CN101838803B - Substitutive treatment agent for metal surface phosphating and preparation method thereof - Google Patents
Substitutive treatment agent for metal surface phosphating and preparation method thereof Download PDFInfo
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- CN101838803B CN101838803B CN201010181093.4A CN201010181093A CN101838803B CN 101838803 B CN101838803 B CN 101838803B CN 201010181093 A CN201010181093 A CN 201010181093A CN 101838803 B CN101838803 B CN 101838803B
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- metal surface
- rinsing
- silane
- phosphating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
- C23C2222/20—Use of solutions containing silanes
Abstract
The invention discloses a substitutive treatment agent for metal surface phosphating and a preparation method thereof, and relates to the metal surface treatment technology. The substitutive treatment agent for phosphating consists of the following components of: gamma-APS, anhydrous alcohol, fluozirconate and de-ionized water, wherein the substitutive treatment agent for phosphating consisting of the components is a silane and nanoceramic composite film; the preparation method for the silane and nanoceramic composite film which consists of the components and is used for pre-treating the metal surface comprises the following steps of: rinsing with hot water; degreasing in advance; rinsing for the first time; rinsing for the second time; rinsing for the third time; performing phosphate-free conversion; rinsing a straight bar; rinsing for the fourth time; rinsing for the fifth time; and finishing the preparation. The substitutive treatment agent and the preparation method have the advantages that: the silane and nanoceramic composite film does not rust in 48 hours after being formed on the metal surface of a cold rolled steel sheet and the like and naturally cooled so as to meet the requirement on corrosion resistance in the production process; and meanwhile, the composite silane film has high bonding force with polyester coating layers, the cross-cut test for the adhesion reaches the first grade, the comprehensive impact resistance reaches 50CM/KG, the bending resistance is less than 1mm, and the salt spray test is more than or equal to 500 hours.
Description
Technical field
The present invention relates to metal surface treatment technology, specifically a kind of for metal surface phosphating alternate process agent and preparation method thereof.
Background technology
Along with people are to the more and more attention of environment protection, environmentally-friendly coating replaces traditional application has become a kind of trend and developing direction, and this tempo is just more and more faster along with the day by day maturation of China's household appliance industry.Nearly one or two years, domestic household appliances enterprise environmental consciousness generally strengthens, and greatly improves the acceptance of environmentally-friendly coating pre-treating technology.All the time; the part workpiece of household appliances has higher requirement to rotproofing; solution commonplace is at present in coated metal pre-treating technology; (this process is called for short phosphatization to use a kind of chemistry to form phosphate chemical conversion film with electrochemical reaction; the phosphate conversion film formed is referred to as phosphatize phosphate coat), there is not rust in the time that it protects the metal productss such as household electrical appliances to ensure 10 years or more together with the application of rear road and the problem such as to wear.
Although the performance such as anticorrosive of phosphatization is very excellent, it also produces problems simultaneously, and such as energy consumption is high, it is comparatively serious to pollute, easily tube wall and pipeline in the series of problems such as slagging scorification more difficult containing harmful heavy metal, wastewater treatment.Along with the continuous progress of science and technology and improving constantly of environmental requirement, more the Metal Surface Pretreatment Process of environmental protection grows up just in the world, and the research work of current this respect concentrates on asepsis environment-protecting phosphatization and abandons brand-new technique two aspects of phosphorous formula completely.
Between past 60 years, zinc and nickel two metal ion species are the cores of phosphatization, the Environmental policy of increasingly stringent and the nickel improved constantly and the zinc prices of raw and semifnished materials, become the driving factors of the suitable substitute of exploitation.First people assess the monomer of nano particle, zirconium, titanium, polymkeric substance and other metal ions and synthetics each other, final decision exploitation substitutes the new conversion film of phosphatization, this substitute should not phosphate-containing and other traditional heavy metal ion or the metal ion by RoHS isotactic definite limitation, ionic concn contained by each treatment process is all less than current zinc phosphate technique, thus save energy and water, meet the performance requriements of current pre-treatment industry, film weight is no more than traditional lithoform, and scope is at 20 ~ 200mg/m
2.
The nineties in last century, external environment-friendly type Pretreatment Technology Before Finishing becomes the focus studied in the industry gradually.Due to the mainly nitrite that phosphorization treatment process toxic is comparatively large, damage ratio is more serious, heavy metal Ni 2+, Cr6+, Mn2+ plasma.So the research in this field also mainly concentrates on as these materials are found in substitute, is mainly divided into without nitrite phosphatization and unnickeled phosphide.
Silane technology is as a kind of comparatively ripe metal surface pre-treatment utilisation technology, overcome the congenital defect that in Zinc phosphating process, those cannot overcome, through years development, now there is higher industrial applications level, the service requirements of the industry such as automobile, household electrical appliances can have been met.Silane technology has the following advantages: form firmly covalent linkage between silane energy and metal base, strengthens metal base and the bonding force and the erosion resistance that are coated with interlayer; Easy silane operation, original phosphating process directly can be transformed into silane treatment, only need groove be adjusted to change washing bath or vacant into table; Working and room temperature, film forming is rapid, energy efficiency; Substantially without slag, heavy metal free, without phosphorus, safeguard and wastewater treatment easy; Unit consumption is low, and comprehensive treating process cost declines; Can be supporting with various rear roads processing mode, such as dust, electrophoresis, to spray paint.
The research of other phosphatization alternative techniques known today also has: the chromium-free metal surface treatment agent of the rich man's invention of Amada Co., Ltd. electric discharge precision sizing institute rattan Kang Yan far away, wine well; The pretty bright non-chromate metal surface treatment agent waiting people's invention in storehouse, Nippon Paint Co., Ltd island; The metal conditioner of people's inventions such as Amada Co., Ltd. day pit wood material imperial palace Gao Zhi.
Summary of the invention
Technical problem solved by the invention is to provide one can at various different-alloy on the surface; especially metal surface phosphating alternate process agent of the optimum filming condition of the polynary silane film of high corrosion resistant composite Nano and preparation method thereof is prepared on the surface at cold-rolled steel, for the silane technology of industrial scale metal finishing industry.
Technical problem solved by the invention realizes by the following technical solutions:
A kind of metal surface phosphating alternate process agent and preparation method thereof, is characterized in that: the agent of described phosphatization alternate process is made up of following composition:
γ-APS 1-3 part;
Dehydrated alcohol 18-30 part;
Fluorine zirconic acid 5-10 part;
Deionized water 50-90 part.
The described phosphatization alternate process agent be made up of above-mentioned composition is silane and nano ceramics composite membrane.
Be used for the preparation method of pretreatment of metal surface at the described silane that is made up of γ-APS, dehydrated alcohol, fluorine zirconic acid, deionized water and nano ceramics composite membrane, comprise the following steps:
Hot water wash → pre-degreasing → the first step washing → second step washing the → the three step washing → without phosphorus conversion → wash in line → the 4th step washing the → the five step to wash → complete.
Describedly formed in silane and nano ceramics composite membrane process according to above-mentioned steps on cold-rolled steel surface, hydrolysis temperature is 30 DEG C, hydrolysis time is 8 hours, hydrating solution pH value is 12, volume ratio γ-the APS of hydrating solution composition: dehydrated alcohol: fluorine zirconic acid: deionized water=3: 22: 8: 67, time of immersion 15 minutes, dip-coating temperature are 30 DEG C, solidification value 120 DEG C, 15 minutes set times.
Described hot water wash adopts normal temperature cleaning.
Described each water-washing step keeps continuous overflow to avoid polluting.
The in line middle maintenance continuous overflow of described washing, controls specific conductivity at below 25us/cm.
The cold-rolled steel forming silane and nano ceramics composite membrane is provided with good corrosion resisting property to 3.50%NaCl solution.
The beneficial effect that the present invention has is that silane and nano ceramics composite membrane are after the metallic surface film forming such as cold bundle steel plate, corrosion phenomena can not be there is in 48 hours after seasoning, meet the requirement to erosion resistance in operation in producing, simultaneously compound silane film and polyester paint coatings bonding force good, the test of sticking power hundred lattice reaches 1 grade, comprehensive shock-resistant ability reaches 50CM/KG, and bend resistance is less than 1mm, and salt-fog resistant test is more than or equal to 500 hours.
Embodiment
The technique means realized to make the present invention, creation characteristic, reaching object and effect is easy to understand, below in conjunction with embodiment, setting forth the present invention further.
A kind of metal surface phosphating alternate process agent and preparation method thereof, wherein the agent of phosphatization alternate process is made up of following composition:
γ-APS 1-3 part;
Dehydrated alcohol 18-30 part;
Fluorine zirconic acid 5-10 part;
Deionized water 50-90 part;
The phosphatization alternate process agent consisted of above-mentioned composition is silane and nano ceramics composite membrane.
The silane be made up of γ-APS, dehydrated alcohol, fluorine zirconic acid, deionized water and nano ceramics composite membrane are used for the preparation method of pretreatment of metal surface, comprise the following steps: hot water wash → pre-degreasing → the first step washing → second step washing the → the three step washing → without phosphorus conversion → wash in line → the 4th step washing the → the five step to have washed, wherein hot water wash adopts normal temperature cleaning, each water-washing step keeps continuous overflow to avoid polluting, wash in line middle maintenance continuous overflow, control specific conductivity at below 25us/cm.
And form silane and nano ceramics composite membrane according to above-mentioned steps on cold-rolled steel surface, its hydrolysis temperature is 30 DEG C, hydrolysis time is 8 hours, hydrating solution pH value is 12, volume ratio γ-the APS of hydrating solution composition: dehydrated alcohol: fluorine zirconic acid: deionized water=3: 22: 8: 67, time of immersion 15 minutes, dip-coating temperature are 30 DEG C, solidification value 120 DEG C, 15 minutes set times just can realize.
More than show and describe ultimate principle of the present invention and principal character and advantage of the present invention.The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (4)
1. the preparation method of metal surface phosphating alternate process agent, it is characterized in that: by γ-APS, dehydrated alcohol, fluorine zirconic acid, the silane of deionized water composition and nano ceramics composite membrane are used for the preparation method of pretreatment of metal surface, comprise the following steps: hot water wash-pre-degreasing-the first step washing-second step washing the-the three step washing-without phosphorus conversion-wash in line-the 4th step washing the-the five step wash-to complete, formed in silane and nano ceramics composite membrane process according to above-mentioned steps on cold-rolled steel surface, hydrolysis temperature is 30 DEG C, hydrolysis time is 8 hours, hydrating solution pH value is 12, volume ratio γ-the APS of hydrating solution composition: dehydrated alcohol: fluorine zirconic acid: deionized water=3: 22: 8: 67, time of immersion 15 minutes, dip-coating temperature is 30 DEG C, solidification value 120 DEG C, 15 minutes set times.
2. the preparation method of metal surface phosphating alternate process agent according to claim 1, is characterized in that: described hot water wash adopts normal temperature cleaning.
3. according to the preparation method of metal surface phosphating alternate process agent described in claim 1, it is characterized in that: described each water-washing step keeps continuous overflow to avoid polluting.
4. the preparation method of metal surface phosphating alternate process agent according to claim 1, is characterized in that: the in line middle maintenance continuous overflow of described washing, controls specific conductivity at 25 μ s/below cm.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201010181093.4A CN101838803B (en) | 2010-05-20 | 2010-05-20 | Substitutive treatment agent for metal surface phosphating and preparation method thereof |
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| CN201010181093.4A CN101838803B (en) | 2010-05-20 | 2010-05-20 | Substitutive treatment agent for metal surface phosphating and preparation method thereof |
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| CN101838803A CN101838803A (en) | 2010-09-22 |
| CN101838803B true CN101838803B (en) | 2015-07-22 |
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Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011114B (en) * | 2010-12-31 | 2012-06-20 | 沈阳帕卡濑精有限总公司 | Phosphorous ion-free treating agent for treating steel plate |
| CN103031584A (en) * | 2012-12-06 | 2013-04-10 | 安徽未来表面技术有限公司 | Process of silane-zirconium salt conversion treatment before metal cathode electrophoresis coating |
| CN104630765A (en) * | 2013-11-11 | 2015-05-20 | 安徽未来表面技术有限公司 | Environmental-protection type metal coating pre-treatment agent and preparation method thereof |
| CN104209252B (en) * | 2014-08-20 | 2016-05-18 | 杭州兴达通信有限公司 | Technique before a kind of application |
| CN106835109A (en) * | 2017-01-18 | 2017-06-13 | 帝业化学品（上海）有限公司 | Environment-friendly type metal surface pre-treatment coating |
| CN109267051B (en) * | 2018-11-30 | 2021-01-12 | 青岛海创化学品有限责任公司 | Self-cleaning phosphorus-free film-forming agent and preparation method and application thereof |
| CN109468624B (en) * | 2018-11-30 | 2021-01-22 | 青岛海创化学品有限责任公司 | High-adhesion chromium-free color coating passivator and preparation method thereof |
| CN110369244A (en) * | 2019-04-10 | 2019-10-25 | 汉腾汽车有限公司 | A kind of without phosphorus silane process of car body coating environmental protection pre-treatment |
| CN112226755B (en) * | 2020-09-23 | 2023-06-23 | 山东大业股份有限公司 | Phosphating method and device for metal wire surface treatment |
| CN112708880A (en) * | 2020-12-09 | 2021-04-27 | 苏州帝航防护设施有限公司 | Metal surface silanization treating agent and treating process thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US6733579B1 (en) * | 2002-10-10 | 2004-05-11 | Nalco Company | Chrome free final rinse for phosphated metal surfaces |
| US20060099332A1 (en) * | 2004-11-10 | 2006-05-11 | Mats Eriksson | Process for producing a repair coating on a coated metallic surface |
| CN101701336A (en) * | 2009-11-26 | 2010-05-05 | 芜湖市瑞杰环保材料科技有限公司 | Environment-friendly metal surface treating agent and using method thereof |
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- 2010-05-20 CN CN201010181093.4A patent/CN101838803B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6733579B1 (en) * | 2002-10-10 | 2004-05-11 | Nalco Company | Chrome free final rinse for phosphated metal surfaces |
| US20060099332A1 (en) * | 2004-11-10 | 2006-05-11 | Mats Eriksson | Process for producing a repair coating on a coated metallic surface |
| CN101701336A (en) * | 2009-11-26 | 2010-05-05 | 芜湖市瑞杰环保材料科技有限公司 | Environment-friendly metal surface treating agent and using method thereof |
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| CN101838803A (en) | 2010-09-22 |
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Address after: 231201 Ziyi Road, industrial cluster, Zipeng Town, Feixi County, Hefei City, Anhui Province Patentee after: ANHUI WEILAI SURFACE TECHNOLOGY Co.,Ltd. Address before: 230601 No. 367, Jade Road, Hefei economic and Technological Development Zone, Anhui Patentee before: ANHUI WEILAI SURFACE TECHNOLOGY Co.,Ltd. |