CN102212864A - Method for modifying electrolysis phosphorization membrane - Google Patents
Method for modifying electrolysis phosphorization membrane Download PDFInfo
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- CN102212864A CN102212864A CN 201110155460 CN201110155460A CN102212864A CN 102212864 A CN102212864 A CN 102212864A CN 201110155460 CN201110155460 CN 201110155460 CN 201110155460 A CN201110155460 A CN 201110155460A CN 102212864 A CN102212864 A CN 102212864A
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Abstract
The invention discloses a method for modifying an electrolysis phosphorization membrane and belongs to the technical field of surface treatment. A proper amount of nanopowder is added into an electrolysis phosphorated liquid, a steel piece serves as a cathode, an opposite electrode is an insoluble anode, and the electrolysis phosphorization membrane is prepared by virtue of electrolysis phosphorization. The electrolysis phosphorization membrane can be prepared from zinc electrolysis phosphorated liquid, calcium electrolysis phosphorated liquid, zinc-calcium electrolysis phosphorated liquid, manganese electrolysis phosphorated liquid and zinc-manganese electrolysis phosphorated liquid by virtue of electrolysis phosphorization; and the added nanopowder can be one or a mixture of titanium dioxide, silicon dioxide, aluminium oxide, zirconium dioxide, polyaniline and ferrite. The obtained electrolysis phosphorization membrane is even and has the advantages of smooth surface, abrasion and corrosion resistance and the like.
Description
Technical field
The invention belongs to technical field of surface, be suitable for a kind of method that iron and steel electrolytic phosphating rete is modified.
Technical background
It is that metal is placed in the solution that contains phosphoric acid, phosphoric acid salt and other pharmaceutical chemicalss that electrolytic phosphating is handled, pass through additional power source, under certain process conditions, react in the metallic surface, it is complete that the metallic surface is generated, have the insoluble phosphate layer of certain preservative activity, this rete promptly is called the electrolytic phosphating film.
The phosphate conversion film is applied on iron and steel, aluminium, magnesium, zinc, cadmium, lead and the alloy thereof, promptly can be used as final finish layer, also can be used as other tectal middle layers, and its effect mainly contains the solidity to corrosion that following aspect (1) can improve matrix; (2) the phosphorous chemical industry artistic skill improves matrix and the sticking power that is coated with interlayer or other organic finish interlayers; (3) the phosphorous chemical industry artistic skill provides the clean surface; (4) phosphatize phosphate coat can improve the cold-forming property of material; (5) phosphating process can also obviously improve the surface friction performance of workpiece.
But phosphatize phosphate coat is thinner before the application, and its film often will be given birth to yellow the embroidery because hole is many, free area is big, and solidity to corrosion is very poor in the phosphatization drying process.The protection against corrosion phosphatize phosphate coat is thicker, though its solidity to corrosion is more quite a lot of than application phosphatize phosphate coat, but still limited.In order to improve the solidity to corrosion of phosphatize phosphate coat, will carry out passivation, sealing treatment to it, make the phosphatize phosphate coat hole obtain certain filling.And phosphatization liquid all is acid, and strong solution acidity is bigger, so phosphatization liquid has very high activity to steel, particularly to those because chemical ingredients and structural reason and responsive especially material activity is bigger.Electrolytic phosphating moves the negatively charged ion anode in the phosphatization liquid, and analyses oxygen by anodic by impressed voltage, oxidized hydrogen, suppressed the generation of hydrogen, the effect of playing " blockade " positive column impels phosphatization to speed up and obtains fine and closely woven phosphate coating simultaneously as the inhibiter effect.
Because nano particle has surface effects, small-size effect, quantum effect and macro quanta tunnel effect, make nanometer the characteristic of macroscopic material occur being different from aspects such as physicals, mechanical properties, show as high-strength and high ductility, high specific heat, high rate of expansion etc., the research of nano material and application in recent years is a focus of at present domestic and international Materials science research.
In order further to improve the phosphorization membrane outward appearance, strengthen the corrosion-proof wear of phosphatize phosphate coat, the invention provides the method that the adding nano-powder is modified the electrolytic phosphating film.
Summary of the invention
The objective of the invention is to introduce nano-powder the phosphatize phosphate coat of electrolytic phosphating method preparation is modified, contain the electrolytic phosphating film of nano-oxide particles, improve the corrosion resistance nature and the wear resisting property of phosphatize phosphate coat in steel surface preparation place.Add an amount of nano-powder in electrolytic phosphating liquid, steel part is done negative electrode, to insoluble anode very, carries out electrolytic phosphating and prepares the electrolytic phosphating film.Gained electrolytic phosphating film can be by zinc, calcium is, zinc calcium is, manganese is, zinc-manganese is that electrolytic phosphating liquid makes by electrolytic phosphating; The nano-powder that adds can be a titanium dioxide, silicon-dioxide, aluminium sesquioxide, zirconium dioxide, polyaniline, one or several mixed of ferrite.The electrolytic phosphating film even film layer of gained, smooth surface, wear resistance and corrosion resistance all has enhancing.
The technical scheme that adopts:
The method of modification electrolytic phosphating film of the present invention comprises following processing step:
(1) steel piece is after alkaline degreasing, acid liquor etching, and the surface cleans up with deionized water, as the negative electrode of electrolytic phosphating, to insoluble anode very.
(2) add nano powder in the electrolytic phosphating liquid, electrolytic phosphating liquid can be that zinc system, calcium are, zinc calcium is, manganese is, zinc-manganese is an electrolytic phosphating liquid.Nano powder can be titanium dioxide, silicon-dioxide, aluminium sesquioxide, zirconium dioxide, ferrite, the mixed powder of one or more of polyaniline.
(3) electrolytic phosphating makes the steel part surface generate the electrolytic phosphating film.The electrolytic phosphating temperature is 10～50 ℃, and the electrolytic phosphating time is 0.5～30min, and powder content is 5～5000mg/L.
(4) drying.Steel part behind the electrolytic phosphating is dried up the electrolytic phosphating film after obtaining modifying.
(5) add nano powder in the electrolytic phosphating liquid, electrolytic phosphating liquid can be that zinc system, calcium are, zinc calcium is, manganese is, zinc-manganese is an electrolytic phosphating liquid.Nano powder can be titanium dioxide, silicon-dioxide, aluminium sesquioxide, zirconium dioxide, ferrite, the mixed powder of one or more of polyaniline;
(6) electrolytic phosphating makes the steel part surface generate the electrolytic phosphating film.The electrolytic phosphating temperature is 10～50 ℃, and the electrolytic phosphating time is 0.5～30min, and powder content is 5～5000mg/L;
(4) drying.Steel part behind the electrolytic phosphating is dried up the electrolytic phosphating film after obtaining modifying.
Above-mentioned insoluble anode adopts Graphite Electrodes, stainless steel electrode or oxide-coated titanium electrode.
Above-mentioned electrolytic phosphating liquid is that zinc system, calcium system, zinc calcium system, manganese system or zinc-manganese are electrolytic phosphating liquid.
Above-mentioned nano powder is a titanium dioxide, silicon-dioxide, aluminium sesquioxide, zirconium dioxide, ferrite, the mixed powder of one or more of polyaniline.
Embodiment
Embodiment one
1, used metal is a plain carbon stool, and through the silicon carbide paper light of polishing step by step, the surface cleans up with deionized water.
2, through the silicon carbide paper light of polishing step by step, the surface cleans up with deionized water.Contain zinc-nickel manganese triple cationic system phosphorization liquid and get one liter, add amphoteric ion type dispersion agent 1g/L, magnetic agitation adds nanometer Al again
2O
3Powder 1 g/L, magnetic agitation.Transfer pH=2.5 with yellow soda ash, treatment temp is 20 ℃, and the treatment time is 35min.
3, drying.Steel part behind the electrolytic phosphating is dried up the electrolytic phosphating film after obtaining modifying.
Embodiment two
1, used metal is a plain carbon stool, and through the silicon carbide paper light of polishing step by step, the surface cleans up with deionized water.
2, through the silicon carbide paper light of polishing step by step, the surface cleans up with deionized water.Phosphatization liquid contains Mazhev salt, and phosphoric acid, nitric acid, nickelous nitrate etc. add non-ionic dispersing agent 2g/L, and magnetic agitation adds nanometer SiO again
2Powder 1.5 g/L, magnetic agitation.Transfer pH=3 with yellow soda ash, treatment temp is 25 ℃, and the treatment time is 30min.
3, drying.Steel part behind the electrolytic phosphating is dried up the electrolytic phosphating film after obtaining modifying.
Embodiment three
1, used metal is a plain carbon stool, and through the silicon carbide paper light of polishing step by step, the surface cleans up with deionized water.
2, through the silicon carbide paper light of polishing step by step, the surface cleans up with deionized water.Phosphatization liquid contains zinc oxide, calcium oxide, and phosphoric acid, nickelous nitrates etc. add cationic dispersing agent 2g/L, and magnetic agitation adds polyaniline particle 5 g/L, magnetic agitation again.Transfer pH=3.5 with yellow soda ash, treatment temp is 30 ℃, and the treatment time is 25min.
3, drying.Steel part behind the electrolytic phosphating is dried up the electrolytic phosphating film after obtaining modifying.
Embodiment four
1, used metal is a plain carbon stool, and through the silicon carbide paper light of polishing step by step, the surface cleans up with deionized water.
2, through the silicon carbide paper light of polishing step by step, the surface cleans up with deionized water.Phosphatization liquid contains primary zinc phosphate, zinc nitrate, manganous nitrate etc., adds anionic dispersing agent 4g/L, and magnetic agitation adds nanometer SiO again
2Powder 1 g/L nanometer ZrO
21 g/L, magnetic agitation.Transfer pH=3 with yellow soda ash, treatment temp is 35 ℃, and the treatment time is 20min.
3, drying.Steel part behind the electrolytic phosphating is dried up the electrolytic phosphating film after obtaining modifying.
Claims (4)
1. modify the method for electrolytic phosphating film, it is characterized in that comprising following processing step:
(1) steel piece is after alkaline degreasing, acid liquor etching, and the surface cleans up with deionized water, as the negative electrode of electrolytic phosphating, to insoluble anode very;
(2) add nano powder in the electrolytic phosphating liquid, electrolytic phosphating liquid can be that zinc system, calcium are, zinc calcium is, manganese is, zinc-manganese is an electrolytic phosphating liquid, and nano powder can be titanium dioxide, silicon-dioxide, aluminium sesquioxide, zirconium dioxide, ferrite, the mixed powder of one or more of polyaniline;
(3) electrolytic phosphating makes the steel part surface generate the electrolytic phosphating film, and the electrolytic phosphating temperature is 10～50 ℃, and the electrolytic phosphating time is 0.5～30min, and powder content is 5～5000mg/L;
(4) drying dries up the steel part behind the electrolytic phosphating, the electrolytic phosphating film after obtaining modifying.
2. the method for modification electrolytic phosphating film according to claim 1 is characterized in that insoluble anode adopts Graphite Electrodes, stainless steel electrode or oxide-coated titanium electrode.
3. the method for modification electrolytic phosphating film according to claim 1 is characterized in that described electrolytic phosphating liquid is that zinc system, calcium system, zinc calcium system, manganese system or zinc-manganese are electrolytic phosphating liquid.
4. the method for modification electrolytic phosphating film according to claim 1 is characterized in that described nano powder is a titanium dioxide, silicon-dioxide, aluminium sesquioxide, zirconium dioxide, ferrite, the mixed powder of one or more of polyaniline.
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| CN 201110155460 CN102212864A (en) | 2011-06-10 | 2011-06-10 | Method for modifying electrolysis phosphorization membrane |
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| CN 201110155460 CN102212864A (en) | 2011-06-10 | 2011-06-10 | Method for modifying electrolysis phosphorization membrane |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424963A (en) * | 2011-12-23 | 2012-04-25 | 无锡鸿海龙船机有限公司 | Phosphating treatment process for deformation-free anti-scratch inner sleeve |
| CN104294349A (en) * | 2014-09-23 | 2015-01-21 | 沈阳大学 | Method for coating normal-temperature black phosphating film on steel surface |
| CN107419317A (en) * | 2017-07-04 | 2017-12-01 | 马鞍山起劲磁塑科技有限公司 | A kind of method for lifting magnechuck bottom plate wearability |
| CN109609943A (en) * | 2018-11-21 | 2019-04-12 | 天津市朋展钢管有限公司 | A kind of processing method of submerged-arc welding steel pipe |
| CN109898123A (en) * | 2019-03-11 | 2019-06-18 | 山东凤阳佰乐舒家居有限公司 | A kind of steel wire drawing electrolytic phosphating liquid and preparation method thereof |
| CN113073371A (en) * | 2021-03-22 | 2021-07-06 | 领润(南京)绿色化学有限公司 | Clean anode plate friendly electrolytic phosphating solution and phosphating process thereof |
| CN115725964A (en) * | 2022-09-01 | 2023-03-03 | 东莞市颖兴金属表面处理材料有限公司 | Low-temperature less-slag phosphating solution and preparation method thereof |
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| CN101104946A (en) * | 2005-07-15 | 2008-01-16 | 株式会社电装 | Electrolytic phosphating treatment method and warm or hot forging method |
| CN102051616A (en) * | 2010-11-23 | 2011-05-11 | 广东万和新电气股份有限公司 | Surface treatment method for movable iron core of fuel gas proportional valve |
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| JPS5479133A (en) * | 1977-12-06 | 1979-06-23 | Kobe Steel Ltd | Manufacture of zinc-electroplated steel product for phosphating |
| JPS5541930A (en) * | 1978-09-16 | 1980-03-25 | Nippon Paint Co Ltd | After-treatment method of phosphate film |
| JPH0356695A (en) * | 1989-07-24 | 1991-03-12 | Nippon Steel Corp | Composite plated steel sheet with excellent DI workability |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102424963A (en) * | 2011-12-23 | 2012-04-25 | 无锡鸿海龙船机有限公司 | Phosphating treatment process for deformation-free anti-scratch inner sleeve |
| CN102424963B (en) * | 2011-12-23 | 2013-09-18 | 无锡鸿海龙船机有限公司 | Phosphate treatment technology for deformation-free scuffing-resistant inner sleeve |
| CN104294349A (en) * | 2014-09-23 | 2015-01-21 | 沈阳大学 | Method for coating normal-temperature black phosphating film on steel surface |
| CN107419317A (en) * | 2017-07-04 | 2017-12-01 | 马鞍山起劲磁塑科技有限公司 | A kind of method for lifting magnechuck bottom plate wearability |
| CN109609943A (en) * | 2018-11-21 | 2019-04-12 | 天津市朋展钢管有限公司 | A kind of processing method of submerged-arc welding steel pipe |
| CN109898123A (en) * | 2019-03-11 | 2019-06-18 | 山东凤阳佰乐舒家居有限公司 | A kind of steel wire drawing electrolytic phosphating liquid and preparation method thereof |
| CN113073371A (en) * | 2021-03-22 | 2021-07-06 | 领润(南京)绿色化学有限公司 | Clean anode plate friendly electrolytic phosphating solution and phosphating process thereof |
| CN115725964A (en) * | 2022-09-01 | 2023-03-03 | 东莞市颖兴金属表面处理材料有限公司 | Low-temperature less-slag phosphating solution and preparation method thereof |
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Application publication date: 20111012 |