EP0274738A1 - Verfahren zur Erzeugung von Überzügen auf Aluminiumoberflächen - Google Patents

Verfahren zur Erzeugung von Überzügen auf Aluminiumoberflächen Download PDF

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Publication number
EP0274738A1
EP0274738A1 EP87119191A EP87119191A EP0274738A1 EP 0274738 A1 EP0274738 A1 EP 0274738A1 EP 87119191 A EP87119191 A EP 87119191A EP 87119191 A EP87119191 A EP 87119191A EP 0274738 A1 EP0274738 A1 EP 0274738A1
Authority
EP
European Patent Office
Prior art keywords
polymer
monomer
coating
layer
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP87119191A
Other languages
German (de)
English (en)
French (fr)
Inventor
Ryosuke Nihon Parkerizing Co. Ltd. Sako
Takao Nihon Parkerizing Co. Ltd. Ogino
Motoki Nihon Parkerizing Co. Ltd. Kanazawa
Akira Nihon Parkerizing Co. Ltd. Nishihara
Hiroshi Nihon Parkerizing Co. Ltd. Okita
Yoshinori Nihon Parkerizing Co. Ltd. Sakamoto
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nihon Parkerizing Co Ltd
Original Assignee
Nihon Parkerizing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nihon Parkerizing Co Ltd filed Critical Nihon Parkerizing Co Ltd
Publication of EP0274738A1 publication Critical patent/EP0274738A1/de
Withdrawn legal-status Critical Current

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D5/00Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
    • B05D5/04Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a surface receptive to ink or other liquid
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00Metallic substrate
    • B05D2202/20Metallic substrate based on light metals
    • B05D2202/25Metallic substrate based on light metals based on Al
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00Pretreatment of the substrate
    • B05D2350/20Chromatation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2350/00Pretreatment of the substrate
    • B05D2350/60Adding a layer before coating
    • B05D2350/63Adding a layer before coating ceramic layer
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2401/00Form of the coating product, e.g. solution, water dispersion, powders or the like
    • B05D2401/20Aqueous dispersion or solution
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F13/00Arrangements for modifying heat-transfer, e.g. increasing, decreasing
    • F28F13/18Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28HEAT EXCHANGE IN GENERAL
    • F28FDETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
    • F28F2245/00Coatings; Surface treatments
    • F28F2245/02Coatings; Surface treatments hydrophilic

Definitions

  • the invention relates to a method for forming hydrophilic coatings on aluminum surfaces using aqueous polymer solutions or dispersions.
  • the effectiveness of the heat radiation / cooling should be as high as possible.
  • the radiation and cooling components are therefore designed with the largest possible surface area and the distance between them is kept extremely short. If a heat exchanger is used for cooling, this leads to condensation of air humidity on the heat exchanger surface, especially in the spaces between. Water condensed in this way forms droplets, and the more hydrophobic the surface of the ribs, the more so is. The water droplets accumulate in the interstices and prevent air from passing through to an increased extent, which ultimately leads to reduced heat exchanger performance.
  • heat exchanger fans cause the droplets to splash around in the interstices of the fins, so that the drip catchers fitted under the heat exchangers cannot prevent the droplets from falling onto adjacent areas and contaminating them.
  • Japanese Patent Laid-Open Sho 60-101156 (1985) relates to a chemical for forming a hydrophilic layer on aluminum containing alkali silicate and carbonyl compounds (aldehydes, esters, amides, etc.).
  • Japanese Patent Laid-Open Sho 59-205596 describes a method in which organic compounds are applied using an organic solvent.
  • the organic compounds are, in particular, acrylic resins, resins based on epoxy or urethane, vinyl resins, such as, for example, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, resins based on styrene, phenolic resins, fluorine resins, silicone resins, diaryl phthalate resins, polycarbonate resins, polyamide resins, alkyd resins, polyester resins , Urea resins, melamine resins, polyacetal resins and cellulose resins.
  • acrylic resins resins based on epoxy or urethane
  • vinyl resins such as, for example, polyvinyl chloride, polyvinyl acetate, polyethylene, polypropylene, resins based on styrene, phenolic resins, fluorine resins, silicone resins, diaryl phthalate resins, poly
  • polyacrylamide as a chemical for the hydrophilic treatment is known from the Japanese patents Sho-60-101156 and Sho 61-8598.
  • This compound can be mixed uniformly with water as long as the polyacrylamide content is low. With increasing concentration, which is caused by the drying process etc., the alkali silicate and polymer split into two phases, which often leads to non-reproducible results.
  • polyacrylamide is applied to the hydrophilic inorganic film to form a hydrophilic organic layer.
  • the degree of polymerization of the polyacrylamide is adjusted so that removal of the lubricating oil used for processing by means of a solvent is possible without problems and that the organic polymer layer remaining on the hydrophilic inorganic layer after degreasing fills any specks in said inorganic layer.
  • a crosslinking agent composed of Zr, Ti compounds etc. can bring about a crosslinking between the polyacrylamide and the hydrophilic group, but in such a way that there is no total crosslinking of said group.
  • the last layer remaining after solvent cleaning of the heat exchanger fins is an inorganic hydrophilic layer, which is achieved by applying a silicate or boehmite layer as the base layer.
  • the object of the invention is to provide a process for producing hydrophilic coatings on aluminum surfaces which does not have the disadvantages of the known, in particular the aforementioned processes, leads to coatings of high hydrophilicity which, even over a long period of time, are adherent and corrosion-protecting.
  • the coatings should be processable in a simple manner with coating agents, which are in particular free of organic solvents, and be able to withstand any subsequent treatments (the effects of forces and heat).
  • a preferred embodiment of the invention consists in subsequently applying and drying a water glass solution on the polymer coating.
  • a further expedient embodiment of the invention provides for a solution or dispersion of polymer A and / or B to be applied to the surfaces which additionally contains crosslinking agent C.
  • the water-soluble crosslinking agent C can be inorganic, organic or else combined inorganic / organic.
  • Suitable inorganic crosslinking agents are, in particular, metal compounds which can form a complex compound with the water-soluble polymer or copolymer. Such compounds, of which those with a coordination number of more than 4 are particularly effective, can be found in Table 1.
  • Cr, Ti, Al and Zr compounds those with a very high water solubility are particularly effective, for example chromic acid, Bichromic acid and its salts, di-isopropoxy-titanium-bis-acetylazetone, the reaction product of lactic acid and alkoxy-titanium compound, zirconyl nitrate, zirconyl acetate, zirconylammonium carbonate, fluorozirconic acid and its salts, aluminum sulfate etc.
  • chromic acid Bichromic acid and its salts
  • di-isopropoxy-titanium-bis-acetylazetone the reaction product of lactic acid and alkoxy-titanium compound
  • zirconyl nitrate zirconyl acetate
  • zirconylammonium carbonate zirconylammonium carbonate
  • fluorozirconic acid and its salts aluminum sulfate etc.
  • Suitable water-soluble organic crosslinking agents are water-soluble, neutralized polyisocyanate and / or water-soluble polymethylol, polyglycidyl, polyaziridyl compound, for example polyisocyanate neutralized with NaHSO3 (for example ELASTRON: product from DAI-ICHI KOGYO SEIYAKU Co., Ltd.), methylolmelamine, Methylol urea, methylol polyacrylamide, diglycidyl ether of polyethylene oxide, diaziridyl polyethylene oxide etc.
  • NaHSO3 for example ELASTRON: product from DAI-ICHI KOGYO SEIYAKU Co., Ltd.
  • Suitable combined inorganic / organic crosslinking agents are, for example, compounds of Cr, Ti, Al and Zr as inorganic water-soluble compounds and neutralized polyisocyanates, polymethylol / polyglycidyl / polyaziridyl compounds as organic water-soluble compounds.
  • the amount of crosslinking agent (C) used depends on its type. It also plays a role whether the (co) polymer layer serves as a base layer and mainly for corrosion protection or is intended as a single layer. In general, the amount used per 100 parts by weight of polymer or copolymer will be 1 to 400 parts by weight, preferably 5 to 200 parts by weight.
  • (IV) is a nonionic monomer suitable for copolimerization; concrete examples are: 2-hydroxy (metha) acrylate Diazetone acrylamide Methylolacrylamide Acryloylmorpholine Acrylonitrile (Metha) acrylic ester Styrene Vinyl acetate
  • M stands for one of the following formulas 1) to 5).
  • (III) can also be represented by the general formula: or its copolymer with an unsaturated compound containing a carboxylic acid group or anhydride group of maleic anhydride, itaconic acid etc. or a sulfo or phospho group.
  • N has the meaning from 6) to 12).
  • the application can be by dipping, spraying, brushing, rolling or flow
  • the molecular weight should be set to less than 2,000,000, preferably 1,000,000, to avoid that the coating agent pulls strings .
  • suitable values have to be determined according to the coating method used and the desired layer thickness.
  • a further advantageous embodiment of the invention provides for a boehmite layer or a chemical conversion coating, such as a chromate coating, to be applied beforehand.
  • a direct coating the addition of chromic acid, bichromic acid or their salts to the polymer solution particularly effective.
  • these forms of treatment may have a synergistic effect by producing a particularly excellent surface quality.
  • An improvement in the hydrophilic properties of the rib can also be achieved if such an organic polymer layer is applied to a silicate film. If necessary, an organic layer of high hydrophilicity can also be applied to a double layer consisting of a base layer with high corrosion resistance and a sufficiently hydrophilic, even top layer. In this way it is avoided that the formers are exposed to hydrophilic layers such as silica gel and water glass, so that associated problems of tool wear during subsequent processing are eliminated.
  • Corrosion inhibitors such as Corrosion inhibitors, fillers, pigments, surfactants, foam inhibitors, leveling agents, antibacterial / antifungal agents, etc. can be added as long as they do not interfere with the results intended by this invention.
  • water-soluble solvents such as alcohol, ketone, cellosolve in small amounts.
  • the stability of the coating solution varies depending on the composition. In general, it is advisable to design the solution or dispersion in such a way that when a cationic polymer is used it is used in the neutral to acidic range and when an anionic polymer is used it is used in the neutral to alkaline range.
  • the use of the amphoteric polymer close to the isoelectric point should be avoided as the polymer will then experience deposits / cleavages.
  • crosslinking agents are used under the conditions e.g. applied in terms of pH, which are common for them.
  • water glass with an SiO2 / M2O ratio (M stands for Na, K or Li) of 2: 5 is generally used, although there are no special limits here.
  • concentration of the aqueous silicate solution can be set as long as long as an effective hydrophilic surface, i.e. a simple coating is guaranteed.
  • a 0.1 - 5 ⁇ silicate layer is obtained after heating / drying.
  • a thickness of less than 0.1 ⁇ does not result in sufficient long-term hydrophilicity, while more than 5 ⁇ often leads to insufficient hardening (water insolubility) or cracking on the layer, which affects the performance of the heat exchanger.
  • polymer i.e. a water-soluble acrylate to water glass effectively prevents cracking.
  • the heating / drying conditions for silicate should be in the range of 100 - 250 ° C and 20 s - 10 min, with shorter times for higher temperatures and longer times for lower temperatures.
  • the present invention makes it possible to use polymer crosslinked with water-soluble crosslinking agent for coating aluminum because the film formed in the process becomes water-insoluble.
  • excellent corrosion resistance is achieved.
  • a coating with the aforementioned excellent properties is particularly suitable for the treatment of heat exchanger surfaces which are made from aluminum.
  • Water droplets of 1 to 2 mm in diameter were placed on a coated surface and the contact angle using a device for measuring the surface contact angle, model CA-P, manufactured by Kyowa Kaimenkagaku Co., Ltd. certainly. Both fresh layers shortly after application and those that had been immersed in sea water for a week were tested.
  • test specimen was immersed in flowing water at room temperature for 8 hours and then dried at 80 ° C. for 16 hours. After repeating this cycle five times, the water contact angle was measured.
  • Aluminum plate pretreated with chromium chromate was coated with an aqueous solution containing 10 g / l of polymer, which was prepared by methylating the amido group of a copolymer obtained from 95 mol% acrylamide and 5 mol% acrylic acid to 11%.
  • the test specimen was dried at 250 ° C. in an electric oven. The layer weight obtained was 0.3 g / m2.
EP87119191A 1986-12-29 1987-12-24 Verfahren zur Erzeugung von Überzügen auf Aluminiumoberflächen Withdrawn EP0274738A1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP61315818A JP2523114B2 (ja) 1986-12-29 1986-12-29 アルミニウムの親水性処理方法
JP315818/86 1986-12-29

Publications (1)

Publication Number Publication Date
EP0274738A1 true EP0274738A1 (de) 1988-07-20

Family

ID=18069924

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87119191A Withdrawn EP0274738A1 (de) 1986-12-29 1987-12-24 Verfahren zur Erzeugung von Überzügen auf Aluminiumoberflächen

Country Status (7)

Country Link
US (1) US4783224A (ja)
EP (1) EP0274738A1 (ja)
JP (1) JP2523114B2 (ja)
AU (1) AU588149B2 (ja)
CA (1) CA1332329C (ja)
DE (1) DE3744006A1 (ja)
MX (1) MX168763B (ja)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0672467A1 (de) * 1994-03-18 1995-09-20 Basf Aktiengesellschaft Verfahren zur Modifizierung von Metalloberflächen
EP0676250A1 (en) * 1994-04-08 1995-10-11 Nippondenso Co., Ltd. Coated aluminium-containing material and process for producing it
EP1900782A1 (de) * 2006-09-18 2008-03-19 KCH Group GmbH Säurebeständige Hochtemperaturbeschichtung
FR2930023A1 (fr) * 2008-04-09 2009-10-16 Valeo Systemes Thermiques Procede de traitement de surface d'un echangeur de chaleur resistant a la corrosion

Families Citing this family (22)

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Publication number Priority date Publication date Assignee Title
JP2506924B2 (ja) * 1988-04-20 1996-06-12 日本パーカライジング株式会社 アルミニウム製熱交換器
JPH02219876A (ja) * 1989-02-21 1990-09-03 Sumitomo Light Metal Ind Ltd 親水性被覆剤、フィン用アルミニウム又はアルミニウム合金板材および熱交換器
US5211989A (en) * 1992-04-13 1993-05-18 Morton Coatings, Inc. Clear hydrophilic coating for heat exchanger fins
CA2123034C (en) * 1993-05-07 2000-10-17 Katsuyoshi Yamasoe Hydrophilic surface treating aqueous solution, hydrophilic surface treating method and hydrophilic surface treating film
CA2126887A1 (en) * 1993-08-16 1995-02-17 Betzdearborn Inc. Chromium and fluoride free metal treatment
JPH07268274A (ja) * 1994-04-01 1995-10-17 Kansai Paint Co Ltd 親水化処理用組成物および親水化処理方法
US5700523A (en) * 1996-06-03 1997-12-23 Bulk Chemicals, Inc. Method for treating metal surfaces using a silicate solution and a silane solution
AT403914B (de) * 1996-09-24 1998-06-25 Krems Chemie Ag Sprühgetrocknete dispersionen, verfahren zu ihrer herstellung und deren anwendung
JPH10182916A (ja) * 1996-10-21 1998-07-07 Nippon Paint Co Ltd N複素環を含むアクリル樹脂含有金属表面処理組成物、処理方法及び処理金属材料
EP0933408B1 (en) 1996-10-21 2003-02-12 Nippon Paint Co., Ltd. Metal surface treatment for food can using an acrylic resin containing composition and the so treated can
US5910532A (en) * 1997-05-29 1999-06-08 The Dow Chemical Company Multisolvent-based film-forming compositions
US5959016A (en) * 1997-07-31 1999-09-28 The Dow Chemical Company Composition for preparing a solvent-resistant coating
CA2301063A1 (en) * 1997-08-14 1999-02-25 David R. Mccormick Hydrophilicizing surfaces, especially aluminum
EP0937757A1 (en) 1998-02-19 1999-08-25 Nihon Parkerizing Co., Ltd. Composition and method for hydrophilic treatment of aluminium or aluminium alloy, and use of the composition
US6191211B1 (en) 1998-09-11 2001-02-20 The Dow Chemical Company Quick-set film-forming compositions
JP4008620B2 (ja) 1999-06-04 2007-11-14 カルソニックカンセイ株式会社 アルミニウム合金製熱交換器
WO2001098376A1 (fr) * 2000-06-22 2001-12-27 Idemitsu Petrochemical Co., Ltd. Polymere reticule a base d'acide carboxylique insature, son procede de production et matiere absorbant l'eau
US6659171B2 (en) * 2001-03-27 2003-12-09 Nippon Paint Co., Ltd. Hydrophilic modification method and heat exchanger treated thereby
DE10316476A1 (de) * 2003-04-09 2004-10-28 Stockhausen Gmbh & Co. Kg Wasserlösliche Polymere mit verbessertem Löseverhalten, deren Herstellung und Verwendung
JP2007126623A (ja) * 2005-10-05 2007-05-24 Dainippon Ink & Chem Inc 床用水性塗料および床塗工方法
US9574832B2 (en) * 2007-12-28 2017-02-21 Intel Corporation Enabling an aluminum heat exchanger with a working fluid
JP2017043744A (ja) * 2015-08-28 2017-03-02 日本パーカライジング株式会社 表面処理剤、皮膜の製造方法及び皮膜付き金属材料

Citations (5)

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US4205152A (en) * 1976-12-09 1980-05-27 Nippon Paint Co., Ltd. Thermosetting resin and its production
US4335829A (en) * 1978-11-29 1982-06-22 Ppg Industries, Inc. Coated metal surfaces and method of coating metal surfaces with aqueous resinous dispersions of epoxy resins and acrylic polymers
US4421789A (en) * 1981-06-30 1983-12-20 Occidental Chemical Corporation Process for treating the surfaces of aluminum heat exchangers
US4588025A (en) * 1983-11-07 1986-05-13 Showa Aluminum Corporation Aluminum heat exchanger provided with fins having hydrophilic coating
EP0200546A1 (en) * 1985-04-30 1986-11-05 Nippondenso Co., Ltd. Method of protecting a metal surface

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JPS5173938A (en) * 1974-12-25 1976-06-26 Nippon Packaging Kk Aruminiumuoyobi sonogokinnohyomenshoriho
JPS56119782A (en) * 1980-02-25 1981-09-19 Nippon Chem Ind Co Ltd:The Chromate treating agent and chromate treatment using this
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JPS6199679A (ja) * 1984-10-19 1986-05-17 Nisshin Steel Co Ltd 有機被覆処理溶融アルミニウムめつき鋼板
JPS61227877A (ja) * 1985-03-29 1986-10-09 Sumitomo Light Metal Ind Ltd 熱交換器用アルミニウムフイン材の表面処理方法

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Publication number Priority date Publication date Assignee Title
US4205152A (en) * 1976-12-09 1980-05-27 Nippon Paint Co., Ltd. Thermosetting resin and its production
US4335829A (en) * 1978-11-29 1982-06-22 Ppg Industries, Inc. Coated metal surfaces and method of coating metal surfaces with aqueous resinous dispersions of epoxy resins and acrylic polymers
US4421789A (en) * 1981-06-30 1983-12-20 Occidental Chemical Corporation Process for treating the surfaces of aluminum heat exchangers
US4588025A (en) * 1983-11-07 1986-05-13 Showa Aluminum Corporation Aluminum heat exchanger provided with fins having hydrophilic coating
EP0200546A1 (en) * 1985-04-30 1986-11-05 Nippondenso Co., Ltd. Method of protecting a metal surface

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0672467A1 (de) * 1994-03-18 1995-09-20 Basf Aktiengesellschaft Verfahren zur Modifizierung von Metalloberflächen
EP0676250A1 (en) * 1994-04-08 1995-10-11 Nippondenso Co., Ltd. Coated aluminium-containing material and process for producing it
US5538078A (en) * 1994-04-08 1996-07-23 Nippondenso Co., Ltd. Aluminum-containing metal composite material and process for producing same
EP1900782A1 (de) * 2006-09-18 2008-03-19 KCH Group GmbH Säurebeständige Hochtemperaturbeschichtung
FR2930023A1 (fr) * 2008-04-09 2009-10-16 Valeo Systemes Thermiques Procede de traitement de surface d'un echangeur de chaleur resistant a la corrosion

Also Published As

Publication number Publication date
AU8299387A (en) 1988-06-30
US4783224A (en) 1988-11-08
JP2523114B2 (ja) 1996-08-07
AU588149B2 (en) 1989-09-07
MX168763B (es) 1993-06-07
JPS63171684A (ja) 1988-07-15
CA1332329C (en) 1994-10-11
DE3744006A1 (de) 1988-07-07

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