CN1262345A - Plasma intensified electrochemical surface-porcelainizing process and its products - Google Patents
Plasma intensified electrochemical surface-porcelainizing process and its products Download PDFInfo
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- CN1262345A CN1262345A CN 99100407 CN99100407A CN1262345A CN 1262345 A CN1262345 A CN 1262345A CN 99100407 CN99100407 CN 99100407 CN 99100407 A CN99100407 A CN 99100407A CN 1262345 A CN1262345 A CN 1262345A
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Abstract
A process for generating ceramic layer on the surface of metallic substrate features that plasma arc discharge takes place on the surface of metallic substrate as anode for electrochemically oxidizing sinter to generate ceramic structure film. The used electrolyte solution contains polyphosphate and one or more other substances as additive. The voltage of arc discharge is 100-400 V. The current density is 0.2-20 A/sq.dm. The temp of electrolyte solution is 10-50 deg.C.
Description
The present invention relates to chemical conversion treatment, particularly metallic surface chemical treatment.
The plasma intensified electrochemical surface ceramic technology is to place one to specify electrolyte solution valve metal (being referred to as valve metal) such as aluminium, titanium, magnesium, niobium, zirconium, tantalum or its alloy, utilize electrochemical method, make this material surface produce plasma body arc discharge spot, under the effect of reactions such as thermochemistry, plasma chemistry and electrochemistry, generating the technology of ceramic film, is the once newer metal material surface treatment technology of setting up on the anodic oxidation basis.The product that the present invention relates to this technical matters and make with this technology.
In the prior art, to provide with Sodium hexametaphosphate 99 and borax be the electrolytical plasma intensified electrochemical surface potteryization method of main salt to WO96/33300.But under study for action, the present inventor finds, adopting with Sodium hexametaphosphate 99 and borax is that the electrolytical plasma intensified electrochemical surface potteryization method of main salt still has some shortcomings.
At first, WO96/33300 provided still is apparent not enough for its rete of the product that electrolytical technology was provided of main salt and the bonding force of matrix with Sodium hexametaphosphate 99 and borax, and thermal shock resistance properties has much room for improvement; Secondly, the kind by the product that this technology provided seems not enough.The object of the invention is to overcome the deficiencies in the prior art, and a kind of more firm plasma intensified electrochemical surface of rete and matrix bond pottery metallization processes that makes is provided, and increases the kind of the product that technology thus obtains simultaneously.
The objective of the invention is by adopting following method to realize.
The invention provides a kind of method of metal base surface potteryization, this method comprises by making as the arc discharge of anodic metal base surface plasma body, carry out the electrochemical oxidation sintering, generation has the rete of ceramic structure, wherein, used electrolyte solution is main salt with Sodium hexametaphosphate 99 10～50g/l, boric acid and/or borax 5～20g/l, and the material that also contains one or more is an additive, arc discharge voltage is 100～400V, and current density is 0.5～20A/dm
2, the electrolyte solution temperature is 5～50 ℃; Wherein:
Described additive is selected from one or more in the group that following material forms: magnesium salts, zirconates, aluminium salt, mantoquita, nitrate, vanadate, dichromate, molybdate, permanganate, manganate, silicofluoride, thiocyanide, yellow prussiate, the hexacyanoferrate and other contain compound, the nitrogenous compound of aerobic and contain the oxygen nitrogen compound; Described oxygen containing compound is selected from and is included in organic acid and the salt thereof that contains 2～16 oxygen on the molecular structure, contains 1～12 of carbon number; Nitrogenous compound is selected from that to contain 1～6 nitrogen in molecular structure, contain carbon number be 1～12 organic amine and nitrogen-containing heterocycle compound; The compound that contains nitrogen oxygen is selected from organic acid and the salt thereof that contains 1～8 amino, 1～10 carboxyl on molecular structure, contain 1～20 of carbon number.
The present invention further provides the product that adopts aforesaid method to make.
Below, the present invention is further detailed:
What the present invention adopted is and the similar method of WO96/33300 promptly to pass through 100～400V voltage and 0.5～20A/dm in 5～50 ℃ electrolytic solution
2The electric energy that produces of current density make as the plasma arc light discharge takes place on the anodic metal base surface, carry out electrochemical anodic oxidation, and make the ionogen that participates in reaction carry out sintering at matrix surface, form rete with ceramic structure.
The present inventor finds, when the additive that replaces with following additive as WO96/33300, produced following effect.At first, the sticking power of ceramic membrane and matrix increases, and thermal shock resistance increases; Secondly, the kind of product increases to some extent, has widened the field of using; In addition, by the choose reasonable of additive, electrolytic solution obtains prolonging work-ing life.
In the method for the invention, further preferred use to be selected to be included in contain 2～12 oxygen on the molecular structure, contain the organic acid of 1～8 of carbon number and the oxygen containing compound of salt thereof, as be selected from the group that propionic acid, butyric acid, oxalic acid, lactic acid, oxysuccinic acid, propanedioic acid, toxilic acid, phenylformic acid, phthalic acid, Whitfield's ointment, P-hydroxybenzoic acid, sulphosalicylic acid, citric acid, tartrate, gluconic acid form one or more.
In the method for the invention, preferred nitrogenous compound is selected from that to contain 1～4 nitrogen in molecular structure, contain carbon number be 1～10 organic amine and nitrogen-containing heterocycle compound, as be selected from methylamine, ethamine, dimethylamine, triethylamine, diethylamine, quadrol, propylene diamine, butanediamine, 1, one or more in the group that 6-hexanediamine, triethanolamine, Diethylenetriamine, three second tetramines, aniline, cyclohexyl amine, Ursol D, O-Phenylene Diamine, para hydroxybenzene amine, pyridine, pyrroles, pyrazoles, imidazoles, glyoxal ethyline quinoline, oxine are formed.
In the method for the invention, the compound that preferably contains nitrogen oxygen is selected from and contains 1～6 amino on molecular structure, 1～8 carboxyl, the organic acid and the salt thereof that contain 1～18 of carbon number, as be selected from aminosallcylic acid, Threonine, phenylalanine, glycine, Methionin, nitrilotriacetic acid, CDTA, ethylenediamine tetrapropionic acid(EDTP), ethylene glycol-two-(beta-amido ethyl ether)-N, N '-tetraacethyl, diethylenetriamine pentaacetic acid, N, N-two (hydroxyethyl) glycine, teiethylene tetramine-hexacetic acid, 2-hydroxyethylethylenediaminetriacetic acid, in the group that trimethylenedinitrilo-tertraacetic acid is formed one or more.
In addition, in above-mentioned electrolyte solution, its acid-basicity can wait with sulfuric acid, phosphoric acid, sodium hydroxide, potassium hydroxide, ammoniacal liquor and regulate.
Employing contains the different ionogen that polyphosphoric 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 in industry such as finishing material, weaving, automobile, aviation, navigations.Be described in detail the present invention below by several examples: (1) green ceramic membrane process
Electrolyte solution contains: Sodium hexametaphosphate 99 10～50g/l, boric acid 5～20g/l, chromium acetate 2～20g/l, calcium acetate 1～10g/l, trisodium citrate 2～15g/l, CDTA 1～10g/l.More than each material all adopt chemically pure reagent, or the highly industry product of special purpose, prepare with distilled water, preparation is after earlier Sodium hexametaphosphate 99 thoroughly being dissolved, to add other each materials in proper order, adjust pH is in 2～12 scopes, tank liquor temperature is controlled at 10～45 ℃, adopt and force or the injection stirring, or workpiece moves.Process current density D
A0.5～20A/dm
2, plasma body arc voltage 120～400V, oxidization time 10～30 minutes, can make thicknesses of layers and be 5～30 microns by light green to bottle-green ceramic membrane.(2) grey is to the black ceramic membrane process
Electrolyte solution contains: Sodium hexametaphosphate 99 10～50g/l, and borax 5～15g/l, sodium acetate 5～10g/l, sodium dichromate 99 1～15g/l, vanadic acid sodium 1～20g/l, trolamine 1～5g/l, pH are 4～13.Compound method and alr mode are with (1), and solution temperature is controlled 10～45 ℃, process current density D
A=0.5～15A/dm
2, plasma body arc discharge voltage 120～380V, oxidization time is 10～30 minutes, the grey that obtains 6～30 microns is to black ceramic membrane.(3) grey is to black-and-blue ceramic membrane technology
Electrolyte solution contains: Sodium hexametaphosphate 99 10～50g/l, and borax 5～15g/l, yellow prussiate of potash 1～20g/l, Sodium Silicofluoride 5～20g/l, sodium sulfate 1～10g/l, pyridine 1～5g/l, pH are 6～13.Compound method and alr mode are with (1), and solution temperature is controlled 10～45 ℃, process current density D
A=0.5～12A/dm
2, voltage 130～370V, oxidization time 10～30 minutes obtains 5～30 microns ashes to black-and-blue ceramic membrane.
Adopt the product of the inventive method preparation, its ceramic film good uniformity, with the substrate combinating strength height, hardness is big, the space is few, and thermal-shock resistance is good, wear resistance and solidity to corrosion are splendid, and bright-colored, pattern is many, simultaneously, can form pattern, ornamental splendid.
Method of the present invention is applicable to the surface treatment of the matrix workpiece of various size shape and structure.
Further specify the present invention below by two specific embodiment.
Wherein, the various physicalies of indication are measured by following instrument or method:
Adhesion test: adopt the test of WS-92 scrape adhesion tester, measure critical
Pressure;
Heat shock resistance test: adopt heat-resisting to room temperature distilled water water quenching reference membrane by 550 ℃
Impact property is observed the film surface with 100 times of magnifying glasses, determines that nothing be full of cracks, nothing come off
The time test number (TN);
Bath life: have or not deposited phenomenon in the observation solution to determine time length.
Embodiment 1:
Get 100 liters of distilled water and put into oxidation trough, add 4.5 kilograms of Sodium hexametaphosphate 99s, add 1 kilogram of borax more successively after molten fully, 1.5 kilograms of yellow prussiate of potash, 1 kilogram of Sodium Silicofluoride, 0.8 kilogram in sodium sulfate, 0.4 kilogram of pyridine, transfer about pH to 10 the dissolving back fully, get 6063 aluminium section bars of 200 * 150 * 1mm, after cleaning oil removing, with the workpiece aluminium section bar, last anchor clamps are communicated with power supply, stir in the groove, do negative electrode with stainless steel plate, workpiece is an anode, the beginning oxide treatment, keep constant current 36A, electric current descended when voltage slowly rose to 200～230V, and oxidization time totally 20 minutes stops oxidation, take out workpiece, obtain the black-and-blue ceramic membrane of 20 micron thickness.30～40 seconds wear-resisting sandblast time, microhardness (HV) is 800Kg/mm
2, block 9 grades of this experiments.
Embodiment 2:
Get 500 liters of distilled water and put into oxidation trough, add 25 kilograms of Sodium hexametaphosphate 99s, after the dissolving, add 3 kilograms of boraxs successively, 4 kilograms of sodium acetates, 1 kilogram of sodium dichromate 99,5 kilograms of vanadic acid sodiums, 1 kilogram of trolamine fully.After the dissolving, transfer pH fully to alkalescence.Get 10 cast aluminium piston of automobile,, be connected, carry out vigorous stirring in the groove with power supply with anchor clamps on the piston article.Make negative electrode with stainless steel plate, workpiece is an anode, and the beginning oxidation keeps constant current 40A, and voltage slowly rises to 170～200V, and workpiece surface has plasma body arc discharge phenomenon.Electric current descended when voltage rose to 240～300V, and oxidization time is 30 minutes, stops oxidation, and powered-down takes out workpiece, obtains the black ceramic membrane of 25 micron thickness.Through test determination, the heat shock resistance number of times reaches 20 times.
Comparative example
Adopt the physicals of the black ceramic membrane that the method for embodiment 3 among black ceramic membrane that aforesaid method obtains embodiment 2 and the WO96/33300 obtains to compare, the results are shown in the table 1.
Table 1
Such scheme only provides as an example, and does not limit the present invention in any way, and those skilled in the art can carry out various changes or improvement to the present invention, but does not all break away from the protection domain of essence of the present invention and claim.
Claims (11)
1, a kind of method of metal base surface potteryization, comprise by making as the arc discharge of anodic metal base surface plasma body, carry out the electrochemical oxidation sintering, generation has the rete of ceramic structure, wherein, used electrolyte solution is main salt with Sodium hexametaphosphate 99 10～50g/l, boric acid and/or borax 5～20g/l, also contains additive, arc discharge voltage is 100～400V, and current density is 0.5～20A/dm
2, the electrolyte solution temperature is 5～50 ℃; Wherein:
Described additive is selected from one or more in the group that following material forms: magnesium salts, zirconates, aluminium salt, mantoquita, nitrate, vanadate, dichromate, molybdate, permanganate, manganate, silicofluoride, thiocyanide, yellow prussiate, the hexacyanoferrate and other contain compound, the nitrogenous compound of aerobic and contain the oxygen nitrogen compound; Described oxygen containing compound is selected from and is included in organic acid and the salt thereof that contains 2～16 oxygen on the molecular structure, contains 1～12 of carbon number; Nitrogenous compound is selected from that to contain 1～6 nitrogen in molecular structure, contain carbon number be 1～12 organic amine and nitrogen-containing heterocycle compound; The compound that contains nitrogen oxygen is selected from organic acid and the salt thereof that contains 1～8 amino, 1～10 carboxyl on molecular structure, contain 1～20 of carbon number.
2, the method for claim 1 is characterized in that, described oxygenatedchemicals is selected from and is included in organic acid and the salt thereof that contains 2～12 oxygen on the molecular structure, contains 1～8 of carbon number.
3, method as claimed in claim 2, it is characterized in that described oxygen containing compound is selected from one or more in the group that propionic acid, butyric acid, oxalic acid, lactic acid, oxysuccinic acid, propanedioic acid, toxilic acid, phenylformic acid, phthalic acid, Whitfield's ointment, P-hydroxybenzoic acid, sulphosalicylic acid, citric acid, tartrate, gluconic acid form.
4, the method for claim 1 is characterized in that, described nitrogenous compound is selected from that to contain 1～4 nitrogen in molecular structure, contain carbon number be 1～10 organic amine and nitrogen-containing heterocycle compound.
5, method as claimed in claim 4, it is characterized in that, described nitrogenous compound is selected from by methylamine, ethamine, dimethylamine, triethylamine, diethylamine, quadrol, propylene diamine, butanediamine, 1, one or more in the group that 6-hexanediamine, triethanolamine, Diethylenetriamine, three second tetramines, aniline, cyclohexyl amine, Ursol D, O-Phenylene Diamine, para hydroxybenzene amine, pyridine, pyrroles, pyrazoles, imidazoles, glyoxal ethyline quinoline, oxine are formed.
6, the method for claim 1 is characterized in that, the described compound that contains nitrogen oxygen is selected from organic acid and the salt thereof that contains 1～6 amino, 1～8 carboxyl on molecular structure, contain 1～18 of carbon number.
7, method as claimed in claim 6, it is characterized in that, the compound of described nitrogenous oxygen is selected from by aminosallcylic acid, Threonine, phenylalanine, glycine, Methionin, nitrilotriacetic acid, CDTA, ethylenediamine tetrapropionic acid(EDTP), ethylene glycol-two-(beta-amido ethyl ether)-N, N '-tetraacethyl, diethylenetriamine pentaacetic acid, N, one or more in the group that N-two (hydroxyethyl) glycine, teiethylene tetramine-hexacetic acid, 2-hydroxyethylethylenediaminetriacetic acid, trimethylenedinitrilo-tertraacetic acid are formed.
8, the method for claim 1, it is characterized in that, described electrolyte solution contains: Sodium hexametaphosphate 99 10～50g/l, boric acid 5～20g/l, chromium acetate 2～20g/l, calcium acetate 1～10g/l, trisodium citrate 2～15g/l, CDTA 1～10g/l, plasma body arc voltage 120～400V.
9, the method for claim 1, it is characterized in that, described electrolyte solution contains: Sodium hexametaphosphate 99 10～50g/l, borax 5～15g/l, sodium acetate 5～10g/l, sodium dichromate 99 1～15g/l, vanadic acid sodium 1～20g/l, trolamine 1～5g/l, plasma body arc discharge voltage 120～380V.
10, the method for claim 1, it is characterized in that, described electrolyte solution contains: Sodium hexametaphosphate 99 10～50g/l, borax 5～15g/l, yellow prussiate of potash 1～20g/l, Sodium Silicofluoride 5～20g/l, sodium sulfate 1～10g/l, pyridine 1～5g/l, plasma body arc discharge voltage 130～370V.
11, adopt the product that makes as the described method of claim 1～10.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383292C (en) * | 2004-12-29 | 2008-04-23 | 湖南大学 | Anodizing method for generating ceramic film on aluminium and its alloy material surface |
| CN102312260A (en) * | 2011-08-22 | 2012-01-11 | 吴江市精工铝字制造厂 | Mixed acid hard anodic oxidation AC-DC superposition method for copper-aluminum alloy |
| CN102345151A (en) * | 2011-10-08 | 2012-02-08 | 长安大学 | Method for preparing ZrO2 compound ceramic film on surfaces of magnesium and magnesium alloy through microarc oxidization |
| CN102758233A (en) * | 2011-04-27 | 2012-10-31 | 游鸿文 | Method for treating golf ball head by adopting hard-oxygen oxidation method |
| CN105483793A (en) * | 2015-12-10 | 2016-04-13 | 苏州市嘉明机械制造有限公司 | Manufacturing technology of expansion and shrinkage resisting insulation mirror plate |
| CN108588789A (en) * | 2018-04-26 | 2018-09-28 | 河海大学常州校区 | A kind of preparation method for the processing solution and boron titanium compound preparing boron titanium compound film layer |
| CN106757261B (en) * | 2016-11-29 | 2018-11-09 | 中南大学 | A kind of aluminium material surface oxide ceramic membrane and the compound wear-and corrosion-resistant coating and preparation method thereof of zeolite membrane |
| CN114182260A (en) * | 2021-12-13 | 2022-03-15 | 东莞市润纳实业有限公司 | Aluminum alloy surface treating agent and aluminum alloy surface nano-pore treatment method |
-
1999
- 1999-02-04 CN CN 99100407 patent/CN1262345A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100383292C (en) * | 2004-12-29 | 2008-04-23 | 湖南大学 | Anodizing method for generating ceramic film on aluminium and its alloy material surface |
| CN102758233A (en) * | 2011-04-27 | 2012-10-31 | 游鸿文 | Method for treating golf ball head by adopting hard-oxygen oxidation method |
| CN102312260A (en) * | 2011-08-22 | 2012-01-11 | 吴江市精工铝字制造厂 | Mixed acid hard anodic oxidation AC-DC superposition method for copper-aluminum alloy |
| CN102345151A (en) * | 2011-10-08 | 2012-02-08 | 长安大学 | Method for preparing ZrO2 compound ceramic film on surfaces of magnesium and magnesium alloy through microarc oxidization |
| CN102345151B (en) * | 2011-10-08 | 2013-11-20 | 长安大学 | Method for preparing ZrO2 compound ceramic film on surfaces of magnesium and magnesium alloy through microarc oxidization |
| CN105483793A (en) * | 2015-12-10 | 2016-04-13 | 苏州市嘉明机械制造有限公司 | Manufacturing technology of expansion and shrinkage resisting insulation mirror plate |
| CN106757261B (en) * | 2016-11-29 | 2018-11-09 | 中南大学 | A kind of aluminium material surface oxide ceramic membrane and the compound wear-and corrosion-resistant coating and preparation method thereof of zeolite membrane |
| CN108588789A (en) * | 2018-04-26 | 2018-09-28 | 河海大学常州校区 | A kind of preparation method for the processing solution and boron titanium compound preparing boron titanium compound film layer |
| CN114182260A (en) * | 2021-12-13 | 2022-03-15 | 东莞市润纳实业有限公司 | Aluminum alloy surface treating agent and aluminum alloy surface nano-pore treatment method |
| CN114182260B (en) * | 2021-12-13 | 2024-05-14 | 东莞市润纳实业有限公司 | Aluminum alloy surface treating agent and aluminum alloy surface nano-pore treating method |
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