WO1985005131A1 - Traitement des metaux - Google Patents

Traitement des metaux Download PDF

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Publication number
WO1985005131A1
WO1985005131A1 PCT/US1985/000797 US8500797W WO8505131A1 WO 1985005131 A1 WO1985005131 A1 WO 1985005131A1 US 8500797 W US8500797 W US 8500797W WO 8505131 A1 WO8505131 A1 WO 8505131A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
metal
aqueous solution
salt
acid
Prior art date
Application number
PCT/US1985/000797
Other languages
English (en)
Inventor
Joseph E. Grimes, Jr.
Jeffrey I. Melzer
Original Assignee
Amchem Products, Inc.
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 Amchem Products, Inc. filed Critical Amchem Products, Inc.
Publication of WO1985005131A1 publication Critical patent/WO1985005131A1/fr
Priority to FI860032A priority Critical patent/FI860032A0/fi
Priority to DK2786A priority patent/DK2786A/da

Links

Classifications

    • 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
    • C23C22/68—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 aqueous solutions with pH between 6 and 8
    • 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
    • C23C22/06—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 aqueous acidic solutions with pH less than 6
    • C23C22/34—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 aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides

Definitions

  • This invention relates to the treatment of metals, and more particularly to the treatment of the zinc- surface of galvanized iron, galvanized steel, and the like to increase the resistance to corrosion of these metals.
  • compositions useful for this purpose are (i) acidic compositions and (ii) alkaline compositions.
  • Acidic compositions which form phosphate or chro- mate coatings on the zinc, are described in U.S. patent No. 3,297,494.
  • Alkaline coatings are widely used and examples of such coatings are disclosed in U.S. patents Nos. 3,444,007; 3,515,600 and 4,278,477.
  • an aqueous coating solution for metals such as galvanized iron and steel, aluminum, and ferrous metals such as steel, which contains:
  • a fluorometallic acid such as HBF4, H2SiF ⁇ , H2 iF ⁇ , and ⁇ ZrFg or an ammo ⁇ nium or alkali metal salt thereof;
  • hydrofluoric acid or a salt thereof or
  • a salt or a metal such as cobalt, copper, iron, manga ⁇ nese, nickel, strontium, and zinc, or a mix ⁇ ture of two or more of the foregoing
  • a sequestrant in an amount of from a 1:1 molar
  • ⁇ TiFg is the preferred fluorometallic acid and is commonly used as a 60% aqeous solution in the preparation of the compositions of this invention, and is preferably used in a quantity equal to about 1.4 g/liter of fluoride.
  • the salt of hydrofluoric acid can be an ammonium or alkali metal salt, or a fluoride of a metal of component (b) pro- vided the ranges for fluoride or metal are not exceeded.
  • Component (a)(iii) can be a mixture of (i) and (ii) in any proportion.
  • the preferred salts of cobalt, copper, iron, manganese, nickel, strontium and zinc in addition to the fluoride salts are their carbonates and bicarbonates. This serves to avoid the introduction of anions other than fluoride into the coating composition.
  • any salt of these metals may be used provided the anion which is introduced is not detrimental to the stability of the formulations and to the coating.
  • acceptable anions include sulfate and chloride.
  • sequestrant (c) is an optional ingre ⁇ + While the sequestrant (c) is an optional ingre ⁇ +, it is beneficial to have this component present since the presence of a sequestrant extends the useful pH range of the aqueous coating solution from 2 to 5, preferably about 4, without the sequestrant, to from 2 to 7 with the sequestrant.
  • Sequestrants that can be employed herein include the following compounds, seqestrant-active derivatives thereof, or alkali metal or ammonium salts thereof: nitrilotriacetic acid (NTA), ethylenediamine tetraacetic acid (EDTA), gluconic acid, and citric acid.
  • NTA nitrilotriacetic acid
  • EDTA ethylenediamine tetraacetic acid
  • gluconic acid gluconic acid
  • citric acid citric acid
  • a preferred polymer is ACRYSOL A-l, a 25% aqueous solution of a water-soluble polyacrylic acid having a molecular weight of up to about 500,000 (available from Rohm and Haas Co. ) .
  • ACRYSOL A-l a 25% aqueous solution of a water-soluble polyacrylic acid having a molecular weight of up to about 500,000 (available from Rohm and Haas Co. ) .
  • prior prepared concentrated aqueous solutions of the above ingredients which are added to water in an amount to provide a coating solution of the desired composition and concentration.
  • the concentrated aqueous solutions contain component (a) in a con ⁇ centration of at least about 1 g/1, preferably from about 1 to about 15 g/1 based on fluoride content, with the quantities of the other components increased pro ⁇ portionally so that dilution with water will give the aqueous coating solution compositions disclosed above.
  • the concentrate contains the desired ingre ⁇ washers in sufficient amounts so that a ten-fold dilu ⁇ tion by volume of the concentrate will provide an aqueous coating solution having the desired composition and concentration.
  • concentrates containing the above ingredients up to their solubility limits in water can also be used herein.
  • the concentrates can be formulated as described above, or quantities of bases such as NaOH, NH4OH, (NH4)2C03, or Na2C ⁇ 3 or an acid such as H2SO4 can be added so that upon dilution the correct pH is obtained for the coating solutions.
  • the coating solution can be applied by brushing, spraying, dipping, roll-coating and the like, with spraying or dipping being preferred.
  • the metal is preferably first cleaned, using an alkaline cleaner such as
  • RIDOLINE 1089 which is composed of sodium carbonate, sodium hydroxide, sodium polyphosphate, and surfactants and is available from Amchem Products, Inc. of Ambler, Pa.
  • the cleaned metal is then rinsed with water and sprayed with or dipped into the coating solution of the invention which is kept at 60°F to 160°F, preferably from 110°F to 140°F, for 1 to 300, preferably from 5 to 30 seconds.
  • the coated metals are then rinsed with water.
  • a final rinse such as a final chrome rinse with DEOXYLYTE 41, an aqueous solution containing chromic acid and formaldehyde (available from Amchem Products, Inc.), is then used.
  • a sic ⁇ cative coating can thereafter be applied to the metal.
  • the ingredients therein decrease in concentration and it becomes necessary to replace them. Although it is always possible to prepare a fresh solution, this is wasteful of materials present in the solution which can still be used , and is also time consuming. In practice, it is desirable to use a replenishing concentrate, and the concentrates disclosed above for use in forming the aqueous coating solutions of the invention can also be used as replenishing concentrates.
  • Examples 1 to 10 illustrate concentrate composi ⁇ tions according to this invention.
  • the desired amounts of the ingredients were dissolved in water and additional water added to bring the concentrate to the desired volume.
  • Examples 11 through 12 illustrate coating solu ⁇ tions prepared from various concentrates and the pro ⁇ Defines of treating galvanized metals with these coating solutions.
  • a coating solution was prepared by diluting 10 liters of the concentrate of Example 1 to 100 liters with deionized water. The pH of the solutions was adjusted to about 4.0 by the addition of ammonium hydroxide.
  • Armo G-60 and G-90 hot dipped galvanized steel panels were first cleaned by spraying for 15 sec. with an aqueous solution (1 oz/gal) of RIDOLINE 1089 at about 130°F. The panels were then rinsed with water and then immersed in the coating solution, prepared as described above, for 15 seconds at a temperature of about 130°F. The coated panels were then rinsed in water and dried. The protective coating was dark in color. The coated panels were very resistant to corrosion and the protec ⁇ tive coatings thereon possessed good adherence to sub ⁇ sequently applied siccative coatings such as polyester, polyester melamines, siliconized polyesters, fluorocar- bons, and the like using epoxy or acrylic primers.
  • siccative coatings such as polyester, polyester melamines, siliconized polyesters, fluorocar- bons, and the like using epoxy or acrylic primers.
  • Example 11 The procedure of Example 11 was repeated using the concentrate of Example 5.
  • the coating was somewhat lighter in color than the coating of Example 11. This is apparently due to the presence of the acrylic polymer.
  • the coating provided good protection against corrosion and possessed good adhesion to subsequently applied siccative coatings.
  • similar dark coatings providing good resistance to corrosion and having good adhesion to applied siccative coatings, were obtained.
  • the replenisher concentrate is added until the pH of the bath is brought into the operating range given above.
  • Replenisher concentrates for coating solutions containing other ingredients may be prepared by having in the replenisher concentrate the same fluorometallic acid and the same metallic ion which are present in the coating solution.
  • a coating solution was prepared by adding the following ingredients to deionized water:
  • Armo G-60 and G-90 hot dipped galvanized steel panels were first cleaned by spraying for 15 sec. with an aqueous solution (1 oz/gal) of RIDOLINE 1089 at about 130°F. The panels were then rinsed with water and then immersed in the coating solution, prepared as described above, for 7 seconds at a temperatre of about 130°F. The coated panels were then rinsed in water and dried. The protective coating was dark in color. The coated panels were very resistant to corrosion and the protective coatings thereon possessed good aherence to subsequently applied siccative coatings such as poly ⁇ esters, polyester melamines, siliconized polyesters, fluorocarbons, and the like using epoxy or acrylic pri- mers.
  • siccative coatings such as poly ⁇ esters, polyester melamines, siliconized polyesters, fluorocarbons, and the like using epoxy or acrylic pri- mers.
  • Example 14 The process of Example 14 was carried out except that in A. 4.2 g/1 of disodium EDTA was used instead of 0.6 g/1 of citric acid, and B. the treatment time was 15 seconds. The same results were obtained.
  • Example 14 The process of Example 14 was carried out except that in A. 4.9 g/1 of gluconic acid was present in place of 0.6 g/1 of citric acid. The same results were obtained. "
  • a coating solution was prepared by adding the following ingredients to deionized water:
  • Armo G-60 and G-90 hot dipped galvanized steel panels were first cleaned by spraying for 15 sec. with an aqueous solution (1 oz/gal) of RIDOLINE 1089 at about 130°F. The panels were then rinsed with water and then immersed in the coating solution, prepared as described above, for 15 seconds at a temperature of about 130°F. The coated panels were then rinsed in water and dried. The protective coating was dark in color. The coated panels were very resistant to corro ⁇ sion and the protective coatings thereon possessed good adherence to subsequently applied siccative coatings such as polyesters, polyester melamines, siliconized polyesters, fluorocarbons, and the like using epoxy or acrylic primers.
  • siccative coatings such as polyesters, polyester melamines, siliconized polyesters, fluorocarbons, and the like using epoxy or acrylic primers.

Abstract

Une solution aqueuse acide de revêtement est appliquée sur des métaux galvanisés pour accroître leur résistance à la corrosion. Cette solution contient entre 0,1 et 10 g/l, d'un composé contenant du fluor, calculé d'après la teneur en fluor, et entre 0,015 et 6 g/l d'un sel de cobalt, de cuivre, de fer, de manganèse, de nickel, de strontium ou de zinc, calculé d'après la teneur en métal. Eventuellement, un agent de séquestration et/ou un polymère d'un acide (méth)acrylique ou un ester de celui-ci peuvent également être présents. L'invention concerne également des concentrés de préparation des solutions de revêtement ainsi que des procédés d'utilisation de ces solutions de revêtement.
PCT/US1985/000797 1984-05-04 1985-05-03 Traitement des metaux WO1985005131A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
FI860032A FI860032A0 (fi) 1984-05-04 1986-01-03 Behandling av metaller.
DK2786A DK2786A (da) 1984-05-04 1986-01-03 Metalbehandling

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US60707584A 1984-05-04 1984-05-04
US607,075 1984-05-04
US72556185A 1985-04-25 1985-04-25
US725,561 1985-04-25

Publications (1)

Publication Number Publication Date
WO1985005131A1 true WO1985005131A1 (fr) 1985-11-21

Family

ID=27085416

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1985/000797 WO1985005131A1 (fr) 1984-05-04 1985-05-03 Traitement des metaux

Country Status (5)

Country Link
EP (1) EP0181377A4 (fr)
AU (1) AU4295885A (fr)
DK (1) DK2786A (fr)
FI (1) FI860032A0 (fr)
WO (1) WO1985005131A1 (fr)

Cited By (44)

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FR2609725A1 (fr) * 1987-01-21 1988-07-22 Nihon Parkerizing Solution aqueuse pour le traitement de conversion chimique du titane ou de ses alliages
WO1993005198A1 (fr) * 1991-08-30 1993-03-18 Henkel Corporation Procede de traitement de metaux a l'aide d'une composition aqueuse acide pratiquement exempte de chrome (vi)
US5282905A (en) * 1991-02-12 1994-02-01 Betz Laboratories, Inc. Method and composition for treatment of galvanized steel
US5328525A (en) * 1993-01-05 1994-07-12 Betz Laboratories, Inc. Method and composition for treatment of metals
US5344504A (en) * 1993-06-22 1994-09-06 Betz Laboratories, Inc. Treatment for galvanized metal
US5389405A (en) * 1993-11-16 1995-02-14 Betz Laboratories, Inc. Composition and process for treating metal surfaces
US5441580A (en) * 1993-10-15 1995-08-15 Circle-Prosco, Inc. Hydrophilic coatings for aluminum
US5505792A (en) * 1993-03-26 1996-04-09 Betz Laboratories, Inc. Visible dried-in-place non-chrome polyacrylamide based treatment for aluminum
US5518770A (en) * 1995-02-23 1996-05-21 Betz Laboratories, Inc. Methods and compositions for pretreatment of metals
EP0713540A1 (fr) * 1993-07-30 1996-05-29 Henkel Corporation Composition et procede de traitement des metaux
WO1996016205A1 (fr) * 1994-11-23 1996-05-30 Henkel Kommanditgesellschaft Auf Aktien Traitement anticorrosion et reduisant le frottement pour surfaces metalliques
US5534082A (en) * 1992-04-01 1996-07-09 Henkel Corporation Composition and process for treating metal
EP0739428A4 (fr) * 1993-11-29 1996-07-30 Henkel Corp Composition et procédé de traitement de métaux
WO1996027698A2 (fr) * 1995-03-08 1996-09-12 Henkel Kommanditgesellschaft Auf Aktien Procede sans chrome permettant d'ameliorer l'adherence d'une peinture ou d'un vernis applique(e) par anodisation en couche mince
WO1996035745A1 (fr) * 1992-04-01 1996-11-14 Henkel Corporation Compositions pour le traitement de metaux et procede correspondant
EP0777763A1 (fr) * 1994-09-02 1997-06-11 Henkel Corporation Composition et procede de traitement des metaux
US5641542A (en) * 1995-10-11 1997-06-24 Betzdearborn Inc. Chromium-free aluminum treatment
US5693371A (en) * 1996-10-16 1997-12-02 Betzdearborn Inc. Method for forming chromium-free conversion coating
EP0812934A1 (fr) * 1996-06-14 1997-12-17 Nippon Paint Co., Ltd. Agent et procédé de traitement de surfaces en aluminium et aluminium ainsi obtenu
DE19634222A1 (de) * 1996-08-24 1998-02-26 Basf Lacke & Farben Beschichtete Metallrohre, beschichteter Armierungsstahl oder Spannstahl
US5804652A (en) * 1993-08-27 1998-09-08 Bulk Chemicals, Inc. Method and composition for treating metal surfaces
US5859106A (en) * 1992-11-30 1999-01-12 Bulk Chemicals, Inc. Method and composition for treating metal surfaces
US5873952A (en) * 1996-08-20 1999-02-23 Henkel Corporaiton Process for forming a protective coating on zinciferous metal surfaces
US5935348A (en) * 1995-11-14 1999-08-10 Henkel Kommanditgesellschaft Auf Aktien Composition and process for preventing corrosion and reducing friction on metallic surfaces
EP0949353A1 (fr) * 1997-10-03 1999-10-13 Nihon Parkerizing Co., Ltd. Composition de traitement des surfaces pour materiaux metalliques et procede de traitement
US6171706B1 (en) 1997-10-31 2001-01-09 Suzuki Motor Corporation Sliding members comprising aluminum or aluminum alloys
US6569537B1 (en) 1999-04-28 2003-05-27 Suzuki Motor Corporation Surface treatment method sliding member and piston
WO2003048416A1 (fr) * 2001-12-04 2003-06-12 Nippon Steel Corporation Materiau metallique revetu d'un film de revetement d'oxyde metallique et/ou d'hydroxyde metallique et procede de fabrication associe
EP1419288A1 (fr) * 2001-08-23 2004-05-19 MacDermid, Incorporated Procede de passivation sans chrome pour zinc et alliages au zinc
EP1433875A1 (fr) * 2002-12-24 2004-06-30 Nippon Paint Co., Ltd. Agent de revêtement de conversion chimique et surfaces métalliques revêtues
DE19861003B4 (de) * 1997-10-31 2005-02-10 Suzuki Motor Corp., Hamamatsu Umwandlungsschicht auf hin- und hergehenden Teilen aus Aluminium oder Aluminiumlegierungen
DE10161383B4 (de) * 2000-10-11 2006-06-14 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einer wässerigen Zusammensetzung und Verwendung der beschichteten Substrate
WO2009045845A2 (fr) * 2007-09-28 2009-04-09 Ppg Industries Ohio, Inc. Procédés de revêtement d'un substrat métallique et substrats métalliques revêtus à l'aide du procédé
US7531051B2 (en) * 2001-06-15 2009-05-12 Nihon Parkerizing Co., Ltd. Treating solution for metal surface treatment and a method for surface treatment
DE102008014465A1 (de) * 2008-03-17 2009-09-24 Henkel Ag & Co. Kgaa Optimierte Passivierung auf Ti-/Zr-BAsis für Metalloberflächen
US7819989B2 (en) * 2002-03-05 2010-10-26 Nihon Parkerizing Co., Ltd. Surface treating solution for surface treatment of aluminum or magnesium metal and a method for surface treatment
WO2011044099A1 (fr) * 2009-10-08 2011-04-14 Ppg Industries Ohio, Inc. Compositions regenerante et procedes de regeneration de compositions de pre-traitement
US8282801B2 (en) 2008-12-18 2012-10-09 Ppg Industries Ohio, Inc. Methods for passivating a metal substrate and related coated metal substrates
US8309177B2 (en) 2005-06-14 2012-11-13 Henkel Ag & Co. Kgaa Method for treatment of chemically passivated galvanized surfaces to improve paint adhesion
US8673091B2 (en) 2007-08-03 2014-03-18 Ppg Industries Ohio, Inc Pretreatment compositions and methods for coating a metal substrate
US8852357B2 (en) 2011-09-30 2014-10-07 Ppg Industries Ohio, Inc Rheology modified pretreatment compositions and associated methods of use
US9273399B2 (en) 2013-03-15 2016-03-01 Ppg Industries Ohio, Inc. Pretreatment compositions and methods for coating a battery electrode
US9970115B2 (en) 2009-12-28 2018-05-15 Henkel Ag & Co. Kgaa Metal pretreatment composition containing zirconium, copper, zinc, and nitrate and related coatings on metal substrates
US10422042B2 (en) 2008-03-17 2019-09-24 Henkel Ag & Co. Kgaa Metal treatment coating compositions, methods of treating metals therewith and coated metals prepared using the same

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Cited By (84)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2609725A1 (fr) * 1987-01-21 1988-07-22 Nihon Parkerizing Solution aqueuse pour le traitement de conversion chimique du titane ou de ses alliages
US5282905A (en) * 1991-02-12 1994-02-01 Betz Laboratories, Inc. Method and composition for treatment of galvanized steel
KR100292447B1 (ko) * 1991-08-30 2001-06-01 웨인 씨. 제쉬크 금속 기판 표면상의 보호용 변성 코팅 형성 방법
EP0825280A3 (fr) * 1991-08-30 1998-04-01 Henkel Corporation Procédé de traitement de métaux à l'aide d'une composition aqueuse acide pratiquement exempte de chrome (VI)
US5342456A (en) * 1991-08-30 1994-08-30 Henkel Corporation Process for coating metal surfaces to protect against corrosion
WO1993005198A1 (fr) * 1991-08-30 1993-03-18 Henkel Corporation Procede de traitement de metaux a l'aide d'une composition aqueuse acide pratiquement exempte de chrome (vi)
EP0825280A2 (fr) * 1991-08-30 1998-02-25 Henkel Corporation Procédé de traitement de métaux à l'aide d'une composition aqueuse acide pratiquement exempte de chrome (VI)
US5449414A (en) * 1991-08-30 1995-09-12 Henkel Corporation Process for treating metal with aqueous acidic composition that is substantially free from chromium (VI)
AU662758B2 (en) * 1991-08-30 1995-09-14 Henkel Corporation Process for treating metal with aqueous acidic composition that is substantially free from chromium (VI)
WO1996035745A1 (fr) * 1992-04-01 1996-11-14 Henkel Corporation Compositions pour le traitement de metaux et procede correspondant
US5534082A (en) * 1992-04-01 1996-07-09 Henkel Corporation Composition and process for treating metal
US5859106A (en) * 1992-11-30 1999-01-12 Bulk Chemicals, Inc. Method and composition for treating metal surfaces
US5859107A (en) * 1992-11-30 1999-01-12 Bulk Chemicals, Inc. Method and composition for treating metal surfaces
US5905105A (en) * 1992-11-30 1999-05-18 Bulk Chemicals, Inc. Method and composition for treating metal surfaces including dispersed silica
US5328525A (en) * 1993-01-05 1994-07-12 Betz Laboratories, Inc. Method and composition for treatment of metals
EP0664348A1 (fr) * 1993-01-05 1995-07-26 Betz Europe, Inc. Procédé et composition de traitement de métaux
US5505792A (en) * 1993-03-26 1996-04-09 Betz Laboratories, Inc. Visible dried-in-place non-chrome polyacrylamide based treatment for aluminum
US5344504A (en) * 1993-06-22 1994-09-06 Betz Laboratories, Inc. Treatment for galvanized metal
EP0713540A1 (fr) * 1993-07-30 1996-05-29 Henkel Corporation Composition et procede de traitement des metaux
EP0713540A4 (fr) * 1993-07-30 1996-08-21 Henkel Corp Composition et procede de traitement des metaux
US5804652A (en) * 1993-08-27 1998-09-08 Bulk Chemicals, Inc. Method and composition for treating metal surfaces
US5441580A (en) * 1993-10-15 1995-08-15 Circle-Prosco, Inc. Hydrophilic coatings for aluminum
US5451431A (en) * 1993-11-16 1995-09-19 Betz Laboratories, Inc. Composition and process for treating metal surfaces
US5389405A (en) * 1993-11-16 1995-02-14 Betz Laboratories, Inc. Composition and process for treating metal surfaces
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DK2786D0 (da) 1986-01-03
EP0181377A4 (fr) 1986-09-15
FI860032A (fi) 1986-01-03
FI860032A0 (fi) 1986-01-03
DK2786A (da) 1986-03-04
EP0181377A1 (fr) 1986-05-21
AU4295885A (en) 1985-11-28

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