CN100372618C - Aluminium heat exchanger and aluminium foil surface hydrophilic corrosive-resistant filming method - Google Patents
Aluminium heat exchanger and aluminium foil surface hydrophilic corrosive-resistant filming method Download PDFInfo
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- CN100372618C CN100372618C CNB2004100743462A CN200410074346A CN100372618C CN 100372618 C CN100372618 C CN 100372618C CN B2004100743462 A CNB2004100743462 A CN B2004100743462A CN 200410074346 A CN200410074346 A CN 200410074346A CN 100372618 C CN100372618 C CN 100372618C
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Abstract
The present invention relates to an aluminium heat exchanger and a hydrophilic corrosion-resistant film-forming method of an aluminium foil surface. A sol-gel method is adopted to form a hydrophilic corrosion-resistant composite film on the aluminium surface. The method of the present invention comprises two steps of the preparation of film forming agents and film-forming treatment. On the basis that the heat exchange efficiency is ensured, the aluminium heat exchanger and the aluminium foil after film forming simultaneously have hydrophilicity and corrosion resistance, and operating procedures are greatly simplified.
Description
Technical field:
The present invention relates to a kind of aluminium heater or aluminium foil surface hydrophilic corrosive-resistant filming method.
Background technology:
Heat exchanger is one of critical component of air-conditioner, and its radiating fin uses aluminum or aluminum alloy to make usually.A heat exchanger comprises a large amount of parallel fins, and air passes through at interval from fin.The area of heat radiation and refrigerating part should be big as far as possible, to improve heat exchange effect.Simultaneously because the spacing between the aluminium fin is very little, when the result is used to freeze when heat exchanger, by the moisture in the hot-air of fin just in the cooling piece surface condensation, the globule is assembled on fin and is stopped up narrow passage, promptly on fin, form on " water bridge ", stoped the circulation of air, and windage is increased, air quantity descends, and causes heat exchanger effectiveness to descend.In addition, air conditioner aluminium fin is operated in the environment of alternation of wetting and drying, the Al that its surface forms
2O
3H
2The O oxide layer sprays with floury from air outlet slit, brings the problem of service life of a machine minimizing and environmental pollution two aspects.
In order to address these problems, just must carry out hydrophilic and preservative treatment to the fin of aluminum heat exchanger.
Chinese patent publication number CN1181404A has provided the aluminium foil surface treatment process, the film forming agent that the related aluminium foil hydrophilic corrosive-resistant of this invention is handled is made up of hydrophilic film forming agent and corrosive-resistant filming agent two parts, and hydrophilic film forming agent contains silicon compound, water soluble organic substance, alkali compounds, dispersant and water; The corrosive-resistant filming agent contains organic high molecular polymer, crosslinking agent, dispersant and water; Organic macromolecular copolymer is that molecular weight is 800～1500000 and contains two kinds or the copolymer of two or more functional groups in epoxy radicals, carboxyl, hydroxyl, the amide groups.
The method that the related aluminium foil hydrophilic corrosive-resistant of Chinese patent publication number CN1342732A is handled is the coated with nano water wetted material, the nano-hydrophilic material is combined by hydrophilic polymer A and hydrophilic nano polymer particle B, wherein hydrophilic polymer A comprises polyethers, and hydrophilic nano polymer particle B comprises molecules surfactant, acrylamide, acrylic acid, crosslinkable unsaturated monomer.
The film forming agent that the related aluminium foil hydrophilic corrosive-resistant of Chinese patent publication number CN1079998A is handled is made up of halogen contained compound, pyrrole and derivative thereof, polyphosphate, alkali compounds, froth breaking, cosolvent.
Chinese patent publication number CN1424282A relates to a kind of titanium dioxide nano-film and method for making thereof, and particularly a kind of nano thin-film and method for making thereof of mixing at titanium dioxide nano-film discloses a kind of TiO
2/ SiO
2/ rare earth laminated film photocatalytic activity and Superhydrophilic are increased synchronously, and Superhydrophilic can be kept the long period in the dark.
Although above-mentioned patented technology has been improved the anti-corrosive properties and the hydrophily on heat exchanger top layer, but also exist and to satisfy hydrophily and anti-corrosive properties simultaneously, problems such as film-forming process complexity, the technology that has makes the heat exchanger top layer form the high molecular polymer hydrophilic membrane, and film forming thickness is wayward, and the film of formation is thicker, influence thermal conductivity, influence rate of heat exchange, consequently hydrophily has improved, and thermal conductivity has but descended, and therefore is applied to industrialized technology and few.
The purpose of this invention is to provide a kind of aluminium heater or aluminium foil surface hydrophilic corrosive-resistant filming method, adopt sol-gal process to form the hydrophilic corrosive-resistant composite membrane on the aluminium surface, on the basis that guarantees heat exchange efficiency, make aluminium heater after the film forming or aluminium foil possess hydrophilic property and corrosion resistance simultaneously, simplify preparation and operating procedure.
Summary of the invention:
The present invention is a kind of aluminium heater or aluminium foil surface hydrophilic corrosive-resistant filming method, comprises preparation and two steps of film forming processing of film forming agent, is specially:
(1) preparation of film forming agent: cerium salt is dissolved in the absolute ethyl alcohol, add collodion then, that is: the ethanolic solution of 5% cellulose iii nitric acid fat, the collodion of adding and the volume ratio of absolute ethyl alcohol are 1: 1.5～4, fully stir, make the salting liquid A of 40～60g/L.
Titanate esters under stirring condition, is added drop-wise in the alcohols solvent, fully stirs, adding a certain amount of water, is 2～3 with acid for adjusting pH value, obtains titanium alkoxide solution B, wherein, the mol ratio of each component is: butyl titanate: alcohols solvent: water=1: 9～24: 3～9.
Esters of silicon acis being dissolved in the alcohols solvent, adding a certain amount of water, fully stir hydrolysis, is 2～3 with acid for adjusting pH value, obtains the silicon alkoxide solution C, and wherein, the mol ratio of each component is: esters of silicon acis: alcohols solvent: water=1: 4～12: 1～2.
With above-mentioned solution be by volume: A: B: the ratio of C=3.3～10: 1: 0.2～0.5 is mixed, and fully stirs, and obtains the mixed sols film forming agent.
(2) film forming is handled: the aluminium heater after the degreasing or aluminium foil sample are vertically immersed in the mixed sols film forming agent that step (1) makes, leave standstill, behind to be filmed dose of liquid level stabilizing, the vertical proposition, the speed that lifts is 2～5 cm per minute preferably, after room temperature is placed surface drying, 400 ℃～500 ℃ roastings 0.5～1 hour, can on aluminium heater or aluminium foil specimen surface, form the film of one deck hydrophilic corrosive-resistant.
The used cerium salt of preparation salting liquid A is cerous nitrate or cerous sulfate in the above-mentioned steps (1), is preferably cerous nitrate; The used titanate esters of preparation titanium alkoxide solution B is tetraethyl titanate, isopropyl titanate or butyl titanate, is preferably butyl titanate; The used esters of silicon acis of preparation silicon alkoxide solution C is methyl silicate or ethyl orthosilicate, is preferably ethyl orthosilicate; When preparation salting liquid B and C, used alcohols solvent is ethanol or propyl alcohol or isopropyl alcohol or butanols or isobutanol, is preferably absolute ethyl alcohol or isobutanol.
When preparation salting liquid B and C, there are not special requirement to regulating pH value used acid and sour concentration, adopt hydrochloric acid, acetic acid, nitric acid or sulfuric acid all can.
Method of the present invention is applicable to the hydrophilic corrosive-resistant processing of various aluminium and Al-alloy products, the particularly hydrophilic corrosive-resistant of aluminium heater processing.
The present invention compared with prior art, have following advantage: the present invention adopts sol-gal process to form the hydrophilic corrosive-resistant composite membrane on the aluminium surface, film is thin, on the basis that guarantees heat exchange efficiency, make aluminium heater after the film forming or aluminium foil possess hydrophilic property and corrosion resistance simultaneously, solve the problem of water bridge on the heat exchanger well, and simplified operating procedure greatly.
Description of drawings:
Fig. 1 is after the aluminium surface forms composite membrane, the polarization curve in 3.5%NaCl neutral solution.
Fig. 2 is the Bode figure of blank sample and the electrochemical impedance spectroscopy of film forming sample in neutral 3.5%NaCl solution.
As can be seen from Figure 1, behind the aluminium Surface Creation composite membrane, in 3.5%NaCl neutral solution, the current density of its negative electrode and anodic polarization curves all obviously diminishes, far below blank sample, this shows that composite membrane has suppressed cathode reaction and anode reaction in the corrosion process simultaneously, hinders the depolarising reaction of oxygen on anodic solution and the negative electrode, thereby plays good corrosion protection effect.
As can be seen from Figure 2, the resistance value of blank sample is far smaller than the resistance value of film forming sample, illustrates behind the aluminium Surface Creation composite membrane to have excellent corrosion resistance.
The specific embodiment:
Embodiment 1:
The preparation of film forming agent:
With 6g purity is that 99.99% cerous nitrate crystal is dissolved in the absolute ethyl alcohol of 80ml, adds the 20ml collodion then, fully stirs, and obtains the solution A of 60g/L.
With 15ml butyl titanate [Ti (OBu)
4] under stirring condition, be added drop-wise in the 60ml absolute ethyl alcohol, fully stir, add 4.8ml water again, be that 37% salt acid for adjusting pH value is 2～3 with concentration expressed in percentage by weight, fully stir the acquisition solution B.
22ml ethyl orthosilicate (TEOS) being dissolved in the 23ml absolute ethyl alcohol, adding 1.8ml water, is that 37% salt acid for adjusting pH value is 2～3 with concentration expressed in percentage by weight, stirs hydrolysis, the acquisition solution C.
With above-mentioned solution A: B: C=3.3 by volume: 1: 0.2 ratio is mixed, and fully stirs, and obtains the mixed sols film forming agent.
Film forming is handled:
Aluminium foil sample (LF21) after the degreasing is vertically immersed in the above-mentioned mixed sols that makes, leave standstill and make the colloidal sol surface steadily, the speed with 2～5cm/min outwards vertically lifts then, forms the film of layer of transparent on the aluminium foil specimen surface.Room temperature is placed, and treats to heat-treat behind the surface drying, and it at 400 ℃ of following roasting 60min, just can be formed thin film on the aluminium foil sample.
Embodiment 2:
The preparation of film forming agent:
With 5g purity is that 99.99% cerous nitrate crystal is dissolved in the absolute ethyl alcohol of 70ml, adds the 30ml collodion then, fully stirs, and obtains the solution A of 50g/L.
The 10ml tetraethyl titanate being added drop-wise under stirring condition in the 27ml isobutanol, after fully stirring, adding 3ml water again, is that 37% salt acid for adjusting pH value is 2～3 with concentration expressed in percentage by weight, fully stirs the acquisition solution B.
The 20ml methyl silicate being dissolved in the 30ml isobutanol, adding 1.6mol water, is that 37% salt acid for adjusting pH value is 2～3 with concentration expressed in percentage by weight, stirs hydrolysis, the acquisition solution C.
With above-mentioned solution A: B: C=6 by volume: 1: 0.3 ratio is mixed, and fully stirs, and obtains the mixed sols film forming agent.
Film forming is handled:
Aluminium foil sample (LY12) after the degreasing is vertically immersed in the mixed sols that makes, leave standstill and make the colloidal sol surface steadily, the speed with 2～5cm/min outwards vertically lifts then, forms the film of layer of transparent on the aluminium foil specimen surface.Room temperature is placed, and treats to heat-treat behind the surface drying, and it at 500 ℃ of following roasting 30min, just can be formed thin film on the aluminium foil sample.
Embodiment 3:
The preparation of film forming agent:
With 4g purity is that 99.99% cerous nitrate crystal is dissolved in the absolute ethyl alcohol of 60ml, adds the 40ml collodion then, fully stirs, and obtains the solution A of 40g/L.
The 10ml butyl titanate being added drop-wise in the 15ml absolute ethyl alcohol in stirring down, fully stirring, add 1.5ml water again, is that 99% vinegar acid for adjusting pH value is 2～3 with concentration expressed in percentage by weight, the acquisition solution B.
Dissolving 10ml ethyl orthosilicate adds 1.6ml water in the 30ml absolute ethyl alcohol, be that 99% vinegar acid for adjusting pH value is 2～3 with concentration expressed in percentage by weight, stirs hydrolysis, the acquisition solution C.
With above-mentioned solution A: B: C=10 by volume: 1: 0.5 ratio is mixed, and fully stirs, and obtains the mixed sols film forming agent.
Film forming is handled:
Aluminium foil sample (fine aluminium) after the degreasing is vertically immersed in the mixed sols that makes, leave standstill and make the colloidal sol surface steadily, the speed with 2～5cm/min outwards vertically lifts then, forms the film of layer of transparent on the aluminium foil specimen surface.Room temperature is placed, and treats to heat-treat behind the surface drying, and it at 450 ℃ of following roasting 45min, just can be formed thin film on the aluminium foil sample.
Performance test:
1. hydrophily test: with the test of angle of wetting measuring instrument, tested aluminium foil level is placed on the work top, drawing volume with microsyringe is the pure water of 10 μ L, vertically drops in tested aluminium foil surface, measures the angle of wetting θ of the globule at aluminium foil surface after 30 seconds.The results are shown in Table 1:
Table 1 angle of wetting measurement result
| The aluminium foil sample | The water droplet contact angle/° |
| |
6 8 5 56 |
From the data of table 1 as can be seen, after film forming of the present invention was handled, the water droplet contact angle of all samples showed that all less than 10 ° the aluminium foil of filming has good hydrophily.
2. water resistance test: reflect by the water dissolution rate.The sample of will filming is accurately weighed, and then sample is immersed in the running water down at 25 ℃, takes out behind 12h, 24h, the 48h, is dried to constant weight, weighing.The computational methods of water dissolution rate are as follows:
Water dissolution rate ω (%)=(m
1-m
2)/m
1* 100%
Wherein, m
1And m
2Be respectively the quality of sample before and after immersing.The results are shown in Table 2:
Table 2 water resistance test result
By the test result of table 2 as can be seen, after film forming of the present invention was handled, the water dissolution rate of filming was less with the variation of soak time, and the water dissolution rate is very little, and the variation at hydrophilic angle is also very little, and the appearance color of film does not have change yet.This shows that the hydrophilic corrosive-resistant film has water resistance preferably.
3. corrosion proof test
Sample with after the processing of the embodiment of the invention 1,2,3 film forming soaked 500 hours in neutral salt spray test and 5%NaCl solution, and the film forming aluminium foil does not have obvious rust staining, shows that the sample corrosion resistance is good.
Claims (3)
1. aluminium heater or aluminium foil surface hydrophilic corrosive-resistant filming method comprise that the preparation of film forming agent and film forming handle two steps, are specially:
(1) preparation of film forming agent: cerium salt is dissolved in the absolute ethyl alcohol, adds collodion then, the collodion of adding and the volume ratio of absolute ethyl alcohol are 1: 1.5～4, fully stir, and make the salting liquid A of 40～60g/L;
Titanate esters under stirring condition, being added drop-wise in the alcohols solvent, fully stirring, add a certain amount of water, is 2～3 with acid for adjusting pH value, obtains titanium alkoxide solution B, and wherein, the mol ratio of each component is: titanate esters: alcohols solvent: water=1: 9～24: 3～9;
Esters of silicon acis being dissolved in the alcohols solvent, adding a certain amount of water, fully stir hydrolysis, is 2～3 with acid for adjusting pH value, obtains the silicon alkoxide solution C, and wherein, the mol ratio of each component is: esters of silicon acis: alcohols solvent: water=1: 4～12: 1～2;
With above-mentioned solution be by volume: A: B: the ratio of C=3.3～10: 1: 0.2～0.5 is mixed, and fully stirs, and obtains the mixed sols film forming agent;
(2) film forming is handled: the aluminium heater after the degreasing or aluminium foil sample are vertically immersed in the mixed sols film forming agent that step (1) makes, leave standstill, behind to be filmed dose of liquid level stabilizing, the vertical proposition, after room temperature is placed surface drying, 400 ℃～500 ℃ roastings 0.5～1 hour, can on aluminium heater or aluminium foil specimen surface, form the film of one deck hydrophilic corrosive-resistant.
2. according to the method for claim 1, it is characterized in that: adopt cerous nitrate or cerous sulfate to prepare salting liquid A in the step (1), adopt tetraethyl titanate, isopropyl titanate or butyl titanate to prepare titanium alkoxide solution B, adopt methyl silicate or ethyl orthosilicate to prepare the silicon alkoxide solution C, when preparation salting liquid B and C, used alcohols solvent is ethanol, propyl alcohol, isopropyl alcohol, butanols or isobutanol, with the pH value of hydrochloric acid, acetic acid, nitric acid or sulfuric acid regulation solution; The speed that aluminium heater or aluminium foil sample outwards lift in the step (2) is 2～5 cm per minute.
3. according to the method for claim 1 or 2, it is characterized in that: step (1) adopts cerous nitrate to prepare salting liquid A, adopt butyl titanate to prepare titanium alkoxide solution B, adopt ethyl orthosilicate to prepare the silicon alkoxide solution C, when preparation salting liquid B and C, used alcohols solvent is ethanol or isobutanol, with the pH value of hydrochloric acid or acetic acid regulator solution.
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|---|---|---|---|
| CNB2004100743462A CN100372618C (en) | 2004-09-10 | 2004-09-10 | Aluminium heat exchanger and aluminium foil surface hydrophilic corrosive-resistant filming method |
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|---|---|---|---|
| CNB2004100743462A CN100372618C (en) | 2004-09-10 | 2004-09-10 | Aluminium heat exchanger and aluminium foil surface hydrophilic corrosive-resistant filming method |
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|---|---|
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| CN100372618C true CN100372618C (en) | 2008-03-05 |
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| CN102199371B (en) * | 2011-04-06 | 2012-09-12 | 重庆大学 | Method for preparing photoinduced ultra hydrophilic automatically cleaning paint |
| CN108854533B (en) * | 2018-06-29 | 2022-01-18 | 四川大学 | Ultrapure oxygen-16 water distillation filler and preparation process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256579A (en) * | 1999-03-08 | 2000-09-19 | Nippon Light Metal Co Ltd | Hydrophilic coating material composition and hydrophilic coating film formed from the same composition |
| CN1323976A (en) * | 2000-05-12 | 2001-11-28 | 日本油漆株式会社 | Hydrophilic treatment method for heat-exchanger, and heat-exchanger treated by said method |
| CN1336342A (en) * | 2001-08-17 | 2002-02-20 | 长春新世纪纳米技术研究所 | Self-cleaning nanometer level glass and its production process |
| KR20020088029A (en) * | 2001-05-16 | 2002-11-25 | 한라공조주식회사 | Heat exchanger having hydrophilic, deodorization and antibacterial coating, and method for fabricating coating of heat exchanger |
| CN1424282A (en) * | 2003-01-06 | 2003-06-18 | 华东理工大学 | Titania nano film containing rare earth and silica and production thereof |
-
2004
- 2004-09-10 CN CNB2004100743462A patent/CN100372618C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000256579A (en) * | 1999-03-08 | 2000-09-19 | Nippon Light Metal Co Ltd | Hydrophilic coating material composition and hydrophilic coating film formed from the same composition |
| CN1323976A (en) * | 2000-05-12 | 2001-11-28 | 日本油漆株式会社 | Hydrophilic treatment method for heat-exchanger, and heat-exchanger treated by said method |
| KR20020088029A (en) * | 2001-05-16 | 2002-11-25 | 한라공조주식회사 | Heat exchanger having hydrophilic, deodorization and antibacterial coating, and method for fabricating coating of heat exchanger |
| CN1336342A (en) * | 2001-08-17 | 2002-02-20 | 长春新世纪纳米技术研究所 | Self-cleaning nanometer level glass and its production process |
| CN1424282A (en) * | 2003-01-06 | 2003-06-18 | 华东理工大学 | Titania nano film containing rare earth and silica and production thereof |
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