CN1026902C - Hydrophilic corrosion-resistant film former used on surface of aluminium heat exchanger and Al foil and film forming process - Google Patents

Hydrophilic corrosion-resistant film former used on surface of aluminium heat exchanger and Al foil and film forming process Download PDF

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Publication number
CN1026902C
CN1026902C CN 93107761 CN93107761A CN1026902C CN 1026902 C CN1026902 C CN 1026902C CN 93107761 CN93107761 CN 93107761 CN 93107761 A CN93107761 A CN 93107761A CN 1026902 C CN1026902 C CN 1026902C
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China
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forming agent
aluminium
membrane
film forming
acid
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Expired - Fee Related
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CN 93107761
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CN1079998A (en
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陈旭俊
陈振家
李锐
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BEIJING COLLEGE OF CHEMICAL TECHNOLOGY
Beijing University of Chemical Technology
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BEIJING COLLEGE OF CHEMICAL TECHNOLOGY
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • C23C22/66—Treatment of aluminium or alloys based thereon

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)

Abstract

The present invention relates to an aluminium heat exchanger, a hydrophile anticorrosive film forming agent of aluminium foil surfaces and a film forming method. The film forming agent is prepared from preparations, such as amine salts, compounds containing halogen, polyphosphate, etc. The film forming method comprises the preparation of the film forming agent and the film forming technology. When the film forming agent is used for processing the aluminium heat exchanger and aluminium foil, the existing film forming technology can be greatly simplified, and the surface of the processed aluminium materials can form an anticorrosive hydrophile layer. Simultaneously, the surface hardness of aluminium is not increased, and the corrosion of treating liquid for copper pipes of the heat exchanger is avoided. The film forming agent can be used for the anticorrosive hydrophile processing on the surface of the aluminium heat exchanger for an air conditioner.

Description

Hydrophilic corrosion-resistant film former used on surface of aluminium heat exchanger and Al foil and film forming process
The present invention relates to the hydrophilic corrosion-resistant film former used and film of a kind of aluminium heater and aluminium foil surface, surface filming agent of particularly a kind of idle call aluminium heater hydrophilic corrosion-resistant and film.
Interchanger is one of key part of conditioner, and its radiating fin is an aluminum, if used aluminium foil surface is dealt with improperly, not only can cause aluminium foil corrosion, and water of condensation forms " water bridge " between fin, influences heat exchange efficiency, reduces refrigerating duty, increases energy consumption.The hydrophilic treatment method of present aluminium foil, the aqueous solution of employing amine that has or hydramine etc., soak aluminium heater to produce the diaspore film at comparatively high temps (70-100 ℃) long-time (30-60min), aluminium foil after the processing can produce hydrophilic surface, but owing to the copper pipe on amine and the hydramine heat exchanging device has serious abrasion to limit its widespread use.All there are serious drawbacks such as the pollution of chromium, the loss of filming, coating thermal resistance be excessive in the employing chromium-silicon that has-aluminium method, antirust oil process, coating method etc. and are difficult to promote.
Two patented technologies (JP86-222629, JP86-222630) that announce in the Japan special permission Room have provided the surface treatment manufacturing process of two kinds of heat exchange materials and heat exchanger.First kind of treatment process the aluminium of manufacturing heat exchanger by coating to form hydrophilic surface, promptly aluminium foil is immersed the NaICl aqueous solution of the 200PPM of pH10.5, immerse water glass again, wash then to form hydrophilic layer, further apply the tripoly phosphate sodium STPP of 1000PPM again, 150 ℃ of dryings, formed surface, contact angle 10 degree of water.Another kind of treatment process is that the aluminium foil of cleaning is applied a kind of hydrophilic inorganic materials, as SiO 2Colloidal sol, with the mixture process of inorganic phosphate or phosphite and nonionogenic tenside, dry post-treatment is a heat exchanger again.Though these class methods can be carried out hydrophilic treatment to aluminium foil or aluminium heater, have following problem:, adopt NaOCl processing reaction condition to be not easy to control 1, because NaOCl is extremely unstable; 2, Na 3PO 4And the treatment agent of other type oxide film is (as Na 3PO 4, Na 2SiO 3, Na 2CrO 4) aluminium handled, Cl is being arranged -Environment in be easy to generate pitting; 3. apply SiO 4The method of colloidal sol causes the surface hardness of aluminium to improve, impair towards tool work-ing life; 4. multiple tracks treatment process, formality is numerous and diverse, condition harshness (temperature height, time long).
The purpose of this invention is to provide a kind of corrosion-resistant film former used and film of surface hydrophilic that is used for aluminium heater and aluminium foil.Use this membrane-forming agent to handle aluminium heater and aluminium foil, can simplify the film-forming process of prior art greatly, and the aluminium material surface of handling can generate one deck hydrophilic layer against corrosion, simultaneously do not increase the aluminium surface hardness, and can avoid the corrosion of the corrosion of copper pipe on the treatment solution heat exchanging device and cupric ion aluminium.
Main points of the present invention: hydrophilic corrosion-resistant surface filming provided by the invention agent, its essentially consist and concentration range are:
Amine salt 0.06-50g/l
Halogen contained compound 0.2-75g/l
Pyrrole and derivative 5-1000mg/l thereof
Polyphosphoric acid salt 0.4-55g/l
Basic cpd 10-200g/l
Froth breaking, solubility promoter 0.01-5g/l
Amine salt is by amine and mineral acid or organic acid reaction generation in the membrane-forming agent, purpose be with membrane-forming agent in other component act synergistically on the aluminium surface, can generate amorphous hydrophilic film against corrosion rapidly, form membrane-forming agent with this amine salt form and overcome in the prior art amine and hydramine the serious abrasion of copper pipe.Said amine can be aliphatic amide and diamines and the hydramine etc. of carbon content at 8-18; Said mineral acid or organic acid can be HNO 2, HCl, H 2SO 4, H 3PO 4, H 3BO 3, H 2M 0O 4Reach acetic acid, sebacic acid, lauric acid, Whitfield's ointment, phenylformic acid etc.
Halogen contained compound in the membrane-forming agent can be a halogenide, as KF, NaF, NH 4F, KBr, NaBr, LiCl, NaCl, NH 4Cl, KCl, KI, NaI and H 2SIF 6Deng halogen silicic acid and salt thereof.
Basic cpd in the membrane-forming agent can be NaOH, KOH, Na 2CO 3, Na 3PO 4, Na 2SiO 3, K 2SiO 3, NaAc, KAc etc., it mainly acts on is to make membrane-forming agent have certain basicity.In phenolphthalein alkalinity, the basicity of this membrane-forming agent can be controlled in the 0.05-1.00mol/l scope, with the effect of 0.1-0.4mol/l for well.
The present invention adopts pyrrole and derivative thereof, to reduce aluminium to greatest extent because of Cu 2+Exist and the tendency of generation pitting and the possibility of growth white powder.
In above-mentioned membrane-forming agent, add a little silicone antifoam agent and co-solvent, to guarantee carrying out smoothly of continuous processing technique.
The 0.01%-0.1% that the defoamer usage quantity accounts for the membrane-forming agent total amount is for well.
Film of the present invention comprises membrane-forming agent preparation and film-forming process two portions.
The compound method of membrane-forming agent is as follows: by the concentration measurement of the membrane-forming agent of giving, basic cpd and polyphosphoric acid salt is water-soluble, be heated to the 50-90 degree, add pyrrole or derivatives thereof and solubility promoter etc. again, fully stir, dissolving, add amine salt and defoamer again, be stirred to evenly, leave standstill, remove insoluble impurity, become light blue clear solution and be membrane-forming agent.
Film-forming process is as follows: after aluminium heater or aluminium foil are carried out cleaning and degreasing, static state is soaked entirely in membrane-forming agent, temperature ℃ all can by room temperature to 90, having evenly fine and closely woven bubble to produce in several minutes later on to the aluminium surface proposes, behind the water hydro-peening, promptly disposed in 1-15 minute 140-280 ℃ environment baking.
Handle aluminium heater and aluminium foil with membrane-forming agent provided by the invention, its surface forms amorphous film, have good wetting ability, corrosion stability, persistence, and the corrosion of inhibition copper pipe, can make " water bridge " between heat exchanger fin to disappear mildewproof bacterium, thereby heat exchange efficiency improves, refrigerating duty increases, and windage and energy consumption descend, and the minitype high-performanceization of conditioner can realize.Surface film hardness ratio base material hardness owing to generation is low again, thereby can reduce towards the corruption of tool and decrease, and is easy to machine-shaping.This film-forming process is simple, has simplified existing technology greatly, makes it easy system, and is easy to control, is very suitable for applying.Handle the interchanger and the used aluminium foil thereof of KC-18, KC-35 conditioner with this membrane-forming agent and film technique, can reach following effect:
1. film outward appearance: silver gray.
2. film wetting ability and life-span: new film forming aluminium flake, the contact angle of water are 0 degree; The room temperature drying and watering cycle is greater than 300 times, and the contact angle of water is less than 25 degree; Tap water soaked 120 days entirely, and water contact angle is less than 25 degree; Aluminium foil is attached on the ice cube, and at 40 degree Celsius, HR is greater than in 90 ℃ the damp and hot case, and condensation film is even.
3. the moisture-resistant of film is hot, 40 degree Celsius, and HR is greater than 90%, and greater than 500 hours, the film forming aluminium foil did not have obvious corrosion.
4. the resistance to salt water of film: room temperature, 5%NaCl solution soaks entirely, and greater than 500 hours, the film forming aluminium foil did not have obvious corrosion, and the contact angle of water is less than 20 degree.
5. the NaOH solution of the anti-cleaning performance of film: pH9.8 or 4%SUC-Q clean-out system and gasoline, acetone, room temperature was soaked 2 hours entirely, the outward appearance no change, the contact angle of water is less than 10 degree, and weightlessness is 0.
6. the thermotolerance of film and flex resistance: 400 ℃ of bakings 5 minutes, outward appearance no change.
7. the flex resistance of film: 20 * 8mm aluminium foil, come and go crooked 45 degree 10 times around the axle of radius 3.86mm, the flexure plane of aluminium foil, the contact angle of water still be to spend less than 10, show that pliability test do not make film forming obvious crackle.
8. the hardness of film: Vickers' hardness (Hv), the substrate 32.18 of aluminium, surface film 29.35, the hardness of surface film is less than the hardness of substrate.
9. the ventilation impedance of interchanger: KC-18 and KC-35 air-condition heat exchanger after film forming is handled, ventilation is constant under dried wet state.
10. the refrigerating duty of interchanger: the refrigerating duty of the KC-18 after the film forming, KC-35 air conditioning machinery increases about 8%.
Embodiment 1:
The Na of 150g 2CO 3And the tripoly phosphate sodium STPP of 0.4g adds in a certain amount of tap water, be heated to about 70 ℃, stir and to make it dissolving, add the 10mgBZT(pyrrole again), 50g alcohol acid phosphate amine salt, 8.2gKBr, add water to 1 liter, stir to leave standstill and remove insolubles after 2 hours and be formed into film.
Aluminium foil was immersed in 25 ℃ of membrane-forming agents of being prepared 10 minutes after abundant degreasing entirely, took out, with baking 5 minutes in 200 ℃ baking oven behind the water rinse.
Result: the contact angle of aluminium foil water＜10 degree; Soak entirely more than 500 hours at room temperature 5%NaCl solution, the film forming aluminium foil does not have obvious corrosion.
Embodiment 2:
Membrane-forming agent preparation and film-forming process are with embodiment 1, and used each concentration of component is:
KCl 6.09g/l
Phosphorylethanolamine 250mg/l
Tolytriazole (pyrrole) 620mg/l
Sodium polyphosphate 0.41g/l
With NaOH the phenolphthalein alkalinity of solution is transferred to 0.45mol/l
Aluminium heater soaked under 45 ℃ 2 minutes entirely, toasted 5 minutes results at 190 ℃:
The contact angle of aluminium surface water＜10 degree.
Embodiment 3:
Membrane-forming agent preparation and film-forming process are with embodiment 1, and used each component concentration is:
Na 2SiF 631.0g/l
Phenylformic acid thanomin 1.30g/l
1-hydroxybenzene a pair of horses going side by side triazole (pyrrole) 20mg/l
Sodium polyphosphate 10g/l
Use Na 3PO 4The phenolphthalein alkalinity of solution is transferred to 0.51mol/l
Aluminium foil soaked 4 minutes in 50 ℃ of membrane-forming agents of being prepared entirely
Toasted 6 minutes down at 140 ℃
Result: the contact angle of aluminium surface water＜10 degree

Claims (7)

1, a kind of aluminium heater and aluminium foil surface is hydrophilic corrosion-resistant film former used, is characterised in that: its essentially consist and concentration range are as follows:
Amine salt 0.06-50g/l
Halogen contained compound 0.2-75g/l
Pyrrole and derivative 5-1000mg/l thereof
Polyphosphoric acid salt 0.4-55g/l
Basic cpd 10-200g/l
Froth breaking, solubility promoter 0.01-5g/l
2, membrane-forming agent according to claim 1 is characterized in that: amine salt is by amine and mineral acid or organic acid reaction generation.
3, membrane-forming agent according to claim 2 is characterized in that amine is meant aliphatic amide and diamines and the hydramine of carbon content at 8-18, and described mineral acid or organic acid can be HNO 2, HCl, H 2SO 4, H 3PO 4, H 3BO 3, H 2MoO 4Reach acetic acid, sebacic acid, lauric acid, Whitfield's ointment, phenylformic acid.
4, membrane-forming agent according to claim 1 is characterized in that: its halogen contained compound can be a halogenide as KF, NaF, NH 4F, KBr, NaBr, LiCl, NaCl, NH 4Cl, KCl, KI, NaI and H 2SIF 6Deng halogen silicic acid and salt thereof.
5, membrane-forming agent according to claim 1 is characterized in that: basic cpd can be NaOH, KOH, Na 2CO 3, Na 3PO 4, Na 2SiO 3, K 2SiO 3, NaAc, KAc etc. are in phenolphthalein alkalinity, the basicity of this membrane-forming agent can be controlled in the 0.05-1.00mol/l scope, with the effect of 0.1-0.4mol/l for well.
6, membrane-forming agent according to claim 1 is characterized in that: the concentration range of its defoamer: 0.1-1g/l can be silicone antifoam agent and co-solvent.
7, a kind of aluminium heater and aluminium foil hydrophilic corrosion-resistant surface filming method comprise membrane-forming agent preparation and film-forming process two portions, it is characterized in that:
(1) compound method is as follows: by described membrane-forming agent component of claim 1 and concentration dose, basic cpd and polyphosphoric acid salt is water-soluble, be heated to 50-90 ℃, add pyrrole or derivatives thereof and solubility promoter etc. again, fully stir, dissolving, add amine salt and defoamer again, be stirred to evenly, leave standstill, remove insoluble impurity;
(2) film-forming process is as follows: aluminium heater and aluminium foil are carried out cleaning and degreasing, static state is soaked entirely in membrane-forming agent, temperature by room temperature to 90 ℃ all can, propose in several minutes after having evenly fine and closely woven bubble to produce to the aluminium surface, behind the water hydro-peening, 140-280 ℃ environment baking 1-15 minute.
CN 93107761 1993-07-02 1993-07-02 Hydrophilic corrosion-resistant film former used on surface of aluminium heat exchanger and Al foil and film forming process Expired - Fee Related CN1026902C (en)

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Application Number Priority Date Filing Date Title
CN 93107761 CN1026902C (en) 1993-07-02 1993-07-02 Hydrophilic corrosion-resistant film former used on surface of aluminium heat exchanger and Al foil and film forming process

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Application Number Priority Date Filing Date Title
CN 93107761 CN1026902C (en) 1993-07-02 1993-07-02 Hydrophilic corrosion-resistant film former used on surface of aluminium heat exchanger and Al foil and film forming process

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CN1026902C true CN1026902C (en) 1994-12-07

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104169674A (en) * 2012-03-29 2014-11-26 株式会社神户制钢所 Aluminum fin material for heat exchanger

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102825260A (en) * 2012-06-28 2012-12-19 北京工业大学 Method for preparing super-hydrophilic infiltrating surface on aluminum surface
JP6300341B2 (en) * 2013-03-29 2018-03-28 株式会社神戸製鋼所 Aluminum fin material
CN109468630B (en) * 2018-10-30 2021-02-05 昆明理工大学 Electrogalvanizing alkaline golden passivation solution

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104169674A (en) * 2012-03-29 2014-11-26 株式会社神户制钢所 Aluminum fin material for heat exchanger
CN104169674B (en) * 2012-03-29 2016-08-24 株式会社神户制钢所 Aluminum fin material for heat exchanger

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