CN101805908B - Method for preparing titanium dioxide anti-corrosion fouling-resistant film on surface of steel substrate - Google Patents
Method for preparing titanium dioxide anti-corrosion fouling-resistant film on surface of steel substrate Download PDFInfo
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- CN101805908B CN101805908B CN2010101407106A CN201010140710A CN101805908B CN 101805908 B CN101805908 B CN 101805908B CN 2010101407106 A CN2010101407106 A CN 2010101407106A CN 201010140710 A CN201010140710 A CN 201010140710A CN 101805908 B CN101805908 B CN 101805908B
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- ethyl alcohol
- absolute ethyl
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Abstract
The invention discloses a method for preparing a titanium dioxide anti-corrosion fouling-resistant film on the surface of a steel substrate, which comprises the steps of: firstly, preparing absolute ethyl alcohol solution of tetrabutyl titanate and film forming additive, adding the mixed liquor of alcohol and water, stirring and adding stabilizing agent DMF and corrosion inhibitor benzoic acid, ageing for 24 hours under the normal condition after continuously stirring for 2 hours, preprocessing and soaking the steel substrate in the ageing glue, carrying out lifting and pulling, carrying out the second soaking, lifting and pulling before completely drying, and roasting the obtained thin film in a muffle furnace, thus obtaining the titanium dioxide anti-corrosion fouling-resistant film. The method does not need acid catalyst to be added and the pH value of sol rubber to be controlled and simplifies the preparation technology of the sol rubber.
Description
Technical field
The invention belongs to loading type mineral membrane preparation field, particularly a kind of is the preparation technology of the nano titanium dioxide film of matrix with the metallic substance, can be applicable to the scale inhibition of Industrial Boiler and heat exchanger heat transfer face and anti-corrosion.
Background technology
Titanic oxide nano-membrane has received extensive concern because of chemistry, the physical property with excellences such as resistance to acids and bases, chemicalstability, hydrophobicity and self-cleaning properties in fields such as semi-conductor, solar energy converting, catalyzer, high tension battery, environment protection.
At present, the technology of preparation titanium dioxide film mainly contains galvanic deposit, sol-gel, ion sputtering deposition and chemical vapour deposition etc.Wherein sol-gel method compare with other film-forming methods have the product purity height, component evenly, form and be easy to control, simple to operate, less investment, and can be on the matrix of various different shapeies, differing materials the film forming characteristics of big area.Therefore sol-gel method is generally believed it is the prefered method of preparation inorganic ceramic film.
Adopt sol-gel method prepare the titanium dioxide film multiselect with glass and pottery as matrix, but the fragility that glass and pottery exist greatly, its range of application that has been difficult for post forming, drawbacks limit such as non-conductive.Not only can address the above problem as matrix with metal, and the titanium dioxide film of the preparation in the metallic surface can also improve the anti-corrosion of metallic matrix and anti-tartar performance.But because exist between inorganic oxide film and the metallic carrier coefficient of expansion and Young's modulus than big-difference, in thermal treatment and sintering process, cause problems such as cracking, film poor adhesive force easily.In addition, in preparation colloidal sol process, usually need add an acidic catalyst such as HCl, HNO
3Solution improves the hydrolysis rate of presoma, but for the most metal carrier, adds an acidic catalyst and can destroy its surface passivated membrane, produces corrosion.Japanese Patent JP 331919/2001 has introduced the technology for preparing titanium dioxide film with sol-gel method in aluminium, surface of stainless steel; This technology uses organic acid as catalyzer; Reduced the corrosion of inorganic acid, yet organic acid exists still certain corrodibility that this technology can't be used at material surfaces such as carbon steels to metal material surface.
Summary of the invention
The objective of the invention is to prepare problems such as the etched the matrix, the film sticking power that exist in the titanium oxide membrane process are low, easy to crack in the metallic surface, and proposed a kind of method for preparing the anti-corrosion fouling-resistant titanium dioxide film at steel substrate surface to sol-gel method.
For realizing above-mentioned purpose, the present invention takes following technical scheme:
(1) with absolute ethyl alcohol as non-polar solvent, tetrabutyl titanate, film coalescence aid diethylolamine added in the absolute ethyl alcohol mix absolute ethyl alcohol: tetrabutyl titanate: the mol ratio of film coalescence aid is 10: 0.3-0.5: 0.1-0.3, at room temperature stirred 1 hour;
(2) press absolute ethyl alcohol: the mixed in molar ratio of water=1: 0.1-0.2; Stir after 5 minutes, this mixed solution is added drop-wise in the solution of (1) step that keeps stirring, making ethanol/water solution and the volume ratio of (1) step solution is 1: 2; Add stablizer N (DMF) and inhibiter phenylformic acid after finishing again; The concentration that makes stablizer is 0.06mol/L, and the concentration of inhibiter is 0.01mol/L, continues to stir 2 hours;
(3) with the conventional ageing of the colloidal sol for preparing 24 hours;
(4) will use 360# successively, 800#, 1000# water-proof abrasive paper polishing matrix guarantees that matrix surface is smooth, carries out degreasing with acetone or absolute ethyl alcohol;
(5) pretreated base steel impregnated in 30s in the colloidal sol after the ageing, at the uniform velocity lift, do not carrying out flooding the second time and lifting before the complete drying with the speed of 5cm/min, time of immersion 30s, at the uniform velocity pull rate is 5cm/min, seasoning;
(6) put into retort furnace and carry out roasting, be warming up to 250 ℃ of roastings 30 minutes with 2 ℃/min speed program, be warming up to 450 ℃ of roastings 1 hour with 2 ℃/min speed program then, furnace cooling can obtain titanium dioxide film to room temperature.
XRD analysis is illustrated in metal base surface and has generated anatase titanium dioxide.SEM characterizes has proved that the metal base surface symphysis is continuous complete.Adhesive tape method sticking power testing experiment is qualified.(Ca in simulation high firmness industrial circulating cooling water environment
2+: 800mg/L, HCO
3 -: 600mg/L, all with Ca (HCO
3)
2Meter) more the raising of covering material solidity to corrosion is not more than 60% in, and the raising of anti-tartar property is more than 70%.
The present invention need not to add acid catalyst, need not to control colloidal sol pH value, has simplified colloidal sol preparation technology, is applicable to carbon steel, stainless steel and other metal materials.
Embodiment
Embodiment 1
Get 10: 0.4: 0.2 in molar ratio mixed of absolute ethyl alcohol, tetrabutyl titanate, diethylolamine, stirring at room 1 hour, again with absolute ethyl alcohol: the water mol ratio is that 1: 0.18 mixed solution joins in the above-mentioned tetrabutyl titanate solution; Wherein the volume ratio of ethanol/water mixed solution and tetrabutyl titanate solution is 1: 2, stirs after 5 minutes, adds DMF and phenylformic acid; The concentration that makes DMF is 0.06mol/L; Benzoic concentration is 0.01mol/L, continues to stir after 2 hours conventional ageing 24 hours.The test piece of A3 steel (50 * 25 * 2mm) use 360# successively, 800#, and the 1000# water-proof abrasive paper is polished to smooth surface, carries out degreasing with acetone or absolute ethyl alcohol.A3 steel disc after handling impregnated in the colloidal sol after the ageing 30 seconds, at the uniform velocity lift, do not carrying out flooding the second time and lifting before the complete drying with the speed of 5cm/min; Time of immersion 30s, at the uniform velocity pull rate is 5cm/min, puts into retort furnace after the seasoning and carries out roasting; Be warming up to 250 ℃ of roastings 30 minutes with 2 ℃/min speed program; Be warming up to 450 ℃ of roastings 1 hour with 2 ℃/mi n speed program then, the lamination patch that makes is No. 1, and its performance measurement result sees table 1.
Embodiment 2
Get 10: 0.3: 0.1 in molar ratio mixed of absolute ethyl alcohol, tetrabutyl titanate, diethylolamine, stirring at room 1 hour, again with absolute ethyl alcohol: the water mol ratio is that 1: 0.18 mixed solution joins in the above-mentioned tetrabutyl titanate solution; Wherein the volume ratio of ethanol/water mixed solution and tetrabutyl titanate solution is 1: 2, stirs after 5 minutes, adds DMF and phenylformic acid; The concentration that makes DMF is 0.06mol/L; Benzoic concentration is 0.01mol/L, continues to stir after 2 hours conventional ageing 24 hours.The test piece of A3 steel (50 * 25 * 2mm) use 360# successively, 800#, and the 1000# water-proof abrasive paper is polished to smooth surface, carries out degreasing with acetone or absolute ethyl alcohol.A3 steel disc after handling impregnated in the colloidal sol after the ageing 30 seconds; Speed with 5cm/min at the uniform velocity lifts, and is not carrying out flooding the second time and lifting, time of immersion 30s before the complete drying; At the uniform velocity pull rate is 5cm/min; Put into retort furnace after the seasoning and carry out roasting, be warming up to 250 ℃ of roastings 30 minutes, be warming up to 450 ℃ of roastings 1 hour with 2 ℃/min speed program then with 2 ℃/min speed program.The lamination patch that makes is No. 2, and its performance measurement result sees table 1.
Embodiment 3
Get 10: 0.5: 0.2 in molar ratio mixed of absolute ethyl alcohol, tetrabutyl titanate, diethylolamine, stirring at room 1 hour, again with absolute ethyl alcohol: the water mol ratio is that 1: 0.18 mixed solution joins in the above-mentioned tetrabutyl titanate solution; Wherein the volume ratio of ethanol/water mixed solution and tetrabutyl titanate solution is 1: 2, stirs after 5 minutes, adds DMF and phenylformic acid; The concentration that makes DMF is 0.06mol/L; Benzoic concentration is 0.01mol/L, continues to stir after 2 hours conventional ageing 24 hours.The A3 steel disc (50 * 25 * 2mm) use 360# successively, 800#, and the 1000# water-proof abrasive paper is polished to smooth surface, carries out degreasing with acetone or absolute ethyl alcohol.A3 steel disc after handling impregnated in the colloidal sol after the ageing 30 seconds; Speed with 5cm/min at the uniform velocity lifts, and is not carrying out flooding the second time and lifting, time of immersion 30s before the complete drying; At the uniform velocity pull rate is 5cm/min; Put into retort furnace after the seasoning and carry out roasting, be warming up to 250 ℃ of roastings 30 minutes, be warming up to 450 ℃ of roastings 1 hour with 2 ℃/min speed program then with 2 ℃/min speed program.The lamination patch that makes is No. 3, and its performance measurement result sees table 1.
Embodiment 4
Get 10: 0.4: 0.2 in molar ratio mixed of absolute ethyl alcohol, tetrabutyl titanate, diethylolamine, stirring at room 1 hour, again with absolute ethyl alcohol: the water mol ratio is that 1: 0.18 mixed solution joins in the above-mentioned tetrabutyl titanate solution; Wherein the volume ratio of ethanol/water mixed solution and tetrabutyl titanate solution is 1: 2, stirs after 5 minutes, adds DMF and phenylformic acid; The concentration that makes DMF is 0.06mo l/L; Benzoic concentration is 0.01mol/L, continues to stir after 2 hours conventional ageing 24 hours.304 stainless steel substrates (50 * 25 * 2mm) use 360# successively, 800#, and the 1000# water-proof abrasive paper is polished to smooth surface, carries out degreasing with acetone or absolute ethyl alcohol.304 stainless steel substrates after handling impregnated in the colloidal sol after the ageing 30 seconds; Speed with 5cm/min at the uniform velocity lifts, and is not carrying out flooding the second time and lifting, time of immersion 30s before the complete drying; At the uniform velocity pull rate is 5cm/min; Put into retort furnace after the seasoning and carry out roasting, be warming up to 250 ℃ of roastings 30 minutes, be warming up to 450 ℃ of roastings 1 hour with 2 ℃/min speed program then with 2 ℃/min speed program.The lamination patch that makes is No. 4, and its performance measurement result sees table 1.
Embodiment 5
Get 10: 0.4: 0.2 in molar ratio mixed of absolute ethyl alcohol, tetrabutyl titanate, diethylolamine, stirring at room 1 hour, again with absolute ethyl alcohol: the water mol ratio is that 1: 0.18 mixed solution joins in the above-mentioned tetrabutyl titanate solution; Wherein the volume ratio of ethanol/water mixed solution and tetrabutyl titanate solution is 1: 2, stirs after 5 minutes, adds DMF and phenylformic acid; The concentration that makes DMF is 0.06mol/L; Benzoic concentration is 0.01mol/L, continues to stir after 2 hours conventional ageing 24 hours.316 stainless steel substrates (50 * 25 * 2mm) use 360# successively, 800#, and the 1000# water-proof abrasive paper is polished to smooth surface, carries out degreasing with acetone or absolute ethyl alcohol.316 stainless steel substrates after handling impregnated in the colloidal sol after the ageing 30 seconds; Speed with 5cm/min at the uniform velocity lifts, and is not carrying out flooding the second time and lifting, time of immersion 30s before the complete drying; At the uniform velocity pull rate is 5cm/min; Put into retort furnace after the seasoning and carry out roasting, be warming up to 250 ℃ of roastings 30 minutes, be warming up to 450 ℃ of roastings 1 hour with 2 ℃/min speed program then with 2 ℃/min speed program.The lamination patch that makes is No. 5, and its performance measurement result sees table 1.
Table 1 is the performance measurement result of the foregoing description.
Table 1 titanium dioxide film performance measurement result
| Sample number | 1 | 2 | 3 | 4 | 5 |
| Sticking power | +++ | ++ | +++ | +++ | +++ |
| Corrosion inhibition rate | 65％ | 61％ | 63％ | 80％ | 72％ |
| Anti-dirty rate | 70％ | 70％ | 71％ | 82％ | 75％ |
Annotate: sticking power ++ represent that 5 adhesive tapes draw the striping not damaged, ++ 10 adhesive tapes of+expression draw the striping not damaged.
Claims (1)
1. method for preparing the anti-corrosion fouling-resistant titanium dioxide film at steel substrate surface; It is characterized in that; May further comprise the steps: (1) with absolute ethyl alcohol as polar solvent; With mixing absolute ethyl alcohol in tetrabutyl titanate, the film coalescence aid diethylolamine adding absolute ethyl alcohol: tetrabutyl titanate: the mol ratio of film coalescence aid is 10: 0.3-0.5: 0.1-0.3, at room temperature stirred 1 hour;
(2) press absolute ethyl alcohol: the mixed in molar ratio of water=1: 0.1-0.2; Stir after 5 minutes, this mixed solution is added drop-wise in the solution of (1) step that keeps stirring, making absolute ethyl alcohol/aqueous solution and the volume ratio of (1) step solution is 1: 2; Add stablizer N (DMF) and inhibiter phenylformic acid after finishing again; The concentration that makes stablizer is 0.06mol/L, and the concentration of inhibiter is 0.01mol/L, continues to stir 2 hours;
(3) with the conventional ageing of the colloidal sol for preparing 24 hours;
(4) will use 360# successively, 800#, 1000# water-proof abrasive paper polishing matrix guarantees that matrix surface is smooth, carries out degreasing with acetone or absolute ethyl alcohol;
(5) pretreated base steel impregnated in 30s in the colloidal sol after the ageing, at the uniform velocity lift, do not carrying out flooding the second time and lifting before the complete drying with the speed of 5cm/min, time of immersion 30s, at the uniform velocity pull rate is 5cm/min, seasoning;
(6) put into retort furnace and carry out roasting, be warming up to 250 ℃ of roastings 30 minutes with 2 ℃/min speed program, be warming up to 450 ℃ of roastings 1 hour with 2 ℃/min speed program then, furnace cooling can obtain titanium dioxide film to room temperature.
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