CN102527613A - Liquid-phase deposition-impregnation preparation method of micro/nano low-surface hydrophobic composite anti-scaling coating - Google Patents
Liquid-phase deposition-impregnation preparation method of micro/nano low-surface hydrophobic composite anti-scaling coating Download PDFInfo
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Abstract
The invention discloses a liquid-phase deposition-impregnation preparation method of a micro/nano low-surface hydrophobic composite anti-scaling coating, which includes the following steps of (a) grinding, polishing and cleaning a stainless steel substrate to be deposited; (b) treating the stainless steel substrate with diluted acid ultrasonically, forming a coarse structural layer on the surface of the stainless steel substrate, washing and cleaning the surface with distilled water and then drying the same at the room temperature; (c) placing the stainless steel substrate with the surface having the coarse structural layer into mixed solution in a constant-temperature water bath with the temperature ranging from 20 degrees to 80 degrees to prepare a substrate chip by means of deposition; (e) sintering the dried substrate chip in a resistance furnace under protection of N2 and taking the sintered substrate chip out of the resistance furnace after reducing the temperature of the sintered substrate chip to the normal temperature; (f) impregnating the substrate chip with a TiO2 coating into fluorosilane hydrophobic solution of the mass concentration ranging from 0.1% to3%, taking out the same and then drying in an oven with the temperature ranging from 100 DEG C to 200 DEG C. The coating prepared by the method is thin, compact, uniform and free of cracking and can be combined with the substrate firmly.
Description
Technical field
The present invention relates to a kind of method for preparing the nano thin-film surface of low-surface-energy, relate in particular to a kind of liquid phase deposition that adopts and combine infusion process to prepare the method for the film surface of hydrophobic nano thickness at stainless steel surfaces.
Background technology
At present, heat transmission equipment all exists fouling problem in running, and the deposition of dirt causes the heat exchange resistance to increase, and heat exchange efficiency reduces, and has caused the wearing and tearing of energy waste and equipment, even the safe operation of the equipment of threat.In order to reduce the deposition of dirt, adopt machinery to clean or the chemical scale removal, ubiquity cost height and secondary pollution problem.Research shows that the formation of dirt can be able to be significantly reduced on the surface that reduces heating surface.The researcher has taked process for treating surface heat exchanging surface to carry out surface treatment, thereby reduces the surface ability of heating surface.Inject H, N, molecule self assembly etc. like magnetron sputtering polytetrafluoroethylene (PTFE), ion sputtering DLC, dynamic ion and be used to antiscale.But these method ubiquities problems such as expensive or complex equipments.Liquid phase deposition has many advantages as a kind of method for manufacturing thin film of development in recent years, and is comparatively simple like preparation equipment, and preparation temperature is gentle, can be used for the suprabasil production of coatings of non-refractory, and size of foundation base, shape are unrestricted or the like.Be 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 at present.
Because the hydrophobic or super-hydrophobic surface of solids has very low surface free energy, compare its boiling performance and dirt deposition characteristic with general surface and have more differently, so the research that low-energy surface is used for pool Boiling Heat Transfer and antiscale also more and more causes extensive concern.With silicon fluoride heating surface is carried out hydrophobization and handle the surface ability that reduces heat exchange surface, can reach heat conduction reinforced simultaneously and dual purpose antiscale.
The document that chemical liquid deposition is relevant has: Chinese patent 03100475.X processes saturated hydrofluosillicic acid solution through in hydrofluosillicic acid solution, adding silica etc., and with the low temperature liquid phase sedimentation semiconductor subassembly is applied protective film.Chinese patent 200710168732.1 provides a kind of method with producing titanium dioxide coating capillary column with liquid deposition method; With the ammonium titanium fluoride is raw material, at quartz capillary inwall deposition of titanium oxide thin layer, and is used for separating of albumen and polypeptide through liquid phase deposition; Because capillary column non-refractory; Therefore film sintered temperature is lower, combines fields such as not too firm, the dirt that is difficult to be applied to conduct heat between film and capillary.Chinese patent ZL 200710060653.9 has reported and in the red copper substrate, has adopted liquid phase deposition to prepare the method for the titanium deoxid film of nano thickness; But in this patent during the substrate of preliminary treatment red copper; What use is manual finishing method; Be difficult to large-scale production and application, and because red copper non-refractory sintering, the coating sintering temperature is lower.Ceng Zhenou etc. (Ceng Zhenou, Xiao Zhengwei, State of Zhao roc. modern coating technology, 2007:45-51) use liquid phase deposition on 304 stainless steels, to prepare coating of titanium dioxide.Chinese patent CN 101760737A has reported and has adopted liquid phase deposition on the stainless steel-based end, to prepare fine and close micro-nano TiO
2Coating, but the surface of coating can be higher, and hydrophobicity is not so good.The pertinent literature that improves thin-film hydrophobic property has: (Akamatsu Y et al.Thin Solid Films such as Akamatsu Y; 2001; 389:138-145) study the hydrolytic process principle of 17 fluorine decyl trimethoxy silanes, and prepared antifog vehicle glass, improved the hydrophobicity of glass; But the film to after the preparation is not heat-treated, and is difficult to be applied to field of heat transfer.Chinese patent ZL 02115493.7 discloses the method with ten trifluoro octyls, three TMOSs, ethyl orthosilicate, hydrochloric acid, deionized water and hydrochloric acid preparation hydrophobic liquid and manufacturing hydrophobic glass; The contact angle of the hydrophobic glass of being reported can reach 90-100 °; But this method relatively is fit to the surface modification before glass is installed; But vitreous coating also needs the heat treatment through 200-350 ℃ after crossing hydrophobic liquid, and this method is difficult to use in the vitreous coating of installing in back and the use.Chinese patent CN1211500C uses ethyl acetoacetate, ethanol, water and butyl titanate to prepare TiO
2Colloidal sol prepares TiO with czochralski method on metallic matrix
2Film carries out the processing of silicon fluoride base to the film surface, has improved TiO
2The hydrophobicity of film makes the corrosion of metal electric current reduce about 3 one magnitude; Though the film that uses sol-gel process to prepare has anticorrosion ability preferably, the film that makes is thicker, is easy to cracking and TiO
2The preparation method of coating is comparatively complicated.Chinese patent CN100429009C has reported a kind of method that can form hydrophobic transparent film at substrate surfaces such as glass, pottery, metal or paint; With aluminium oxide, silica or titanium oxide to the substrate surface modification; And to use hydroxylating silicon fluoride formulations prepared from solutions to go out thickness be several hydrophobic films to tens nanometers; The water contact angle of preparing film is 105-111 °, but when using titanium oxide sol that metal substrate surface is handled, does not use sintering technology; It is not firm that this will make this film combine with metallic substrates, is difficult to be applied to boiling heat transfer and dirt field.Make a general survey of document, do not see the report that the hydrophobic composite coating of low energy silicon fluoride is used for micro-nano enhanced boiling heat transfer and antiscaling method at present as yet.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of liquid deposition-impregnation preparation method with compound antiscale coating of a kind of micro-nano low surface hydrophobicity type of strengthening explosive evaporation heat transfer and antiscale dual-use function is provided.
Liquid deposition-the impregnation preparation method of the compound antiscale coating of a kind of micro-nano low surface hydrophobicity type of the present invention, it may further comprise the steps:
(a) polish, polish and cleans at the stainless steel-based end that will be to be deposited, obtains the surface of clean light;
(b) use mass percent to make stainless steel-based basal surface form the coarse structure layer as the stainless steel-based end of diluted acid sonicated of 1%-3%, clean with distilled water flushing, room temperature is dried;
(c) the stainless steel-based end that the surface is had a coarse structure layer, place the mixed solution deposition preparation substrate of the water bath with thermostatic control that is in 20-80 ℃, and the compound method of described mixed solution is following: with chemical pure (NH
4)
2TiF
6, analytically pure H
3BO
3Be mixed with the mixed solution of homogeneous, (NH in the mixed solution
4)
2TiF
6And H
3BO
3Amount of substance concentration be respectively 0.05-0.5mol/L, 0.07-0.6mol/L;
(d) will be in described mixed solution post-depositional substrate remain in the TiO of substrate surface with removal with distilled water flushing
2Solid particle dries then;
The substrate that (e) will dry is put into N
2Carry out sintering in the resistance furnace of protection, reduce to normal temperature after sintering is accomplished and take out, promptly on substrate, obtain TiO
2Coating;
(f) will have TiO
2The substrate of coating impregnated in the silicon fluoride hydrophobic sol that mass concentration is 0.1%-3%, and the baking oven of putting into temperature after the taking-up and be 100-200 ℃ is dried, and promptly on the stainless steel-based end, prepares the composite hydrophobic coating; The preparation method of described silicon fluoride hydrophobic sol is: (1) is solvent with the isopropyl alcohol; In solvent, add perfluor decyl three isopropoxy silane and mass concentration successively and be 3% watery hydrochloric acid and prepare solution; The addition of described perfluor decyl three isopropoxy silane is 0.001-0.03 a times of isopropyl alcohol quality; The addition of described watery hydrochloric acid is that the 0.0003-0.006 of isopropyl alcohol quality doubly two (2) puts into the magneton agitator with solution and stirs 10-60min; And then the adding active carbon, at room temperature leaving standstill polycondensation dehydration 0.5-2h, filter cloth filters; Making mass concentration is the silicon fluoride hydrophobic sol of 0.1%-3%, and the addition of described active carbon is 0.006-0.06 a times of isopropyl alcohol quality.
Chemical liquid deposition preparation method of the present invention according to not synsedimentary concentration, sedimentation time, resistance furnace temperature programming speed and sintering temperature, can obtain the light coating of different colours respectively in actual mechanical process, each appearance of coat is evenly fine and close.The coating of preparation is thinner, and the fine and close evenly nothing of coating cracking combines more firm with substrate.In addition, this patent carries out follow-up hydrophobic treatments to titania coating, has improved the hydrophobicity of coating greatly; Reduced surperficial ability; Significantly improved the augmentation of heat transfer and the anti-scaling property of coating, and the stainless steel-based end through the roughened method, make the surface of the coating that makes can be lower.This method makes the contact angle of film surface greater than 110 °, and the surface can be between 1.2-13.0mJm
-2, compare obvious reduction with stainless steel and titanium dioxide surface.Measure and the AFM detection through roughmeter, the Ra value after the Ra value of sintering thickness surface coating and the polishing is basic identical.Using this heating surface carries out pool Boiling Heat Transfer and antiscale research and shows; This surface can effectively stop dirt deposition in the boiling liquid in the surface; Because its coating layer thickness is far smaller than 304 stainless steel print thickness; But print that makes and enhanced boiling heat transfer process are respond well, have the industrialization promotion prospect.Compare the gull document that once shakes, the coating of this patent preparation is nanometer grade thickness (32.6-180.5nm), and is thinner.When therefore being used for field of heat transfer, surperficial additional thermal resistance is less.
Description of drawings
Fig. 1 is the process chart of a kind of micro-nano hydrophobic type liquid deposition of the present invention-compound antiscale coating production of dipping;
Fig. 2-a and Fig. 2-b are respectively the stereoscan photograph of the composite coating of embodiment 1 and embodiment 2;
Fig. 2-c is the stereoscan photograph of embodiment 3 super-hydrophobic silicon fluoride coatings;
Fig. 3 is XPS (x-ray photoelectron power spectrum) figure of silicon fluoride composite coating among the embodiment 1;
Fig. 4 is AES (Auger electron spectroscopy) figure of silicon fluoride composite coating among the embodiment 2;
Fig. 5 is XPS (x-ray photoelectron power spectrum) figure of silicon fluoride composite coating among the embodiment 3;
Fig. 6 puts into pool boiling apparatus for different surfaces and carries out the dirtiness resistance curve that the dirt experiment obtains.
The specific embodiment
Below in conjunction with the specific embodiment and embodiment the present invention is described further.
The inventive method is in literature research such as Ceng Zhenou, and improvement and the optimization carried out on the basis of referenced patent ZL 200710060653.9 and CN 101760737A.
Referring to Fig. 1 a kind of micro-nano hydrophobic type liquid deposition of the present invention-compound antiscale coating production of dipping, it may further comprise the steps: polish, polish and cleans at the stainless steel-based end that (a) will be to be deposited, obtains the surface of clean light; (b) make stainless steel-based basal surface form the coarse structure layer with the stainless steel-based end of mass percent 1%-3% diluted acid sonicated, clean with distilled water flushing, room temperature is dried, and preferred described diluted acid is hydrochloric acid or nitric acid; (c) the stainless steel-based end that the surface is had a coarse structure layer places 20-80 ℃ the mixed solution deposition preparation substrate of water bath with thermostatic control, and (be lower than this water bath with thermostatic control temperature range value, the sedimentation time that the coating of preparation desired thickness needs is longer; Be higher than this temperature range value, the solution water evaporates is prone to form bulky grain, is difficult to prepare coating), the compound method of described mixed solution is following: with chemical pure (NH
4)
2TiF
6, analytically pure H
3BO
3Be mixed with the mixed solution of homogeneous, (NH in the mixed solution
4)
2TiF
6And H
3BO
3Amount of substance concentration be respectively 0.05-0.5mol/L, (be lower than this concentration range, reaction volume is few, is difficult to prepare coating for 0.07-0.6mol/L; Be higher than this concentration, deposit fluid is muddy, is unfavorable for preparing coating); (d) will be in described mixed solution post-depositional substrate remain in the TiO of substrate surface with removal with distilled water flushing
2Solid particle dries then; The substrate that (e) will dry is put into N
2Carry out sintering in the resistance furnace of protection, reduce to normal temperature after sintering is accomplished and take out, promptly on substrate, obtain TiO
2Coating; (f) will have TiO
2The substrate of coating impregnated in the silicon fluoride hydrophobic sol that mass concentration is 0.1%-3%, dip time preferably 1h-3h (be lower than this time scope, the coating hydrophobicity of preparing is bad; Be higher than this scope, time of repose is long, and is meaningless to the hydrophobicity of coating); It is that (be lower than this temperature range, coating can not be dried, and is higher than this temperature range for 100-200 ℃ baking oven oven dry that substrate after will flooding is then put into temperature; The coating destructible), promptly on substrate, prepare the composite hydrophobic coating.The preparation method of described silicon fluoride hydrophobic sol is: (1) is solvent with the isopropyl alcohol, in solvent, adds perfluor decyl three isopropoxy silane and mass concentration successively and is 3% watery hydrochloric acid and prepare solution; The addition of described perfluor decyl three isopropoxy silane is 0.001-0.03 a times of isopropyl alcohol quality, and the addition of described watery hydrochloric acid is 0.0003-0.006 a times of isopropyl alcohol quality; (be lower than this scope, silicon fluoride solution amount of hydrolysis is few, is higher than this scope, and the silicon fluoride hydrolysis is too fast, can not form hydrophobic coating); (2) solution being put into the magneton agitator stirs 10-60min (be lower than this time scope, hydrolysis is not thorough, is higher than this scope, and hydrolysis is accomplished; Meaningless after for a long time), and then add active carbon, (the polycondensation time, polycondensation was not thorough less than this scope at room temperature to leave standstill polycondensation dehydration 0.5-2h; Be higher than the polycondensation time range, polycondensation is accomplished, and is meaningless after for a long time), filter cloth filters; Making mass concentration is that (be lower than this concentration range, the hydrophobicity of preparing coating is bad, is higher than this concentration for 0.1%-3%; Waste silicon fluoride reactant) silicon fluoride hydrophobic sol, the addition of described active carbon are that doubly (amount of active carbon is lower than this scope, and the moisture in the absorbent solution is not thorough for the 0.006-0.06 of isopropyl alcohol quality; Be higher than this scope, hydrolysis is too rapid, is difficult to prepare hydrophobic coating).
Grinding and buffing step in the preferred described step (a) is: roughly grind until exposing the stainless steel metal surface the stainless steel outer surfaces of substrates (1); (2) carry out middle mill, remove the dark large texture polishing scratch that pass stays; (3) it is all than open grain until polishing off to select for use the cylindrical blinds emery cloth of 600 purposes wheel to be polished in the stainless steel-based end; (4) select 800-2000 purpose sand paper disc for use, to finish grinding to remove the stria on the polished surface at the stainless steel-based end; (5) adopt the metal polishing machine that is coated with clear boiled soap on the wool polishing wheel that stainless steel-based basal surface is polished, till can't see the polishing texture.
Cleaning step in the preferred described step (a) is: (1) service property (quality) percentage is 10% the stainless steel-based end cleaning of the ultrasonic immersion of NaOH solution 5-10min, removes the intractable grease, rinses well with running water then; (2) mass ratio being put at the stainless steel-based end successively carries out taking out behind the ultrasonic cleaning 5-10min greater than 99.7% absolute ethyl alcohol greater than 99.5% acetone and mass ratio; (3) with the stainless steel-based end 5-10min of distilled water ultrasonic cleaning, thoroughly to remove surface remaining acetone and absolute ethyl alcohol; (4) it is for use to dry up and place closed container to preserve the cleaned stainless steel substrate.
The time of the sonicated in the described step (b) is 30s-10min.(being below or above this time scope, all unfavorable) to the hydrophobic preparation of follow-up coating
Sedimentation time in the described step (c) is 2-30 hour.(be lower than this scope, be difficult to prepare coating of titanium dioxide, be higher than this scope, coating is easy to crack)
The heating rate of the sintering in the described step (e) is 2-8 ℃/min, and sintering temperature is 300-800 ℃, and (be lower than this heating rate scope, it is long to arrive the sintering temperature required time, is higher than this scope, and coating is prone to come off; Be lower than this sintering range, titania coating combines bad with substrate, be not durable, and is higher than this scope, and the stainless steel-based end is prone to oxidation).
Drying time in the baking oven in the described step (f) is 2-3 hour.(be lower than this time scope, coated and dried is not thorough, is higher than this scope, and the hydrophobic coating drying time is long, and is meaningless to production of coatings)
(a)) the stainless steel outer surfaces of substrates is roughly ground until exposing the stainless steel metal surface; Carry out middle mill, remove the dark large texture polishing scratch that pass stays; It is all than open grain until polishing off to select for use the cylindrical blinds emery cloth of 600 purposes wheel to be polished in the stainless steel-based end; Select 1000 purpose sand paper discs for use, to finish grinding to remove the stria on the polished surface at the stainless steel-based end; Bore hole adopt the metal polishing machine that is coated with clear boiled soap on the wool polishing wheel that stainless steel-based basal surface is polished, till can't see the polishing texture; Re-use mass percent and be 10% the ultrasonic soaking and washing 5min of NaOH, remove the intractable grease, rinse well with running water then; Afterwards mass ratio being put at this stainless steel-based end successively carries out taking out behind the ultrasonic cleaning 8min greater than 99.7% absolute ethyl alcohol greater than 99.5% acetone and mass ratio; At last; With the stainless steel-based end 7min of distilled water ultrasonic cleaning; Thoroughly to go out surface remaining acetone and absolute ethyl alcohol, dry up with hair dryer, place closed container to preserve; (b) the use mass percent is 1% the stainless steel-based end 30s of watery hydrochloric acid sonicated, makes stainless steel-based basal surface form the coarse structure layer, and clean with distilled water flushing, room temperature is dried; (c) with chemical pure (NH
4)
2TiF
6, analytically pure H
3BO
3Be mixed with the mixed solution of homogeneous, (NH in the mixed liquor
4)
2TiF
6And H
3BO
3Amount of substance concentration be respectively 0.05mol/L and 0.07mol/L; It is that solution is put at the stainless steel-based end that the surface is had coarse structure in 20 ℃ the water bath with thermostatic control that the deposit fluid of preparation is placed on temperature, and sedimentation time is 5h; (d) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove the TiO of substrate surface with distilled water
2Solid particle at room temperature dries then; The substrate that (e) will dry is put into Muffle furnace and is heated, and the rate of heat addition is 2 ℃/min, when temperature is elevated to 500 ℃, keeps constant temperature 2h, closes heater, obtains the TiO of even compact after the cooling
2Film surface; (f) take by weighing the isopropanol solvent of 160g; The perfluor decyl three isopropoxy silane that in solvent, add 0.16g add mass percent and are 3% watery hydrochloric acid 0.05g again in solution, making the mass concentration of preparation back perfluor decyl three isopropoxy silane is 0.1%; Add magneton and stir the 10min hydrolysis; The active carbon that adds 1g, polycondensation 0.5h at room temperature, filter cloth filters and obtains hydrophobic solution.Print is placed hydrophobic solution, take out behind the room temperature dipping 1h, dry, put into 100 ℃ of baking oven 2h.Make nanometer film surface hydrophobization fully, construct the hydrophobic nano film.Table 1 is the contact angle measurement data of embodiment 1.
The contact angle of table 1 embodiment 1 coating and surperficial ability
Can be found out by Fig. 2-a: coating surface deposits the bigger titanium dioxide nanoparticle of particle diameter, and face coat is comparatively fine and close; Many circles or strip nano-pore are contained in the surface.
Can be found out by Fig. 3: the electronics on the Si2p track is excited out; Its binding energy is 102.6 eV; Correspond to the characteristic peak of Si-O key, prove the existence of silicon oxygen bond in the coating, binding energy is the characteristic peak that the XPS peak of 529.4 eV and 532.5 eV corresponds to O-Ti key and O-Si key respectively; Binding energy is the characteristic peak that the XPS peak of 458.7 eV and 464.9 eV corresponds to the Ti-O key, and binding energy is that the XPS peak of 688.9 eV is at-CF
2Group and-CF
3Near the characteristic peak of group.
The Ti-O key corresponds to suprabasil titania coating, and the Si-O key is the chemical bond that silicon fluoride is connected with titania coating ,-CF
2Group and-CF
3Group then comes from the silicon fluoride coating.
Find out that by Fig. 6 the dirtiness resistance of silicon fluoride hydrophobic surface is significantly less than stainless steel, and the dirt slope of curve of the initial time of silicon fluoride hydrophobic surface (dirt deposition speed) is less than on the stainless steel surfaces.
(a) preliminary treatment is carried out at the stainless steel-based end, used the angle grinding machine of fit on louvre blade that the stainless steel print outer surface after cutting is roughly ground, remove surface contaminants, oxide skin and big hole defect, expose the stainless steel metal surface; Change nylon grinding disc then and carry out middle mill, remove the dark large texture polishing scratch that pass stays, the selected substrate surface of wanting deposited coatings of intending; Use the die sinking handle of metal polishing machine instead, select for use the cylindrical blinds emery cloth of 600 purposes wheel that substrate is polished, need guarantee the surface polish off fully one go on foot stay than open grain.90 ° of angle machines of fit on or fit on rifle formula reciprocating engine are selected 800 purpose sand paper discs for use then, substrate are finish grinded, to remove the stria on the polished surface; The die sinking handle of using metal polishing machine then instead combines wool polishing wheel and applies commercially available green clear boiled soap, the print surface is polished, till can't see the polishing texture; Re-use mass percent and be 10% the ultrasonic soaking and washing 8min of NaOH, remove the intractable grease, rinse well with running water then; Afterwards mass ratio being put at this stainless steel-based end successively carries out taking out behind the ultrasonic cleaning 10min greater than 99.7% absolute ethyl alcohol greater than 99.5% acetone and mass ratio; At last; With the stainless steel-based end 5min of distilled water ultrasonic cleaning; Thoroughly to go out surface remaining acetone and absolute ethyl alcohol, dry up with hair dryer, place closed container to preserve; (b) the use mass percent is 2% the stainless steel-based end 3min of rare nitric acid sonicated, makes stainless steel-based basal surface form the coarse structure layer, and clean with distilled water flushing, room temperature is dried; (c) with chemical pure (NH
4)
2TiF
6, analytically pure H
3BO
3Be mixed with the mixed solution of homogeneous, (NH in the mixed liquor
4)
2TiF
6And H
3BO
3Amount of substance concentration be respectively 0.5mol/L and 0.6mol/L; It is that solution is put at the stainless steel-based end that the surface is had coarse structure in 50 ℃ the water bath with thermostatic control that the deposit fluid of preparation is placed on temperature, and sedimentation time is 15h; (d) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove the TiO of substrate surface with distilled water
2Solid particle dries then; The Muffle furnace that the substrate that (e) will dry is put into nitrogen protection heats, and the rate of heat addition is 5 ℃/min, when temperature is elevated to 300 ℃, keeps constant temperature 2h, closes heater, obtains the TiO of even compact after the cooling
2Film surface; (f) take by weighing the isopropanol solvent of 160g; The perfluor decyl three isopropoxy silane that in solvent, add 1.62g add mass percent and are 3% watery hydrochloric acid 0.3g again in solution, make the mass concentration of preparation back perfluor decyl three isopropoxy silane be about 1%; Add and stir the 25min hydrolysis in the magneton agitator; The active carbon that adds 2g, polycondensation 1h at room temperature, filter cloth filters and obtains hydrophobic solution.Print is placed hydrophobic solution, take out behind the room temperature dipping 3h, dry, put into 140 ℃ of baking oven 2.5h.Make nanometer film surface hydrophobization fully, construct the hydrophobic nano film.Table 2 is the contact angle measurement data of embodiment 2.
The contact angle of table 2 embodiment 2 and surperficial ability
Can be found out by Fig. 2-b: coating surface then deposits a large amount of big and fine and close titan oxide particles, surface compact; Many circles or strip nano-pore are contained in the surface.After silicon fluoride was handled, the aperture diminished through coating of titanium dioxide.
Can be found out by Fig. 4: the element section curve is divided into three parts, and Far Left is the silicon fluoride coating, and middle Ti and O element platform area are TiO
2Coated areas, rightmost are the boundary zone at the coating and the stainless steel-based end.The coating surface place, the content of F and Si element is considerably less, and the high-load of F element is about 2.3%, and the high-load of Si element is 10.23%; A spot of F and Si element are also arranged in coating of titanium dioxide inside in addition, and this possibly be that small amount of fluorosilane penetrates into TiO
2Coating inside causes.
Find out that by Fig. 6 the dirtiness resistance of silicon fluoride hydrophobic surface is significantly less than stainless steel, and the dirt slope of curve of the initial time of silicon fluoride hydrophobic surface (dirt deposition speed) is less than on the stainless steel surfaces.
(a) preliminary treatment is carried out at the stainless steel-based end, used the angle grinding machine of fit on louvre blade that the stainless steel print outer surface after cutting is roughly ground, remove surface contaminants, oxide skin and big hole defect, expose 304 stainless steel metals surface; Change nylon grinding disc then and carry out middle mill, remove the dark large texture polishing scratch that pass stays, the selected substrate surface of wanting deposited coatings of intending; Use the die sinking handle of metal polishing machine instead, select for use the cylindrical blinds emery cloth of 800 purposes wheel that substrate is polished, need guarantee the surface polish off fully one go on foot stay than open grain.90 ° of angle machines of fit on or fit on rifle formula reciprocating engine are selected 2000 purpose sand paper discs for use then, substrate are finish grinded, to remove the stria on the polished surface; The die sinking handle of using metal polishing machine then instead combines wool polishing wheel and applies commercially available green clear boiled soap, the print surface is polished, till can't see the polishing texture; Re-use mass percent and be 10% the ultrasonic soaking and washing 10min of NaOH, remove the intractable grease, rinse well with running water then; Afterwards mass ratio being put at this stainless steel-based end successively carries out taking out behind the ultrasonic cleaning 5min greater than 99.7% absolute ethyl alcohol greater than 99.5% acetone and mass ratio; At last; With the stainless steel-based end 10min of distilled water ultrasonic cleaning; Thoroughly to go out surface remaining acetone and absolute ethyl alcohol, dry up with hair dryer, place closed container to preserve; (b) the use mass percent is 3% the stainless steel-based end 10min of watery hydrochloric acid sonicated, makes stainless steel-based basal surface form the coarse structure layer, and clean with distilled water flushing, room temperature is dried; (c) with chemical pure (NH
4)
2TiF
6, analytically pure H
3BO
3Be mixed with the mixed solution of homogeneous, (NH in the mixed liquor
4)
2TiF
6And H
3BO
3Amount of substance concentration be respectively 0.1mol/L and 0.2mol/L; It is to heat in 80 ℃ the water-bath that the deposit fluid of preparation is placed on temperature, and solution is put at the stainless steel-based end that the surface is had coarse structure, and sedimentation time is 30h; (d) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove the TiO of substrate surface with distilled water
2Solid particle dries then; The substrate that (e) will dry is put into Muffle furnace and is heated, and the rate of heat addition is 8 ℃/min, when temperature is elevated to 800 ℃, keeps constant temperature 2h, closes heater, obtains the TiO of even compact after the cooling
2Film surface; (f) take by weighing the isopropanol solvent of 160g; The perfluor decyl three isopropoxy silane that in solvent, add 4.98g add mass percent and are 3% watery hydrochloric acid 1.0g again in solution, make the mass concentration of preparation back perfluor decyl three isopropoxy silane be about 3%; Add magneton and stir the 1h hydrolysis; The active carbon that adds 10g, polycondensation 2h at room temperature, filter cloth filters and obtains hydrophobic solution.Print is placed hydrophobic solution, take out behind the room temperature dipping 3h, dry, put into 200 ℃ of baking oven 3h.Make nanometer film surface hydrophobization fully, construct the hydrophobic nano film.Table 3 is the contact angle measurement data of embodiment 3.
The contact angle of table 3 embodiment 3 coatings and surperficial ability
Can be found out by Fig. 2-c: coating surface then deposits a large amount of big and fine and close titan oxide particles, surface compact; Many circles or strip nano-pore are contained in the surface.After silicon fluoride was handled, the aperture diminished through coating of titanium dioxide.
Can find out by Fig. 5: obviously exist among the figure Ti-O key, Si-O key characteristic peak and-CF
2Group and-CF
3The characteristic peak of group.The Ti-O key corresponds to suprabasil titania coating, and the Si-O key is the chemical bond that silicon fluoride is connected with titania coating ,-CF
2Group and-CF
3Group then comes from the silicon fluoride coating.
Compare with embodiment 1, the ratio of F element obviously improves among the embodiment 3, and the content of the coating surface F element that illustrative embodiment 3 makes is apparently higher than embodiment 1 prepared surface.
Find out that by Fig. 6 the dirtiness resistance of silicon fluoride hydrophobic surface is significantly less than stainless steel, and the dirt slope of curve of the initial time of silicon fluoride hydrophobic surface (dirt deposition speed) is less than on the stainless steel surfaces.
Claims (7)
1. liquid deposition-the impregnation preparation method of the compound antiscale coating of micro-nano low surface hydrophobicity type is characterized in that it may further comprise the steps:
(a) polish, polish and cleans at the stainless steel-based end that will be to be deposited, obtains the surface of clean light;
(b) use mass percent to make stainless steel-based basal surface form the coarse structure layer as the stainless steel-based end of diluted acid sonicated of 1%-3%, clean with distilled water flushing, room temperature is dried;
(c) the stainless steel-based end that the surface is had a coarse structure layer, place the mixed solution deposition preparation substrate of the water bath with thermostatic control that is in 20-80 ℃, and the compound method of described mixed solution is following: with chemical pure (NH
4)
2TiF
6, analytically pure H
3BO
3Be mixed with the mixed solution of homogeneous, (NH in the mixed solution
4)
2TiF
6And H
3BO
3Amount of substance concentration be respectively 0.05-0.5mol/L, 0.07-0.6mol/L;
(d) will be in described mixed solution post-depositional substrate remain in the TiO of substrate surface with removal with distilled water flushing
2Solid particle dries then;
The substrate that (e) will dry is put into N
2Carry out sintering in the resistance furnace of protection, reduce to normal temperature after sintering is accomplished and take out, promptly on substrate, obtain TiO
2Coating;
(f) will have TiO
2The substrate of coating impregnated in the silicon fluoride hydrophobic sol that mass concentration is 0.1%-3%, and the baking oven of putting into temperature after the taking-up and be 100-200 ℃ is dried, and promptly on the stainless steel-based end, prepares the composite hydrophobic coating; The preparation method of described silicon fluoride hydrophobic sol is: (1) is solvent with the isopropyl alcohol; In solvent, add perfluor decyl three isopropoxy silane and mass concentration successively and be 3% watery hydrochloric acid and prepare solution; The addition of described perfluor decyl three isopropoxy silane is 0.001-0.03 a times of isopropyl alcohol quality, and the addition of described watery hydrochloric acid is 0.0003-0.006 a times of isopropyl alcohol quality; (2) solution is put into the magneton agitator and stir 10-60min; And then the adding active carbon, at room temperature leaving standstill polycondensation dehydration 0.5-2h, filter cloth filters; Making mass concentration is the silicon fluoride hydrophobic sol of 0.1%-3%, and the addition of described active carbon is 0.006-0.06 a times of isopropyl alcohol quality.
2. liquid deposition-the impregnation preparation method of the compound antiscale coating of micro-nano low surface hydrophobicity type according to claim 1, it is characterized in that: the grinding and buffing step in the described step (a) is: roughly grind until exposing the stainless steel metal surface the stainless steel outer surfaces of substrates (1); (2) carry out middle mill, remove the dark large texture polishing scratch that pass stays; (3) it is all than open grain until polishing off to select for use the cylindrical blinds emery cloth of 600 purposes wheel to be polished in the stainless steel-based end; (4) select 800-2000 purpose sand paper disc for use, to finish grinding to remove the stria on the polished surface at the stainless steel-based end; (5) bore hole adopt the metal polishing machine that is coated with clear boiled soap on the wool polishing wheel that stainless steel-based basal surface is polished, till can't see the polishing texture.
3. liquid deposition-the impregnation preparation method of the compound antiscale coating of micro-nano low surface hydrophobicity type according to claim 1 and 2; It is characterized in that: the cleaning step in the described step (a) is: (1) service property (quality) percentage is 10% the stainless steel-based end cleaning of the ultrasonic immersion of NaOH solution 5-10min; Remove the intractable grease, rinse well with running water then; (2) mass ratio being put at the stainless steel-based end successively carries out taking out behind the ultrasonic cleaning 5-10min greater than 99.7% absolute ethyl alcohol greater than 99.5% acetone and mass ratio; (3) with the stainless steel-based end 5-10min of distilled water ultrasonic cleaning, thoroughly to remove surface remaining acetone and absolute ethyl alcohol; (4) it is for use to dry up and place closed container to preserve the cleaned stainless steel substrate.
4. liquid deposition-the impregnation preparation method of the compound antiscale coating of micro-nano low surface hydrophobicity type according to claim 1, it is characterized in that: the time of the sonicated in the described step (b) is 30s-10min.
5. liquid deposition-the impregnation preparation method of the compound antiscale coating of micro-nano low surface hydrophobicity type according to claim 1, it is characterized in that: the sedimentation time in the described step (c) is 2-30 hour.
6. liquid deposition-the impregnation preparation method of the compound antiscale coating of micro-nano low surface hydrophobicity type according to claim 1, it is characterized in that: the heating rate of the sintering in the described step (e) is 2-8 ℃/min, sintering temperature is 300-800 ℃.
7. liquid deposition-the impregnation preparation method of the compound antiscale coating of micro-nano low surface hydrophobicity type according to claim 1, it is characterized in that: the drying time in the baking oven in the described step (f) is 2-3 hour.
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| CN114191610A (en) * | 2021-12-24 | 2022-03-18 | 华中科技大学 | Magnesium-based multifunctional composite active coating and preparation method and application thereof |
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