US3810792A - Process for the application of phosphate coatings on steel,iron and zinc surfaces - Google Patents

Process for the application of phosphate coatings on steel,iron and zinc surfaces Download PDF

Info

Publication number
US3810792A
US3810792A US00210539A US21053971A US3810792A US 3810792 A US3810792 A US 3810792A US 00210539 A US00210539 A US 00210539A US 21053971 A US21053971 A US 21053971A US 3810792 A US3810792 A US 3810792A
Authority
US
United States
Prior art keywords
phosphate
iron
steel
cations
zinc
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.)
Expired - Lifetime
Application number
US00210539A
Other languages
English (en)
Inventor
C Ries
M Prymak
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.)
Callarden G dt GmbH
CALLARDEN G GmbH
Original Assignee
CALLARDEN G GmbH
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 CALLARDEN G GmbH filed Critical CALLARDEN G GmbH
Application granted granted Critical
Publication of US3810792A publication Critical patent/US3810792A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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
    • C23C22/06—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
    • C23C22/36—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 containing also phosphates

Definitions

  • phosphatizing solutions which, besides zinc ions, also contain other layer-forming divalent metal cations, such as calcium, manganese, iron, nickel, cobalt or cadmium cations. With these phosphatizing solutions, the amounts of the layer-forming cations present are generally calculated so that the zinc cations form the substantial portion of the total layer-forming cations.
  • phosphatizing solutions can be modified by a number of additives.
  • they contain, as a rule, oxidizing agents for the acceleration of the layer formation.
  • they also may contain copper salts, titanium salts, boric acid, silicic acid and both simple and complex fluorides, in order to attain certain effects.
  • An object of the present invention is the obtention of acidic phosphate solutions for application of phosphate coatings on iron, steel and zinc surfaces consisting essentially of water containing (1) from 2.0 to 10.0 gm./liter of oxidizing agents, calculated as nitrate ions, (2) from 0.1 to 5.0 gm./liter of complex fluoride ions, (3) from 0.5 to 15.0 gm./liter of divalent layer-forming metal cations consisting of (a) from 59 to mol percent of nickel cations and (b) 0 to 41 mol percent of divalent metal cations selected from the group consisting of calcium, manganese, iron, cobalt, cadmium and zinc, and (4) an amount of phosphate ions at least sufficient to form dihydrogen phosphates with said divalent layerforming metal cations, said acidic phosphate solutions having a total acid of from 5 to 30 points, a free acid of from 0.5 to 6 points and a ratio of total
  • a further object of the present invention is the development of, in the process for the application of phosphate coatings on steel, iron and zinc surfaces consisting essentially of contacting steel, iron and zinc surfaces with an acidic aqueous solution containing di-valent layer-forming metal cations, phosphate ions, fluoride ions and oxidizing agents for a time and at a temperature sufiicient to eifect formation of a phosphate coating on said surfaces, and recovering said phosphate coated steel, iron and zinc surfaces, the improvement which consists in utilizing (a) from 59 to 100 mol percent of nickel cations and (b) from 0 to 41 mol percent of divalent layer-forming metal cations other than nickel, as said divalent layer-forming cations.
  • a yet further object of the invention is the development of a continuous process for obtaining continuous phosphate layers on iron, steel and zinc surfaces having DESCRIPTION OF THE INVENTION
  • the present invention relates to a process for the application of phosphate layers on steel, iron and zinc surfaces with the aid of solutions that contain film-forming cations, phosphate ions, fluoride ions and oxidizing agents.
  • zinc surfaces shall include both surfaces of objects from zinc and zinc alloys and galvanized iron and steel surfaces.
  • nickel ions are present as layerforming cations.
  • solutions that contain, besides nickel ions, also a minor amount of layer-forming cations of another divalent metal As such other divalent cations, calcium, manganese, iron, cobalt, cadmium, and preferably zinc ions can be utilized.
  • the amounts of the layer-forming cations are thereby calculated so that the molar ratio of nickel ions to the other divalent metal cations is in the range of 1:0.001 to 1:07.
  • the overall molar ratio of nickel ions to the other divalent layer-forming metal cations in the process of the invention is, therefore, from 1:0 to 120.7.
  • the total amount of layer-forming cations employed in the process of the invention consists, therefore, of (a) from 59 to 100 mol percent of nickel cations and (b) from to 41 mol percent of divalent layer-formin metal cations, other than nickel.
  • the invention therefore, involved, in the process for the application of phosphate coatings on steel, iron and zinc surfaces consisting essentially of contacting steel, iron and zinc surfaces with an acidic aqueous solution containing divalent layer-forming metal cations, phosphate ions, fluoride ions and oxidizing agents for a time and at a temperature sufficient to effect formation of a phosphate coating on said surfaces, and recovering said phosphate coated steel, iron and zinc surfaces, the improvement which consists in utilizing (a) from 59 to 100 mol percent of nickel cations and (b) from 0 to 41 mol percent of divalent layer-forming metal cations other than nickel, as said divalent layer-forming metal cations.
  • the divalent layer-forming cations are employed in the forms such as oxides, carbonates, sulfates, phosphates, nitrates or fluorides introduced into the solutions or charge concentrates.
  • the applied phosphatizing solutions contain fluorides ions, as a rule in the form of complex fluorides, particularly as fluoborate, fluotitanate and fluosilicate.
  • the complex fluorides can be introduced into the solutions as alkali metal borofluorides, alkali metal fluotitanates and alkali metal fluosilicates or in the form of the corresponding acid complex fluorides. They can, however, also be prepared in situ, for example by addition of boric acid and a corresopnding amount of hydrofluoric acid. A slight excess of non-complex bound fluoride is not damaging.
  • the oxidizing agents customary in the phosphatizing technique.
  • accelerators particularly nitrates, chlorates and mixtures of nitrates and chlorates are used.
  • sodium m-nitrobenzenesulfonate or the combinations nitrite/nitrate or nitrite/ chlorate are possible.
  • Solutions have been found as particularly suitable for the process, that contain 2.0 to 10.0 gm./l. of oxidizing agents, calculated as the nitrate ion, 0.1 to 5.0 gm./l. of complex fluoride ions, 0.5 to 15.0 gm./l. of nickel ions or nickel ions and ions of another divalent metal, preferably of zinc, in a molar ratio in the range of 1:0.001 to 1:07 and an amount of P0 that is at least suflicient to form dihydrogen phosphate with the divalent metal cations present.
  • bath solutions consisting of acidic phosphate solutions for application of phosphate coatings on iron, steel and zinc surfaces consisting essentially of water containing (1) from 3.0 to 10.0 gm./liter of oxidizing agents, calculated as nitrate ions, (2) from 0.1 to 5.0 gm./liter of complex fluoride ions, (3) from 0.1 to 15.0 gm./liter of divalent layer-forming metal cations consisting of (a) from 59 to 100 mol percent of nickel cations and (b) 0 to 41 mol percent of divalent metal cations selected from the group consisting of calcium, manganese, iron, cobalt, cadmium and zinc, and (4) an amount of phosphate ions at least sufficient to form dihydrogen phosphates with said divalent layer-forming metal cations, said acidic phosphate solutions having a total acid of from 5 to 30 points, a free acid of from 0.5 to 6 points and a ratio of total acid to free acid in points of from 5:
  • the phosphatizing solutions are appropriately prepared by diluting of aqueous concentrates in which the components are already contained in the respective proportions.
  • the concentration of the active ingredients decreases continuously in the operating phosphatizing baths by layer formation and by bath solution remaining on the metal surfaces.
  • the phosphatizing solutions have, therefore, to be periodically or continuously supplemented.
  • concentrates are used in which the ratio of total acid to free acid in points lies in the range of from 2.5 :1 to 60:1.
  • Total acid is the amount of milliliters (points of 11/10 NaOH which is consumed in the titration of 10 ml. of concentrate to the end point of phenolphthalein.
  • Free acid is defined as the amount of milliliters (points) of n/ 10 NaOH that is required for the titration of 10 ml. of the bath solution against methyl orange.
  • the process of the invention therefore, also involves a continuous process for the application of phosphate coatings on steel, iron and zinc surfaces consisting essentially of continuously contacting steel, iron and zinc surfaces with acidic phosphate solutions for application of phosphate coatings on iron, steel and zinc surfaces consisting essentially of water containing (1) from 2.0 to 10.0 gm./liter of oxidizing agents, calculated as nitrate ions, (2) from 0.1 to 5.0 gm./liter of complex fluoride ions, (3) from 0.5 to 15.0 gm./liter of divalent layerforming metal cations consisting of (a) from 59 to mol percent of nickel cations and (b) 0 to 41 mol percent of divalent metal cations selected from the group consiting of calcium, manganese, iron, cobalt, cadmium and zinc, and (4) an amount of phosphate ions at least sufficient to form dihydrogen phosphates with said divalent layer-forming metal cations, said acidic phosphate solutions having a total acid of
  • the phosphatizing solutions can be applied to the metal surfaces in the dipping, flow coat or spraying processes. With steel and iron surfaces, treating temperatures between 55 C. and 75 C. have been found advantageous.
  • the favorable temperature range for the treatment of the zinc surfaces is between 45 C. and 75 C.
  • the duration of the treatment amounts to between 2 and seconds, depending upon the desired weight of the coat. If the process is applied in coil-coating installations, the exposure (contact) times lie preferably in the range of from 5 to 15 seconds.
  • the surfaces to be treated are normally alkaline-cleaned and degreased in a conventional way. In certain cases, this precleaning is not required, as for example, when a galvanized material is immediately phosphatized following the galvanizing.
  • the protective layers are after-treated with dilute chromic acid that contains chromium (III)-ions.
  • concentrations of the hexavalent chromium are between 0.2 and 2 gm./l., calculated as CrO and that of the trivalent chromium are between 0.05 and 1.0 gm./l. calculated as Cr O
  • a rinsing with water can be applied. This rinsing is, however, not absolutely required and above all can be omitted if squeeze rolls are utilized. Subsequently to the after-passivating the phosphate layers are conventionally dried.
  • the plates were rinsed with tap water, after-passivated with a solution that contained 0.2 gm./l. of CrO and finally dried in a stream of warm air.
  • hot-galvanized steel plates were treated by the flooding process with above-described solution, at the following temperatures and treating times:
  • the plates were after-passivated, as described above, and subsequently dried. On the galvanized surfaces ocher-colored to greyish-black phosphate layers were obtained.
  • the free acid concentration was 2.0 points and the total acid concentration was 12.3 points.
  • Standard plates of cold-rolled steel of the grade St 14.05 were treated with this solution in the dipping process at the following temperatures and dipping times:
  • the phosphate layers produced on the surfaces of steel and hot-galvanized material are an excellent adhesion base for lacquer and synthetic resin coats.
  • the layers are not damaged in subsequent mechanical shaping. In corrosion tests, they were, as shown by condensed water and salt spray tests, mostly superior to the known zinc phosphate layers, or at least equivalent.
  • the borofiuoric acid may be replaced by equivalent amounts of fluosilicic acid or potassium fluotitanate, without any essential changes in the quality of the coatings.
  • the plates were rinsed with completely demineralized water and dried. In all cases, thin, completely homogeneous and continuous phosphate layers were obtained.
  • the average layer weight of the coating depending upon the exposure time and the treating temperature, was in the range from 0.3 to 0.8 gm./m.
  • hot-galvanized steel plates were treated with the same solution in the flooding process at the following temperatures and exposure times:
  • the steel surfaces possess after this treatment dark-grey to greyish-black phosphate coats with an average layer weight of coating of 0.3 to 0.4 gm./m.
  • phosphate coatings on steel, iron and zinc surfaces consisting essentially of contacting steel, iron and zinc surfaces with an acidic aqueous solution containing divalent layer-forming metal cations, phosphate ions, fluoride ions and oxidizing agents for a time and at a temperature sufficient to effect formation of a phosphate coating on said surfaces, and recovering said phosphate coated steel, iron and zinc surfaces, the improvement which consists in utilizing from 0.5 to 15.0 gm./liter of divalent layer-forming metal cations consisting of (a) from 59 to 99.9 mol percent of nickel cations and (b) from 0.1 to 41 mol percent of zinc cations.
  • a continuous process for the application of phosphate coatings on steel, iron and zinc surfaces consisting essentially of continuously contacting steel, iron and zinc surfaces with acidic phosphate solutions for application of phosphate coatings on iron, steel and zinc surfaces consisting essentially of water containing (1) from 2.0 to 10.0 gm./liter of oxidizing agents, calculated as nitrate ions, (2) from 0.1 to 5.0 gm./liter of complex fluoride ions, (3) from 0.5 to 15.0 gm./liter of divalent layerforming metal cations consisting of (a) from 59 to 99.9 mol percent of nickel cations and (b) 0.1 to 41 mol percent of zinc cations, and (4) an amount of phosphate ions at least sufiicient to form dihydrogen phosphates with said divalent layer-forming metal cations, said acidic phosphate solutions having a total acid of from 5 to 30 points, a free acid of from 0.5 to 6 points and a ratio of total acid to free acid in points of from
  • Acidic phosphate solutions for application of phosphate coatings on iron, steel and zinc surfaces consisting essentially of water containing (1) from 2.0 to 10.0 gm./ liter of oxidizing agents, calculated as nitrate ions, (2) from 0.1 to 5.0 gm./liter of complex fluoride ions, (3) from 0.5 to 15.0 gm./liter of divalent layer-forming metal cations consisting of (a) from 59 to 99.9 mol percent of nickel cations and (b) 0.1 to 41 mol percent of zinc cations, and (4) an amount of phosphate ions at least sufficient to form dihydrogen phosphate with said divalent layer-forming metal cations, said acidic phosphate solutions having a total acid of from 5 to 30 points, a free acid of from 0.5 to 6 points and a ratio of total acid to free acid in points of from 5:1 to 10:1.

Landscapes

  • 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)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
US00210539A 1971-01-02 1971-12-21 Process for the application of phosphate coatings on steel,iron and zinc surfaces Expired - Lifetime US3810792A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19712100021 DE2100021A1 (de) 1971-01-02 1971-01-02 Verfahren zum Aufbringen von Phos phatschichten auf Stahl, Eisen und Zinkoberflachen

Publications (1)

Publication Number Publication Date
US3810792A true US3810792A (en) 1974-05-14

Family

ID=5795086

Family Applications (1)

Application Number Title Priority Date Filing Date
US00210539A Expired - Lifetime US3810792A (en) 1971-01-02 1971-12-21 Process for the application of phosphate coatings on steel,iron and zinc surfaces

Country Status (8)

Country Link
US (1) US3810792A (enrdf_load_stackoverflow)
DE (1) DE2100021A1 (enrdf_load_stackoverflow)
FR (1) FR2120141B1 (enrdf_load_stackoverflow)
GB (1) GB1373129A (enrdf_load_stackoverflow)
IT (1) IT944569B (enrdf_load_stackoverflow)
SE (1) SE373882B (enrdf_load_stackoverflow)
SU (1) SU426375A3 (enrdf_load_stackoverflow)
TR (1) TR17896A (enrdf_load_stackoverflow)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108690A (en) * 1976-04-05 1978-08-22 Amchem Products, Inc. Method for producing an amorphous, light weight calcium phosphate coating on ferrous metal surfaces
US4389260A (en) * 1981-01-22 1983-06-21 Occidental Chemical Corporation Composition and process for the phosphatizing of metals
WO1984000386A1 (en) * 1982-07-12 1984-02-02 Ford Motor Canada Alkaline resistant phosphate conversion coatings and method of making
US4497668A (en) * 1982-12-08 1985-02-05 Gerhard Collardin Gmbh Phosphating process for zinc-plated metals
WO1985003089A1 (en) * 1984-01-06 1985-07-18 Ford Motor Company Alkaline resistance phosphate conversion coatings
US4681641A (en) * 1982-07-12 1987-07-21 Ford Motor Company Alkaline resistant phosphate conversion coatings
US4713121A (en) * 1985-05-16 1987-12-15 Parker Chemical Company Alkaline resistant phosphate conversion coatings
US4722753A (en) * 1985-05-16 1988-02-02 Parker Chemical Company Alkaline resistant phosphate conversion coatings
US4762572A (en) * 1985-10-18 1988-08-09 Gerhard Collardin Gmbh Process for phosphating electrolytically zinc-coated metals
US4950339A (en) * 1988-02-03 1990-08-21 Metallgesellschaft Aktiengesellschaft Process of forming phosphate coatings on metals
US20040005476A1 (en) * 2000-12-04 2004-01-08 Jfe Steel Corporation Zinc-base plated steel sheet and method for manufacturing same
RU2251590C2 (ru) * 2003-04-10 2005-05-10 Закрытое акционерное общество "ЭКОХИММАШ" Раствор для фосфатирования и способ обработки этим раствором металлической поверхности
US20080314479A1 (en) * 2007-06-07 2008-12-25 Henkel Ag & Co. Kgaa High manganese cobalt-modified zinc phosphate conversion coating
US7514153B1 (en) 2005-03-03 2009-04-07 The United States Of America As Represented By The Secretary Of The Navy Method for deposition of steel protective coating

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5339945A (en) * 1976-09-25 1978-04-12 Nippon Packaging Kk Surface treatment of zinc or zinc alloy
JPS5811515B2 (ja) * 1979-05-11 1983-03-03 日本ペイント株式会社 金属表面にリン酸亜鉛皮膜を形成するための組成物
US4486241A (en) * 1981-09-17 1984-12-04 Amchem Products, Inc. Composition and process for treating steel
GB8329250D0 (en) * 1983-11-02 1983-12-07 Pyrene Chemical Services Ltd Phosphating processes
GB8527833D0 (en) * 1985-11-12 1985-12-18 Pyrene Chemicals Services Ltd Phosphate coating of metals
DE3636390A1 (de) * 1986-10-25 1988-04-28 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen auf metallen
GB2259920A (en) * 1991-09-10 1993-03-31 Gibson Chem Ltd Surface conversion coating solution based on molybdenum and phosphate compounds
WO1994002661A1 (en) * 1992-07-20 1994-02-03 Henkel Corporation Process for treating steel to minimize filiform corrosion

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2312855A (en) * 1940-09-07 1943-03-02 Parker Rust Proof Co Method of coating aluminum
FR1451329A (fr) * 1964-06-29 1966-01-07 Parker Ste Continentale Procédé perfectionné de revêtement de surfaces métalliques

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4108690A (en) * 1976-04-05 1978-08-22 Amchem Products, Inc. Method for producing an amorphous, light weight calcium phosphate coating on ferrous metal surfaces
US4389260A (en) * 1981-01-22 1983-06-21 Occidental Chemical Corporation Composition and process for the phosphatizing of metals
WO1984000386A1 (en) * 1982-07-12 1984-02-02 Ford Motor Canada Alkaline resistant phosphate conversion coatings and method of making
US4681641A (en) * 1982-07-12 1987-07-21 Ford Motor Company Alkaline resistant phosphate conversion coatings
US4497668A (en) * 1982-12-08 1985-02-05 Gerhard Collardin Gmbh Phosphating process for zinc-plated metals
WO1985003089A1 (en) * 1984-01-06 1985-07-18 Ford Motor Company Alkaline resistance phosphate conversion coatings
US4713121A (en) * 1985-05-16 1987-12-15 Parker Chemical Company Alkaline resistant phosphate conversion coatings
US4722753A (en) * 1985-05-16 1988-02-02 Parker Chemical Company Alkaline resistant phosphate conversion coatings
US4762572A (en) * 1985-10-18 1988-08-09 Gerhard Collardin Gmbh Process for phosphating electrolytically zinc-coated metals
US4950339A (en) * 1988-02-03 1990-08-21 Metallgesellschaft Aktiengesellschaft Process of forming phosphate coatings on metals
US20040005476A1 (en) * 2000-12-04 2004-01-08 Jfe Steel Corporation Zinc-base plated steel sheet and method for manufacturing same
US6861160B2 (en) * 2000-12-04 2005-03-01 Jfe Steel Corporation Zinc-based plated steel sheet and method for manufacturing same
RU2251590C2 (ru) * 2003-04-10 2005-05-10 Закрытое акционерное общество "ЭКОХИММАШ" Раствор для фосфатирования и способ обработки этим раствором металлической поверхности
US7514153B1 (en) 2005-03-03 2009-04-07 The United States Of America As Represented By The Secretary Of The Navy Method for deposition of steel protective coating
US7803428B1 (en) 2005-03-03 2010-09-28 The United States Of America As Represented By The Secretary Of The Navy Method for deposition of steel protective coating
US20080314479A1 (en) * 2007-06-07 2008-12-25 Henkel Ag & Co. Kgaa High manganese cobalt-modified zinc phosphate conversion coating

Also Published As

Publication number Publication date
FR2120141A1 (enrdf_load_stackoverflow) 1972-08-11
DE2100021A1 (de) 1972-09-07
SU426375A3 (ru) 1974-04-30
FR2120141B1 (enrdf_load_stackoverflow) 1974-09-27
TR17896A (tr) 1976-11-01
IT944569B (it) 1973-04-20
SE373882B (enrdf_load_stackoverflow) 1975-02-17
GB1373129A (en) 1974-11-06

Similar Documents

Publication Publication Date Title
US3810792A (en) Process for the application of phosphate coatings on steel,iron and zinc surfaces
US3682713A (en) Process for applying protective coatings on aluminum,zinc and iron
EP0106459B1 (en) Phosphate coating metal surfaces
EP0315059B1 (en) Process and composition for zinc phosphate coating
US7776448B2 (en) Conversion coatings including alkaline earth metal fluoride complexes
US4793867A (en) Phosphate coating composition and method of applying a zinc-nickel phosphate coating
US2796370A (en) Composition and method for producing corrosion resistant protective coating on aluminum and aluminum alloys
JP3063920B2 (ja) リン酸塩で金属表面を処理する方法
US4486241A (en) Composition and process for treating steel
JP2680618B2 (ja) 金属のりん酸塩処理方法
CA2234819C (en) Zinc phosphate conversion coating compositions and process
US4600447A (en) After-passivation of phosphated metal surfaces
CA1308338C (en) Process of producing phosphate coatings on metal surfaces
US6027579A (en) Non-chrome rinse for phosphate coated ferrous metals
US6749694B2 (en) Conversion coatings including alkaline earth metal fluoride complexes
US3539403A (en) Solutions for the deposition of protective layers on zinc surfaces and process therefor
US4963198A (en) Composition and process for treating metal surfaces
CA1322147C (en) Zinc-nickel phosphate conversion coating composition and process
US3819424A (en) Method and composition for treating metal surfaces
GB2046312A (en) Processes and compositions for coating metal surfaces
US4622078A (en) Process for the zinc/calcium phosphatizing of metal surfaces at low treatment temperatures
GB1534517A (en) Aqueous zinc phosphatizing solutions and method of coating steel therewith prior to cold deformation
JP2001508123A (ja) スチールバンドをホスフェート化するための方法
US3404046A (en) Chromating of zinc and aluminum and composition therefor
US3720547A (en) Permanganate final rinse for metal coatings