CN101838803A - 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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- CN101838803A CN101838803A CN201010181093A CN201010181093A CN101838803A CN 101838803 A CN101838803 A CN 101838803A CN 201010181093 A CN201010181093 A CN 201010181093A CN 201010181093 A CN201010181093 A CN 201010181093A CN 101838803 A CN101838803 A CN 101838803A
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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
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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 is a kind of metal surface phosphating alternate process agent and preparation method thereof that is used for.
Background technology
Along with the more and more attention of people to 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 maturation day by day of China's household appliance industry.Nearly one or two years, domestic household appliances enterprise environmental consciousness generally strengthens, and the acceptance of environmentally-friendly coating pre-treating technology is improved greatly.All the time; the part workpiece of household appliances has higher requirement to rotproofing; commonplace solution is in the coated metal pre-treating technology at present; (this process is called for short phosphatization to use a kind of chemistry and electrochemical reaction to form the phosphate chemical conversion film; formed phosphate conversion film is referred to as phosphatize phosphate coat), it and back road application protect metal products such as household electrical appliances to guarantee 10 years or problem such as do not take place that rust is worn in above time together.
Although the performance such as anticorrosive of phosphatization is very excellent, its also produces problems simultaneously, such as the energy consumption height, pollute serious, contain harmful heavy metal, wastewater treatment difficulty, a series of problems such as slagging scorification in tube wall and pipeline easily.Along with the continuous progress of science and technology and improving constantly of environmental requirement, more the metallic surface pre-treating technology of environmental protection grows up just in the world, and the research work of this respect at present concentrates on the asepsis environment-protecting phosphatization and abandons two aspects of brand-new technology of phosphorous prescription fully.
In the period of past 60, zinc and nickel two metal ion species are cores of phosphatization, and the Environmental policy of increasingly stringent and the nickel that improves constantly and the zinc prices of raw and semifnished materials become the driving factors of developing suitable substitute.People at first assess the monomer of nano particle, zirconium, titanium, polymkeric substance and other metal ions and synthetics each other, the final decision exploitation substitutes the new conversion film of phosphatization, this substitute should not phosphorous hydrochlorate and other traditional heavy metal ion or is subjected to the metal ion of RoHS isotactic fixed limit system, the contained ionic concn of each treatment process all is less than current zinc phosphate technology, thereby save energy and water, satisfy 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 application pre-treating technology becomes the focus of research in the industry gradually.Because what the phosphorization treatment process toxic was big, damage ratio is more serious mainly is nitrite, heavy metal Ni 2+, Cr6+, Mn2+ plasma.So the research in this field also mainly concentrates on to these materials and seeks on the substitute, mainly is divided into no nitrite phosphatization and no nickel phosphatization.
The silane technology is as a kind of comparatively sophisticated novel metal surface pre-treatment utilisation technology, those congenital defects that can't overcome in the Zinc phosphating process have been overcome, through years development, now had higher industrial applications level, can satisfy the service requirements of industries such as automobile, household electrical appliances.The silane technology has the following advantages: form firm covalent linkage between silane energy and metal base, strengthen metal base and the bonding force and the erosion resistance that are coated with interlayer; Easy silane uses technology, and original phosphating process can directly be transformed into silane treatment, only needs to transfer groove to change washing bath or vacant getting final product in table; Working and room temperature, film forming is rapid, energy efficiency; Substantially there is not slag, heavy metal free, without phosphorus, maintenance and wastewater treatment are easy; Unit consumption is low, and the comprehensive treating process cost descends; Can be supporting with roads, various back processing modes, such as dusting, electrophoresis, spraying paint etc.
The research of other phosphatization alternative techniques known today also has: the chromium-free metal surface treatment agent of the discharge precision sizing rattan Kang Yan far away of institute of Amada Co., Ltd., the rich man's invention of wine well; The pretty bright non-chromate metal surface treatment agent that waits people's invention in storehouse, Nippon Paint Co., Ltd island; The metal conditioner of people such as the day pit wood material imperial palace Gao Zhi of Amada Co., Ltd. invention.
Summary of the invention
Technical problem solved by the invention be to provide a kind of can be on various different-alloys surface; especially metal surface phosphating alternate process agent of the optimum filming condition of preparation high corrosion resistant composite Nano polynary silane film and preparation method thereof on the cold-rolled steel surface is used 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 of being made up of above-mentioned composition is silane and nano ceramics composite membrane.
Be used for the pretreated preparation method in metallic surface at described silane and the nano ceramics composite membrane of forming by γ-APS, dehydrated alcohol, fluorine zirconic acid, deionized water, may further comprise the steps:
Hot water wash → pre-degreasing → the first step washing → the second step washing → the three goes on foot washing → without phosphorus conversion → washing, and in line → → the five step of the 4th step washing washes → finishes.
Describedly form in silane and the nano ceramics composite membrane process on cold-rolled steel surface according to above-mentioned steps, hydrolysis temperature is that 30 ℃, hydrolysis time are that 8 hours, hydrating solution pH value are 12, volume ratio γ-APS that hydrating solution is formed: dehydrated alcohol: fluorine zirconic acid: deionized water=3: 22: 8: 67, time of immersion 15 minutes, dip-coating temperature are 30 ℃, 120 ℃ of solidification values, 15 minutes set times.
Described hot water wash adopts normal temperature to clean.
Described each water-washing step keeps continuous overflow to avoid pollution.
Keep continuous overflow during described washing is in line, the control specific conductivity is below 25us/cm.
The cold-rolled steel that forms silane and nano ceramics composite membrane has had 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 metallic surface film forming such as cold bundle steel plate, after the seasoning corrosion phenomena can not take place in 48 hours, in satisfy producing in the operation to the requirement of erosion resistance, compound silane film and polyester paint coatings bonding force are good simultaneously, 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 was more than or equal to 500 hours.
Embodiment
For technique means, creation characteristic that the present invention is realized, reach purpose and effect is easy to understand, below in conjunction with embodiment, further set forth the present invention.
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 of forming by above-mentioned composition is silane and nano ceramics composite membrane.
Silane and the nano ceramics composite membrane be made up of γ-APS, dehydrated alcohol, fluorine zirconic acid, deionized water are used for the pretreated preparation method in metallic surface, may further comprise the steps: hot water wash → pre-degreasing → the first step washing → the second step washing → the three goes on foot washing → without phosphorus conversion → washing, and in line → the 4th step washing → the five step washing is finished, wherein hot water wash adopts normal temperature to clean, each water-washing step keeps continuous overflow to avoid pollution, wash the in line middle continuous overflow that keeps, the control specific conductivity is below 25us/cm.
And form silane and nano ceramics composite membrane on the cold-rolled steel surface according to above-mentioned steps, its hydrolysis temperature is that 30 ℃, hydrolysis time are that 8 hours, hydrating solution pH value are 12, volume ratio γ-APS that hydrating solution is formed: dehydrated alcohol: fluorine zirconic acid: deionized water=3: 22: 8: 67, time of immersion 15 minutes, dip-coating temperature are that 30 ℃, 120 ℃ of solidification values, 15 minutes set times just can be realized.
More than show and described 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; that describes in the foregoing description and the 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.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (6)
1. 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 phosphatization alternate process agent of forming by above-mentioned composition is silane and nano ceramics composite membrane.
2. according to the described metal surface phosphating alternate process of claim 1 agent and preparation method thereof, it is characterized in that: described silane and the nano ceramics composite membrane of being made up of γ-APS, dehydrated alcohol, fluorine zirconic acid, deionized water is used for the pretreated preparation method in metallic surface, may further comprise the steps:
Hot water wash → pre-degreasing → the first step washing → the second step washing → the three goes on foot washing → without phosphorus conversion → washing, and in line → → the five step of the 4th step washing washes → finishes.
3. according to the described metal surface phosphating alternate process of claim 2 agent and preparation method thereof, it is characterized in that: described hot water wash adopts normal temperature to clean.
4. according to the described metal surface phosphating alternate process of claim 2 agent and preparation method thereof, it is characterized in that: described each water-washing step keeps continuous overflow to avoid pollution.
5. according to the described metal surface phosphating alternate process of claim 2 agent and preparation method thereof, it is characterized in that: keep continuous overflow during described washing is in line, the control specific conductivity is below 25us/cm.
6. according to the described metal surface phosphating alternate process of claim 2 agent and preparation method thereof, it is characterized in that: describedly form in silane and the nano ceramics composite membrane process on cold-rolled steel surface according to above-mentioned steps, hydrolysis temperature is that 30 ℃, hydrolysis time are that 8 hours, hydrating solution pH value are 12, volume ratio γ-APS that hydrating solution is formed: dehydrated alcohol: fluorine zirconic acid: deionized water=3: 22: 8: 67, time of immersion 15 minutes, dip-coating temperature are 30 ℃, 120 ℃ of solidification values, 15 minutes set times.
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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 true CN101838803A (en) | 2010-09-22 |
| CN101838803B CN101838803B (en) | 2015-07-22 |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011114A (en) * | 2010-12-31 | 2011-04-13 | 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 |
| CN104209252A (en) * | 2014-08-20 | 2014-12-17 | 杭州兴达通信有限公司 | Technology before 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 |
| 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 |
| CN109267051A (en) * | 2018-11-30 | 2019-01-25 | 青岛海创化学品有限责任公司 | A kind of self-cleaning phosphorus-free film forming agent and its preparation method and application |
| CN109468624A (en) * | 2018-11-30 | 2019-03-15 | 青岛海创化学品有限责任公司 | A kind of high attachment Chrome-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 |
| CN112226755A (en) * | 2020-09-23 | 2021-01-15 | 山东大业股份有限公司 | Phosphating method and device for surface treatment of metal wire |
| 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 |
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| US6733579B1 (en) * | 2002-10-10 | 2004-05-11 | Nalco Company | Chrome free final rinse for phosphated metal surfaces |
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| 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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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102011114A (en) * | 2010-12-31 | 2011-04-13 | 沈阳帕卡濑精有限总公司 | Phosphorous ion-free treating agent for treating steel plate |
| 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 |
| CN104209252A (en) * | 2014-08-20 | 2014-12-17 | 杭州兴达通信有限公司 | Technology before coating |
| 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 |
| CN109267051A (en) * | 2018-11-30 | 2019-01-25 | 青岛海创化学品有限责任公司 | A kind of self-cleaning phosphorus-free film forming agent and its preparation method and application |
| CN109468624A (en) * | 2018-11-30 | 2019-03-15 | 青岛海创化学品有限责任公司 | A kind of high attachment Chrome-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 |
| CN112226755A (en) * | 2020-09-23 | 2021-01-15 | 山东大业股份有限公司 | Phosphating method and device for surface treatment of metal wire |
| 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 |
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| Publication number | Publication date |
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| CN101838803B (en) | 2015-07-22 |
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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. |