CN1403507A - Prepn of nano level anticorrosive oxide coating - Google Patents
Prepn of nano level anticorrosive oxide coating Download PDFInfo
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- CN1403507A CN1403507A CN 01127373 CN01127373A CN1403507A CN 1403507 A CN1403507 A CN 1403507A CN 01127373 CN01127373 CN 01127373 CN 01127373 A CN01127373 A CN 01127373A CN 1403507 A CN1403507 A CN 1403507A
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Abstract
The present invention discloses the preparation process of nano level anticorrosive oxide coating. The nano level anticorrosive amorphous and crystalline oxide coating with Si-Ti as main component is synthesized with Si salt, Ti salt, neutral Zn/Al salt as source material, anhydrous ethanol as solvent, additive, surfactant and small amount of distilled water and via a sol-gel technological process. In the coating, the Si oxide exists in amorphous state and the Ti oxide and other oxide in nano level crystal structure with lower degree of crystallization. The coating of the present invention has excellent acid resistance and high temperature oxidation resistance and is compact and well adhered to the base metal.
Description
The present invention relates to a kind of preparation method of nano level anticorrosive oxide coating, exactly, it is the preparation method of nano level anticorrosive oxide coating on a kind of structural carbon steel.
Structural carbon steel is a structure iron the most frequently used in the engineering, yet its acid resistance, pyro-oxidation resistance are relatively poor, have influenced use.Strengthened the general methods such as all anti-corrosion (microalloying method) and surface modification (be mainly turn blue, phosphatization and zinc-plated) that adopt of the corrosion proof method of structural carbon steel, these methods have all won application widely in the past.But these method preparation process complexity, coat-thickness is thicker, increases overall weight, particularly not acidproof and high temperature corrosion.
Sol-gel (Sol-gel) technology is one of emerging surface engineering technology that surface modification and coating technology are united two into one, and is that the world today extremely pays close attention to, and with the technology of preparing that makes a breakthrough.It has advantages such as good manufacturability, stoichiometric ratio are easily controlled, goods are pure, the crystalline phase invert point is low, can apply crystalline state and non-crystalline state coating on metal material surface.The eighties just the someone adopt this technology on stainless steel, to be prepared into ceramic coating, and explored it at 850 ℃ and have use properties in the oxidative environment.The nineties, studied with colloidal sol-gel technique in succession and prepared TiO
2, ZrO
2, SiO
2Be coated on steel alloy and the superalloy steel Deng ceramic coating, studied different corrosive environments and the provide protection under 1100 ℃ of high temperature.
After retrieving a large amount of documents and materials, also do not see the report that utilizes sol-gel (Sol-gel) technology to prepare the adulterated nano level anticorrosive coating of non-crystalline state-crystalline state on the structural carbon steel.The performance of the structure of coating, composition and state of aggregation and coating is closely related.Nano material is current hot research problem both domestic and external.Coated with nano level coating does not have the important application prospects of being suspected to have by state of aggregation and the structure raising solidity to corrosion of improving coating in its surface.
In addition, when the preparation coating, the repeatedly methods of coating, cycle heat treatment that adopt certainly will cause the difference of coating from the surface to the interface of bringing owing to cycle heat treatment like this, influence the performance of coating.Simultaneously, the expansion coefficient difference of this two classes material of coating and metal is bigger, under environmental influences such as temperature, pressure, also will influence the performance of coating.Temperature, pressure also can influence the phase transformation of coating, and the phase transformation meeting causes the variation of structural stress.These factors are with solidity to corrosion, the weathering resistance of final decision matrix.The suitable property of expansion contraction phase that non-crystalline state and crystalline state are mixed and solved matrix and coating effectively.
Defective in view of above-mentioned coating, task of the present invention is the technology of preparing in conjunction with present nano material, invent a kind of nano level non-crystalline state---crystalline oxide coating, make full use of the good expansion character of non-crystal oxide and intensity, guarantee the coating not only acid corrosion-resistant but also high-temperature corrosion resistance that obtain with oxide compound of crystalline structure.
The present invention seeks to design a kind of preparation method of the nano level anticorrosive oxide coating on structural carbon steel.
The present invention is realized that by following technical proposals this coating production comprises the following steps:
(1) preparation of mixed stability colloidal sol: respectively with source substance dissolves such as Si salt, Ti salt, Zn/Al salt in dehydrated alcohol, fully stir, the dehydrated alcohol that will dissolve neutral salt then is divided into two, slowly in the dehydrated alcohol of having gone into to dissolve Si salt and Ti salt, continue fully to stir, after treating the nearly 24h of Si salt solution mix, mix with the dehydrated alcohol that contains a small amount of distilled water and additive, tensio-active agent, last above-mentioned solution all mixes, ceaselessly stir until the complete clear of solution, about restir 3h, sealing and standing.
(2) matrix is handled: structural carbon steel is deoiled after the skimming treatment, and the rusty stain on surface is removed in the dilute hydrochloric acid pickling, carries out chemical rightenning then, obtains even curface, through the water flushing, is placed in distilled water or the spirituous solution.
(3) the above-mentioned masking liquid that is in collosol state for preparing is brushed or adopted on the carbon structure guiding principle after dip-coating method is coated in processing, in drying at room temperature, repetitive coatings technology is 3-5 time then, and dry 30min in 200 ℃ ± 10 ℃ loft drier repeats above-mentioned coating processes once more then.
SiO in the coating
2Non-crystalline state is a network structure, mainly plays a part coated carrier, and the bonding force of this carrier and matrix is stronger, and its another effect is and the performance basically identical that expands with heat and contract with cold of matrix, can avoid causing because of expanding with heat and contract with cold cracking, but pure SiO
2A little less than the non-crystalline state coating resistance of oxidation, resistance to acid attack is also poor.Crystalline structure in the coating has been strengthened the non-crystalline state network, and they are dispersed in the non-crystalline state, has further improved the bonding force of coating and matrix.Therefore, the cohesive strength of resulting coating and matrix is good, can be by the tearing experiment confirm of transparent adhesive tape.Add the nanocrystalline TiO of part in the coating
2During (B) with anatase octahedrite, bonding force, resistance of oxidation and solidity to corrosion all improve, but work as TiO
2(B) further increase with anatase octahedrite content after, these performances descend again.Therefore, for the proportioning that makes non-crystalline state and crystalline state is suitable, the Si in the coating: Ti is 0.95～0.6: 0.05～0.4 than (atomic ratio, down together).When Si: Ti was 0.8: 0.2, its solidity to corrosion was best.In addition, add the titanium of element instead of part such as a spot of zinc, aluminium, can improve crystallization degree like this.
Tensio-active agent has improved the dispersiveness of crystal in non-crystalline state in preparation process, and particle diameter is evenly distributed, and has improved the homogeneity of coating when applying.Tensio-active agent has also improved the bonding force of coating and matrix.
Because the hydrolysis ability difference of every kind of material, the hydrolysis ability of colloidal sol has determined the final performance of coating.The present invention has selected several neutral salt, and neutral salt is Zn or Al salt, and content is not less than 0.5%, is used for improving the stability of colloidal sol, has effectively suppressed hydrolysis and polycondensation process.Stablizer also plays a part to strengthen the non-crystalline state network.
Have anti-corrosion, weather-proof, fine and close and have good adhesive property by the coating of the present invention preparation with matrix metal.Its acid resistance, oxidation-resistance property are all good than zinc coating.
This preparation method's advantage is: this coating is non-crystalline state-crystalline state nano-scale oxide, guaranteeing coating and matrix and being coated with interlayer has good binding intensity, component surface to Any shape all can apply, coating method is various, coat-thickness is controlled, the temperature of loft drier is 200 ℃ ± 10 ℃, and be half an hour time of drying, down dryly just can obtain anti-corrosion, weatherable, fine and close and has the nano level coating of good adhesion with matrix metal at 200 ℃.Coating wt is light, guarantees face body geometrical precision, and is high temperature resistant.This coating also can be applicable to stainless steel and other steel alloy and superalloy steel.
Below the present invention is described in further detail by specific embodiment.
Embodiment one:
The processing of carbon structure steel matrix is adopted and conventional is deoiled, pickling, and with the chemical brightening solution polishing that contains chromic anhydride, alcohol is put in washing.In dehydrated alcohol, add a small amount of Zn/Al salt, additive, tensio-active agent and a small amount of distilled water then, be divided into two, get tetraethoxy 19ml and butyl (tetra) titanate 2.1ml, stirring and dissolving is in above-mentioned dehydrated alcohol respectively, after allowing the dehydrated alcohol that contains tetraethoxy leave standstill 24h, above-mentioned solution all mixes, stir, apply after leaving standstill 3h, drying at room temperature, repetitive coatings technology is 3-5 time then, and dry 30min in 200 ℃ ± 10 ℃ loft drier repeats above-mentioned coating processes once more then.Static anti-oxidant experiment is to heat different time in 750 ℃ retort furnace, the weightening finish situation of sample before and after the weighing experiment, and with galvanized sheet (commercially available), blank sample (structural carbon steel through deoil, pickling, with the chemical brightening solution polishing that contains chromic anhydride, washing) compares, result such as table 1, therefrom visible the present invention is stronger than the resistance of oxidation of zinc coating, blank sample.
The preparation condition of table 1 coating and high temperature oxidation resistance
Preface is coated with oxidation weight gain rate (g/m
2)
Number floor 2h 4h 6h
1 this case 8.9 36.69 157.53
2 blank samples 209.05 1373.65 7991.14
3 galvanized sheets 188.68 483.01 569.86
Embodiment two:
Coating production is same as described above, carries out the acid resistance experiment then.The acid resistance experiment is at 6%FeCl
30.05N hydrochloric acid in 35 ℃ soak 24h after the weightening finish situation of sample before and after the weighing experiment, and with galvanized sheet (commercially available), blank sample (structural carbon steel through deoil, pickling, with the chemical brightening solution polishing that contains chromic anhydride, washing), stainless steel (import) compares, result such as table 2, therefrom visible acid resistance is better than zinc coating, stainless steel.The preparation condition of table 2 coating and acid resistance sequence number coating rate of weight loss (gm
-2H
-1) 1 this case, 46.592 blank sample 84.9783 galvanized sheets 73.7044 stainless steels 52.608
Claims (4)
1. the preparation method of a nano level anticorrosive oxide coating, it is characterized in that: this method comprises the following steps:
(1) preparation of mixed stability colloidal sol: respectively with source substance dissolves such as Si salt, Ti salt, Zn/Al salt in dehydrated alcohol, fully stir, the dehydrated alcohol that will dissolve neutral salt then is divided into two, slowly in the dehydrated alcohol of having gone into to dissolve Si salt and Ti salt, continue fully to stir, after treating the nearly 24h of Si salt solution mix, mix with the dehydrated alcohol that contains a small amount of distilled water and additive, tensio-active agent, last above-mentioned solution all mixes, ceaselessly stir until the complete clear of solution, about restir 3h, sealing and standing;
(2) matrix is handled: structural carbon steel is deoiled after the skimming treatment, and the rusty stain on surface is removed in the dilute hydrochloric acid pickling, carries out chemical rightenning then, obtains even curface, through the water flushing, is placed in distilled water or the spirituous solution;
(3) the above-mentioned masking liquid that is in collosol state for preparing is brushed or adopted on the carbon structure guiding principle after dip-coating method is coated in processing, in drying at room temperature, repetitive coatings technology is 3-5 time then, and drying in loft drier repeats above-mentioned coating processes once more then.
2 preparation methods according to a kind of nano level anticorrosive oxide coating of claim 1, it is characterized in that: neutral salt is Zn or Al salt, and content is not less than 0.5%.
3 preparation methods according to a kind of nano level anticorrosive oxide coating of claim 1, it is characterized in that: the temperature of loft drier is 200 ℃ ± 10 ℃, and be half an hour time of drying.
4 preparation methods according to a kind of nano level anticorrosive oxide coating of claim 1, it is characterized in that: the Si in the coating: the Ti ratio is 0.95～0.6: 0.05～0.4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127373 CN1211438C (en) | 2001-09-02 | 2001-09-02 | Prepn of nano level anticorrosive oxide coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01127373 CN1211438C (en) | 2001-09-02 | 2001-09-02 | Prepn of nano level anticorrosive oxide coating |
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| Publication Number | Publication Date |
|---|---|
| CN1403507A true CN1403507A (en) | 2003-03-19 |
| CN1211438C CN1211438C (en) | 2005-07-20 |
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ID=4667335
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 01127373 Expired - Fee Related CN1211438C (en) | 2001-09-02 | 2001-09-02 | Prepn of nano level anticorrosive oxide coating |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105627812A (en) * | 2015-12-21 | 2016-06-01 | 江苏格林威尔金属材料科技有限公司 | Light stainless steel heat radiator |
| CN107880751A (en) * | 2017-11-22 | 2018-04-06 | 四川凯茨阀门制造有限公司 | A kind of preparation method of metal corrosion-resistant coating |
| CN109200342A (en) * | 2017-07-06 | 2019-01-15 | 先健科技(深圳)有限公司 | Implantable device |
| CN110804396A (en) * | 2019-12-09 | 2020-02-18 | 万华化学集团股份有限公司 | Anticorrosive paint and preparation method and application thereof |
-
2001
- 2001-09-02 CN CN 01127373 patent/CN1211438C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105627812A (en) * | 2015-12-21 | 2016-06-01 | 江苏格林威尔金属材料科技有限公司 | Light stainless steel heat radiator |
| CN109200342A (en) * | 2017-07-06 | 2019-01-15 | 先健科技(深圳)有限公司 | Implantable device |
| CN107880751A (en) * | 2017-11-22 | 2018-04-06 | 四川凯茨阀门制造有限公司 | A kind of preparation method of metal corrosion-resistant coating |
| CN110804396A (en) * | 2019-12-09 | 2020-02-18 | 万华化学集团股份有限公司 | Anticorrosive paint and preparation method and application thereof |
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| Publication number | Publication date |
|---|---|
| CN1211438C (en) | 2005-07-20 |
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