CN102433559A - Rare earth cerium-containing metal treatment fluid and production method thereof - Google Patents
Rare earth cerium-containing metal treatment fluid and production method thereof Download PDFInfo
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- CN102433559A CN102433559A CN2011103260187A CN201110326018A CN102433559A CN 102433559 A CN102433559 A CN 102433559A CN 2011103260187 A CN2011103260187 A CN 2011103260187A CN 201110326018 A CN201110326018 A CN 201110326018A CN 102433559 A CN102433559 A CN 102433559A
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Abstract
The invention discloses a rare earth cerium-containing metal treatment fluid and a production method thereof. The rare earth cerium-containing metal treatment fluid is characterized by consisting of 0.5 to 2 parts of fluorozirconic acid, 1.5 to 3.5 parts of zinc molybdate, 0.2 to 1 part of sodium nitrate, 0.04 to 0.06 part of ethylene diamine tetraacetic acid, 0.4 to 0.6 part of sodium fluoride, 0.2 to 0.8 part of lanthanum nitrate and 100 parts of water. A ceramic technology is adopted, and after the metal surface treatment fluid is coated, sprayed or deposited on the surface of metal, a zirconium oxide ceramic film can be formed on the surface of the metal, and the activity of the zirconium oxide ceramic film formed on the surface of the metal is greatly improved under the action of a rare earth element of cerous nitrate; compared with the similar ceramic technology, the production method has the advantages that: the surface of the zirconium oxide ceramic film has higher activity, and the formed zirconium oxide ceramic film can be well bonded with the surface of the metal and also can be well bonded with a subsequent film required to be coated; and compared with a silane technology, the production method has a wider application range and high adaptability.
Description
Technical field
The present invention relates to a kind of metal surface treatment technology, particularly a kind of metal treatment fluid and working method thereof that contains the rare earth cerium.
Background technology
Phosphatization is carried out in the metallic surface, all is the sheet metal component application pre-treating process of (containing electrophoresis, electrostatic spraying) usually, use T&B, but this method all has very big pollution to environment and operator, is seeking other substitute technology at present.
In order to substitute the phosphorization technology of high pollution, having a kind of at present is the silane technology, and another kind is a ceramic technology, their without phosphorus, heavy metal frees, and increase combines with paint film.
One Chinese patent application number is a kind of environment-friendly type metal surface finishing agent of 200910116134.9 and preparation method thereof; A kind of wetting back adding of aqueous solution coupling agent that membrane-forming agent usefulness is contained dispersion agent is disclosed; Dispersed with stirring is to obtaining stable colloid; What add water miscible Si or IV family element again contains the F complex compound, and adding as the water of the acid of stablizer and surplus and the pH value that is adjusted to system again is 1.0～3.0, promptly obtains environment-friendly type metal surface finishing agent.Be diluted with water to the working fluid of pH value 3.0～6.0 during use, adopt immersion or spray mode that pending clean metallic surfaces is contacted with the environment-friendly type metal surface finishing agent of this invention, can obtain the compound conversion rete of micro-crystalline ceramic; Characteristics such as this invention treatment agent has the performance index that are superior to or are equal to existing zinc system, phosphating liquor of iron series, has environmental protection, harmless, subzero treatment, low slag and need not to do table and transfer, and is simple to operation; It is the new generation of environment protection product of instead traditional metal surface treatment agent.But this metal conditioner, the still activity of security deposit's metal surface rete better can't reach with the long-term of paint film and combines.
Summary of the invention
The objective of the invention is to provide a kind of bonderizing that substitutes the metallic surface for the deficiency that solves above-mentioned prior art; Form ceramic membrane in the metallic surface; And improve the surfactivity of metallic surface ceramic membrane, thereby improve a kind of metal treatment fluid and the working method thereof that contains the rare earth cerium that combines fastness of metallic surface and paint film.
To achieve these goals; A kind of metal treatment fluid that contains the rare earth cerium that the present invention designed is characterized in that prescription consists of: 0.5 part to 2 parts of fluorine zirconic acid, 1.5 parts to 3.5 parts of zinc molybdates, 0.2 part to 1 part in SODIUMNITRATE, 0.04 part to 0.06 part of EDTA Disodium, 0.4 part to 0.6 part of Sodium Fluoride, 0.2 part to 0.8 part of cerous nitrate, 100 parts in water.
A kind of metal treatment fluid and working method thereof that contains the rare earth cerium provided by the invention, it comprises the reaction kettle that adopts water tank, header tank and band to stir, and it is characterized in that process step is:
1) produce before earlier with industrial tap water to cleaning in the reaction kettle, again with alcoholic solvent further to cleaning in the reaction kettle, wash number is not less than twice, each stirring and washing time was not less than five minutes, did not contain pure soluble substance in the maintenance reaction kettle;
2) pure water is evacuated to header tank from water tank, injects reaction kettle through measuring the back;
3) finished product pure water IR per ton is controlled at 990kg, and error control is in positive 5kg scope;
4) start the stirring back and inject SODIUMNITRATE, rotating speed is controlled at this 30r/min to 60r/min;
5) treat that SODIUMNITRATE fully dissolves the back and injects zinc molybdate;
6) continue to stir after 30 minutes, inject fluorine zirconic acid, EDTA Disodium, Sodium Fluoride successively, wait to inject raw material and all dissolve back adding cerous nitrate;
7) continue to stir after 15 minutes, with sodium hydroxide or nitric acid regulate and the controlled liq pH value about 2.0;
8) stop after pH value is stabilized in about 2.0 stirring and carry out the can of branch bucket;
9) no longer need cleaning equipment again during continuous production.
Optimal selection prescription of the present invention is 1 part of fluorine zirconic acid, 2.5 parts of zinc molybdates, 0.5 part in SODIUMNITRATE, 0.05 part of EDTA Disodium, 0.5 part of Sodium Fluoride, 0.5 part of cerous nitrate, 100 parts in water.
A kind of metal treatment fluid and working method thereof that contains the rare earth cerium provided by the invention; Adopt ceramic technology,, can form the zirconia ceramics film in the metallic surface through brushing, spray or soaking and amass behind the metallic surface; And under the effect of REE cerous nitrate; Improved the activity of the zirconia ceramics film of metallic surface formation greatly, compared with similar ceramic technology, its surface has stronger activity; Make the zirconia ceramics film of formation form good binding, can keep good binding with the follow-up paint film of coating that needs again again with the metallic surface; Than silane technical application more face width, better adaptability.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further specified.
Embodiment 1:
A kind of metal treatment fluid that contains the rare earth cerium that present embodiment provides, its prescription consists of: 1 part of fluorine zirconic acid, 2.5 parts of zinc molybdates, 0.5 part in SODIUMNITRATE, 0.05 part of EDTA Disodium, 0.5 part of Sodium Fluoride, 0.5 part of cerous nitrate, 100 parts in water.
Its working method comprises the reaction kettle that adopts water tank, header tank and band to stir, and process step is:
1) produce before earlier with industrial tap water to cleaning in the reaction kettle, again with alcoholic solvent further to cleaning in the reaction kettle, wash number is not less than twice, each stirring and washing time was not less than five minutes, did not contain pure soluble substance in the maintenance reaction kettle;
2) pure water is evacuated to header tank from water tank, injects reaction kettle through measuring the back;
3) finished product pure water IR per ton is controlled at 990kg, and error control is in positive 5kg scope;
4) start the stirring back and inject SODIUMNITRATE, rotating speed is controlled at this 30r/min to 60r/min;
5) treat that SODIUMNITRATE fully dissolves the back and injects zinc molybdate;
6) continue to stir after 30 minutes, inject fluorine zirconic acid, EDTA Disodium, Sodium Fluoride successively, wait to inject raw material and all dissolve back adding cerous nitrate;
7) continue to stir after 15 minutes, with sodium hydroxide or nitric acid regulate and the controlled liq pH value about 2.0;
8) stop after pH value is stabilized in about 2.0 stirring and carry out the can of branch bucket, every barrel of net weight is controlled at and is not less than 25+0.1kg.
A kind of metal treatment fluid and the working method thereof that contains the rare earth cerium that obtains according to above-mentioned prescription; The metal parts of the light face low-carbon steel material that will handle during use was immersed in the metal surface treating liquid that present embodiment provides 1 minute, formed the zirconia ceramics film, through under 180 centigradetemperatures to 10 fens clock times of zirconia ceramics film burin-in process; Adopt spectrographic technique that it is carried out surface-active test then; Reach and receive crystalline substance, coat paint film again after, under 35 centigradetemperatures; Tested through 500 hour time, its corrosion-resistant index reaches the salt-fog test standard.
Embodiment 2:
A kind of metal treatment fluid that contains the rare earth cerium that present embodiment provides, its prescription consists of: 0.5 part of fluorine zirconic acid, 1.5 parts of zinc molybdates, 0.2 part in SODIUMNITRATE, 0.04 part of EDTA Disodium, 0.4 part of Sodium Fluoride, 0.2 part of cerous nitrate, 100 parts in water.Working method is with embodiment 1.
A kind of metal treatment fluid and the working method thereof that contains the rare earth cerium that obtains according to above-mentioned prescription; The metal parts of the hair side low-carbon steel material that will handle during use was immersed in the metal surface treating liquid that present embodiment provides 2 minutes, formed the zirconia ceramics film, through under 200 centigradetemperatures to 20 fens clock times of zirconia ceramics film burin-in process; Adopt spectrographic technique that it is carried out surface-active test then; Reach and receive crystalline substance, coat paint film again after, under 35 centigradetemperatures; Tested through 500 hour time, its corrosion-resistant index reaches the salt-fog test standard.
Embodiment 3:
A kind of metal treatment fluid that contains the rare earth cerium that present embodiment provides; Its prescription consists of: 2 parts of fluorine zirconic acids, 3.5 parts of zinc molybdates, 1 part in SODIUMNITRATE, 0.06 part of EDTA Disodium, 0.6 part of Sodium Fluoride, 0.8 part of cerous nitrate, 100 parts in water, its working method is identical with embodiment 1.
A kind of metal treatment fluid and the working method thereof that contains the rare earth cerium that obtains according to the prescription of present embodiment; The metal parts of the zinc plated mild carbon steel material that will handle during use was immersed in the metal surface treating liquid that present embodiment provides 0.5 minute, formed the zirconia ceramics film, through under 160 centigradetemperatures to 15 fens clock times of zirconia ceramics film burin-in process; Adopt spectrographic technique that it is carried out surface-active test then; Reach and receive crystalline substance, coat paint film again after, under 35 centigradetemperatures; Tested through 500 hour time, its corrosion-resistant index reaches the salt-fog test standard.
Claims (3)
1. a metal treatment fluid that contains the rare earth cerium is characterized in that prescription consists of: 0.5 part to 2 parts of fluorine zirconic acid, 1.5 parts to 3.5 parts of zinc molybdates, 0.2 part to 1 part in SODIUMNITRATE, 0.04 part to 0.06 part of EDTA Disodium, 0.4 part to 0.6 part of Sodium Fluoride, 0.2 part to 0.8 part of cerous nitrate, 100 parts in water.
2. a kind of metal treatment fluid that contains the rare earth cerium according to claim 1 is characterized in that prescription consists of: 1 part of fluorine zirconic acid, 2.5 parts of zinc molybdates, 0.5 part in SODIUMNITRATE, 0.05 part of EDTA Disodium, 0.5 part of Sodium Fluoride, 0.5 part of cerous nitrate, 100 parts in water.
3. working method that contains the metal treatment fluid of rare earth cerium, it comprises the reaction kettle that adopts water tank, header tank and band to stir, and it is characterized in that process step is:
1) produce before earlier with industrial tap water to cleaning in the reaction kettle, again with alcoholic solvent further to cleaning in the reaction kettle, wash number is not less than twice, each stirring and washing time was not less than five minutes, did not contain pure soluble substance in the maintenance reaction kettle;
2) pure water is evacuated to header tank from water tank, injects reaction kettle through measuring the back;
3) finished product pure water IR per ton is controlled at 990kg, and error control is in positive 5kg scope;
4) start the stirring back and inject SODIUMNITRATE, rotating speed is controlled at this 30r/min to 60r/min;
5) treat that SODIUMNITRATE fully dissolves the back and injects zinc molybdate;
6) continue to stir after 30 minutes, inject fluorine zirconic acid, EDTA Disodium, Sodium Fluoride successively, wait to inject raw material and all dissolve back adding cerous nitrate;
7) continue to stir after 15 minutes, with sodium hydroxide or nitric acid regulate and the controlled liq pH value about 2.0;
8) stop after pH value is stabilized in about 2.0 stirring and carry out the can of branch bucket.
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| CN 201110326018 CN102433559B (en) | 2011-10-24 | 2011-10-24 | Rare earth cerium-containing metal treatment fluid and production method thereof |
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| CN 201110326018 CN102433559B (en) | 2011-10-24 | 2011-10-24 | Rare earth cerium-containing metal treatment fluid and production method thereof |
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| CN102433559A true CN102433559A (en) | 2012-05-02 |
| CN102433559B CN102433559B (en) | 2013-09-04 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102787313A (en) * | 2012-07-19 | 2012-11-21 | 华南理工大学 | Treatment solution for preparing molybdenum-cerium composite conversion membrane on surface of magnesium alloy, and treatment method thereof |
| CN102808172A (en) * | 2012-08-24 | 2012-12-05 | 安徽启明表面技术有限公司 | Universal environment-friendly non-phosphorus phosphating solution |
| CN106194610A (en) * | 2016-08-31 | 2016-12-07 | 常熟市强盛电力设备有限责任公司 | Wind power generator rotor |
| US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102787313A (en) * | 2012-07-19 | 2012-11-21 | 华南理工大学 | Treatment solution for preparing molybdenum-cerium composite conversion membrane on surface of magnesium alloy, and treatment method thereof |
| CN102808172A (en) * | 2012-08-24 | 2012-12-05 | 安徽启明表面技术有限公司 | Universal environment-friendly non-phosphorus phosphating solution |
| CN102808172B (en) * | 2012-08-24 | 2014-04-02 | 安徽启明表面技术有限公司 | Universal environment-friendly non-phosphorus phosphating solution |
| US10435806B2 (en) | 2015-10-12 | 2019-10-08 | Prc-Desoto International, Inc. | Methods for electrolytically depositing pretreatment compositions |
| US11591707B2 (en) | 2015-10-12 | 2023-02-28 | Ppg Industries Ohio, Inc. | Methods for electrolytically depositing pretreatment compositions |
| CN106194610A (en) * | 2016-08-31 | 2016-12-07 | 常熟市强盛电力设备有限责任公司 | Wind power generator rotor |
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