnesium alloy substrate With preferable film-substrate cohesion, its excellent properties concrete manifestation is as follows:
(1)Titanium oxide photochemical catalyst layer is prepared as matrix using magnesium alloy, relative to based on Ti, cost is low, machinability It is better;Simultaneously cold spraying Ti coating rough surface itself, beneficial to the specific surface area for increasing composite coating, improves its photocatalytic Can, differential arc oxidation layer is prepared on transition zone Ti surfaces, and can carry out metal-doped, to be so combined together composite coating energy The photocatalytic activity of magnesium alloy matrix surface is enough increased substantially, photocatalysis performance, 3 h degradation of methylene blue are further improved Photocatalysis efficiency can reach more than 90%;
(2)Cold spraying Ti coating is relative to matrix Mg, and the performance of its own is more excellent, and the further differential arc oxidations of Jing process shape Into titanium oxide layer, the composite coating being combined together can significantly improve in anti-corrosion abrasion-resistant aspect of performance, the composite membrane Though layer is relative to the direct differential arc oxidation layer of magnesium surface with higher coefficient of friction, the polishing scratch on its surface is not obvious;Corrosion Current density is substantially less than magnesium-based surface cold spraying titanium coating or magnesium-based surface by micro-arc oxidation prepares magnesium oxide layer;
(3))It is applied widely:The present invention solves the strong combination of hundred micron-sized cold spraying Ti layers and magnesium matrix, and further Realize prepared by the ceramic layer of surface some tens of pm using differential arc oxidation, significantly improve the barrier propterty of magnesium surface(Anti- corruption is resistance to Mill).While the architectural feature of composite film(The surface irregularity of cold spray layer, the porous surface of differential arc oxidation layer)Be conducive to Increase its specific surface area, and further realize significantly improving for composite coating photocatalysis performance by metal-doped.This is combined Film layer has excellent photocatalysis performance and corrosion-resisting wear-proof performance concurrently, is application of the magnesium alloy product in fields such as photocatalysis, biologies Promote and provide an effective way, expanded the application of magnesium, this technology may extend to aluminum alloy surface and be modified.
(4)Photocatalysis composite coating is prepared based on magnesium, relative to traditional Ti matrixes photocatalysis coating, product are prepared Machinability become easy, reliable preparation process is easy, it is not necessary to which original technique is adjusted, and overall manufacturing cost is big Amplitude declines.
Description of the drawings
Fig. 1 is the surface SEM pattern photos of coating prepared by magnesium alloy Jing different process,
Wherein,(a)Mg+MAO-380V;(b)Mg+Ti+MAO-350V;(c)Mg+Ti+MAO-380V;(d)Mg+Ti+MAO- 400V;
Fig. 2 is the polishing scratch SEM pattern photos of coating prepared by magnesium alloy Jing different process,
Wherein,(a)Mg+MAO;(b)Mg+Ti+MAO- abrasion 5min;
The photocatalysis experimental result of Fig. 3 Mg alloy surface composite coatings.
Specific embodiment
The present invention is described in further detail below in conjunction with specific embodiment.
In the Ti coating of the previously prepared tens of micrometers thick in magnesium-based surface, and can prepare as base by cold spray technique Differential arc oxidation film layer, obtains cold spraying Ti+ differential arc oxidation composite coatings, the differential arc oxidation of magnesium-based surface Ti is realized, due to Ti bases Differential arc oxidation layer has the performance more excellent compared with magnesium-based differential arc oxidation layer, so as to realize significantly changing to magnesium matrix performance It is kind;Meanwhile, cold spraying Ti coating itself has rough surface, the process of Jing differential arc oxidations, its surface formation titanium oxide layer, by it The bigger specific surface area in surface, photocatalytic activity and more preferable barrier propterty that titanium oxide has, it is possible to achieve magnesium alloy table Face has photocatalysis concurrently and prepares with the composite coating of corrosion-resisting wear-proof performance, is the process for modifying surface means for improving magnesium alloy, extension The application of magnesium alloy provides technical support.
Embodiment 1:
In the present embodiment, the composite coating of Mg alloy surface is cold spraying Ti/MAO composite coatings, i.e. magnesium alloy matrix surface elder generation Preparing Ti transition zones carries out again differential arc oxidation, and the transition zone is to utilize cold spray technique, makes magnesium alloy matrix surface define tool The Ti for having uneven surface characteristics crosses coating, and the thickness of the transition zone is about 200 μm, and its surface forms the thickness of MAO layers About 10 μm of degree.
The preparation method of above-mentioned Mg alloy surface composite coating comprises the steps:
Step 1:Magnesium alloy substrate Jing is mechanically polished, and using cold spray process Ti coating, Ti powder particles used a diameter of 6 are prepared μm, the powder feeding gas based on nitrogen, nitrogen is technical grade purity nitrogen, is heated to 650 DEG C, and by air compressor 3 Mpa are reached, Ti powder is sprayed on into magnesium matrix surface, in cold spray process, nozzle is held in 20 mm with the distance of matrix, and walking rifle speed is 40 mm/s, in Mg alloy surface 200 μm of Ti coating is prepared.
Step 2:Magnesium alloy substrate Jing acetone Jing after step 2 process is cleaned by ultrasonic, and removes cold spraying Ti coating surfaces and contains Some impurity post-dryings;
Step 3:Using DC pulse mao power source, from the silicate differential arc oxidation electrolysis introduced without harmful element Liquid;
Step 4:Using DC pulse mao power source, adjustment pulse output voltage is 400V, and frequency is 400Hz, duty Than for 10%, oxidization time is 6 min, and in magnesium alloy matrix surface the arc differential oxide ceramic layer that thickness is 10 μm is prepared.
The surface microscopic topographic of cold spraying Ti transition zones+MAO composite coatings obtained above is as shown in figure 1, and magnesium surface Differential arc oxidation layer is contrasted, and wear scar width and depth are obviously reduced, and wearability strengthens, as shown in Fig. 2 itself and the direct differential of the arc in Ti surfaces Oxidation prepares ceramic layer contrast, with excellent photocatalysis performance, as shown in Figure 3.
Embodiment 2:
In the present embodiment, the composite coating of Mg alloy surface is cold spraying Ti/V-MAO composite coatings, i.e. magnesium alloy matrix surface First preparing Ti transition zones carries out again differential arc oxidation, and the transition zone is to utilize cold spray technique, defines magnesium alloy matrix surface Ti with uneven surface characteristics crosses coating, and the thickness of the transition zone is about 150 μm, by allocating differential arc oxidation electricity Solution liquid, the thickness for forming V doping MAO layers on its surface is about 15 μm.
The preparation method of above-mentioned Mg alloy surface composite coating comprises the steps:
Step 1:Magnesium alloy substrate Jing is mechanically polished, and using cold spray process Ti coating, Ti powder particles used a diameter of 6 are prepared μm, the powder feeding gas based on nitrogen, nitrogen is technical grade purity nitrogen, is heated to 600 DEG C, and by air compressor 2 Mpa are reached, Ti powder is sprayed on into magnesium matrix surface, in cold spray process, nozzle is held in 25 mm with the distance of matrix, and walking rifle speed is 45 mm/s, in Mg alloy surface 150 μm of Ti coating is prepared.
Step 2:Magnesium alloy substrate Jing acetone Jing after step 2 process is cleaned by ultrasonic, and removes cold spraying Ti coating surfaces and contains Some impurity post-dryings;
Step 3:Using DC pulse mao power source, from the silicate differential arc oxidation electrolysis for being added with ammonium metavanadate Liquid;
Step 4:Using DC pulse mao power source, adjustment pulse output voltage is 420V, and frequency is 500Hz, duty Than for 8%, oxidization time is 8 min, and in magnesium alloy matrix surface the arc differential oxide ceramic layer that thickness is 15 μm is prepared.
Cold spraying Ti transition zones V-MAO composite coatings obtained above have excellent photocatalysis performance, as shown in Figure 3.
Embodiment 3:
In the present embodiment, the composite coating of Mg alloy surface is cold spraying Ti/Sn-MAO composite coatings, i.e. magnesium alloy matrix surface First preparing Ti transition zones carries out again differential arc oxidation, and the transition zone is to utilize cold spray technique, defines magnesium alloy matrix surface Ti with uneven surface characteristics crosses coating, and the thickness of the transition zone is about 250 μm, by allocating differential arc oxidation Electrolyte, the thickness for forming Sn doping MAO layers on its surface is about 20 μm.
The preparation method of above-mentioned Mg alloy surface composite coating comprises the steps:
Step 1:Magnesium alloy substrate Jing is mechanically polished, and using cold spray process Ti coating, Ti powder particles used a diameter of 6 are prepared μm, the powder feeding gas based on nitrogen, nitrogen is technical grade purity nitrogen, is heated to 700 DEG C, and by air compressor 3 Mpa are reached, Ti powder is sprayed on into magnesium matrix surface, in cold spray process, nozzle is held in 15 mm with the distance of matrix, and walking rifle speed is 35 mm/s, in Mg alloy surface 250 μm of Ti coating is prepared.
Step 2:Magnesium alloy substrate Jing acetone Jing after step 2 process is cleaned by ultrasonic, and removes cold spraying Ti coating surfaces and contains Some impurity post-dryings;
Step 3:Using DC pulse mao power source, from the silicate micro-arc oxidation electrolyte for being added with sodium stannate;
Step 4:Using DC pulse mao power source, adjustment pulse output voltage is 380V, and frequency is 400Hz, duty Than for 10%, oxidization time is 10 min, and in magnesium alloy matrix surface the arc differential oxide ceramic layer that thickness is 20 μm is prepared.
Cold spraying Ti transition zones V-MAO composite coatings obtained above have excellent photocatalysis performance, as shown in Figure 3.
The cold spraying Ti transition zone surface irregularities that embodiment 1 is obtained, specific surface area is relative to differential arc oxidation porous layer Significantly increase, and cold spraying Ti+MAO composite coatings surface still has the uneven structure of cold spray layer, while its surface Porous character with arc differential oxide ceramic layer, corrosion-resisting wear-proof performance directly prepares MAO layers and photocatalytic better than magnesium surface MAO layers can be directly prepared better than titanium surface, as shown in Figure 1;The polishing scratch of magnesium surface cold spraying Ti+MAO composite coatings is significantly less than The magnesium alloy of differential arc oxidation process is directly carried out, as shown in Figure 2;The corrosion current of the composite film is substantially less than cold spraying Ti layers And MAO ceramic layers(As shown in table 1), and arc differential oxide ceramic layer is directly prepared relative to titanium surface, the composite coating has More excellent photocatalysis performance, and the photocatalysis performance of composite film can further improve by doping, as shown in Figure 3.
The electrochemical corrosion acquired results of coating prepared by the magnesium alloy Jing different process of table 1

Claims (4)

1. Mg alloy surface has photocatalysis concurrently with wear-resistant composite coating, it is characterised in that:By positioned at magnesium alloy matrix surface Cold spraying Ti coating, and positioned at the Ti coating surfaces differential arc oxidation prepare titanium oxide layer composition;The Ti coating is to utilize Cold spray technique, forms magnesium alloy matrix surface and has rough surface features, the Ti coating that thickness is 100~300 μm;The differential of the arc Oxidation is prepared containing vanadium, titanium oxide layer stanniferous or without other metallic element doping, and by regulating and controlling electrolyte composition and technique Parameter, obtains and has photocatalytic activity, and thickness is 6~20 μm of titanium oxide layer.
2. Mg alloy surface according to claim 1 has photocatalysis concurrently with wear-resistant composite coating, it is characterised in that:Institute The thickness of the cold spraying Ti coating stated is 150~200 μm, and described titanium oxide layer thickness is 8~10 μm.
3. Mg alloy surface has the preparation method of photocatalysis and the composite coating of corrosion-resisting wear-proof performance concurrently, it is characterised in that:
Specifically include following steps:
Step 1:Ti powder particles used by cold spraying preparation Ti coating are a diameter of 5 ~ 28 μm, the powder feeding gas based on nitrogen, nitrogen For technical grade purity nitrogen, 600 ~ 900 DEG C are heated to, 1 ~ 5 Mpa is reached by air compressor, Ti powder is sprayed on into magnesium-based body surface Face, in cold spray process, nozzle is held in 10 ~ 30 mm with the distance of matrix, and it is 10 ~ 50 mm/s to walk rifle speed, is closed in magnesium Gold surface prepares 100~300 μm of Ti coating;
Step 2:Magnesium alloy substrate is cleaned by ultrasonic Jing after step 1 process, removes the impurity post-drying that T coating surfaces contain;
Step 3:Chemical reagent is selected according to the matching principle of magnesium alloy differential arc oxidation electrolyte, silicate differential arc oxidation is prepared Electrolyte;
Step 4:Using DC pulse mao power source, energy and oxidization time are exported by adjusting pulse, make cold spraying The top layer Ti atoms of Ti coating are formed in situ the titanium oxide layer that thickness is 5~40 μm.
4. according to claim 3 Mg alloy surface has the preparation side of photocatalysis and the composite coating of corrosion-resisting wear-proof performance concurrently Method, it is characterised in that:
In the step 3, ammonium metavanadate or sodium stannate are added in electrolyte, so as to obtain that the MAO layers of V or Sn doping can be prepared Electrolyte, detailed process is:Add 10g/L ammonium metavanadates or 15g/L sodium stannates in 30g/L silicic acid sodium based solutions, stirring is mutual Molten, in described step 4, the pulse output voltage of DC pulse mao power source is 300~450V, frequency is 300~ 600 Hz, dutycycle is 5~20%, and oxidization time is 3~10 min.
CN201610987262.0A 2016-11-10 2016-11-10 Preparing method for composite coating integrating photocatalysis and protection performance of magnesium alloy surface Pending CN106637183A (en)

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CN108962602A (en) * 2018-07-13 2018-12-07 四川华保新能源科技有限公司 A method of improving high-voltage capacitance battery aluminium foil specific volume
CN113679253A (en) * 2020-05-18 2021-11-23 佛山市顺德区美的电热电器制造有限公司 Container and cooking utensil

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