CN102304704A - Aqueous silane treatment agent for improving metal surface protection performance - Google Patents

Aqueous silane treatment agent for improving metal surface protection performance Download PDF

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Publication number
CN102304704A
CN102304704A CN201110268508A CN201110268508A CN102304704A CN 102304704 A CN102304704 A CN 102304704A CN 201110268508 A CN201110268508 A CN 201110268508A CN 201110268508 A CN201110268508 A CN 201110268508A CN 102304704 A CN102304704 A CN 102304704A
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treatment agent
silane
metallic surface
silane treatment
metal surface
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周志明
冉长荣
赵朔
羡小超
田婉洁
谭世语
王瑶环
林震
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Chongqing University
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Chongqing University
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Abstract

The invention discloses an aqueous silane treatment agent for improving metal surface protection performance, and relates to a silane treatment agent for the metal surface pretreatment. The aqueous silane treatment agent provided by the present invention comprises vinyltriacetoxysilane, bis-(trimethoxysilylpropyl)amine, lanthanum nitrate and deionized water. The aqueous silane treatment agent provided by the present invention has characteristics of high corrosion resistance, high storage stability, high adhesion, low cost, easy popularization and application, and the like. The aqueous silane treatment agent can be widely applicable for the metal surface pretreatment, and is the ideal treatment agent for improving the metal surface protection performance.

Description

A kind of water-based silane treatment agent that improves the protecting metallic surface performance
Technical field
The invention belongs to field of metal surface treatment technology, be specifically related to the silane finish that handle in earlier stage the metallic surface.
Background technology
The most gold metal products is in processes such as transportation and storage and use, and various forms of corrosion be prone to take place on its surface, particularly form the atomospheric corrosion of various rust stainings, these corrosion can have a strong impact on the quality of metal and thus metal process the quality of product.The corrosion of metallic surface has simultaneously brought enormous economic loss; In China; The financial loss that annual according to statistics corrosion causes accounts for 4% of gross national product; Corrosion loss even surpassed the damnous summation of fire, disaster caused by a windstorm and earthquake, so surprising loss is stimulating market to metallic surface aseptic production growth of requirement.Though the rust staining that corrosion produces can be removed from metallic matrix, these methods length usually consuming time and also can reduce the intensity of metal.In addition, when metallic surface coated polymer coating, tackiness agent or rubber anti-corrosive agent, the corrosion of metallic surface can cause the forfeiture of sticking power between sanitas coating and the metallic surface or weaken, and can not play good preservative effect.Therefore, before applying sanitas, must carry out early stage and handle, could effectively prevent the generation of metal products its surface corrosion in processes such as transportation, storage and use, prolong the work-ing life of metal products the metallic surface.
Surging along with the environmental protection cry presses for the surface treatment agent of research and development excellent property, metallic surface silane finish wherein, and antiseptic property is good, energy-conservation because of having, advantages of environment protection, has good economic benefit and social benefit, is widely used.
The silane finish of existing metallic surface is " can improve the environment-friendly nano water-based silane treatment agent of anti-corrosion performance of metal surface " patent of 200910273383.9 like application number, and disclosed metallic surface silane finish is every liter and includes:
Figure BSA00000571809500011
The main drawback of this treatment agent is: 1. nano silicon costs an arm and a leg, and consumption is up to 5~200mg/L, and cost is high.2. rare earth cerium salt costs an arm and a leg, and consumption increases cost up to 10~500mg/L.3. add nano silicon, need to use the Ultrasonic Cleaners ultra-sonic dispersion, complicated operating process further increases cost; 4. a kind of bis-silyl silane is the bis-silyl silane that comprises at least a non-hydrophilic functional group, poorly water-soluble, and the silane hydrolyzate time is long, is prone to cause the silanol polycondensation that produces crosslinked, thereby causes the corrosion-resistant of product.5. the storage stability of silane finish is poor, for improving the stability of metal conditioner, in use, needs further to add ethanol, thereby increases the biochemical oxygen demand BOD of waste water, increases the processing cost of waste water, is difficult for applying.
Summary of the invention
The objective of the invention is weak point to existing metallic surface silane finish; A kind of water-based silane treatment agent that improves the protecting metallic surface performance is provided; It is good to have treatment agent solution storage stability height, strong adhesion, anticorrosion effect; Energy-saving and environmental protection, easy and simple to handle, low cost and other advantages.
The technical scheme that realizes the object of the invention is: a kind of water-based silane treatment agent that improves the protecting metallic surface performance, and the component of said treatment agent and mass percent thereof are:
Figure BSA00000571809500021
Wherein: described vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 3~5.
The preparing method's of treatment agent of the present invention concrete steps are following:
(1) gets the raw materials ready
Component and proportioning thereof according to treatment agent of the present invention are got all the raw material ready.That is:
Figure BSA00000571809500022
Wherein: described vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 3~5.
(2) mix
After the completion of (1) step; By vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 3~5, in stirring tank, adds vinyltriacetoxy silane and two-(trimethoxy-silylpropyl) amine earlier; After mixing, left standstill 3~4 hours.Add deionized water and Lanthanum trinitrate again, mix become complete clear to mixing solutions after, just prepare water-based silane treatment agent of the present invention.
The method of use of treatment agent of the present invention:
To the surface of pending metallic matrix, elder generation is with the alkaline cleaner of 0.3g/L sodium hydroxide and 2g/L tsp and 20g/L Sodium Nitrite composition, 50~60 ℃ of following ultrasonic cleaning 5 minutes.With tap water the metallic surface was washed 1 minute again.Then, again the metallic surface is washed, made the metallic surface form seamless moisture film with deionized water.At last the metallic matrix after the surface washing is put in the water-based silane treatment agent of the present invention, flooded after 5~30 seconds and take out, dried 0.5~2 hour down, just accomplish the protection of metallic surface is handled in earlier stage at 80~150 ℃.
After the present invention adopts above technical scheme, mainly contain following effect:
(1) the present invention replaces rare earth cerium salt with Lanthanum trinitrate, and anticorrosion effect is better and cheap.Silane film can improve the corrosion resistance nature of metallic matrix.Yet usually there are defectives such as pin hole, tiny crack in silane film; Because Lanthanum trinitrate has good corrosion-inhibiting; The siloxane network structure of Lanthanum trinitrate in silane film can be carried out the defectives such as tiny crack and pin hole that silane film is repaired in self-assembly; Make silane film even, fine and close, complete, thereby can obviously improve the corrosion resistance nature of silane film.
(2) storage stability of water-based silane treatment agent solution of the present invention is high.The present invention selects for use vinyltriacetoxy silane and two-(trimethoxy-silylpropyl) amine can improve the storage stability of solution; Be mainly reflected in: vinyltriacetoxy silane and two-(trimethoxy-silylpropyl) amine silanol that hydrolysis produces in deionized water; Can be in time with two-(trimethoxy-silylpropyl) amine in the nitrogen element form hydrogen bond; It is crosslinked that polycondensation takes place between the silanol that prevents to produce; Guaranteed that silanol can stably secularly exist in solution, thereby effectively improved the stability of solution.At this moment, aqueous silane solution of the present invention need not use to contain the alcohols organic substance and improve the stability of solution as solvent, thereby significantly reduce the biochemical oxygen demand BOD of metallic surface silanization processed waste water.
(3) strong adhesion of water-based silane treatment agent of the present invention is applicable to that a greater variety of coating carry out the post-processed of metallic surface.Be mainly reflected in: 1. the silicon hydroxyl in the silane finish of metallic surface can form chemical bond with the hydroxyl reaction of metallic surface, makes silane film and metal form very strong sticking power; 2. silane film enough improves the roughness of metallic surface, in the post-processed of metallic surface, helps to improve metallic surface and ADHESION OF PAINTS power; 3. silane film can form physical crosslinking effect or chemical bond with the post-processed coating of metallic surface, makes silane film and coating obtain very strong sticking power; 4. select vinyltriacetoxy silane for use among the present invention; Vinyl in this material has very high reactive behavior; Coating reaction very enough and that adhesiveproperties is relatively poor forms chemical bond, obtains very strong sticking power, thereby has increased the scope of application of metallic surface aftertreatment coating type.
(4) corrosion resistance nature is high, need not to adopt nano material just can reach good preservative effect, and cost is low.Nano material such as nano silicon are very easily reunited, and form deposition, cause that the solution transparency reduces, and in the metal finishing process, if do not remove deposition, can have a strong impact on treatment effect; The present invention is not owing to use nano silicon, and raw material still less and in the layoutprocedure of solution, does not use Ultrasonic Cleaners that nano material is carried out ultra-sonic dispersion, and simple to operate, cost is lower, and is easy to utilize.
The present invention can be widely used in the processing in early stage of metallic surface, is the ideal treatment agent that improves the protecting metallic surface performance.
Embodiment
Below in conjunction with embodiment, further specify the present invention.
Embodiment 1
A kind of component and mass percent thereof of the water-based silane treatment agent that improves the protecting metallic surface performance are following:
Figure BSA00000571809500031
Figure BSA00000571809500041
Wherein: described vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 5.
Embodiment 2
A kind of component and mass percent thereof of the water-based silane treatment agent that improves the protecting metallic surface performance are following:
Wherein: described vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 4.
Embodiment 3
A kind of component and mass percent thereof of the water-based silane treatment agent that improves the protecting metallic surface performance are following:
Figure BSA00000571809500043
Wherein: described vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 3.33.
Embodiment 4
A kind of component and mass percent thereof of the water-based silane treatment agent that improves the protecting metallic surface performance are following:
Figure BSA00000571809500044
Wherein: described vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 3.
Test-results
Water-based silane treatment agent with the raising protecting metallic surface performance of present embodiment 1~4; After the metallic surface carried out handling early stage; Respectively according to 5% plumbic acetate pittingtest with 3.5% sodium-chlor soaks corrosion test GB 9794-1988 entirely and adhesion test GB/T9286-1988 carries out the erosion resistance evaluation test; With existing silane finish the erosion resistance evaluation test after handle early stage is carried out in the metallic surface, compare, its result is following:
Figure BSA00000571809500051
Know from above-mentioned test-results:
(1) Corrosion Protection of treatment agent of the present invention is high, and in carrying out 5% plumbic acetate pittingtest, the time that the plumbic acetate drop of metallic surface begins blackening is higher than 221 seconds, is superior to 208 seconds of existing silane finish.Soak entirely in the corrosion test carrying out 3.5% sodium-chlor, the time that the metallic surface begins a small amount of hot spot to occur is superior to 12 days of existing silane finish more than 16 days.
(2) sticking power of treatment agent of the present invention is high, in the adhesion test of silane film and acroleic acid aerosol paint, does not peel off situation between metallic surface and the coating, and the sticking power grade reaches maximum 0 grade, can satisfy the requirement of metallic surface pre-treatment fully.
In sum; Water-based silane treatment agent of the present invention; Than the excellent corrosion resistance of existing silane finish, and have solution storage stability height, strong adhesion, good corrosion resistance, energy-saving and environmental protection, characteristics such as cost is low, Recipe is simple, easy to utilize.

Claims (5)

1. water-based silane treatment agent that improves the protecting metallic surface performance is characterized in that the component of said treatment agent and mass percent thereof are following:
Wherein: described vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 3~5.
2. according to the described a kind of water-based silane treatment agent that improves the protecting metallic surface performance of claim 1, it is characterized in that the component of said treatment agent and mass percent thereof are following:
Wherein: described vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 5.
3. according to the described a kind of water-based silane treatment agent that improves the protecting metallic surface performance of claim 1, it is characterized in that the component of said treatment agent and mass percent thereof are following:
Figure FSA00000571809400013
Wherein: described vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 4.
4. according to the described a kind of water-based silane treatment agent that improves the protecting metallic surface performance of claim 1, it is characterized in that the component of said treatment agent and mass percent thereof are following:
Figure FSA00000571809400014
Wherein: described vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 3.33.
5. according to the described a kind of water-based silane treatment agent that improves the protecting metallic surface performance of claim 1, it is characterized in that the component of said treatment agent and mass percent thereof are following:
Figure FSA00000571809400021
Wherein: described vinyltriacetoxy silane: the volume ratio of two-(trimethoxy-silylpropyl) amine is 1: 3.
CN201110268508A 2011-09-09 2011-09-09 Aqueous silane treatment agent for improving metal surface protection performance Pending CN102304704A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103059722A (en) * 2012-12-18 2013-04-24 安徽翔艺达机械有限公司 Metal surface silicane treating agent containing carboxymethylcellulose and preparing method thereof
CN103254771A (en) * 2013-04-08 2013-08-21 马鞍山拓锐金属表面技术有限公司 Acidproof metal surface silane treatment agent and preparation method thereof
CN105586587A (en) * 2016-03-25 2016-05-18 大连新锋钢管厂 Hoop surface protection process
CN111058021A (en) * 2019-12-30 2020-04-24 南京精德丰新材料科技有限公司 High-corrosion-resistance metal surface treating agent and preparation method thereof
CN112717878A (en) * 2020-11-30 2021-04-30 中国科学院重庆绿色智能技术研究院 Substrate adsorption material with nitrogen and phosphorus removal functions and preparation method and application thereof

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103059722A (en) * 2012-12-18 2013-04-24 安徽翔艺达机械有限公司 Metal surface silicane treating agent containing carboxymethylcellulose and preparing method thereof
CN103059722B (en) * 2012-12-18 2016-01-20 安徽翔艺达机械有限公司 A kind of Metal surface silane treatment agent containing carboxymethyl cellulose and preparation method thereof
CN103254771A (en) * 2013-04-08 2013-08-21 马鞍山拓锐金属表面技术有限公司 Acidproof metal surface silane treatment agent and preparation method thereof
CN105586587A (en) * 2016-03-25 2016-05-18 大连新锋钢管厂 Hoop surface protection process
CN111058021A (en) * 2019-12-30 2020-04-24 南京精德丰新材料科技有限公司 High-corrosion-resistance metal surface treating agent and preparation method thereof
CN112717878A (en) * 2020-11-30 2021-04-30 中国科学院重庆绿色智能技术研究院 Substrate adsorption material with nitrogen and phosphorus removal functions and preparation method and application thereof

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Inventor after: Zhou Zhiming

Inventor after: Ran Changrong

Inventor after: Zhao Shuo

Inventor after: Xian Xiaochao

Inventor after: Li Ji

Inventor after: Tian Wanjie

Inventor after: Tan Shiyu

Inventor after: Wang Yaohuan

Inventor after: Lin Zhen

Inventor before: Zhou Zhiming

Inventor before: Ran Changrong

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Application publication date: 20120104