CN101556126B - Film with high heat conduction efficiency and antifouling capability and preparation method thereof - Google Patents
Film with high heat conduction efficiency and antifouling capability and preparation method thereof Download PDFInfo
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- CN101556126B CN101556126B CN2008101036128A CN200810103612A CN101556126B CN 101556126 B CN101556126 B CN 101556126B CN 2008101036128 A CN2008101036128 A CN 2008101036128A CN 200810103612 A CN200810103612 A CN 200810103612A CN 101556126 B CN101556126 B CN 101556126B
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Abstract
The invention relates to a film with high heat conduction efficiency and antifouling capability for a heater and a preparation method thereof, in particular to a film with special wettability based onthe surface of metal or a metal alloy and a preparation method thereof. The film of the invention is obtained on the surface of the metal or the metal alloy for heat exchange by adopting a method com bining an electrochemistry method, a hydro-thermal reaction method, a chemical vapor deposition method, a sol-gel method, a laser etching method and chemical vapor deposition, or a method combining laser etching and sol-gel; and by evaluation on the antifouling capability, the boiling process in water and the heat exchange efficiency of the film, various performances of the obtained metal or metalalloy heater containing the film of the invention are markedly improved compared with a metal or metal alloy heater without the film of the invention.
Description
Technical field
The present invention relates to film that is used for high heat conduction efficiency of having of heater and anti-tartar ability and preparation method thereof, particularly a kind of have special infiltrating film and preparation method thereof based on the metal or metal alloy surface.
Background technology
Present hot switch technology is in the developing period of a key, and the demand with excessive heat flow cooling device is constantly increased.Extensive use along with laser, superconducting magnet, high-octane X-ray and overspeed computer chip treatment technology, and to demand based on the continuous miniaturization of equipment of this technology, require these equipment not only to have high precision, and take minimum space, so the design of core devices and heat treatment all are faced with new challenges.Though the cooling system based on air of widespread usage is effective, ever-increasing heat flux finally can make the cooling system lose efficacy.Thereby, having the very application of high flux of heat at great majority, liquid cools is more effective.Normally used cooling fluid is water/chilled water, and this cooling fluid refrigerant commonly used is ammonia, freon etc., or similarly be used for the refrigerant of specific occasion, as liquid nitrogen.Water is as tradition and safe cooling fluid, and main deficiency is its more weak hot conversion character relatively.Refrigerant commonly used such as ammonia or freon not only have very big harm to environment, and need complicated production technology and expensive production equipment.Before 100 years, people just know that mud can be used for improving pyroconductivity, but because the sedimentation of mud and the increase of its caused burn into dirt and pressure drop never are used to the heat conversion.Along with the continuous progress of materials processing technology, it is that so-called nano-fluid receives increasing concern as cooling agent that hydrophilic nano particle is introduced conventional fluid.Nano-fluid not only can overcome mud as cooling agent and introduce most problem of being brought, can also improve thermal conversion efficiency and critical heat flow (J.A.Eastman, S.U.S.Choi significantly, S.Li, W.Yu, L.J.Thompson.Appl.Phys.Lett.2001,78,718～720.).Discover that owing to the deposition of nano particle, can make hot conversion equipment is the nanoparticle layers that the heating of metal surface produces porous to nano-fluid in heating process.This loose structure makes the surface hydrophilicity of heating of metal further improve, and has reduced the active hole on heating of metal surface, and having reduced the nucleation of bubble on the heating of metal surface is the enrichment of bubble in the metal surface, thereby has improved critical heat flux.Yet the introducing of nano particle has increased the cost of hot conversion equipment.
Summary of the invention
The objective of the invention is in order to overcome the deficiencies in the prior art, provide a kind of and can improve the heat conduction efficiency of hot conversion equipment (as heater) and the film with high heat conduction efficiency and anti-tartar ability of anti-tartar performance.
Another object of the present invention provides a kind of film that has high heat conduction efficiency of having of special wellability and structure and anti-tartar ability based on the metal or metal alloy surface.
An also purpose of the present invention provides a kind of preparation method with film of high heat conduction efficiency and anti-tartar ability.
The present invention is that the method that combines of the method that combines with the method for electrochemical method, hydro-thermal reaction, chemical vapour deposition technique, sol-gal process, laser ablation method and chemical vapour deposition (CVD) or laser ablation and collosol and gel is at the metal or metal alloy surface filming that is being used for the heat conversion, by to its anti-tartar, the evaluation of boiling process and thermal conversion efficiency in water, confirm that the acquired more simple metal or metal alloy heater that does not have film of the present invention of metal or metal alloy heater that contains film of the present invention all is significantly increased on every performance.
Film with high heat conduction efficiency and anti-tartar ability of the present invention, being based on the metal or metal alloy substrate surface is had (as hydroxyl or carboxyl etc.) nonmetal formation of hydrophilic functional groups by hydrophilic metal oxides or superficial growth, it is to be sphere or celestial being's spheroidal particle of the hydrophilic metal oxides of 100～300nm by particle diameter that this hydrophilic metal oxides film or superficial growth have the non-metallic film of hydrophilic functional groups, is that hydrophilic metal oxides clavate or the box-shaped build-up of particles of 100～300nm forms coarse structure by diameter perhaps; Or
By diameter is that the superficial growth of 100～300nm has nonmetal clavate, tubular shape or the box-shaped build-up of particles of hydrophilic functional groups to form coarse structure.
The thickness of film of the present invention is 50～500nm, and the contact angle of film and water is less than 20 ° (if the surface of hydrophilic metal oxides is a smooth surface, the surface contact angle of water and hydrophilic metal oxides is at 30～60 °).The thermal conversion rate of the thermoconverter that the thermal conversion rate of this film is more traditional improves 20～200%, and thermal conversion efficiency increases with the increase of film thickness in this film thickness scope, and the anti-tartar performance obviously improves.
Described base metal is Ag, Cu, Fe or Al etc.
Described base metal alloy is stainless steel, nichrome or ferrochrome etc.
Described metal oxide is Al
2O
3, TiO
2, ZnO
2, SnO
2, GeO
2Or ZrO
2Deng.
Described nonmetal be graphite, diamond or CNT.
Of the present invention based on the special wellability of having of metal or metal alloy surface and have high thermal conversion efficiency and the preparation method of the film of anti-tartar ability comprises:
Electrochemical method: under the room temperature metal or metal alloy is immersed in the electrolyte in the electrolytic cell, use be immersed in electrolytic cell in the identical metal of metal as reaction electrode, this metal or Pt do electrode; Or use be immersed in electrolytic cell in the identical metal alloy of metal alloy as reaction electrode, this metal alloy or Pt do electrode; Two distance between electrodes are controlled at 2～10cm, and Control of Voltage is at 4～8V, and the cell reaction time is 1～3 hour; It is that 100～200 ℃ Muffle furnace was ablated 10～20 minutes that reaction electrode after the cell reaction is put into furnace temperature; Use deionized water and alcohol immersion after 10～30 minutes respectively the reaction electrode after ablating, in air drying, then directly preparing based on the metal or metal alloy surface is sphere or celestial being's spheroidal particle of the hydrophilic metal oxides of 100～300nm by particle diameter, is that hydrophilic metal oxides clavate or the box-shaped build-up of particles of 100～300nm forms the hydrophilic metal oxides film with coarse structure by diameter perhaps.
Described metal is: Cu, Zn, Fe or Al etc.
Described metal alloy is stainless steel, nichrome or ferrochrome etc.
The electrolyte of the described Cu of being used for, Zn, Fe electrochemical reaction is the ethanolic solution of n-14 aliphatic acid of 0.2～1.0mol/L; The electrolyte that is used for the Al electrochemical reaction is the sulfuric acid solution of 0.3～0.8mol/L.
The hydro-thermal reaction method: coating one deck mass concentration is that 2%～8% butyl titanate or mass concentration are the ethanolic solution of 2%～8% zinc acetate on metal or metal alloy, ablates 1～3 hour in the reaction furnace temperature is 300～500 ℃ reacting furnace; Metal or metal alloy after ablating is taken out, and putting into concentration is the titanium trichloride aqueous hydrochloric acid solution (mass concentration of hydrochloric acid is 1%～35%, and preferred mass concentration is 3%～10%) of 0.1mol/L～0.2mol/L; Or
Put into the mixed aqueous solution of the hexamethylenetetramine of the zinc nitrate that contains 0.02mol/L～0.05mol/L and 0.01mol/L～0.03mol/L, reaction is after 10 minutes～12 hours under temperature is 100～200 ℃, thoroughly clean with deionized water and ethanol respectively, behind the air drying, then directly preparing based on the metal or metal alloy surface is sphere or celestial being's spheroidal particle of the hydrophilic metal oxides of 100～300nm by particle diameter, is that hydrophilic metal oxides clavate or the box-shaped build-up of particles of 100～300nm forms the hydrophilic metal oxides film with coarse structure by diameter perhaps.
Chemical vapour deposition technique: with Ti (C
10H
14O
5) to put into the quartz container temperature be 200～300 ℃ low-temperature region, is 1: 1 N with volume ratio
2/ O
2Mist, as carrier gas, by N
2/ O
2It is in 500～1000 ℃ the high-temperature area that carrier gas is brought the solid reactant steam that evaporates in the low-temperature region into be placed with metal or metal alloy temperature, makes (the C through the Ti of peroxidization
10H
14O
5) generate metal oxide and directly be deposited on the metal or metal alloy surface; Then directly preparing based on the metal or metal alloy surface is sphere or celestial being's spheroidal particle of the hydrophilic metal oxides of 100～300nm by particle diameter, is that the hydrophilic metal oxides clavate build-up of particles of 100～300nm forms the hydrophilic metal oxides film with coarse structure by diameter perhaps; Or
It is 200～300 ℃ low-temperature region that the metal phthalocyanine dyestuff is put into the quartz container temperature, is 2: 1 Ar/H with volume ratio
2Mist as carrier gas, by Ar/H
2It is in 500～1000 ℃ the high-temperature area that carrier gas is brought the solid reactant steam that evaporates in the low-temperature region into be placed with metal or metal alloy temperature, makes the metal phthalocyanine dyestuff through reduction reaction generate the nonmetal metal or metal alloy surface that directly is deposited on; Then directly preparing based on the metal or metal alloy surface is that the superficial growth of 100～300nm has the tubular shape build-up of particles of hydrophilic functional groups to form the non-metallic film with coarse structure by diameter.This film is further carried out post processing (is in 1: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA) mixed liquor as this film being immersed volume ratio), can increase and produce hydrophilic radical (hydroxyl or carboxyl).
Described metal phthalocyanine dyestuff is FeC
32N
8H
16/ YC
32N
8H
16, be called for short FePc/Ypc.
Sol-gal process: in reactor, be the ethanolic solution of the zinc acetate of 3～10mol/L with concentration, slowly be warmed up to 60～100 ℃ under strong agitation, stirring and refluxing is 1～3 hour under this temperature, boils off liquid ethanol then and obtains solid gel; Be cooled to room temperature, be diluted to colloidal sol with absolute ethyl alcohol once more, slowly be warmed up to 80～100 ℃ under strong agitation, stirring and refluxing is 2～3 hours under this temperature; Be cooled to room temperature with the ice-water bath cooling reactor, in with the ice-water bath cooling, add the catalyst lithium hydroxide, carry out ultrasonic dispersion hydrolysis then and obtained colloid in 1～2 hour, colloid is coated on the metal or metal alloy surface, air dry, then directly preparing based on the metal or metal alloy surface is sphere or celestial being's spheroidal particle of the hydrophilic metal oxides of 100～300nm by particle diameter, is that the hydrophilic metal oxides clavate build-up of particles of 100～300nm forms the hydrophilic metal oxides film with coarse structure by diameter perhaps.
The addition of described catalyst lithium hydroxide is the absolute ethyl alcohol adding 0.01～0.1g lithium hydroxide with every 30ml.
(available Germany produces etching laser machining by laser ablation, Karsuss MA6) directly prepares coarse structure in the metal surface, by the method or the sol-gal process of chemical vapour deposition (CVD) the metal or metal alloy laminar surface that the surface that obtains has coarse structure is modified then, make its surface form hydrophilic metal oxide or contain the nonmetal of hydrophilic functional groups, thereby improve the wellability on surface, improve the anti-tartar performance, obtain by hydrophilic metal oxide or non-metallic film.
The method that laser ablation and chemical vapour deposition (CVD) combine: directly go out coarse structure in the metal or metal alloy surface etch with laser (available Germany produces etching laser machining, Karsuss MA6); Then will the surface behind laser ablation be that to be placed on temperature in the quartz container be in 500～1000 ℃ the high-temperature area, with Ti (C for the metal or metal alloy of coarse structure
10H
14O
5) to put into the quartz container temperature be 200～300 ℃ low-temperature region, is 1: 1 N with volume ratio
2/ O
2Mist, as carrier gas, by N
2/ O
2It is in 500～1000 ℃ the high-temperature area that carrier gas is brought the solid reactant steam that evaporates in the low-temperature region into be placed with metal or metal alloy temperature, makes (the C through the Ti of peroxidization
10H
14O
5) generate metal oxide and directly be deposited on the metal or metal alloy surface; Then directly preparing based on the metal or metal alloy surface is sphere or celestial being's spheroidal particle of the hydrophilic metal oxides of 100～300nm by particle diameter, is that the hydrophilic metal oxides clavate build-up of particles of 100～300nm forms the hydrophilic metal oxides film with coarse structure by diameter perhaps; Or
It is 200～300 ℃ low-temperature region that the metal phthalocyanine dyestuff is put into the quartz container temperature, is 2: 1 Ar/H with volume ratio
2Mist as carrier gas, by Ar/H
2It is in 500～1000 ℃ the high-temperature area that carrier gas is brought the solid reactant steam that evaporates in the low-temperature region into be placed with metal or metal alloy temperature, makes the metal phthalocyanine dyestuff through reduction reaction generate the nonmetal metal or metal alloy surface that directly is deposited on; Then directly preparing based on the metal or metal alloy surface is that the superficial growth of 100～300nm has the tubular shape build-up of particles of hydrophilic functional groups to form the non-metallic film with coarse structure by diameter.
The coarse structure of described laser ablation is: groove that micron-sized groove, micron-sized pillar, micron order and nanoscale are compound or micron order and the compound pillar of nanoscale.
The method that laser ablation and collosol and gel combine: directly go out coarse structure in the metal or metal alloy surface etch with laser (available Germany produces etching laser machining, Karsuss MA6); In reactor, be the ethanolic solution of the zinc acetate of 3～10mol/L with concentration then, slowly be warmed up to 60～100 ℃ under strong agitation, stirring and refluxing is 1～3 hour under this temperature, boils off liquid ethanol then and obtains solid gel; Be cooled to room temperature, be diluted to colloidal sol with absolute ethyl alcohol once more, slowly be warmed up to 80～100 ℃ under strong agitation, stirring and refluxing is 2～3 hours under this temperature; Be cooled to room temperature with the ice-water bath cooling reactor, in with the ice-water bath cooling, add the catalyst lithium hydroxide, carry out ultrasonic dispersion hydrolysis then and obtained colloid in 1～2 hour, it is on the metal or metal alloy surface of coarse structure that colloid is coated in through the surface behind the laser ablation, air dry, then directly preparing based on the metal or metal alloy surface is sphere or celestial being's spheroidal particle of the hydrophilic metal oxides of 100～300nm by particle diameter, is that the hydrophilic metal oxides clavate build-up of particles of 100～300nm forms the hydrophilic metal oxides film with coarse structure by diameter perhaps.
The addition of described catalyst lithium hydroxide is the absolute ethyl alcohol adding 0.01～0.1g lithium hydroxide with every 30ml.
The coarse structure of described laser ablation is: groove that micron-sized groove, micron-sized pillar, micron order and nanoscale are compound or micron order and the compound pillar of nanoscale.
The present invention can have the monofilm of rough surface by the preparation of several different methods such as physics and chemistry, and the suitable most of metals of selected method, and simple and easy to do, good film-forming property, easily large tracts of land system film.The thermal conversion efficiency of monofilm the best is 200%, and surface wettability obviously improves, and anti-tartar obviously improves.Result of the test shows, the monofilm of the inventive method preparation is between 50～500nm at thickness, and the contact angle of film and water is during less than 20 °, and its thermal conversion efficiency is further increase with the increase of thickness of monolayer, and the anti-tartar performance further improves.Especially when the contact angle of this monofilm during near 0 °, this film surface is heating 50 days scaling not continuously.These data show that the monofilm with special wellability and anti-tartar performance of the present invention has potential application prospect as heat such as boiler conduction resistive connection dirt material.
Adopt the experimental rig of typical pool boiling, as shown in Figure 1.By the heat flux formula
Wherein, h
FgBe heat of vaporization, ρ
vBe vapour density, σ is a surface tension, and Δ ρ is the difference of vapour density and fluid density, and g is an acceleration of gravity.By calculating thermal conversion efficiency
Shown in Figure 2, wherein q is a heat flux, T
2And T
1Be respectively t
2The moment and t
1Temperature constantly.The anti-tartar performance of heater is taked the method for continuous heating in running water.Test shows that the resistive connection dirt performance with heater surfaces of monofilm obviously is better than not having the heater surfaces (Fig. 3) of monofilm.
Monofilm with high heat conduction efficiency and anti-tartar ability involved in the present invention, improved the thermal conductivity of metal surface, improved the thermal conversion efficiency of metal heater, and implementation method is various, machinability is stronger, simultaneously, this monofilm has improved the anti-tartar performance of metal surface, has prolonged its service life.The present invention is that the micro-processing technology with physics and chemistry is applied in traditional heating material, compares with the mode of traditional raising thermal conversion efficiency, not only saves cost but also improve service life.The prepared film of method of the present invention is at boiler, and hot conversion such as nuclear power station field has novelty and using value more.
Description of drawings
Fig. 1. the embodiment of the invention 3 thermal conversion efficiency testing arrangements.
Fig. 2. the thermal conversion efficiency curve of the embodiment of the invention 3 METAL HEATING PROCESS bodies.
Fig. 3. the anti-tartar performance on the embodiment of the invention 7 heating of metal surfaces;
Wherein Fig. 3 a is the preceding metal surface with monofilm of heating, and Fig. 3 b is 15 days the metal surface with monofilm of continuous heating; Fig. 3 c is the preceding level and smooth metal surface that does not have film of heating, and Fig. 3 d is 15 days the level and smooth metal surface that does not have film of continuous heating.
Fig. 4. the microstructure on the embodiment of the invention 6 heating of metal surfaces.
The specific embodiment
Below by embodiment the present invention is done further specific descriptions, but embodiments of the present invention are not limited thereto, can not be interpreted as limiting the scope of the invention.
Electrochemical method: (100mm * 50mm * 1mm) be immersed in the sulfuric acid solution of the 0.5mol/L in the electrolytic cell, two aluminium flakes be respectively as reaction electrode with to electrode, and the distance between two aluminium flakes is 6cm with a pair of aluminium flake under the room temperature.Current density is controlled present 10mA/cm
2Reacted 3 hours.The temperature of reaction solution is controlled at below 40 ℃ in the course of reaction.Aluminium flake after the oxidation washes away sulfuric acid residual on it with deionized water, and aluminium flake was put into Muffle furnace 20 minutes then, and Control for Kiln Temperature is at 180 ℃.Use deionized water and alcohol immersion after 30 minutes respectively the product after ablating, in air drying, then directly preparing based on metal A l surface is the hydrophilic Al of the rod-shaped particle accumulation of 200nm by diameter
2O
3Film, the about 300nm of thickness, the contact angle of film and water is less than 20 °.
Embodiment 2
Electrochemical method: two clean copper sheets are placed the electrolytic cell that is placed with electrolyte, and conduct is to electrode and working electrode respectively for two copper sheets, and two distance between electrodes are 5cm.Electrolyte is the ethanolic solution of n-14 aliphatic acid of 0.5mol/L.Voltage with dc source under the room temperature is set at 5V reaction 3 hours, and the metal surface of working electrode will deposit Cu[CH
3-(CH
2)
12COO]
2To deposit Cu[CH
3-(CH
2)
12COO]
2The Cu sheet, put into Muffle furnace 10 minutes, Control for Kiln Temperature is at 100 ℃.Use deionized water and alcohol immersion after 20 minutes respectively the product after ablating, in air drying, then directly preparing based on metal Cu surface is the hydrophilic CuO film with coarse structure that the box-shaped build-up of particles of 150nm forms by diameter, about 100nm behind the film, the contact angle of film and water is less than 20 °.
Embodiment 3
The hydro-thermal reaction method: contain the ethanolic solution that mass concentration is 5% butyl titanate in the Cu that cleans and nichrome surface coating, the reacting furnace temperature is controlled at 300 ℃, fires in reacting furnace 1 hour, obtains being coated with the Cu and the nichrome of titanium oxide crystal seed.The titanium trichloride aqueous hydrochloric acid solution of the 0.15mol/L of preparation 50mL, wherein the mass concentration of hydrochloric acid is 5%.In solution, add the NaCl solid and reach supersaturation.Solution is transferred to (internal tank and external heat device are equipped with temp probe respectively and come the inside and outside temperature of detection reaction still in the stainless steel cauldron of teflon lined; Pressue device and atmospheric pipe have been covered at reactor).Cu that is coated with the titanium oxide crystal seed and the nichrome that to prepare this moment are put into reaction vessel, closed container.Slowly heating by monitoring reaction still internal temperature, allows the slow temperature of internal tank temperature be raised to 160 ℃, and this moment, external temperature was about 220 ℃.Under this temperature, react certain hour.After the reactor internal temperature is reduced to room temperature, open the venting valve, take out metal or alloy, thoroughly clean with deionized water, absolute ethyl alcohol.Prepared film heated 12 hours in the vacuum drying oven of 120 ℃ of temperature, placed for 6 weeks in the dry atmosphere in dark place then, obtaining based on metal Cu and nichrome surface is that the spherical or ball cactus shape build-up of particles of 100～300nm forms the hydrophilic TiO with coarse structure by particle diameter
2Film, the about 500nm of thickness, the contact angle of film and water is less than 20 °.
Adopt the experimental rig of typical pool boiling, as shown in Figure 1.The area of heater to be measured is 10 * 10mm
2Assisted heating device is installed to improve firing rate in heater to be measured below.In order to keep the constant pressure in the test system, the temperature of control working fluid is installed condenser, the steam that produces on the condensation testing heater on experimental rig.In order to keep the temperature of whole system, heat-insulation layer is installed in the outside of device.Fluid temperature, the temperature of steam, the system side wall temperatures, the testing heater temperature is by the thermocouple measurement of K type, self-compiling program real time record.Obtain the thermal conversion efficiency curve by conversion, shown in Figure 2.As seen, this film can significantly improve the thermal conversion efficiency of metal Cu and nichrome, and along with the increase of film roughness, thermal conversion efficiency also constantly increases.
Embodiment 4
The hydro-thermal reaction method: the mass concentration that contains hydrolysis in the stainless steel surfaces coating is the ethanolic solution of 5% zinc acetate, fires in reacting furnace 1 hour, and the reacting furnace temperature is controlled at 420～460 ℃, obtains being coated with the stainless steel of zinc oxide crystal seed.The zinc nitrate of the 0.03mol/L that preparation 50mL contains and the mixed aqueous solution of 0.02mol/L hexamethylenetetramine.Mixed solution is added in the stainless steel reaction container of teflon lined (in the container and external heat device the temperature that temp probe comes the inside and outside portion of detection reaction container is housed respectively) respectively, slowly drip glacial acetic acid, regulate pH value to 5～about 7.This moment is heating slowly, allows the slow temperature of internal tank temperature be raised to 92～100 ℃, and this moment, external temperature was about 110 ℃.Wait for 10 minutes, the stainless steel substrates that is coated with zinc oxide crystal seed that will prepare this moment is put into reaction vessel, closed container, and under this temperature, react certain hour.After solution temperature is reduced to room temperature, take out stainless steel substrates, carry out thoroughly clearly with deionized water, absolute ethyl alcohol.Obtaining based on stainless steel surfaces is that the box-shaped build-up of particles of 200nm forms the hydrophilic ZnO with coarse structure by diameter
2Monofilm, thickness 450nm, the contact angle of film and water is less than 20 °.
Embodiment 5
Chemical vapour deposition (CVD): with metal phthalocyanine dyestuff FeC
32N
8H
16/ YC
32N
8H
16, being called for short FePc/YPc, to put into the quartz container temperature be 200～300 ℃ low-temperature region, is 2: 1 Ar/H with volume ratio
2Mist as carrier gas, by Ar/H
2It is in 500～1000 ℃ the high-temperature area that carrier gas is brought the solid reactant steam that evaporates in the low-temperature region into be placed with Cu temperature, directly prepare based on the tubular shape build-up of particles that by diameter is 100～300nm and form ACNT film with coarse structure, this thickness 300nm, it is in 1: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA) mixed liquor that the long Cu that the ANCT film arranged is immersed volume ratio, carbon nano tube surface is increased produce hydrophilic radical (hydroxyl or carboxyl), the contact angle of film and water is less than 20 °.
Embodiment 6
Sol-gal process: in reactor, 0.35g zinc acetate and 20mL absolute ethyl alcohol are mixed, under strong agitation, slowly be warmed up to 60～100 ℃,, boil off liquid ethanol then and obtain solid gel this temperature stirring and refluxing 1～3 hour.Reduce the temperature to room temperature, add the 20mL absolute ethyl alcohol once more and be diluted to colloidal sol, under strong agitation, slowly be warmed up to 80 ℃, this temperature stirring and refluxing 2～3 hours.Be reduced to room temperature with the ice-water bath cooling reactor, add catalyst 0.06g lithium hydroxide when cooling off with ice-water bath, carry out ultrasonic dispersion hydrolysis one hour then, colloid is placed on metal Fe and goes up air dry, obtain is that the hydrophilic ZnO box-shaped build-up of particles of 100～150nm forms the hydrophilic ZnO film with coarse structure based on the Fe surface by diameter, thickness is 70nm, and the contact angle of film and water is less than 20 °; Its microstructure as shown in Figure 4.
Embodiment 7
The method that laser ablation and chemical vapour deposition (CVD) combine: directly going out the length of side in metal Cu surface etch with laser (available Germany produces etching laser machining, Karsuss MA6) is that 10 μ m spacings are that 10 μ m highly are the micron pillar structure of 20 μ m; Then will the surface behind laser ablation be that to be placed on temperature in the quartz container be in 500～1000 ℃ the high-temperature area, with Ti (C for the metal Cu of coarse structure
10H
14O
5) to put into the quartz container temperature be 200～300 ℃ low-temperature region, is 1: 1 N with the volume ratio of 1000-sccm
2/ O
2Mist as carrier gas, by N
2/ O
2It is in 500～1000 ℃ the high-temperature area that carrier gas is brought the solid reactant steam that evaporates in the low-temperature region into be placed with metal or metal alloy temperature, makes (the C through the Ti of peroxidization
10H
14O
5) generate metal oxide and directly be deposited on the metal or metal alloy surface; Then directly preparing based on the Cu surface is the rod-shaped particle of the hydrophilic metal oxides of 150nm by diameter, piles up to form the hydrophilic TiO with coarse structure
2Film, this thickness are 200nm, and the contact angle of film and water is less than 20 °.
Fig. 3 a is depicted as the metal Cu surface with monofilm before the heating, and by 15 days the metal Cu surface with monofilm of continuous heating shown in Fig. 3 b as can be known, it is not obvious to heat 15 days surface scale phenomenons continuously; Fig. 3 c is depicted as the level and smooth metal Cu surface that does not have monofilm before the heating, is depicted as 15 days the level and smooth metal Cu surface that does not have monofilm of continuous heating as can be known by Fig. 3 d, heats continuously and adheres to a large amount of continuous incrustation scales in 15 days in the metal surface.
Claims (2)
1. preparation method with film of high heat conduction efficiency and anti-tartar ability, this film is based on metallic substrates or metal alloy substrate surface, is made of the hydrophilic metal oxides film;
It is characterized in that:
Adopt electrochemical method: under the room temperature metal or metal alloy is immersed in the electrolyte in the electrolytic cell, use be immersed in electrolytic cell in the identical metal of metal as reaction electrode, this metal or Pt do electrode; Or use be immersed in electrolytic cell in the identical metal alloy of metal alloy as reaction electrode, this metal alloy or Pt do electrode; Described metal is Cu, Zn, Fe or Al; Described metal alloy substrate is stainless steel, nichrome or ferrochrome; The electrolyte that is used for Cu, Zn, Fe electrochemical reaction is the ethanolic solution of n-14 aliphatic acid of 0.2～1.0mol/L; The electrolyte that is used for the Al electrochemical reaction is the sulfuric acid solution of 0.3～0.8mol/L;
Two distance between electrodes are controlled at 2～10cm; Control of Voltage is at 4～8V, and it is that 100～200 ℃ Muffle furnace was ablated 10～20 minutes that the reaction electrode of cell reaction after 1～3 hour put into furnace temperature; With the reaction electrode soaking and washing drying after ablating, obtaining by particle diameter is that the sphere or the spherical build-up of particles of celestial being of the hydrophilic metal oxides of 100～300nm forms the hydrophilic metal oxides film with coarse structure.
2. preparation method with film of high heat conduction efficiency and anti-tartar ability, this film is based on metallic substrates or metal alloy substrate surface, is made of the hydrophilic metal oxides film; Described metallic substrates is Ag, Cu, Fe or Al; Described metal alloy substrate is stainless steel, nichrome or ferrochrome;
It is characterized in that:
Adopt the hydro-thermal reaction method: coating one deck contains the ethanolic solution of butyl titanate or zinc acetate on metal or metal alloy, and wherein, the mass concentration of butyl titanate is 2～8%, and the mass concentration of zinc acetate is 2～8%;
In the reaction furnace temperature is to ablate 1～3 hour in 300～500 ℃ the reacting furnace; Metal or metal alloy after ablating is taken out, and putting into concentration is the titanium trichloride aqueous hydrochloric acid solution of 0.1mol/L～0.2mol/L, and wherein the mass concentration of the hydrochloric acid in the titanium trichloride aqueous hydrochloric acid solution is 1%～35%; Or put into the mixed aqueous solution of the hexamethylenetetramine of the zinc nitrate that contains 0.02mol/L～0.05mol/L and 0.01mol/L～0.03mol/L; Reaction is after 10 minutes to 12 hours under temperature is 100～200 ℃, thoroughly clean with deionized water and ethanol respectively, behind the air drying, obtaining by particle diameter is that the sphere of hydrophilic metal oxides or the spherical build-up of particles of celestial being of 100～300nm forms the hydrophilic metal oxides film with coarse structure.
Priority Applications (1)
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| SE535734C2 (en) * | 2010-12-06 | 2012-11-27 | Tetra Laval Holdings & Finance | Apparatus for heat treating a liquid food product |
| CN102817955B (en) * | 2012-06-07 | 2014-09-03 | 北方材料科学与工程研究院有限公司 | Method for modifying giant electrorheological fluid damper polar plate |
| CN103469216B (en) * | 2013-09-15 | 2015-11-18 | 西北有色金属研究院 | A kind of preparation method of the porous C u surface for heat exchange |
| CN104987047B (en) * | 2015-06-03 | 2017-04-05 | 浙江沁园水处理科技有限公司 | Load nanometer ZrO2Microcrystalline balls and its preparation method and application |
| CN105803447B (en) * | 2016-04-14 | 2018-05-04 | 东北电力大学 | A kind of preparation of super hydrophilic micro-nano copper oxide film with anti-fouling performance and detection method |
| CN109974512B (en) * | 2019-03-21 | 2020-10-02 | 中国科学院理化技术研究所 | Micro-nano composite reinforced boiling structure on material surface and preparation method and application thereof |
| CN110237554A (en) * | 2019-07-08 | 2019-09-17 | 中国科学院理化技术研究所 | A kind of falling film evaporation system and method |
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