CN101760737A - Method for preparing enhanced heat-transfer and scale prevention coating of micron/nanometer titanium dioxide on stainless steel substrate - Google Patents
Method for preparing enhanced heat-transfer and scale prevention coating of micron/nanometer titanium dioxide on stainless steel substrate Download PDFInfo
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- CN101760737A CN101760737A CN200910245168A CN200910245168A CN101760737A CN 101760737 A CN101760737 A CN 101760737A CN 200910245168 A CN200910245168 A CN 200910245168A CN 200910245168 A CN200910245168 A CN 200910245168A CN 101760737 A CN101760737 A CN 101760737A
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Abstract
The invention discloses a method for preparing an enhanced heat-transfer and scale prevention coating of micron/nanometer titanium dioxide on a stainless steel substrate, comprising the following steps of: (a) pre-treating the stainless steel substrate; (b) preparing ammonium fluorotitanate and boric acid into uniform solutions, and mixing the two solutions uniformly; (c) placing the prepared mixed solution in a water bath and controlling the temperature thereof at 20-80 DEG C, suspending the stainless steel substrate perpendicularly in the mixed solution and starting to deposit to prepare the substrate coated with TiO2 thin film after the temperature of the mixed solution is stable; (d) after deposition, picking the substrate out and washing the surface of the substrate with distilled water; and (e) drying the substrate naturally, then placing the substrate in a resistance furnace to heat to obtain the micron/nanometer TiO2 surface coating. The coating prepared by adopting the method is compact and uniform in appearance and the Ra value of the sintered surface coating is substantially equal to that of the polished surface coating. The coating is high-temperature resistant and is combined with the substrate more firmly.
Description
Technical field
The present invention relates to a kind ofly on the stainless steel-based end, prepare micro-nano TiO with liquid phase deposition
2The method of coating, relate in particular to a kind of on the stainless steel-based ends such as austenite 300 series, martensite 400 series micro/nano level thickness T iO
2The liquid deposition preparation method on enhancement of heat transfer and antiscale surface.
Background technology
At present, the ubiquity fouling problem that is in operation of the heat-exchange equipment more than 90%.The formation of heat-exchange equipment surface dirt not only influences heat energy utilization and produces normal safe handling, and increased production cost.Statistic data in 2007 shows that the heat exchanger fouling loss of developed country accounts for the 0.15-0.25% of GNP, and developing country is then higher, reaches 0.3%.The prevention of industrial dirt and eliminate general chemical processes such as adding the chemical scale-inhibiting agent and the machinery of adopting and clean, apply physical methods such as outfield, ubiquity cleaning cost height and secondary pollution problems.
The deposition of dirt is relevant with the sticking power between dirt-heating surface, and the surface energy of the size of sticking power and heating surface is closely related, and surface energy is more little, and sticking power is just more little.Therefore can handle by the heat exchanging surface, reduce its surface energy, thereby reduce dirt deposition.A series of comparatively effectively antiscale that grown up at present both at home and abroad or the technology of strengthening pool boiling or flow boiling heat transfer mainly comprise: magnetron sputtering, ion implantation, Ni-P, thermospray, chemical vapour deposition, sol-gel, molecule self-assembly etc.But these preparation method's ubiquities preparation expense costliness, equipment complexity, industrialization difficulty or coating is inhomogeneous, thermal resistance is big, combine shortcomings such as not firm with substrate.
Liquid phase deposition is a kind of method that relatively is suitable for the large-area preparation film surface.This method reported first in 1988.That its film has is easy to operate, equipment simple, filming condition is gentle and can be on complex-shaped substrate advantage such as film forming, now being widely used in preparation, the especially microelectronic industry of function film super large-scale integration, Metal-Oxide Semiconductor and liquid crystal display device forms in the sull process and has obtained application.
The patent that liquid phase deposition is relevant has: the method for Chinese patent 200710168732.1 usefulness producing titanium dioxide coating capillary column with liquid deposition method, it is characterized in that with the ammonium titanium fluoride being raw material, by liquid phase deposition at quartz capillary inwall deposition of titanium oxide thin film layer, exist sintering temperature lower, be 300 ℃, property of thin film is not had detailed sign etc. yet.200710060653.9 1 kinds of Chinese patents prepare the method for the film surface of nano thickness at red copper surface, it is characterized in that adopting the liquid deposition method to prepare nano thickness TiO in the red copper substrate
2Deng film, and be used for fortified water pool Boiling Heat Transfer, antiscale and anticorrosion.The easy oxidation of substrate when there is under the air atmosphere sintering in this method, sintering temperature is lower, problem such as non-refractory, intensity are low.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of preparation micron/nanometer titanium dioxide enhancement of heat transfer and antiscale coating process on the stainless steel-based end is provided, the coating that adopts present method to make is fine and close evenly, surface energy is lower, high temperature resistant and intensity is high.
Preparation micron/nanometer titanium dioxide enhancement of heat transfer and antiscale coating process on the stainless steel-based end, it may further comprise the steps:
(a) pre-treatment is carried out at the stainless steel-based end, made its surperficial roughness Ra＜50nm;
(b) chemical pure ammonium titanium fluoride, analytically pure boric acid are mixed with the solution of homogeneous respectively, and impurity screening obtains clear soln, two kinds of solution are mixed, and the concentration of ammonium titanium fluoride and boric acid is respectively 0.05-0.5mol/L and 0.07-0.6mol/L in the mixed solution that obtains;
(c) mixed solution with preparation is placed in the water-bath its temperature of control at 20-80 ℃, after mixeding liquid temperature is constant, stainless steel-based dolly directly hung on to begin to deposit 2-50 hour in the mixing solutions and make is coated with TiO
2The substrate of film;
(d) after deposition finishes, will be coated with TiO
2The substrate of film takes out, and uses the distilled water flushing surface to remove surface residue;
(e) substrate is dried naturally, put into N then
2Heat in the resistance furnace of protection, heating rate is 2-8 ℃/min, when temperature is elevated to 300-800 ℃, keeps constant temperature 30-150 minute, closes resistance furnace, naturally cools to room temperature and obtains micro-nano TiO
2Top coat;
Pre-treatment step in the described step (a) comprises polishing step and ultrasonic cleaning step successively; Roughness Ra＜the 50nm on the surface at the stainless steel-based end after the polishing of described polishing step wherein, described ultrasonic cleaning step comprises: with coupon is 3-10% in mass percent at first, temperature is ultrasonic soaking and washing 5-10min in 30-60 ℃ the NaOH solution, removes the intractable grease; Print being immersed mass percent is 3% again, and temperature is ultrasonic soaking and washing 5-10min in 30-60 ℃ the hydrochloric acid, removes the print surface oxide layer; Clean with distilled water flushing at last, air-dry being placed in the encloses container preserved.
The invention has the beneficial effects as follows: liquid deposition preparation method of the present invention can obtain the different colours coating in actual mechanical process, and each appearance of coat is evenly fine and close.Through measuring coat-thickness between 32.6-180.5nm, surperficial distilled water contact angle is between 81.6-94.4 °, and surface energy is lower, and its numerical value is between 29.8-47.5mJ/m
2(standardized liquid is selected water and methylene iodide for use, down with) is lower than the surface energy (88mJ/m of polishing stainless steel
2).Detect through X-ray diffractometer (XRD), that the coating crystal formation can be is armorphous, Detitanium-ore-type and rutile-type.Measure and atomic force microscope (AFM) detection through roughmeter, the Ra value after the Ra value of sintering rear surface coating and the polishing is basic identical.Compare with 200710060653.9 patents, coat-thickness, contact angle and surface energy are approaching, still, the market value of used substrate is more cheap, and the roughness after the substrate polishing is littler, and coating is high temperature resistant, combine more firmly with substrate, the highest 800 ℃ of coatings still do not come off, and more help being used for surperficial antiscale.
Description of drawings
Fig. 1 is the schematic flow sheet for preparing micron/nanometer titanium dioxide enhancement of heat transfer and antiscale coating process on the stainless steel-based end of the present invention;
Fig. 2 a-Fig. 2 b be respectively adopt 2000 times of micron/nanometer titanium dioxide coatings that the embodiment of the invention 1 method makes Electronic Speculum figure and can spectrogram;
Fig. 3 is the x-ray diffraction pattern that adopts the micron/nanometer titanium dioxide coating that the embodiment of the invention 1 method makes;
Fig. 4 a-Fig. 4 b be respectively adopt 2000 times of micron/nanometer titanium dioxide coatings that the embodiment of the invention 2 methods make Electronic Speculum figure and can spectrogram;
Fig. 5 is the x-ray diffraction pattern that adopts the micron/nanometer titanium dioxide coating that the embodiment of the invention 2 methods make;
Fig. 6 a-Fig. 6 b be respectively adopt 2000 times of micron/nanometer titanium dioxide coatings that the embodiment of the invention 3 methods make Electronic Speculum figure and can spectrogram;
Fig. 7 is the x-ray diffraction pattern that adopts the micron/nanometer titanium dioxide coating that the embodiment of the invention 3 methods make;
Fig. 8 a-Fig. 8 b be respectively adopt 2000 times of micron/nanometer titanium dioxide coatings that the embodiment of the invention 4 methods make Electronic Speculum figure and can spectrogram;
Fig. 9 is the x-ray diffraction pattern that adopts the micron/nanometer titanium dioxide coating that the embodiment of the invention 4 methods make;
Figure 10 a-Figure 10 b be adopt 2000 times of micron/nanometer titanium dioxide coatings that the embodiment of the invention 5 methods make Electronic Speculum figure and can spectrogram;
Figure 11 is the x-ray diffraction pattern that adopts the micron/nanometer titanium dioxide coating that the embodiment of the invention 5 methods make.
Embodiment
Below in conjunction with the drawings and specific embodiments the present invention is described in detail.
Operating gear of the present invention comprises: a cover water bath with thermostatic control, deposition are with hanger etc.Required reagent: coating deposits required chemical pure ammonium titanium fluoride, analytically pure boric acid, and required dehydrated alcohol and analytically pure acetone etc. are cleaned in substrate.
The principles of chemistry of preparation film: hydrolysis generation metal hydroxides takes place in the ion by metal fluoride in water, and adding fluorion depleting agents boric acid is kept reaction in solution.Reaction equation is
(TiF
6)
2-+nH
2O→[TiF
6-n(OH)
n]
2-+nHF
[TiF
6-n(OH)
n]
2-+(6-n)H
2O?→[Ti(OH)
6]
2-+(6-n)HF
H
3BO
3+4HF→BF
4 -+H
3O
++2H
2O
Again by [Ti
6-n(OH)
n]
2-Dehydration reaction forms the orderly cancellated coating of titanium dioxide of metal-oxygen.
The present invention is the improvement on Chinese patent 200710060653.9 bases.
The inventive method may further comprise the steps: (a) pre-treatment is carried out at the stainless steel-based end, made its surperficial roughness Ra＜50nm; The described stainless steel-based end, can be austenite 300 series, martensite 400 series etc.; (b) chemical pure ammonium titanium fluoride, analytically pure boric acid are mixed with the solution of homogeneous respectively, and impurity screening obtains clear soln, two kinds of solution are mixed, and the concentration of ammonium titanium fluoride and boric acid is respectively 0.05-0.5mol/L and 0.07-0.6mol/L in the mixed solution that obtains; Be lower than this concentration interval and can not deposit coating, be higher than this concentration interval, make the solution muddiness because of producing a large amount of white particles in the deposit fluid, consume stock liquid.(c) mixed solution with preparation is placed in the water-bath its temperature of control at 20-80 ℃, after mixeding liquid temperature is constant, stainless steel-based dolly directly hung on to begin to deposit 2-50 hour in the mixing solutions and make is coated with TiO
2The substrate of film; (d) after deposition finishes, will be coated with TiO
2The substrate of film takes out, and repeatedly washes the surface to remove surface residue with distilled water; (e) substrate is dried naturally, put into N then
2Heat in the resistance furnace of protection, heating rate is 2-8 ℃/min, when temperature is elevated to 300-800 ℃, keeps constant temperature 30-150 minute, closes heating unit, naturally cools to room temperature and obtains micro-nano TiO
2Top coat; Adopt N in this step
2The resistance furnace of protection can prevent coating oxidation, and sintering temperature is 300-800 ℃ in this step, when temperature is lower than 300 ℃; then because the atonic heat capacity diffusion is little between coating and substrate interface; coating combines insecure with substrate, when sintering temperature is higher than 800 ℃, easily come off from substrate during the coating sintering.Temperature in step (e) is elevated to the 450-800 ℃ of coating that can obtain Detitanium-ore-type and rutile-type crystal formation.
Pre-treatment step in the described step (a) comprises polishing step and ultrasonic cleaning step successively; Roughness Ra＜the 50nm on the surface at the stainless steel-based end after the polishing of described polishing step wherein, described ultrasonic cleaning step comprises: with coupon is 3-10% in mass percent at first, temperature is ultrasonic soaking and washing 5-10min in 30-60 ℃ the NaOH solution, removes the intractable grease; Print being immersed mass percent is 3% again, and temperature is ultrasonic soaking and washing 5-10min in 30-60 ℃ the hydrochloric acid, removes the print surface oxide layer; Clean with distilled water flushing at last, air-dry being placed in the encloses container preserved.
Described polishing step can comprise corase grind, correct grinding, polishing and ultrasonic cleaning step successively; Wherein,
Corase grind step: at first remove surface contaminants and substrate initial trench along same direction polishing, all cover 300#-400# sand paper texture until substrate surface with 300#-400# sand paper; Along spending the direction polishing at an angle of 90, cover 500#-900# sand paper texture with 500#-900# sand paper until substrate surface with 300#-400# sand paper texture; The direction polishing of spending at an angle of 90 with 1000#-1800# sand paper edge and 500#-900# sand paper texture covers 1000#-1800# sand paper texture until substrate surface then;
Correct grinding step: remove striped with 2000# or 3000# sand papering;
Polishing step: the wool polishing wheel with metal polishing machine applies commercially available green clear boiled soap, stainless steel-based basal surface is polished the surface roughness Ra＜50nm after the polishing; The metal polishing machine (model is C121) that metal polishing machine can select for use Japanese MINIMO company to produce.
Adopt the comparing result of the inventive method and control methods (Chinese patent 200710060653.9) to see the following form:
| Adopt present method | Control methods | |
| Roughness (nm) after the substrate polishing | ??10-49 | Less than 500 |
| Coat-thickness (nm) | ??32.6-180.5 | ??18.6-108 |
| The contact angle of laminar surface (degree, distilled water) | ??81.6-94.4 | ??80-95 |
| Surface energy (mJ/m 2) | ??29.8-47.5 | ??20-60 |
| The Ra value (nm) of coating crystal formation sintering rear surface coating | ??15-49 | Less than 500 |
| The coating crystal formation | Can be armorphous, anatase octahedrite or rutile-type | Armorphous |
| Appearance of coat | Wheat yellow-light blue-blueness-golden yellow-pansy-yellow-green colour-green-smooth densification of cyan coating appears successively with the coat-thickness increase | Yellow or lavender |
As can be seen from the above table: the coating crystal formation that makes by the inventive method can be armorphous, Detitanium-ore-type and rutile-type.Control methods (200710060653.9) is armorphous, compare with armorphous, Detitanium-ore-type and rutile-type have higher thermostability, and rutile-type crystal reticulated structure is more tight, and because sintering temperature is higher, interface atonic heat capacity scattering and permeating degree is better between coating and substrate, and is higher with the substrate bonding strength.Thereby the coating that adopts the inventive method to make is more high temperature resistant, and intensity is higher.The coatingsurface roughness that adopts present method to make simultaneously is littler, the smooth densification of coating, and appearance color is abundanter.
(a) corase grind: remove surface contaminants and substrate initial trench with the 300# sand papering, all cover 300# sand paper texture until substrate surface; Use the 500# sand papering, cover 500# sand paper texture until substrate surface; Use the 1000# sand papering then, cover 1000# sand paper texture until substrate surface.Correct grinding: remove striped with the 2000# sand papering, substrate this moment texture is very fine and closely woven, bright.Polishing: the wool polishing wheel with C121 shaped metal polishing machine applies commercially available green clear boiled soap, the stainless steel substrate surface is polished 5 minutes the surface roughness Ra=23.0nm after the polishing; The ultrasonic cleaning step: with coupon is 3% in mass percent at first, and temperature is a ultrasonic soaking and washing 5 minutes in 40 ℃ the NaOH solution, removes the intractable grease; Print being immersed mass percent is 3% again, and temperature is a ultrasonic soaking and washing 10 minutes in 30 ℃ the hydrochloric acid, removes the print surface oxide layer; Clean with distilled water flushing at last, air-dry being placed in the encloses container preserved.(b) chemical pure ammonium titanium fluoride, analytically pure boric acid are mixed with the solution of homogeneous respectively, and impurity screening obtains clear soln, the concentration of ammonium titanium fluoride and boric acid is respectively 0.05mol/L and 0.15mol/L in mixed mixed solution; (c) mixed solution with preparation is placed on and is heated to 55 ℃ in the water-bath, after mixeding liquid temperature is constant, the stainless steel substrate vertical hanging is deposited 33h in mixing solutions; (d) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove surface residue with distilled water; (e) substrate is dried naturally, put into heating unit then and heat, it is 8 ℃/min that heating rate is set, N
2Protection when temperature is elevated to 300 ℃, kept constant temperature 120 minutes, closed heating unit, obtained the light blue micro-nano TiO of light behind the naturally cooling
2Top coat.Coating is armorphous, and coat-thickness is 103.2nm, and coatingsurface distilled water contact angle is 84.2 °, and surface energy is 35.9mJ/m
2
The SEM figure that adopts XL30ESEM Electronic Speculum (secondary electron high vacuum resolving power 3.0nm, rough vacuum resolving power 3.5nm, acceleration voltage 0.2-30kV, low vacuum 20torr) to obtain among Fig. 2 a.Find out the more smooth densification of coating, flawless and cover substrate fully by SEM figure.The hole that the dark zone of color among the figure stays when being the substrate grinding and polishing.Find out that by Fig. 2 b power spectrum graphs (its ultimate analysis sees the following form) the titanium elements content of coatingsurface is 1.96%, can draw substrate surface by TiO
2Coating covers.
Adopt Japanese RIGAKU D/MAX2500X x ray diffractometer x (Cuk α of science among Fig. 3
1Ray, 18KW superpower change target x ray generator, 0.0001 ° of minimum step, 1500 °/min of locating speed, sweep velocity 0001-100 °/min, scope-60-163 ° of 2 θ angle measurement) XRD figure that obtains.Find out that by XRD figure all diffraction peaks are the stainless characteristic peak of substrate, no TiO
2The crystalline characteristic peak, it is armorphous can drawing the coating that obtains at this sintering temperature.
(a) corase grind: remove surface contaminants and substrate initial trench with 400# sand paper along same direction polishing, all cover 400# sand paper texture until substrate surface; Along polishing, cover 700# sand paper texture with 700# sand paper until substrate surface with 90 ° of directions of 400# sand paper texture; With 90 ° of directions polishings of 1500# sand paper edge and 700# sand paper texture, cover 1500# sand paper texture then until substrate surface.Correct grinding: remove striped with the 2500# sand papering, substrate this moment texture is very fine and closely woven, bright.Polishing: the wool polishing wheel with C121 shaped metal polishing machine applies commercially available green clear boiled soap, the stainless steel substrate surface is polished 10 minutes the surface roughness Ra=36.2nm after the polishing; The ultrasonic cleaning step: with coupon is 8% in mass percent at first, and temperature is a ultrasonic soaking and washing 10 minutes in 60 ℃ the NaOH solution, removes the intractable grease; Print being immersed mass percent is 3% again, and temperature is a ultrasonic soaking and washing 10 minutes in 50 ℃ the hydrochloric acid, removes the print surface oxide layer; Clean with distilled water flushing at last, air-dry being placed in the encloses container preserved.(b) chemical pure ammonium titanium fluoride, analytically pure boric acid are mixed with the solution of homogeneous respectively, and impurity screening obtains clear soln, the concentration of ammonium titanium fluoride and boric acid is respectively 0.1mol/L and 0.6mol/L in mixed mixed solution; (c) mixed solution with preparation is placed on 20 ℃ of insulations in the water-bath, after mixeding liquid temperature is constant, the stainless steel substrate vertical hanging is deposited 22 hours in mixing solutions; (d) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove surface residue with distilled water; (e) substrate is dried naturally, put into heating unit then and heat, it is 6 ℃/min that heating rate is set, N
2Protection when temperature is elevated to 500 ℃, kept constant temperature 120 minutes, closed heating unit, obtained the sky blue micro-nano TiO of light behind the naturally cooling
2Top coat.The crystal formation of coating is a Detitanium-ore-type, and coat-thickness is 77.3nm.Coatingsurface distilled water contact angle is 88.7 °, and surface energy is 31.3mJ/m
2
Fig. 4 a is the SEM photo of coating.Find out by SEM figure, the more smooth flawless of coating, and cover substrate fully.The hole that the dark zone of color among the figure stays when being the substrate grinding and polishing.Find out that by Fig. 4 b power spectrum graphs (its ultimate analysis sees the following form) the titanium elements content of coatingsurface is 1.11%, can draw substrate surface by TiO
2Coating covers.
Fig. 5 is the XRD figure of coating.Analysis of X RD figure also finds with the contrast of standard P DF card, and diffraction angle 2 θ=25.229 ° locate to exist the strongest diffractive features peak (2 θ=25.281 °, the spacing of lattice of anatase octahedrite
), can draw the coating that obtains at this sintering temperature is Detitanium-ore-type.
(a) corase grind: remove surface contaminants and substrate initial trench with 300# sand paper along same direction polishing, all cover 300# sand paper texture until substrate surface; Along polishing, cover 900# sand paper texture with 900# sand paper until substrate surface with 90 ° of directions of 300# sand paper texture; With 90 ° of directions polishings of 1800# sand paper edge and 900# sand paper texture, cover 1800# sand paper texture then until substrate surface.Correct grinding: remove striped with the 2000# sand papering, substrate this moment texture is very fine and closely woven, bright.Polishing: the wool polishing wheel with C121 shaped metal polishing machine applies commercially available green clear boiled soap, the stainless steel substrate surface is polished 5 minutes the surface roughness Ra=45.9nm after the polishing; The ultrasonic cleaning step: with coupon is 3% in mass percent at first, and temperature is a ultrasonic soaking and washing 5 minutes in 40 ℃ the NaOH solution, removes the intractable grease; Print being immersed mass percent is 3% again, and temperature is a ultrasonic soaking and washing 10 minutes in 50 ℃ the hydrochloric acid, removes the print surface oxide layer; Clean with distilled water flushing at last, air-dry being placed in the encloses container preserved.(b) chemical pure ammonium titanium fluoride, analytically pure boric acid are mixed with the solution of homogeneous respectively, and impurity screening obtains clear soln, the concentration of ammonium titanium fluoride and boric acid is respectively 0.5mol/L and 0.07mol/L in mixed mixed solution; (c) mixed solution with preparation is placed on and is heated to 30 ℃ in the water-bath, after mixeding liquid temperature is constant, the stainless steel substrate vertical hanging is deposited 11 hours in mixing solutions; (d) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove surface residue with distilled water; (e) substrate is dried naturally, put into heating unit then and heat, it is 2 ℃/min that heating rate is set, N
2Protection when temperature is elevated to 700 ℃, kept constant temperature 120 minutes, closed heating unit, obtained the micro-nano TiO of bright yellow-green colour behind the naturally cooling
2Top coat.The crystal formation of coating is a rutile-type, and coat-thickness is 130.3nm.Coatingsurface distilled water contact angle is 89.2 °, and surface energy is 30.5mJ/m
2
Fig. 6 a is the SEM photo of coating.Find out by SEM figure, the more smooth flawless of coating, and cover substrate fully.The hole that the dark zone of color among the figure stays when being the substrate grinding and polishing.Find out that by Fig. 6 b power spectrum graphs (its ultimate analysis sees the following form) the titanium elements content of coatingsurface is 2.93%, can draw substrate surface by TiO
2Coating covers.
Fig. 7 is the XRD figure of coating.Analysis of X RD figure also finds with the contrast of standard P DF card, and diffraction angle 2 θ=27.318 ° locate to exist the strongest diffractive features peak (2 θ=27.446 °, the spacing of lattice of anatase octahedrite
), can draw the coating that obtains at this sintering temperature is rutile-type.
(a) corase grind: remove surface contaminants and substrate initial trench with 300# sand paper along same direction polishing, all cover 300# sand paper texture until substrate surface; Along polishing, cover 500# sand paper texture with 500# sand paper until substrate surface with 90 ° of directions of 300# sand paper texture; With 90 ° of directions polishings of 1000# sand paper edge and 500# sand paper texture, cover 1000# sand paper texture then until substrate surface.Correct grinding: remove striped with the 3000# sand papering, substrate this moment texture is very fine and closely woven, bright.Polishing: the wool polishing wheel with C121 shaped metal polishing machine applies commercially available green clear boiled soap, the stainless steel substrate surface is polished 10 minutes the surface roughness Ra=34.6nm after the polishing; The ultrasonic cleaning step: with coupon is 5% in mass percent at first, and temperature is a ultrasonic soaking and washing 8 minutes in 60 ℃ the NaOH solution, removes the intractable grease; Print being immersed mass percent is 3% again, and temperature is a ultrasonic soaking and washing 5 minutes in 50 ℃ the hydrochloric acid, removes the print surface oxide layer; Clean with distilled water flushing at last, air-dry being placed in the encloses container preserved.(b) chemical pure ammonium titanium fluoride, analytically pure boric acid are mixed with the solution of homogeneous respectively, and impurity screening obtains clear soln, the concentration of ammonium titanium fluoride and boric acid is respectively 0.1mol/L and 0.15mol/L in mixed mixed solution; (c) mixed solution with preparation is placed on and is heated to 80 ℃ in the water-bath, after mixeding liquid temperature is constant, the stainless steel substrate vertical hanging is deposited 2 hours in mixing solutions; (d) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove surface residue with distilled water; (e) substrate is dried naturally, put into heating unit then and heat, it is 3 ℃/min that heating rate is set, N
2Protection when temperature is elevated to 600 ℃, kept constant temperature 30 minutes, closed heating unit, obtained the yellow micro-nano TiO of bright wheat behind the naturally cooling
2Top coat.The crystal formation of coating is a Detitanium-ore-type, and coat-thickness is 32.6nm.Coatingsurface distilled water contact angle is 81.6 °, and surface energy is 47.5mJ/m
2
Fig. 8 a is the SEM photo of coating.Find out by SEM figure, the more smooth flawless of coating, and cover substrate fully.The hole that the dark zone of color among the figure stays when being the substrate grinding and polishing.Find out that by Fig. 8 b power spectrum graphs (its ultimate analysis sees the following form) the titanium elements content of coatingsurface is 0.81%, can draw substrate surface by TiO
2Coating covers.
Fig. 7 is the XRD figure of coating.Analysis of X RD figure also finds with the contrast of standard P DF card, and diffraction angle 2 θ=25.081 ° locate to exist the strongest diffractive features peak (2 θ=25.281 °, the spacing of lattice of faint anatase octahedrite
), can draw the coating that obtains at this sintering temperature is Detitanium-ore-type, the more weak reason of diffraction peak is that the coating depositing time is shorter, and thinner thickness, surface titanium dioxide content is lower.
(a) corase grind: remove surface contaminants and substrate initial trench with 300# sand paper along same direction polishing, all cover 300# sand paper texture until substrate surface; Along polishing, cover 500# sand paper texture with 500# sand paper until substrate surface with 90 ° of directions of 300# sand paper texture; With 90 ° of directions polishings of 1000# sand paper edge and 500# sand paper texture, cover 1000# sand paper texture then until substrate surface.Correct grinding: remove striped with the 2000# sand papering, substrate this moment texture is very fine and closely woven, bright.Polishing: the wool polishing wheel with C121 shaped metal polishing machine applies commercially available green clear boiled soap, the stainless steel substrate surface is polished 5 minutes the surface roughness Ra=49.7nm after the polishing; The ultrasonic cleaning step: with coupon is 10% in mass percent at first, and temperature is a ultrasonic soaking and washing 10 minutes in 30 ℃ the NaOH solution, removes the intractable grease; Print being immersed mass percent is 3% again, and temperature is a ultrasonic soaking and washing 6 minutes in 60 ℃ the hydrochloric acid, removes the print surface oxide layer; Clean with distilled water flushing at last, air-dry being placed in the encloses container preserved.(b) chemical pure ammonium titanium fluoride, analytically pure boric acid are mixed with the solution of homogeneous respectively, and impurity screening obtains clear soln, the concentration of ammonium titanium fluoride and boric acid is respectively 0.25mol/L and 0.25mol/L in mixed mixed solution; (c) mixed solution with preparation is placed on and is heated to 60 ℃ in the water-bath, after mixeding liquid temperature is constant, the stainless steel substrate vertical hanging is deposited 50 hours in mixing solutions; (d) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove surface residue with distilled water; (e) substrate is dried naturally, put into heating unit then and heat, it is 2.5 ℃/min that heating rate is set, N
2Protection when temperature is elevated to 800 ℃, kept constant temperature 150 minutes, closed heating unit, obtained the micro-nano TiO of bright cyan behind the naturally cooling
2Top coat.The crystal formation of coating is a rutile-type, and coat-thickness is 180.5nm.Coatingsurface distilled water contact angle is 94.4 °, and surface energy is 29.8mJ/m
2
Figure 10 a is the SEM photo of coating.Find out by SEM figure, the more smooth flawless of coating, and cover substrate fully.The hole that the dark zone of color among the figure stays when being the substrate grinding and polishing.Find out that by Figure 10 b power spectrum graphs (its ultimate analysis sees the following form) the titanium elements content of coatingsurface is 4.74%, can draw substrate surface by TiO
2Coating covers.Comparison diagram 2, Fig. 4, Fig. 6, Fig. 8 and Figure 10 floating coat constituent content table know that with the increase of coat-thickness, titanium content increases.
Figure 11 is the XRD figure of coating.Analysis of X RD figure also finds with the contrast of standard P DF card, and diffraction angle 2 θ=27.382 ° locate to exist the strongest diffractive features peak (2 θ=27.446 °, the spacing of lattice of anatase octahedrite
), can draw the coating that obtains at this sintering temperature is rutile-type.
Claims (3)
1. prepare micron/nanometer titanium dioxide enhancement of heat transfer and antiscale coating process on a stainless steel-based end, it is characterized in that it may further comprise the steps:
(a) pre-treatment is carried out at the stainless steel-based end, made its surperficial roughness Ra＜50nm;
(b) chemical pure ammonium titanium fluoride, analytically pure boric acid are mixed with the solution of homogeneous respectively, and impurity screening obtains clear soln, two kinds of solution are mixed, and the concentration of ammonium titanium fluoride and boric acid is respectively 0.05-0.5mol/L and 0.07-0.6mol/L in the mixed solution that obtains;
(c) mixed solution with preparation is placed in the water-bath its temperature of control at 20-80 ℃, after mixeding liquid temperature is constant, stainless steel-based dolly directly hung on to begin to deposit 2-50 hour in the mixing solutions and make is coated with TiO
2The substrate of film;
(d) after deposition finishes, will be coated with TiO
2The substrate of film takes out, and uses the distilled water flushing surface to remove surface residue;
(e) substrate is dried naturally, put into N then
2Heat in the resistance furnace of protection, heating rate is 2-8 ℃/min, when temperature is elevated to 300-800 ℃, keeps constant temperature 30-150 minute, closes resistance furnace, naturally cools to room temperature and obtains micro-nano TiO
2Top coat;
Pre-treatment step in the described step (a) comprises polishing step and ultrasonic cleaning step successively; Roughness Ra＜the 50nm on the surface at the stainless steel-based end after the polishing of described polishing step wherein, described ultrasonic cleaning step comprises: with coupon is 3-10% in mass percent at first, temperature is ultrasonic soaking and washing 5-10min in 30-60 ℃ the NaOH solution, removes the intractable grease; Print being immersed mass percent is 3% again, and temperature is ultrasonic soaking and washing 5-10min in 30-60 ℃ the hydrochloric acid, removes the print surface oxide layer; Clean with distilled water flushing at last, air-dry being placed in the encloses container preserved.
2. prepare micron/nanometer titanium dioxide enhancement of heat transfer and antiscale coating process according to claim 1, it is characterized in that: the temperature in the described step (e) is 450-800 ℃ at stainless steel-based the end.
3. prepare micron/nanometer titanium dioxide enhancement of heat transfer and antiscale coating process according to claim 1, it is characterized in that: described polishing steps in sequence comprises corase grind, correct grinding, polishing and ultrasonic cleaning step at stainless steel-based the end; Wherein,
Corase grind step: at first remove surface contaminants and substrate initial trench along same direction polishing, all cover 300#-400# sand paper texture until substrate surface with 300#-400# sand paper; Along spending the direction polishing at an angle of 90, cover 500#-900# sand paper texture with 500#-900# sand paper until substrate surface with 300#-400# sand paper texture; The direction polishing of spending at an angle of 90 with 1000#-1800# sand paper edge and 500#-900# sand paper texture covers 1 000#-1800# sand paper texture until substrate surface then;
Correct grinding step: remove striped with 2000# or 3000# sand papering;
Polishing step: the wool polishing wheel with metal polishing machine applies commercially available green clear boiled soap, stainless steel-based basal surface is polished the surface roughness Ra＜50nm after the polishing.
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