CN101787526A - Method for preparing micro-nano-silica film on red copper substrate - Google Patents
Method for preparing micro-nano-silica film on red copper substrate Download PDFInfo
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Abstract
The invention discloses a method for preparing a micro-nano-silica film on a red copper substrate, comprising the following steps of: (a) pre-treating the red copper substrate; (b) adding analytically pure silicic acid to analytically pure fluosilicic acid to prepare a homogeneous first solution, then putting the first solution in a water bath for magnetic stirring; (c) adding de-ionized water to the first solution to prepare a second solution, and then putting the second solution in the water bath for magnetic stirring; (d) weighing the analytically pure boric acid and adding the boric acid to the second solution to prepare a third solution, and then putting the third solution in the water bath for magnetic stirring; (e) putting the substrate in the third solution for depositing to prepare a base plate which is coated by a silica film; (f) taking out the base plate after the depositing, washing the surface of the base plate to remove the surface residues; (g) putting the base plate to an electrical resistance furnace for heating after drying the base plate; (h) closing the electrical resistance furnace, and obtaining the silica micro-nano film coating layer after natural cooling of the electrical resistance furnace. The invention has the advantages that the film prepared by the method provided by the invention is uniform and dense; and the combination of the coating layer and the substrate is more solid.
Description
Technical field
The invention belongs to a kind of liquid deposition preparation method of metal material surface anti-corrosion anti-scale coating, be specifically related to micro/nano level thickness SiO in a kind of red copper substrate
2The liquid phase deposition preparation method of film.
Background technology
Burn into scale problems in the underground heat water utilization system is the serious hindrance of development and use Geothermal energy always, is one of world today's property important subject.According to statistics, about 700,000,000,000 dollars of the financial loss that global annual invar iron rot causes accounts for the 2%-4% of various countries' gross national product; And the appearance of dirt layer and thickening increases fluid resistance on the one hand, increases energy expenditure, reduces aquifer yield, normally operation of influence, and on the other hand, the imperfect place of dirt layer can cause local corrosion.For the corrosion that reduces equipment and the deposition of dirt, investigators adopt Chemical Inhibition Method, magnetization to handle or be coated with methods such as organic coating, but there is secondary pollution in above method or is difficult to extensive use, and is coated with organic coating and comes off easily and increase shortcomings such as additional thermal resistance.
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.Its film process does not need expensive equipment, and is simple to operate, and can make film in complex-shaped substrate.Super large-scale integration, metal monooxide semi-conductor and liquid crystal display device form in the sull process and have obtained application in preparation functional film, especially microelectronic industry.
The patent that liquid phase deposition is relevant has: Chinese patent 01119229.1, it is characterized in that wafer placement on a wafer carrier, and an opening of a growth liquid bath is engaged with wafer on the wafer carrier, after carrying out the liquid deposition technological process, with above-mentioned opening up, to take out the wafer on the described wafer carrier.In addition, also propose a kind of single face growth and mass production device of liquid phase deposition, it is to be made of wafer carrier and growing liquid slot, by engaging to carry out the liquid deposition technological process of wafer on the opening of growing liquid slot and the wafer carrier.Chinese patent 03100475.X is characterized in that forming one deck low-temperature epitaxy film or fabulous progressively spreadability film in order to make in advance on the semiconductor subassembly sample surface of finishing, have the independent circuits function having at least one.Chinese patent 200320109851.7, this utility model patent have been set up one and have been overlapped the chemical liquid deposition device of the densification technology that is used for carbon/carbon, carbon/matrix materials such as pottery.Chinese patent 200580038193.9, it is characterized in that providing a kind of metal or metal oxide of making only to be deposited on hydrocarbon cracking catalyst on the zeolite surface, and the method for preparing this hydrocarbon cracking catalyst, the hydrocarbon cracking catalyst of its invention can improve alkene and greatly as the productivity of the aromatics of BTX.
Chinese patent 200610171664.X adopts liquid phase deposition, prepares SiO with hexafluorosilicic acid, silicic acid, boric acid or fine aluminium at nonmetallic surface
2Film is with its application and technical field of semiconductors.
Chinese patent 200710168732.1 is characterized in that with the ammonium titanium fluoride being raw material, at quartz capillary inwall deposition of titanium oxide thin film layer, the coating of titanium dioxide capillary column of preparation gained successfully is used for the separation and the pre-concentration of biological sample.
Chinese patent 200710060653.9 is to adopt the liquid deposition method to prepare films such as nano thickness TiO2 at red copper surface, and is used for fortified water pool Boiling Heat Transfer, antiscale and anticorrosion.
All there is the incomplete shortcoming of substrate pretreatment in aforesaid method.As Chinese patent 200710168732.1, it has used alkali lye and salt acid treatment substrate, and the mineral oil of substrate surface uses alkali lye to remove, must be with an organic solvent, otherwise cause coating not firm with combining of substrate easily, coating has also lost significance of application; Liquid phase deposition is a kind of optionally film, can only be at hydroxyl surface deposition, and Chinese patent 200710060653.9, not takeing effective measures makes metallic surface enrichment hydroxyl; Chinese patent 200610171664.X is with non-metallic material, is substrate to be applied to technical field of semiconductors as silicon chip etc., and its, deposit fluid preparation process time was also longer in early stage.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, provide that a kind of cost is low, equipment is simple, easy to operate, be easy to control, be applicable to complex geometry, be easy to industrialization, film combined firmly and can improve the anticorrosion anti-tartar effect of geothermal utilization interchanger with substrate the method that in the red copper substrate, prepares micro-nano-silica film.
Prepare the method for micro-nano-silica film in the red copper substrate, it may further comprise the steps:
(a) pre-treatment is carried out in the red copper substrate, made its surperficial roughness Ra be controlled at Ra＜0.2 μ m;
(b) in every liter of analytical pure silicofluoric acid, add first solution that 60-80 gram analytical pure silicic acid is mixed with homogeneous, place it in magnetic agitation 3h～6h in 20 ℃～30 ℃ the water-bath then;
(c) adding in described first solution that deionized water makes second solution and make the concentration of silicofluoric acid in second solution is 1-2mol/L, places it in magnetic agitation 0.5h～1h in 40 ℃～50 ℃ the water-bath then;
(d) take by weighing analytically pure boric acid and join in described second solution and make the 3rd solution, making the boric acid concentration in the 3rd solution is 0.0～0.03mol/L, places it in magnetic agitation 0.5h～1h in 40 ℃～50 ℃ the water-bath then;
(e) substrate is vertically put into the 3rd solution deposition 10-20h and make the substrate that is coated with silica membrane;
(f) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove surface residue with deionized water;
(g) substrate is dried naturally, put into N then
2Heat in the resistance furnace of protection, heating rate is 1-5 ℃/min, when temperature is elevated to 100～400 ℃, keeps constant temperature 1-5h;
(h) close resistance furnace, obtain homogeneous compact silicon oxide micro-nano film coating layer behind the naturally cooling.
Pre-treatment step in the described step (a) comprises polishing step and ultrasonic cleaning step successively; Roughness Ra＜0.2 μ the m on the surface at the stainless steel-based end after the polishing of described polishing step wherein, described ultrasonic cleaning step comprises: (1) is 5%～15% with mass percent, temperature is sodium hydroxide solution ultrasonic cleaning substrate 5～10min of 60 ℃, removes the part grease on surface; (2) substrate being immersed mass percent is 2%～10%, and temperature is 20 ℃ a hydrochloric acid soln, and ultrasonic cleaning 5～10min is to remove oxide on surface; (3) with washed with de-ionized water substrate 5～15min, to remove the acid of remained on surface; (4) substrate is put into mass percent respectively and carry out taking out behind the ultrasonic cleaning 15-25min greater than 99.5% acetone, to remove residual grease greater than 99.7% dehydrated alcohol and mass percent; (5) with deionized water ultrasonic cleaning substrate 5～20min, thoroughly to remove surface remaining dehydrated alcohol and acetone; (6) substrate being put into mass percent is hydrofluoric acid etching 2～4min of 2～4%, at last deionized water is put in substrate and is soaked 2-3h.
Adopt the beneficial effect of the inventive method to be:
(1) liquid deposition preparation method of the present invention is in actual mechanical process, and the film even compact of preparing characterizes through surface property, the micro-nano SiO that makes with this technology
2The surface energy on surface is 9.2～42.5mJ.m
-2
(2) with patent 200710060653.9 contrast, the present invention is a coated material with silicon-dioxide, and than titanium dioxide, silicon-dioxide wear resistance, erosion-resisting characteristics are better; In addition, when substrate pretreatment, use hydrofluoric acid that metal base is carried out etching, make and adhere to a large amount of hydrogen bonds on it, again deionized water being put in substrate soaks, make water molecules and hydrogen bonded releasing hydrogen gas, then at a large amount of hydroxyl of surface attachment, hydroxyl exist for follow-up SiO
2Deposition condition is provided, also make coating more firm with combining of substrate.
(3) with patent 200610171664.X contrast, the present invention has shortened the deposit fluid preparation time, reduces to 3h by original 6h; No longer adopting sulfuric acid and hydrogen peroxide aspect base treatment, is the hydrofluoric acid of 2-4% but adopt massfraction, so that its surface enrichment O-H, thereby simplify the operation course.
Description of drawings
Fig. 1 (a)-Fig. 1 (b) is scanning electron microscope (SEM) figure of embodiment 1 coating;
Fig. 1 (c) is power spectrum (EDS) the ultimate analysis figure of embodiment 1 coating;
Fig. 2 (a)-Fig. 2 (b) is respectively scanning electron microscope (SEM) figure and power spectrum (EDS) the ultimate analysis figure of embodiment 2 coatings;
Fig. 3 (a)-Fig. 3 (b) is respectively scanning electron microscope (SEM) figure and power spectrum (EDS) the ultimate analysis figure of embodiment 3 coatings;
Fig. 4 liquid phase deposition of the present invention prepares the process flow diagram of micro/nano film.
Embodiment
Below in conjunction with specific embodiment, and with reference to accompanying drawing, the present invention is described further:
The operating gear of liquid phase deposition of the present invention comprises: a cover constant temperature magnetic agitation water-bath Controlling System.Required reagent: analytically pure silicofluoric acid, analytically pure silicic acid, analytically pure boric acid, dehydrated alcohol and analytically pure acetone, hydrofluoric acid etc.
The principles of chemistry of preparation film: by in silicate fluoride solution, adding silicic acid, water, boric acid, make solution remain on hypersaturated state, thus the spontaneous SiO that separates out
2Be deposited on the metallic surface and finish, mechanism is as follows:
H
2SiF
6+(4-m)H
2O＝S
iF
m(OH)
4-m+(6-m)HF
SiO
2？xH2O+mHF＝S
iF
m(OH)
4-m+(x+m-2)H
2O
H
3BO
3+4HF＝BF
4 -+H
3O
++2H
2O
The method that in the red copper substrate, prepares micro-nano-silica film of the present invention as shown in Figure 4, it may further comprise the steps: (a) pre-treatment is carried out in the red copper substrate, made its surperficial roughness Ra be controlled at Ra＜0.2 μ m; (b) in every liter of analytical pure silicofluoric acid, add first solution that 60-80 gram analytical pure silicic acid is mixed with homogeneous, place it in magnetic agitation 3h～6h in 20 ℃～30 ℃ the water-bath then; Magnetic agitation can adopt devices such as digital display thermostat water bath.(c) adding in described first solution that deionized water makes second solution and make the concentration of silicofluoric acid in second solution is 1-2mol/L, (temperature is lower than this interval and obtains the time that identical thickness then need be longer to place it in 40 ℃～50 ℃ then, efficient is lower, be higher than this interval, sedimentation rate is too fast, film quality is poor, and the solution evaporation amount is big, consumes feed liquid) magnetic agitation 0.5h～1h in the water-bath; The concentration of silicofluoric acid is lower than 1-2mol/L concentration interval can not deposit coating in the identical time, be higher than this concentration interval, and deposit fluid is the gel dress, and produces many white particles, and film quality is poor.(d) taking by weighing analytically pure boric acid joins in described second solution and makes the 3rd solution, making the boric acid concentration in the 3rd solution is that 0.0～0.03mol/L (is higher than this interval, deposit fluid is gel), place it in magnetic agitation 0.5h～1h in 40 ℃～50 ℃ water-baths then; (e) substrate is vertically put into the 3rd solution deposition 10-20h and make the substrate that is coated with silica membrane; (f) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove surface residue with deionized water; (g) substrate is dried naturally, put into N then
2Heat in the resistance furnace of protection, heating rate is 1-5 ℃/min, when temperature is elevated to 100～400 ℃, keeps constant temperature 1-5h; Because the thermal expansivity of copper is bigger, heating rate and thermal treatment temp are too high, and the internal stress that substrate produces will be damaged film, and film produces a large amount of crackles, and film quality is descended, and are unfavorable for that antiscale and rot-resistant carry out.Adopt N in this step
2The resistance furnace of protection can prevent the substrate oxidation.(h) close resistance furnace, obtain the silicon-dioxide micro-nano film coating layer of homogeneous densification behind the naturally cooling.
Pre-treatment step in the described step (a) comprises polishing step and ultrasonic cleaning step successively; Roughness Ra＜0.2 μ the m on the surface at the stainless steel-based end after the polishing of described polishing step wherein, described ultrasonic cleaning step comprises: (1) is 5%～15% with mass percent, temperature is sodium hydroxide solution ultrasonic cleaning substrate 5～10min of 60 ℃, removes the part grease on surface; (2) substrate being immersed mass percent is 2%～10%, and temperature is 20 ℃ a dilute hydrochloric acid solution, and ultrasonic cleaning 5～10min is to remove oxide on surface; (3) with washed with de-ionized water substrate 5～15min, to remove the acid of remained on surface; (4) substrate is put into mass percent respectively and carry out taking out behind the about 15-25min of ultrasonic cleaning greater than 99.5% acetone, to remove residual grease greater than 99.7% dehydrated alcohol and mass percent; (5) with deionized water ultrasonic cleaning substrate 5～20min, thoroughly to remove surface remaining dehydrated alcohol and acetone; (6) substrate being put into mass percent is hydrofluoric acid etching 2～4min of 2～4%, at last deionized water is put in substrate and is soaked 2-3h.
Described polishing step comprises corase grind and polished finish step; Wherein,
The corase grind step: the waterproof abrasive paper that utilizes 500～2000# to red copper substrate polish, each only towards a direction polishing, until the striped that can only see this direction, then substrate is cleaned one time and remain in lip-deep sand grains to wash away, conversion 90 degree directions continue polishing, until required smooth finish;
Polishing step: with polishing machine and the cylindricality wool felt that scribbles clear boiled soap to red copper substrate polish, to remove thinner striped, the surface roughness Ra after the polishing＜0.2 μ m.The metal polishing machine (model is C121) that metal polishing machine can select for use Japanese MINIMO company to produce.
(a) substrate pretreatment polishing: remove surface contaminants and substrate initial trench with the 500# sand papering, all cover 500# sand paper texture until substrate surface; Use the 800# sand papering, the polishing direction changes 90 °, till the polishing vestige of substrate surface 500# sand paper loses; Use the 1000# sand papering then, the polishing direction changes 90 °, till the polishing vestige of substrate surface 800# sand paper loses; Use the 1600# sand papering, the polishing direction changes 90 °, till the polishing vestige of substrate surface 1000# sand paper loses; Use the 2000# sand papering at last, the polishing direction changes 90 °, and till the polishing vestige of substrate surface 1600# sand paper loseed, substrate this moment texture was 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 red copper substrate surface is polished, until reaching needed smooth finish; Surface roughness Ra=0.198um after the polishing.The ultrasonic cleaning step: with coupon is 5% in mass percent at first, and temperature is ultrasonic soaking and washing 10min in 60 ℃ the NaOH solution, removes the saponification grease; Print being immersed mass percent is 2% again, and temperature is ultrasonic soaking and washing 10min in 20 ℃ the hydrochloric acid, removes the print surface oxide layer; With deionized water rinsing 5min clean after, place mass percent to carry out taking out behind the ultrasonic cleaning 25min greater than 99.5% acetone, to remove residual non-saponification quasi-grease greater than 99.7% dehydrated alcohol and mass percent; With deionized water rinsing 5min clean after, put into 2% hydrofluoric acid etching 4min, at last substrate is put into deionized water and soaks 2h and move into deposit fluid.
(b) in every liter of analytical pure silicofluoric acid, add first solution that 60 gram analytical pure silicic acid are mixed with homogeneous, place it in magnetic agitation 3h in 20 ℃ the water-bath then;
(c) adding in described first solution that deionized water makes second solution and make the concentration of silicofluoric acid in second solution is 2mol/L, places it in magnetic agitation 0.5h in 40 ℃ of water-baths then;
(d) take by weighing analytically pure boric acid and join in described second solution and make the 3rd solution, making the boric acid concentration in the 3rd solution is 0.0mol/L, places it in magnetic agitation 0.5h in 40 ℃ of water-baths then;
(e) substrate is vertically put into the 3rd solution deposition 20h and make the substrate that is coated with silica membrane;
(f) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove surface residue with deionized water;
(g) substrate is dried naturally, put into N then
2Heat in the resistance furnace of protection, heating rate is 1 ℃/min, when temperature is elevated to 400 ℃, keeps constant temperature 1h; Close heating unit, get micro-nano SiO behind the naturally cooling
2Top coat, coat-thickness are 174.7nm, are reagent with water, glycerine, record surface free energy 9.23mJ.m
-2
The magnification 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 is respectively 2000X, and the SEM figure of 10000X is shown in Fig. 1 (a) and Fig. 1 (b).Find out that by Fig. 1 (a) coating is fine and close, flawless and cover substrate, SiO fully
2Particle is unordered stacking states (Fig. 1 (b)).The hole that stays when the dark zone of color is for the substrate grinding and polishing among Fig. 1 (a).Found out that by Fig. 1 (c) power spectrum graphs (its ultimate analysis sees the following form) the Si element atomic percentage conc of coatingsurface is 5.33%, O atoms of elements percentage composition is 18.23%, has proved SiO
2The generation of coating.
| Element | Weight percent | Atomic percent |
| CK | 4.37 | 16.24 |
| OK | 6.54 | 18.23 |
| SiK | 3.35 | 5.33 |
| CuK | 85.74 | 60.20 |
| Total amount | 100.00 |
(a) substrate pretreatment polishing: remove surface contaminants and substrate initial trench with the 500# sand papering, all cover 500# sand paper texture until substrate surface; Use the 800# sand papering, the polishing direction changes 90 °, till the polishing vestige of substrate surface 500# sand paper loses; Use the 1000# sand papering then, the polishing direction changes 90 °, till the polishing vestige of substrate surface 800# sand paper loses; Use the 1500# sand papering, the polishing direction changes 90 °, till the polishing vestige of substrate surface 1000# sand paper loses; Use the 2000# sand papering at last, the polishing direction changes 90 °, and till the polishing vestige of substrate surface 1500# sand paper loseed, substrate this moment texture was 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 red copper substrate surface is polished, until reaching needed smooth finish; Surface roughness Ra=0.1137um after the polishing.The ultrasonic cleaning step: with coupon is 10% in mass percent at first, and temperature is ultrasonic soaking and washing 8min in 60 ℃ the NaOH solution, removes the saponification grease; Print being immersed mass percent is 6% again, and temperature is ultrasonic soaking and washing 6min in 20 ℃ the hydrochloric acid, removes the print surface oxide layer; With deionized water rinsing 10min clean after, place mass percent to carry out taking out behind the ultrasonic cleaning 20min greater than 99.5% acetone, to remove residual non-saponification quasi-grease greater than 99.7% dehydrated alcohol and mass percent; With deionized water rinsing 10min clean after, put into 3% hydrofluoric acid etching 3min, at last deionized water is put in substrate and is soaked 2.5h, move in the deposit fluid.
(b) in every liter of analytical pure silicofluoric acid, add first solution that 80 gram analytical pure silicic acid are mixed with homogeneous, place it in magnetic agitation 4h in 25 ℃ the water-bath then;
(c) adding in described first solution that deionized water makes second solution and make the concentration of silicofluoric acid in second solution is 1.0mol/L, places it in magnetic agitation 0.8h in 45 ℃ of water-baths then;
(d) take by weighing analytically pure boric acid and join in described second solution and make the 3rd solution, making the boric acid concentration in the 3rd solution is 0.03mol/L, places it in magnetic agitation 0.8h in 45 ℃ of water-baths then;
(e) substrate is vertically put into the 3rd solution deposition 19h and make the substrate that is coated with silica membrane;
(f) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove surface particles etc. with deionized water;
(g) substrate is dried naturally, put into N then
2Heat in the resistance furnace of protection, heating rate is 4 ℃/min, when temperature is elevated to 300 ℃, keeps constant temperature 4h; Close heating unit, get micro-nano SiO behind the naturally cooling
2Top coat, coat-thickness are 167.3nm, are reagent with water, glycerine, record surface free energy 9.51mJ.m
-2
The magnification that adopts TecnaiG2 F20 field transmission electron microscope (point resolution 0.248nm, linear resolution 0.102nm, acceleration voltage 200kV) to obtain among Fig. 2 (a) is the SEM figure of 1000X.Find out that by Fig. 2 (a) there is crackle in coating but covers substrate fully.Found out that by Fig. 2 (b) power spectrum graphs (its ultimate analysis sees the following form) the Si element atomic percentage conc of coatingsurface is 3.29%, O atoms of elements percentage composition is 13.41%, has proved SiO
2The generation of coating.
| Element | Weight percent | Atomic percent |
| CK | 4.90 | 18.88 |
| OK | 4.64 | 13.41 |
| SiK | 2.00 | 3.29 |
| CuK | 88.46 | 64.41 |
| Total amount | 100.00 |
(a) substrate pretreatment polishing: remove surface contaminants and substrate initial trench with the 500# sand papering, all cover 500# sand paper texture until substrate surface; Use the 800# sand papering, the polishing direction changes 90 °, till the polishing vestige of substrate surface 500# sand paper loses; Use the 1000# sand papering then, the polishing direction changes 90 °, till the polishing vestige of substrate surface 800# sand paper loses; Use the 1800# sand papering, the polishing direction changes 90 °, till the polishing vestige of substrate surface 1000# sand paper loses; Use the 2000# sand papering at last, the polishing direction changes 90 °, and till the polishing vestige of substrate surface 1800# sand paper loseed, substrate this moment texture was 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 red copper substrate surface is polished, until reaching needed smooth finish; Surface roughness Ra=0.0806um after the polishing.The ultrasonic cleaning step: with coupon is 15% in mass percent at first, and temperature is ultrasonic soaking and washing 5min in 60 ℃ the NaOH solution, removes the saponification grease; Print being immersed mass percent is 10% again, and temperature is ultrasonic soaking and washing 5min in 20 ℃ the hydrochloric acid, removes the print surface oxide layer; With deionized water rinsing 15min clean after, place mass percent to carry out taking out behind the ultrasonic cleaning 15min greater than 99.5% acetone, to remove residual non-saponification quasi-grease greater than 99.7% dehydrated alcohol and mass percent; With deionized water rinsing 20min clean after, put into 4% hydrofluoric acid etching 4min, at last deionized water is put in substrate and is soaked 3h, move in the deposit fluid.
(b) in every liter of analytical pure silicofluoric acid, add first solution that 75 gram analytical pure silicic acid are mixed with homogeneous, place it in magnetic agitation 6h in 30 ℃ the water-bath then;
(c) adding in described first solution that deionized water makes second solution and make the concentration of silicofluoric acid in second solution is 1.9mol/L, places it in magnetic agitation 1h in 50 ℃ of water-baths then;
(d) take by weighing analytically pure boric acid and join in described second solution and make the 3rd solution, making the boric acid concentration in the 3rd solution is 0.02mol/L, places it in magnetic agitation 1h in 50 ℃ of water-baths then;
(e) substrate is vertically put into the 3rd solution deposition 10h and make the substrate that is coated with silica membrane;
(f) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove surface particles etc. with deionized water;
(g) substrate is dried naturally, put into N then
2Heat in the resistance furnace of protection, heating rate is 5 ℃/min, when temperature is elevated to 100 ℃, keeps constant temperature 5h; Close heating unit, get micro-nano SiO behind the naturally cooling
2Top coat, coat-thickness are 129.8nm, are reagent with water, glycerine, record surface free energy 10.13mJ.m
-2
Fig. 3 (a) is that the magnification that adopts TecnaiG2 F20 field transmission electron microscope (point resolution 0.248nm, linear resolution 0.102nm, acceleration voltage 200kV) to obtain is the SEM figure of 40000X.By Fig. 3 (a) as can be seen, coating is piled up fine and close and is covered substrate fully.Found out that by Fig. 3 (b) power spectrum graphs (its ultimate analysis sees the following form) the Si element atomic percentage conc of coatingsurface is 0.69%, O atoms of elements percentage composition is 9.48%, has proved SiO
2The generation of coating.
| Element | Weight percent | Atomic percent |
| CK | 5.29 | 21.10 |
| OK | 3.17 | 9.48 |
| SiK | 0.39 | 0.67 |
| CuK | 91.16 | 68.75 |
| Total amount | 100.00 |
Claims (2)
1. the method for preparing micro-nano-silica film in the red copper substrate is characterized in that it may further comprise the steps:
(a) pre-treatment is carried out in the red copper substrate, made its surperficial roughness Ra be controlled at Ra＜0.2 μ m;
(b) in every liter of analytical pure silicofluoric acid, add first solution that 60-80 gram analytical pure silicic acid is mixed with homogeneous, place it in magnetic agitation 3h～6h in 20 ℃～30 ℃ the water-bath then;
(c) adding in described first solution that deionized water makes second solution and make the concentration of silicofluoric acid in second solution is 1-2mol/L, places it in magnetic agitation 0.5h～1h in 40 ℃～50 ℃ the water-bath then;
(d) take by weighing analytically pure boric acid and join in described second solution and make the 3rd solution, making the boric acid concentration in the 3rd solution is 0.0～0.03mol/L, places it in magnetic agitation 0.5h～1h in 40 ℃～50 ℃ water-baths then;
(e) substrate is vertically put into the 3rd solution deposition 10-20h and make the substrate that is coated with silica membrane;
(f) after deposition finishes, substrate is taken out, repeatedly wash the surface to remove surface residue with deionized water;
(g) substrate is dried naturally, the resistance furnace of putting into the N2 protection then heats, and heating rate is 1-5 ℃/min, when temperature is elevated to 100～400 ℃, keeps constant temperature 1-5h;
(h) close resistance furnace, obtain homogeneous compact silicon oxide micro-nano film coating layer behind the naturally cooling.
Pre-treatment step in the described step (a) comprises polishing step and ultrasonic cleaning step successively; Roughness Ra＜0.2 μ the m on the surface at the stainless steel-based end after the polishing of described polishing step wherein, described ultrasonic cleaning step comprises: (1) is 5%～15% with mass percent, temperature is sodium hydroxide solution ultrasonic cleaning substrate 5～10min of 60 ℃, removes the part grease on surface; (2) substrate being immersed mass percent is 2%～10%, and temperature is 20 ℃ a hydrochloric acid soln, and ultrasonic cleaning 5～10min is to remove oxide on surface; (3) with washed with de-ionized water substrate 5～15min, to remove the acid of remained on surface; (4) substrate is put into mass percent respectively and carry out taking out behind the ultrasonic cleaning 15-25min greater than 99.5% acetone, to remove residual grease greater than 99.7% dehydrated alcohol and mass percent; (5) with deionized water ultrasonic cleaning substrate 5～20min, thoroughly to remove surface remaining dehydrated alcohol and acetone; (6) substrate being put into mass percent is hydrofluoric acid etching 2～4min of 2～4%, at last deionized water is put in substrate and is soaked 2-3h.
2. the method for preparing micro-nano-silica film in the red copper substrate according to claim 1 is characterized in that: described polishing step comprises corase grind and polished finish step; Wherein,
The corase grind step: the waterproof abrasive paper that utilizes 500～2000# to red copper substrate polish, each only towards a direction polishing, until the striped that can only see this direction, then substrate is cleaned one time and remain in lip-deep sand grains to wash away, conversion 90 degree directions continue polishing, until required smooth finish;
Polishing step: with polishing machine and the cylindricality wool felt that scribbles clear boiled soap to red copper substrate polish, to remove thinner striped, the surface roughness Ra after the polishing＜0.2 μ m.
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| CN2010103002053A CN101787526B (en) | 2010-01-12 | 2010-01-12 | Method for preparing micro-nano-silica film on red copper substrate |
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| CN2010103002053A CN101787526B (en) | 2010-01-12 | 2010-01-12 | Method for preparing micro-nano-silica film on red copper substrate |
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| CN101787526A true CN101787526A (en) | 2010-07-28 |
| CN101787526B CN101787526B (en) | 2011-08-17 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102437236A (en) * | 2011-11-25 | 2012-05-02 | 中国科学院微电子研究所 | Passivation method for surface of black silicon solar cell |
| CN102527613A (en) * | 2012-02-17 | 2012-07-04 | 天津大学 | Liquid-phase deposition-impregnation preparation method of micro/nano low-surface hydrophobic composite anti-scaling coating |
| CN106816504A (en) * | 2017-01-12 | 2017-06-09 | 西安电子科技大学 | Semi-polarity AlN films based on m faces SiC substrate and preparation method thereof |
-
2010
- 2010-01-12 CN CN2010103002053A patent/CN101787526B/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102437236A (en) * | 2011-11-25 | 2012-05-02 | 中国科学院微电子研究所 | Passivation method for surface of black silicon solar cell |
| CN102527613A (en) * | 2012-02-17 | 2012-07-04 | 天津大学 | Liquid-phase deposition-impregnation preparation method of micro/nano low-surface hydrophobic composite anti-scaling coating |
| CN106816504A (en) * | 2017-01-12 | 2017-06-09 | 西安电子科技大学 | Semi-polarity AlN films based on m faces SiC substrate and preparation method thereof |
| CN106816504B (en) * | 2017-01-12 | 2019-01-29 | 西安电子科技大学 | Semi-polarity AlN film and preparation method thereof based on the face m SiC substrate |
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| Publication number | Publication date |
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| CN101787526B (en) | 2011-08-17 |
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