CN1566408A - Method for plasma electrolytic oxidation preparation of black ceramic oxide film and its products - Google Patents
Method for plasma electrolytic oxidation preparation of black ceramic oxide film and its products Download PDFInfo
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- CN1566408A CN1566408A CN 03139648 CN03139648A CN1566408A CN 1566408 A CN1566408 A CN 1566408A CN 03139648 CN03139648 CN 03139648 CN 03139648 A CN03139648 A CN 03139648A CN 1566408 A CN1566408 A CN 1566408A
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- electrolytic oxidation
- hydrogen phosphate
- electrolyte solution
- dipotassium hydrogen
- oxide film
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Abstract
The invention provides a method for plasma electrolytic oxidation preparation of black ceramic oxide film and its products, wherein the method comprises, light discharging the anodic ground-mass surface plasma arc, proceeding electrolytic oxidation agglomeration, producing film with ceramic structure. The electrolyte solution comprises monomer phosphonate as main salt, as well as one or more substances as addition agents. The invention can be applied to obtain black ceramic oxide film layers.
Description
Technical field
The present invention relates to a kind of surface treatment, the plasma electrolytic oxidation that particularly relates to the metallic surface electrochemical treatment prepares the method and the goods thereof of black ceramic oxide film.
Background technology
The plasma electrolysis oxidation technology is that valve metals (being referred to as valve metal) such as aluminium, titanium, niobium, zirconium, tantalum or its alloy are placed electrolyte solution, utilize electrochemical method, make this material surface produce plasma body arc discharge spot, under thermochemistry, plasma chemistry and electrochemistry acting in conjunction, generating the anodizing technology of ceramic film, is the once newer metal material surface treatment technology of setting up on the anodic oxidation basis.
In existing process for treating surface, anodizing technology is in acid electrolyte, adopts common interchange or direct supply, obtains the non-crystal oxide film layer at alloy surfaces such as aluminium, magnesium.This rete is thin (5～20 μ m), hardness lower (Hv100～400), and non-refractory, intensity is lower, and porous surface needs aftertreatment, and operation is more, and environmental pollution is big, and production efficiency is low.
It is electrolyte solution that the chemical oxidation technology mainly adopts chromic salt and additive, with matrix metal generation chemical reaction, forms film (1～4 μ m), and this film hardness is lower, poor corrosion resistance, and environmental pollution is heavier.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, and a kind of method and goods thereof that make the more firm plasma electrolytic oxidation of rete and matrix bond prepare the black ceramic oxide film are provided, and increases the product that method thus obtains simultaneously.
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 the black ceramic oxide film, this method is by making as anodic metal base surface plasma arc light discharge, carry out the electrolytic oxidation sintering, generating the rete with ceramic structure.Wherein, used electrolyte solution is main salt with monomer phosphoric acid salt, and monomer whose phosphoric acid salt can be the phosphoric acid salt that contains a hydrogen or contains phosphoric acid salt or above-mentioned two kinds of phosphatic mixing of two hydrogen.The material that also contains one or more is an additive, can be with Sodium Tetraborate, and chromium acetate, quadrol, Sodium orthomolybdate is as additive.Arc discharge voltage is 100～400V, and current density is 1.5～5Adm
-2, the electrolyte solution temperature is 10～50 ℃, and the electricity time is 5～12min, and electrolyte ph is 3～12.
The invention provides the goods that on metallic matrix, prepare the black ceramic oxide film that adopt aforesaid method to make.
The contriver finds, when being main salt with monomer phosphoric acid salt, has produced beyond thought effect.At first, the bonding force of rete and matrix is greatly improved, and reaches 9-40MPa; Secondly, the kind of product increases to some extent, and the inventive method can prepare black ceramic membrane; In addition, film hardness has had raising, and that adopt its microhardness maximum of product that method of the present invention obtains is 1500～2000HV.
In addition, employing is surprised to find that electrolytic solution stability generally prolongs after being main salt with monomer phosphoric acid salt, and the electrolyte solution that the present invention adopts is placed does not have precipitation to produce yet after 3 years.
In addition, in above-mentioned electrolyte solution, its acid-basicity can wait with acetic acid, phosphoric acid, ammoniacal liquor and regulate.Employing contains the different electrolyte solutions that monomer phosphoric acid salt is main salt, control different process current density, arc discharge voltage, tank liquor working temperature, stirring intensity and mode, can obtain having different colours, different pattern, the ceramic membrane structure product of different performance, this product has broad application prospects at industrial circles such as finishing material, weaving, automobile, aviation, navigations.
Embodiment
Below, the present invention is further detailed: method provided by the invention is by making as anodic metal base surface plasma arc light discharge, carry out the electrolytic oxidation sintering, generate rete, wherein with ceramic structure, used electrolyte solution is main salt with monomer phosphoric acid salt, the material that also contains one or more is an additive, can be with Sodium Tetraborate, and chromium acetate, quadrol, Sodium orthomolybdate is as additive.Arc discharge voltage is 100～400V, and current density is 1.5～5Adm
-2, the electrolyte solution temperature is 10～50 ℃, and the electricity time is 5～12min, and electrolyte ph is 3～12.
Electrolyte solution contains dipotassium hydrogen phosphate 30～60gl
-1, Sodium Tetraborate 10～20gl
-1, chromium acetate 20gl
-1, quadrol 10～50mll
-1, Sodium orthomolybdate 10gl
-1More than various materials all adopt chemically pure reagent, the highly industry product of special purpose are prepared with distilled water, preparation is in proper order: with after the dipotassium hydrogen phosphate dissolving, add other each materials earlier, the scope of pH value is 3～12, solution temperature is controlled at 10～50 ℃, adopts and forces or the injection stirring.Process current density 1.5～10Adm
-2, the plasma body arc voltage is 100～400V, 5～30 minutes electrolytic oxidation time, can make the black ceramic rete, and thickness is 40～50 μ m.
Embodiment one
With the LD31 aluminum alloy plate materials as metallic matrix, size 50 * 100 * 1.5 (mm).
Electrolyte solution contains dipotassium hydrogen phosphate 50gl
-1, Sodium Tetraborate 15gl
-1, chromium acetate 20gl
-1, quadrol 30mll
-1, Sodium orthomolybdate 10gl
-1More than various materials all adopt chemically pure reagent, the highly industry product of special purpose are prepared with distilled water, preparation is in proper order: with after the dipotassium hydrogen phosphate dissolving, add other each materials earlier, the scope of pH value is 3～12, solution temperature is controlled at 10～50 ℃, adopts and forces or the injection stirring.Process current 3A, plasma body arc voltage are 300V, 30 minutes electrolytic oxidation time, can make the black ceramic rete, and thickness is 40～50 μ m, any surface finish, hardness are 500Hv.
Embodiment two
With ZL102 cast aluminium alloy piece as metallic matrix, size 50 * 50 * 50 (mm)
Electrolyte solution contains dipotassium hydrogen phosphate 50gl
-1, Sodium Tetraborate 10gl
-1, chromium acetate 30gl
-1, quadrol 40mll
-1, Sodium orthomolybdate 10gl
-1More than various materials all adopt chemically pure reagent, the highly industry product of special purpose are prepared with distilled water, preparation is in proper order: with after the dipotassium hydrogen phosphate dissolving, add other each materials earlier, the scope of pH value is 3～12, solution temperature is controlled at 10～50 ℃, adopts and forces or the injection stirring.Process current 7.5A, plasma body arc voltage are 250V, 30 minutes electrolytic oxidation time, can make the black ceramic rete, and thickness is 40～50 μ m, any surface finish, hardness are 700Hv.
The black ceramic oxide film 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.
The product that 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 at plasma body microcell high temperature sintering, 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.Method of the present invention is applicable to the surface treatment of the matrix workpiece of various size, shape, structure.
Claims (8)
1, a kind of plasma electrolytic oxidation prepares the method for black ceramic oxide film, it is characterized in that this method is by making as anodic metal base surface plasma arc light discharge, carry out the electrolytic oxidation sintering, generate rete with ceramic structure at metal base surface, used electrolyte solution is main salt with monomer phosphoric acid salt, and the material that also contains one or more is an additive.
2, the method for claim 1 is characterized in that, described arc discharge voltage is 100～～400V, be 5～12min discharge time, current density is 1.5～10Adm
-2, the electrolyte solution temperature is 10～50 ℃, electrolyte ph is 3～12.
3, method as claimed in claim 2 is characterized in that described monomer phosphoric acid salt is phosphoric acid salt or the above-mentioned two kinds of phosphatic mixing that contain the phosphoric acid salt of a hydrogen or contain two hydrogen.
4, method as claimed in claim 2 is characterized in that with Sodium Tetraborate, chromium acetate, and quadrol, Sodium orthomolybdate is as additive.
5, the method for claim 1 is characterized in that electrolyte solution contains dipotassium hydrogen phosphate 30～60gl
-1, Sodium Tetraborate 10～20gl
-1, chromium acetate 20gl
-1, quadrol 10～50mll
-1, Sodium orthomolybdate 10gl
-1, more than various materials all adopt chemically pure reagent, with distilled water preparation, preparation is in proper order: with after the dipotassium hydrogen phosphate dissolving, add other each materials earlier, pH value scope is 3～12, and solution temperature is controlled at 10～50 ℃, adopts to force or spray and stir; Process current density 1.5～10Adm
-2, the plasma body arc voltage is 100～400V, 5～30 minutes electrolytic oxidation time, can form the black ceramic rete, and thickness is 40～50 μ m.
6, the method for claim 1 is characterized in that, described electrolyte solution contains: dipotassium hydrogen phosphate 50gl
-1, Sodium Tetraborate 15gl
-1, chromium acetate 20gl
-1, quadrol 30mll
-1, Sodium orthomolybdate 10gl
-1, more than various materials all adopt chemically pure reagent, with distilled water preparation, preparation is in proper order: with after the dipotassium hydrogen phosphate dissolving, add other each materials earlier, pH value scope is 3～12, and solution temperature is controlled at 10～50 ℃, adopts to force or spray and stir; Process current density 1.5-10Adm
-2, the plasma body arc voltage is 300V.
7, the method for claim 1 is characterized in that, electrolyte solution contains dipotassium hydrogen phosphate 50gl
-1, Sodium Tetraborate 10gl
-1, chromium acetate 30gl
-1, quadrol 40mll
-1, Sodium orthomolybdate 10gl
-1More than various materials all adopt chemically pure reagent, with distilled water preparation, preparation is in proper order, with after the dipotassium hydrogen phosphate dissolving, adds other each materials earlier, pH value 3～12 scopes, solution temperature is controlled at 10～50 ℃, adopts to force or spray stirring; Process current 7.5A, plasma body arc voltage are 250V.
That 8, adopts that the method for claim 1 makes prepares the goods of black ceramic oxide film at metal base surface.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 03139648 CN1566408A (en) | 2003-06-25 | 2003-06-25 | Method for plasma electrolytic oxidation preparation of black ceramic oxide film and its products |
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| CN 03139648 CN1566408A (en) | 2003-06-25 | 2003-06-25 | Method for plasma electrolytic oxidation preparation of black ceramic oxide film and its products |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101994146A (en) * | 2009-08-25 | 2011-03-30 | 威斯科高新技术有限公司 | Plasma electrolysing oxcidation solution for mg alloys goods |
| CN102321907A (en) * | 2011-06-23 | 2012-01-18 | 兰州理工大学 | Preparation method of composite film on surface of steel and solution formula for preparation method |
| CN102321903A (en) * | 2011-06-23 | 2012-01-18 | 兰州理工大学 | Preparation method of composite film on surface of metallic material and solution composition for preparation method |
| CN102574072A (en) * | 2009-07-20 | 2012-07-11 | 金属膜克姆有限公司 | Method for producing a membrane and such membrane |
-
2003
- 2003-06-25 CN CN 03139648 patent/CN1566408A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574072A (en) * | 2009-07-20 | 2012-07-11 | 金属膜克姆有限公司 | Method for producing a membrane and such membrane |
| CN101994146A (en) * | 2009-08-25 | 2011-03-30 | 威斯科高新技术有限公司 | Plasma electrolysing oxcidation solution for mg alloys goods |
| CN101994146B (en) * | 2009-08-25 | 2012-11-21 | 威斯科高新技术有限公司 | Plasma electrolysing oxcidation solution for mg alloys goods |
| CN102321907A (en) * | 2011-06-23 | 2012-01-18 | 兰州理工大学 | Preparation method of composite film on surface of steel and solution formula for preparation method |
| CN102321903A (en) * | 2011-06-23 | 2012-01-18 | 兰州理工大学 | Preparation method of composite film on surface of metallic material and solution composition for preparation method |
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