CN100467676C - Method for plasma electrolytic oxidation preparation of ceramic oxide film and its products - Google Patents
Method for plasma electrolytic oxidation preparation of ceramic oxide film and its products Download PDFInfo
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- CN100467676C CN100467676C CNB031396496A CN03139649A CN100467676C CN 100467676 C CN100467676 C CN 100467676C CN B031396496 A CNB031396496 A CN B031396496A CN 03139649 A CN03139649 A CN 03139649A CN 100467676 C CN100467676 C CN 100467676C
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Abstract
The invention provides a method for plasma electrolytic oxidation preparation of ceramic oxide film and its products, wherein the method comprises, anodic ground-mass surface plasma electrolytic oxidation, producing films with ceramic structure, wherein the electrolyte solution employs organo-phosphine salts containing hydroxyl or carboxyl radicals as main salts, as well as one or more metal chelating agents as addition agents, inorganic oxy acid salt as film-forming agent and fluorine containing substance as conditioning agent.
Description
Technical field
The present invention relates to a kind of surface treatment, a kind of plasma electrolytic oxidation that particularly relates to the metallic surface electrochemical treatment prepares the method and the goods thereof of ceramic coating.
Background technology
Along with modernized industry and science and technology development, valve metals such as aluminium, magnesium, titanium are widely used in each industrial circle as modern material, because the current potential of these metals is lower, spot corrosion, intergranular corrosion easily take place, surface hardness is low, not wear-resistant, will adopt the process for treating surface process metal surfaces with high and new technology when these shortcomings have determined to use these metals.The treatment technology of these metals is mainly at present:
1, conventional anodization technology (tradition anodic oxidating)
70 years historical conventional anodization technology are arranged, its electrolyte solution generally adopts sulfuric acid or organic acid acidic solution, magnesium alloy then adopts basic solution, obtain rete softer (100～400Hv), non-refractory, intensity is lower, the porous surface structure needs aftertreatment, and operation is many, environmental pollution is big, and efficient is low;
2, chemical transformation (chemical conversion coating)
Main employing chromic salt and additive are treatment solution, with matrix metal generation chemical reaction, form film.This method technology is simple, but the conversion film very thin (being generally 1～4 μ m) that forms, the film poor corrosion resistance, hardness is lower, this film is mainly used in pre-treatment, also must additive method such as application be used.The heavy contamination of this method, other oligosaprobic solution can't put into production at present;
3, organic application (organic coating)
General and chemical transformation is used, and obtains outer organism coating.The hardness of film is lower, and is heat-resisting, heat conductivility is poor, and use range is limited, general only as decorative use; This surface treatment method exists organic solvent evaporates phenomenon, contaminate environment;
4, electrochemical plating (electroplating)
Electrochemical plating are generally ornamental in order to improve, improve surface conductivity, improve surface hardness, improve surface abrasion resistance, reduce frictional coefficient, improve oilness, improve surface reflection etc. carries out.Because aluminium, magnesium, titanium metal and oxygen have very strong avidity, total surface is to have oxide film to exist, so coating easily comes off.Workpiece surface often contains defectives such as trachoma and pore, and in electroplating process, regular meeting is detained electrolyte solution and hydrogen in trachoma and the pore, influences the bonding force of coating and matrix.
Plate and to carry out processing such as mechanical treatment, Solvent degreasing, electrochemical deoiling, alkali etch, sour bright dipping as last, carry out preplating (soaking zinc), transition layer plating (be copper facing) then as chemistry, be required coating (as nickel plating, chromium plating etc.) at last, so just make its pretreatment procedure complexity, and the electroplating wastewater serious environment pollution, belong to restriction and promote technology.
5, differential arc oxidation (microarc oxidation)
The differential arc oxidation method is the full-fledged electrochemical oxidation technology eighties, this technological breakthrough traditional oxidation current, the restriction in voltage faraday zone, anode potential is brought up to several hectovolts by tens volts, oxidation current develops into big electric current by little electric current, power supply develops into interchange by direct current, cause at sample surfaces and micro-arc discharge occurs, even phenomenons such as spark spot appear, oxide layer on surface of material is under the High Temperature High Pressure effect of microplasma, phase and structural changes take place, and are characterized in high-voltage, big electric current forms arc discharge at workpiece surface, through long-time (general 1～2 hour) reaction, produce shaggy rete with ceramic structure, the hardness of this rete can reach more than the 1500Hv, good corrosion resistance, anti-1000V electrical breakdown, this technology has ecologic effect.But the working (machining) efficiency of this technology is very low, and the film surface is extremely coarse, generally needs mechanical mill to handle, and this greatly limits this The Application of Technology.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the method and the goods thereof that provide a kind of plasma electrolytic oxidation to prepare ceramic coating.This method provides a kind of coating growth speed very fast (5 μ m～12 μ m/min), rete and matrix bond is more firm, surface smoothness is higher plasma electrolytic oxidation surface ceramic technology, and increased the kind of the product that technology thus obtains.
The plasma electrolytic oxidation technology is to carry out plasma electrolysis oxidation pottery treatment technology at matrix surface, and its principle is similar to the anodizing technology of alloy materials such as common aluminium, magnesium, titanium, niobium, zirconium.Different is that workpiece is that anode places special electrolytic solution, when feeding the special waveform electric current at workpiece surface fast by the faraday district, produce the discharge of microplasma halation, this plasma body discharge has high-energy-density, has greatly strengthened the electrochemical reaction that takes place on anode.This discharge process is to form under High Temperature High Pressure, micro-area temperature can reach 2000～4000K, even above 10000K, occur in the sintering reaction on the workpiece substrate, make the film material local melting, cause the phase and the structure of rete material to change, the metal oxide of generation has the ceramic structure that forms in little metallurgical mode, and the physics of rete material, chemical property are extremely stable.By reasonable control sedimentation rate, speed of response and sintering energy, can on matrix (anode workpiece) surface, obtain the pottery rete of higher hardness.This rete and matrix bond are functional, simultaneously because the material ion that participates in reaction and form ceramic phase is subjected to the electrical forces effect can evenly be transferred near the matrix space in liquid, the homogeneity of rete is had preferably guarantee.By the control of intelligent power supply, oxidising process is controlled in the halation electrical discharge zone, micro-arc discharge does not take place, the ceramic film surface that obtains like this is very fine and smooth, fine and close.
The objective of the invention is by adopting following method to realize.
The invention provides the method that a kind of plasma electrolytic oxidation prepares ceramic coating, be to utilize electrochemical method, anodic oxidation voltage is controlled at the reaction zone greater than faraday, less than the micro-arc discharge district, under the effect of higher anodic oxidation voltage and current density, make this material surface produce plasma electrolytic oxidation, under thermochemistry, plasma chemistry and electrochemistry acting in conjunction, generate ceramic film.
Specifically be exactly by making as anodic metal base surface plasma electrolysis oxidation, generation has the rete of ceramic structure, wherein, used electrolyte solution is additive, is membrane-forming agent with the inorganic oxysalt, is conditioning agent with fluorine-containing inorganic substance based on the metal chelating agent that contains hydroxyl or carboxyl organic phospho acid, contains one or more, adopting pulse power source control voltage is 200～400V, frequency is 5HZ～250HZ, dutycycle is 10%～95%, and current density is 5～30Adm
-2, the electrolyte solution temperature is 10-50 ℃.
Institute's hydroxyl or carboxyl organic phospho acid are selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 2-phosphono-containing butane-1,2,4 tricarboxylic acid, one or more in the 2-HPAA.
With organic carboxyl acid or its salt is additive, is selected from soluble tartrate, Tripotassium Citrate, one or more in the Sodium Tetraborate.
Contained inorganic oxysalt is selected from tungstate, sodium hydrogen phosphate, molybdate, one or more in the vanadate.
Contained fluorine-containing inorganic substance are selected from and contain F
-, ZrF
6 2-The ionic material.
The invention provides adopt that aforesaid method makes prepare the goods of ceramic coating at metal base surface.
The plasma electrolytic oxidation technology is the anodizing technology that adopts advanced intelligent power supply and extraordinary electrolytic solution to combine.This technology conversion zone is between the faraday district and the differential of the arc, adopts quick up voltage oxidation, obtains any surface finish, ceramic film that porosity is low.This rete has the performance of differential arc oxidation film layer, as characteristics such as wear-resisting, high temperature resistant, corrosion-resistant, high strength, but more saves the energy than micro-arc oxidation process, does not need follow-up surface mechanical attrition to handle.This technology has ecological property.
From development angle, new processing method, optimization potteryization film properties and the preparation technology of exploration is the top priority of this aspect researcher.And the appearance of plasma electrolytic oxidation technology (PEO) is handled major technological breakthrough beyond doubt to the research of this aspect and to light metal surface.Plasma electrolytic oxidation technology (PEO) is owing to adopt the advanced intelligent power technology, the accurate required parameter of CONTROL PROCESS, adopt the suitable electrolytes proportioning, be equipped with reasonable utility appliance, the ceramic layer compactness, glossiness and the adhesion strength that process increase substantially, and have reduced production cost, do not need the complicated mechanical aftertreatment, facility investment is little, proves by production practice, and this technology is present best metal normal plane ceramic technology.
Embodiment
Below, the present invention is carried out the explanation in a step:
The present invention is by making as anodic metal base surface plasma electrolysis oxidation, generation has the rete of ceramic structure, wherein used electrolytic solution is main by containing hydroxyl or carboxyl organic phospho acid, organic carboxyl acid or its salt that the metal chelating agent that contains one or more mainly is organic carboxyl acid, contain amido are additive, with inorganic oxysalt mainly be tungstate, molybdate, vanadate be membrane-forming agent and with fluorine-containing material as containing F
-, ZrF
6 2-The ionic inorganics is that conditioning agent is formed, and adopting pulse power source control voltage is 200～400V, and frequency is 5Hz～250Hz, and dutycycle is 10%～95%, and current density is 5～30Adm
-2, the rete that obtains and the bonding force of matrix are greatly improved, and reach 9～40MPa; Film hardness significantly improves, microhardness up 800HV.
The concentration of the chemical substance that the present invention uses is very low, and generally at several grams per liters, the feature of environmental protection is fabulous.
Be described in detail the present invention below by a plurality of embodiment:
Embodiment one: electrolyte solution contains: phytic acid 0.5～10gl
-1Sodium wolframate 1～5gl
-1, soluble tartrate 2～9gl
-1, sodium hydrogen phosphate 2～5gl
-1More than various materials all adopt chemically pure reagent, the highly industry product of special purpose, with distilled water preparation, pH value is 3～7, solution temperature is controlled at 10～50 ℃, adopts to force or spray stirring.Process current density 4.5～20Adm
-2, plasma oxidation voltage is 200～300V, and frequency is 15Hz, and dutycycle is 1:3,3～7 minutes electrolytic oxidation time.Can make the grey ceramic film, thickness is 12～30 μ m.
The ceramic membrane product that is obtained by aforesaid method is used for decorating, and can adopt coating processs such as dip-coating, showering, spraying, electrophoresis and handle.Be used for aspects such as wear-resisting, anti-corrosion, can not carry out application.
Embodiment two: electrolyte solution contains: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 5～10gl
-1, sodium wolframate 1～5gl
-1, soluble tartrate 2～9gl
-1More than various materials all adopt chemically pure reagent, the highly industry product of special purpose, with distilled water preparation, pH value is 3～7, solution temperature is controlled at 10～50 ℃, adopts to force or spray stirring.Process current density 4.5～20Adm
-2, plasma oxidation voltage is 200～300V, and frequency is 7.5Hz, and dutycycle is 1:3,3～7 minutes electrolytic oxidation time.Can make the grey ceramic film, thickness is 12～30 μ m.
Embodiment three: electrolyte solution contains: 2-phosphonic acids butane-1,2,4 tricarboxylic acid, 5～10gl
-1, Sodium orthomolybdate 1～5gl
-1, Tripotassium Citrate 2～9gl
-1More than various materials all adopt chemically pure reagent, the highly industry product of special purpose, with distilled water preparation, pH value is 3～7, solution temperature is controlled at 10～50 ℃, adopts to force or spray stirring.Process current density 4.5～20Adm
-2, plasma oxidation voltage is 200～300V, and frequency is 7.5Hz, and dutycycle is 1:3,3～7 minutes electrolytic oxidation time.Can make yellow ceramic film, thickness is 30～40 μ m.
Embodiment four: electrolyte solution contains: 2-HPAA 5～10gl
-1, vanadic acid sodium 1～5gl
-1, Tripotassium Citrate 2～9gl
-1More than various materials all adopt chemically pure reagent, the highly industry product of special purpose, with distilled water preparation, pH value is 3～7, solution temperature is controlled at 10～50 ℃, adopts to force or spray stirring.Process current density 4.5～20Adm
-2, plasma oxidation voltage is 200～300V, and frequency is 7.5Hz, and dutycycle is 1:3,3～7 minutes electrolytic oxidation time, can make the grey ceramic film, thickness is 18～30 μ m.
Embodiment five: electrolyte solution contains: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 5～10gl
-1, NaF1～5gl
-1, Na
2ZrF
61～5gl
-1, Tripotassium Citrate 2～9gl
-1More than various materials all adopt chemically pure reagent, the highly industry product of special purpose, with distilled water preparation, pH value is 3～7, solution temperature is controlled at 10～50 ℃, adopts to force or spray stirring.Process current density 4.5～20Adm
-2, plasma oxidation voltage is 300～400V, and frequency is 7.5Hz, and dutycycle is 1:3,3～7 minutes electrolytic oxidation time, can make the grey ceramic film, thickness is 20～30 μ m.
The product that employing the inventive method makes is made of the ceramic film of metallic matrix and matrix surface.Ceramic layer is made up of tight zone and tectorium, and matrix metal and tight zone burn till an integral body, and tectorium and tight zone interlocking are combined closely simultaneously, make that more whole ceramic membrane and matrix bond are firm.Because this film is to produce in the oxidation of plasma body microcell high-temperature electrolysis, so the ceramic film good uniformity of product of the present invention, with substrate combinating strength height, hardness height, heat shock resistance, electrical insulating property and solidity to corrosion are all good again.
The ceramic membrane product that is obtained by aforesaid method is used for decorating, and can adopt coating processs such as dip-coating, showering, spraying, electrophoresis to handle.Be used for aspects such as wear-resisting, anti-corrosion, can not carry out application.
Method of the present invention is applicable to the surface treatment of the matrix workpiece of various size, shape, structure.
Claims (10)
1, a kind of plasma electrolytic oxidation prepares the method for ceramic coating, it is characterized in that this method is by making as anodic metal base surface plasma electrolysis oxidation, generation has the rete of ceramic structure, used electrolyte solution is to contain hydroxyl or carboxyl organic phospho acid, with the metal chelating agent that contains one or more is additive, with the inorganic oxysalt is membrane-forming agent, is conditioning agent with fluorine-containing inorganic substance.
2, the method for claim 1 is characterized in that anodised pulse power source control voltage is 200-400V, and frequency is 5H
Z-250H
Z, dutycycle is 10%-95%, current density is 5-30Adm
-2, be 3-7min discharge time, the electrolyte solution temperature is 10-50 ℃.
3, the method for claim 1 is characterized in that, institute's hydroxyl or carboxyl organic phospho acid are selected from 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 2-phosphono-containing butane-1,2, one or more in 4 tricarboxylic acid, the 2-HPAA.
4, the method for claim 1 is characterized in that, is additive with organic carboxyl acid or its salt.
5, the method for claim 1 is characterized in that, contained inorganic oxysalt is selected from one or more in tungstate, sodium hydrogen phosphate, molybdate, the vanadate.
6, the method for claim 1 is characterized in that, contained fluorine-containing inorganic substance are selected from and contain F
-, ZrF
6 2-The ionic material.
7, the method for claim 1 is characterized in that, described electrolyte solution contains: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 5-10gl
-1, sodium wolframate 1～5gl
-1, Tripotassium Citrate 2～9gl
-1, the pH value is 3-7,10～50 ℃ of solution temperatures, current density 4.5～20Adm
-2, voltage is 200-300V, and frequency is 7.5Hz, and dutycycle is 1:3.
8, the method for claim 1 is characterized in that, described electrolyte solution contains: 2-phosphono-containing butane-1,2,4 tricarboxylic acid, 5～10gl
-1, Sodium orthomolybdate 1～5gl
-1, Tripotassium Citrate 2～9gl
-1, the pH value is 3～7,10～50 ℃ of solution temperatures, current density 4.5～20Adm
-2, voltage is 200-300V, and frequency is 7.5Hz, and dutycycle is 1:3.
9, the method for claim 1 is characterized in that, described electrolyte solution contains: 2-HPAA 5～10gl
-1, vanadic acid sodium 1～5gl
-1, Tripotassium Citrate 2～9gl
-1, the pH value is 3～7,10～50 ℃ of solution temperatures, current density 4.5～20Adm
-2, voltage is 200～300V, and frequency is 7.5Hz, and dutycycle is 1:3.
10, the method for claim 1 is characterized in that, described electrolyte solution contains: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid 5～10gl
-1, NaF1～5gl
-1, Na
2ZrF
61～5gl
-1, Tripotassium Citrate 2～9gl
-1, the pH value is 3～7,10～50 ℃ of solution temperatures, process current density 4.5～20Adm
-2, plasma oxidation voltage is 300-400V, and frequency is 7.5Hz, and dutycycle is 1:3.
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| CN100467676C true CN100467676C (en) | 2009-03-11 |
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| CN105316742A (en) * | 2014-08-05 | 2016-02-10 | 宁波瑞隆表面技术有限公司 | Electrolyte for aluminum alloy micro-arc oxidation to prepare ceramic coating and treatment method |
| CN112981494A (en) * | 2021-02-08 | 2021-06-18 | 深圳市钧诚精密制造有限公司 | Titanium alloy micro-arc oxidation process with high light absorption rate |
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Non-Patent Citations (4)
| Title |
|---|
| 国内铝和铝合金微弧氧化技术研究动态. 徐勇.腐蚀与防护，第24卷第4期. 2003 |
| 国内铝和铝合金微弧氧化技术研究动态. 徐勇.腐蚀与防护，第24卷第4期. 2003 * |
| 镁及其合金阳极氧化技术的进展. 蒋玉思.广东有色金属学报，第11卷第2期. 2001 |
| 镁及其合金阳极氧化技术的进展. 蒋玉思.广东有色金属学报，第11卷第2期. 2001 * |
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Assignee: Xi'an Sefu Energy Technology Co., Ltd. Assignor: Wang Zhenbo Contract fulfillment period: 2006.10.10 to 2012.10.9 contract change Contract record no.: 2009610000115 Denomination of invention: Method for plasma electrolytic oxidation preparation of ceramic oxide film and its products Granted publication date: 20090311 License type: Exclusive license Record date: 2009.12.4 |
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