GB2208876A - Process for forming phosphate coatings on metals - Google Patents

Process for forming phosphate coatings on metals Download PDF

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Publication number
GB2208876A
GB2208876A GB8819791A GB8819791A GB2208876A GB 2208876 A GB2208876 A GB 2208876A GB 8819791 A GB8819791 A GB 8819791A GB 8819791 A GB8819791 A GB 8819791A GB 2208876 A GB2208876 A GB 2208876A
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United Kingdom
Prior art keywords
process according
solution
immersion
zinc
aluminium
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Granted
Application number
GB8819791A
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GB8819791D0 (en
GB2208876B (en
Inventor
Werner Rausch
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ARDROX PYRENE Ltd
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ARDROX PYRENE Ltd
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Application filed by ARDROX PYRENE Ltd filed Critical ARDROX PYRENE Ltd
Publication of GB8819791D0 publication Critical patent/GB8819791D0/en
Publication of GB2208876A publication Critical patent/GB2208876A/en
Application granted granted Critical
Publication of GB2208876B publication Critical patent/GB2208876B/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C22/06—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
    • C23C22/07—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 phosphates
    • C23C22/08—Orthophosphates
    • C23C22/12—Orthophosphates containing zinc cations
    • 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
    • C23C22/368—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 containing magnesium cations

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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)

Description

4, 1 9 1 Ardrox Pyrene Limited Processes for Forming Phosphate Coatings on
Metals U 60/2749/01 This invention relates to processes for forming 5 phosphate coatings on surfaces which are of steel and/or galvanised steel and which may also include aluminium surfaces. The coatings are particularly intended as a base for subsequent painting.
It is standard practice to use zinc phosphate solutions for this purpose, and different effects can be obtained by different ratios of zinc to phosphate and by the incorporation of other metals in the solutions. Thus it is known that phosphate coatings can be formed using zinc-magnesium phosphate solutions but when these are the only divalent cations various disadvantages occur.
It is also known that low zinc phosphating processes can be used, especially prior to painting, to produce coatings having a high phosphophyllite content and that this can lead to beneficial effects in paint adhesion and in infiltration resistance of the film of paint when subjected to corrosive surroundings. Nickel can be included in the low zinc phosphating solutions and can result in the production of coatings that appear perfect from the visual point of view. However the adhesion of the paint films, especially on to zinc surfaces, tends to be unsatisfactory in the presence of moisture. Also there may be defects in the phosphate coating that is formed on zinc surfaces. These defects appear to be due to local crystalline efflorescence, which appears as specks, and impairs the formation of a uniform film of paint. This is a particular problem when application is by an immersion process.
4 1 1, A 2 other problems arise when the surfaces include aluminium surfaces, especially when the phosphate coating is based on zinc and magnesium.
There is therefore a need to devise a process that is capable of giving satisfactory coatings, especially as a base for painting, on metal surfaces that can be of steel andlor galvanised steel, and optionally can include aluminium surfaces.
In the invention, a phosphate coating is formed on a surface of iron and/or zinc, and optionally also of aluminium, by contact of the surface with a phosphating solution that is an aqueous solution containing 0.4 to 2g/ 1 Zn, 0.4 to 5g/1 Mg, 0.05 to 2g/1 Ni, 8 to 20g/1 P2 0 5 and at least one oxidising agent, and which has a free acid:total acid ratio of 0.02:1 to 0.15:1 and in which, when the surface includes aluminium, contains from 80 to 400mg/1 of fluoride as determined by a fluoride-sensitive electrode immersed in the solution.
The surface, or the part of the surface, that is of iron is generally of steel and this may be a non-alloyed or a low-alloyed steel. The surface, or the part of the surface, that is of zinc is generally a galvanised surface, and in particular is generally galvanised steel. Thus the surface may be formed from steel that has been coated with zinc or zinc alloy coatings, for instance having been coated with pure zinc, zinc nickel, zinc iron or zinc aluminium coatings by a suitable process, such as melt immersion. When the surface, or part of the surface, is aluminium, the aluminium may be pure metal or may be an alloy of aluminium with, for instance, magnesium, zinc, copper, silicone or manganese.
The invention is of particular interest when the surface or surfaces that are being coated include components of steel and components of galvanised steel.
It is also of interest when the surface or surfaces 14 3 1 1 include components of aluminium with steel, aluminium with galvanised steel or aluminium with steel and galvanised steel.
Fluoride can be present in the solution when the 5 surfaces being treated do not include aluminium surfaces. However when the surfaces include aluminium surfaces the solution must include fluoride in an amount of 80 to 400mg/1 as determined by a fluoride-sensitive electrode.
The presence of fluoride has the advantage of accelerating coating formation on all surfaces, and is particularly important when aluminium is present. The fluoride can be introduced as simple and/or complex fluoride, for instance as fluoroborate or fluorosilicate.
The concentration of fluoride detected by the fluoride-sensitive electrode corresponds approximately to the content of dissociated fluoride (F present in the phosphating solution. To adjust a F(el) value of from 80 to 400m9/1 in the conventional phosphating bath pH values of the baths, about 0.4 to 0.9g/1 of NH 4 HF 2 or equivalent quantities of other simple fluoride containing compounds must be added. The bath is preferably made up by adding sufficient simple fluoride containing compound to the phosphating bath to attain the desired value of F(el).
The cations zinc, magnesium and nickel are introduced into the phosphating solution, for example as metal oxide, carbonate, phosphate, nitrate, chloride and/or complex fluoride. The phosphate content is supplied to the solution via phosphates and/or phosphoric acid. Further cations, for example Na, K, NH 4 or anions, for example nitrate, chloride, sulphate are also used in order to adjust the desired ratio of free acid to total acid of (0.02 to 0.15):l.
Although it is often preferred that the solution is free of other polyvalent metals, various additives can be 1 4 included in the solution, usually in minor amounts. Such additives include copper, manganese, calcium, iron, cobalt, polyphosphates, polyhydroxycarboxylic acids, surface-active agents as well as agents for influencing 5 sedimentation.
When the surfaces do not include aluminium, the concentration of zinc in the phosphating solution is generally from 0.4 to lg/1 when the application is by spraying and from 0.9 to 1.5g/1 when the application is by spray immersion or immersion. When aluminium is present, the respective concentrations are generally 0.7 to 1.0g/1 and 1.4 to 2.0g/1.
The phosphating bath contains at least one oxidising agent. Preferred materials comprise nitrate, nitrite, chlorate, bromate, peroxide and nitrobenzene sulphonate, and the following quantities can be used, for example, from 2 to 20g/1 of nitrate; from 0.05 to 0.5g/1 of nitrite; from 0.5 to Sg/1 of chlorate; from 0.2 to 3g/1 of bromate; from 0.02 to 0.1g/1 of peroxide; from 0.1 to lg/1 of nitrobenzene sulphonate. The oxidising agents can also be combined with one another, for example, nitrate-nitrite, (nitrate-) chlorate-nitrite, nitrate-bromate, (nitrate-) chlorate-nitrobenzene sulphonate, nitrate-nitrobenzene sulphonate.
To prevent the formation of small spots of crystalline efflorescence (specks) on the phosphate coating during the phosphating of galvanised steel, particularly when adopting the spraying immersion and immersion process it is preferred to control the combinations of particular additives, notably chloride, bromide, nitrate and nickel. Thus preferably only two of the components selected from (chloride and/or bromide), (nitrate) and (nickel) should be present in respective concentrations of above 0.1g/1 while the third should be held at a concentration of not more than 1 1 0. lg/1. Chloride and bromide are counted as a single component and their concentrations are added together. The chloride can, for instance, originate from initial dilution water or from reduction of chlorate accelerator while bromide can originate from bromate accelerator.
- The values of free acid and total acid are the consumption of ml of OAN sodium hydroxide required for neutralisation of a 10m1 sample of the solution to, respectively, the first or second neutralisation points of phosphoric acid.
The surfaces that are to be treated should, as is conventional, be tree of contamination by, for instance, oils, lubricants and oxides and so should preferably have been cleaned in a manner conventional for surfaces that are to be phosphated. The surfaces may be activated, prior to phosphating, with a known activating agent such as an aqueous suspension containing titanium phosphate.
The activating agent can be used in the cleaning solution or as a separate stage between cleaning and phosphating.
The phosphating solution is preferably applied at a temperature of from 40 to 6WC. Application is generally by spray. spray immersion or immersion processes. The contact between the solution and the surfaces typically is 20 seconds to 10 minutes, this range being particularly suitable when the surfaces are of galvanised steel but the higher amounts, for instance 1 to 10 minutes generally being required when the surfaces are of steel and aluminium.
The phosphate coatings are preferably used as the base for a subsequent application of paint, often by an electro-immersion process, generally cathodic electro-immersion.
The resultant paint coatings have high resistance to corrosion caused by normal weathering, weathering accelerated by salt, moisture, salt mist or washing t, Z 6 liquor. The paint coatings also have good adhesion to various environments -for instance ordinary weathering, weathering accelerated by salt, moisture, salt mist and wash liquor even when subjected to scratching or impact before or after the exposure to corrosion conditions.
The process is of particular value for the pre-treatment of metal casings for domestic and industrial appliances, metal furniture, vehicle bodies and vehicle accessories, prior to painting.
The invention is illustrated in the following examples. Examples Steel sheets, electrolytically galvanised steel, hot galvanised steel and AlMgSi were treated at SWC for 2 minutes by spraying and for 3 minutes by immersion with the phosphating solutions listed in the Table after alkaline cleaning, water rinsing and activation in an aqueous titanium phosphate suspension. This was followed by rinsing with water, chromium (VI)-containing aqueous passivating solution, completely desalted water as well as a drying stage.
The Table shows that perfect coatings could be obtained on steel in the entire operating range. The same applies to galvanised steel, with the exception of the case in which nitrate, chloride and nickel were present in respective concentrations above 0.1g/1 (Examples 6 and 11), providing that the ranges essential to the invention for the Zn, Mg and Ni concentration were observed. A uniform crystalline layer was invariably formed on AlMgSi if the fluoride concentration measured electrometrically with a fluoride-sensitive electrode (F(el) lay in the rasnge of between 80 and 400mg/1 (Examples 4 to 6 and 13 to 20).
After visual evaluation, the coatings were provided with a cathodic electro-immersion paint and an automobile !kl 7 p paint composition and were subjected to the conventional application tests. Excellent test results were achieved in all cases where there were crystalline coatings on the metal substrate.
A a Table
Example go. t 04 10 91 12 1) 140 1 94 17 at 19 20 Z0 (gill 0.3 Ol$ 1 0.3 0.5 015 f. 1. 1.4 1,4 &,% AA 9.4 1.5 119 1 AA A's &.a 018 Mg (am 1 1 1 1 2.$ Z.) a 2.3 21) 4P th a 1 A 3 3) $ NA (alit 0.1 0.7 011 O.P 0.1 0.7 0.) 0.7 0.3 0.7_ 0.3 0.7 0,0 o') 0,7 G3- 0,1 0.7 AJ a Ns (ale) 116 0.8 2.0 1.7 0.4 0.) 1,4 B.9 0.4 0,3 0,1 2j, AW6 Gy 1.1 0,3 0, 3 P 01 tall) 12 or 4 14 a th 14 As #5 13 A 13 as 93 is A a 3 As A 3 as at _U NO, (611) a 3 & it 4 a A 3 o.t t 0.21 0,31 0.1ht 7 T 0,21 7 r 0.21 0,21e 0.2t.at C&O 1 11 1 1.3 2 a NAN02 (all) 0.1 0.1 0,1 0.1 0.1 O.A 0.1 0.1 O.A 0.1 0. 0.b 0.1 1 0.) 0.3 0.3 094 0,04 0.4 0.4 Nitro benzene nulphonate-all 0.13 0.1) O.As 0,13 0,13 0,93 01,93 010 @,A)- 0j) 0j) F( ) (01)- SAP& 013 0.9 013 018 &,a 0.9 (911) -- 0.4 0.4 013 0.9 0.7 017 1.6 116 11) 7.3 211 all)43 lee bet all 116 a& 213 113 Fro Acid.
Total Acid 17.6 18.6 21.2 7212 2113 7213 2h.3 23.1 24,9 29.0 20,7 79,4 2A. 4 23.3 32,2 77.3 23.6 24.6 is. 4 55 Free Acid 0.07 10.04 0.0h 0,0) 0.0) 0.07 0.06 0.03 0.09 0,07 0,07 o.al 0. 04 0j) 0.0 1 0.06 0,04 0,09 0,03 Total Acid Application 2)-- spr Sw spr Spr Spr Spir ST To ST To TA To To To To TA TO To TA TO Steel 3) GooO Good Good Good Good Good Good Good Good Good Good Good Good Good Gond Gond Good Good Good Galvanised Goodi Good Good Good Good (Good Good Good Good Good (Coo Good Good Good Good Gno Gond Good Good Good Steel 3) 1 Good ^emits& 3) Good, ('.nnd 1 Good A Good G00.1 Good Good!good 1 Good Good - - -- - - Good Key 1) t additional concentration of Cl bv chloratn reduction diering throughput 2) Spr Spraying Ta - Im^rsion ST - Spray Intersion 3) Coating Formation:
Good: Good, uniforr.ly covering phosphate coating.
(Good). ap above, but appearance of topical crystalline efflorescence (specks) in possible).: Tin rr.51...elline coating on AIMcSi jA 00 m"UIK k 9

Claims (8)

1. A process for forming a phosphate coating on a surface of iron and/or zinc, and optionally also aluminium, by contact of the surface with a phosphating 5 solution which is an aqueous solution containing 0.4 to 2g/1 Zn, 0.4 to 5g/1 Mg, 0.05 to 2g/1 Ni, 8 to 20g/1 P 2 0 5 and at least one oxidising agent, and which has a free acid:total acid ratio of 0.02:1 to 0.15:1 and which, when the surface includes aluminium, contains from 80 to 400mg/1 fluoride as determined by a fluoride-sensitive electrode immersed in the solution.
2. A process according to claim 1 in which the surface is free of aluminium and in which either the solution is applied to the surface by spraying and has a zinc is concentration of 0.4 to lg/1 or is applied by spray immersion or immersion and has a zinc concentration of 0.9 to 1.5g/1.
3. A process according to claim 1 in which the surface includes aluminium and in which either the solution is applied by spraying and has a zinc concentration of from 0.7 to 19/1 or is applied by spray immersion or immersion and has a zinc concentration of 1.4 to 2g/1.
4. A process according to any preceding claim in which the solution contains simple or complex fluoride.
5. A process according to any preceding claim in which at least one of the three components (chloride andlor bromide), (nitrate) and (nickel) has a concentration of not more than 0.1g/1.
6. A process according to any preceding claim in which 30 the contact of the solution with the surface is at a temperature of 40 to 600C.
7. A process according to any preceding claim in which the surface is subsequently painted.
8. A process according to claim 7 in which the painting is by electro-immersion.
g. A process according to claim 7 in which the painting is by cathodic electro-immersion It Pubb.shed 1988 at The Patent O:Mce. State House. 66 71 Hig!i HcOborn. London WClR 4TP Flarther copless njkv be obtained froYn The Patent Office. Sales Branch. St Mary Cray. Orpington. Rent BR5 3RD. Printed by Multiplex techniques ltd. St ma:7 Cray, Kent Con. 1/87.
GB8819791A 1987-08-19 1988-08-19 Processes for forming phosphate coatings on metals Expired - Lifetime GB2208876B (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE3727613 1987-08-19

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GB8819791D0 GB8819791D0 (en) 1988-09-21
GB2208876A true GB2208876A (en) 1989-04-19
GB2208876B GB2208876B (en) 1991-08-14

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GB8819791A Expired - Lifetime GB2208876B (en) 1987-08-19 1988-08-19 Processes for forming phosphate coatings on metals

Country Status (7)

Country Link
EP (1) EP0304108B1 (en)
JP (1) JP2680618B2 (en)
CA (1) CA1333147C (en)
DE (1) DE3871031D1 (en)
ES (1) ES2036666T3 (en)
GB (1) GB2208876B (en)
ZA (1) ZA886167B (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2223239A (en) * 1988-08-24 1990-04-04 Ardrox Pyrene Ltd Phosphating process
DE4131382A1 (en) * 1990-09-21 1992-03-26 Kobe Steel Ltd Surface treated aluminium@ alloy sheet for motor car construction - used in making decorative coloured items, zinc phosphate layer having fine grained structure of uniform thickness
US5399208A (en) * 1989-12-19 1995-03-21 Nippon Paint Co., Ltd. Method for phosphating metal surface with zinc phosphate
US5868874A (en) * 1995-12-14 1999-02-09 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
US6413588B1 (en) 1999-01-11 2002-07-02 E. I. Du Pont De Nemours And Company Method of producing durable layered coatings

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JPH03107469A (en) * 1989-09-21 1991-05-07 Nippon Parkerizing Co Ltd Zinc plated material having phosphate chemical conversion coating film excellent in bare corrosion resistance
JP2695963B2 (en) * 1990-03-16 1998-01-14 マツダ株式会社 Phosphating of metal surfaces
US5144611A (en) * 1990-10-01 1992-09-01 International Business Machines Corporation Optical disk drive cleaner cartridge
US5454882A (en) * 1992-01-13 1995-10-03 Henkel Corporation Process for controlling a fluoride containing conversion coating forming composition during its use for conversion coating aluminum containing metal
JP3181658B2 (en) * 1992-01-13 2001-07-03 日本パーカライジング株式会社 Determination method of effective fluorine concentration in acid chemical conversion treatment of metallic materials
JPH05306497A (en) 1992-04-30 1993-11-19 Nippondenso Co Ltd Phophatizing chemical conversion treatment
DE4306446A1 (en) * 1993-03-02 1994-09-08 Metallgesellschaft Ag Procedures to facilitate cold forming
JPH07173643A (en) * 1993-12-21 1995-07-11 Mazda Motor Corp Method for phosphating metal surface and phosphating solution
US5478413A (en) * 1994-12-27 1995-12-26 Sermatech International, Inc. Environmentally friendly coating compositions
DE19606018A1 (en) * 1996-02-19 1997-08-21 Henkel Kgaa Zinc phosphating with low levels of nickel and / or cobalt
DE19921135A1 (en) * 1999-05-07 2000-11-09 Henkel Kgaa Process for low-zinc zinc phosphating followed by water treatment
JP4658339B2 (en) * 2001-01-17 2011-03-23 日本ペイント株式会社 Metal surface treatment method
DE102005059314B4 (en) * 2005-12-09 2018-11-22 Henkel Ag & Co. Kgaa Acid, chromium-free aqueous solution, its concentrate, and a process for the corrosion protection treatment of metal surfaces
JP5119864B2 (en) * 2006-10-31 2013-01-16 Ｊｆｅスチール株式会社 Phosphate-treated galvanized steel sheet and method for producing the same
SG176435A1 (en) 2006-10-31 2011-12-29 Jfe Steel Corp Phosphate-treated galvanized steel sheet and method for making the same
JP4992385B2 (en) * 2006-10-31 2012-08-08 Ｊｆｅスチール株式会社 Organic resin-coated phosphate-treated zinc-based plated steel sheet and method for producing the same
JP2007314888A (en) * 2007-07-17 2007-12-06 Toyota Motor Corp Multilayer coating film structure
ES2397997B1 (en) * 2010-03-22 2014-01-17 Roberto Ruiz Sanz DEPOSIT BY PASS FOR COMPRESSED AIR.
CN102430506A (en) * 2011-12-15 2012-05-02 江苏腾奇电力设备科技有限公司 Paint coating process for radiator cast
KR101830508B1 (en) * 2016-06-24 2018-02-21 주식회사 포스코 Phosphate-treated zinc-based plated steel sheet having excellent discoloration resistance and film adhesiveness

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Publication number Priority date Publication date Assignee Title
GB648888A (en) * 1947-04-25 1951-01-17 Walterisation Company Ltd Improvements in the production of phosphate coatings on metal surfaces
GB1288103A (en) * 1969-10-08 1972-09-06
GB1498718A (en) * 1974-12-04 1978-01-25 Pyrene Chemical Services Ltd Process for phosphating metal surfaces
EP0114087A1 (en) * 1983-01-03 1984-07-25 Detrex Corporation Zinc phosphate coated metal and process of producing same
GB2137231A (en) * 1983-03-31 1984-10-03 Pyrene Chemical Services Ltd Phosphate coating processes
EP0154367A2 (en) * 1984-03-09 1985-09-11 Metallgesellschaft Ag Process for phosphatizing metals
GB2179680A (en) * 1985-08-26 1987-03-11 Parker Chemical Co Method of forming phosphate coatings on zinc
GB2196024A (en) * 1986-09-05 1988-04-20 Pyrene Chemical Services Ltd Process for producing phosphate coatings

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US3676224A (en) * 1970-10-16 1972-07-11 Lubrizol Corp Phosphating solution with scale suppressing characteristics
DE2327304C3 (en) * 1973-05-29 1982-01-21 Metallgesellschaft Ag, 6000 Frankfurt Process for applying phosphate coatings to metals
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Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB648888A (en) * 1947-04-25 1951-01-17 Walterisation Company Ltd Improvements in the production of phosphate coatings on metal surfaces
GB1288103A (en) * 1969-10-08 1972-09-06
GB1498718A (en) * 1974-12-04 1978-01-25 Pyrene Chemical Services Ltd Process for phosphating metal surfaces
EP0114087A1 (en) * 1983-01-03 1984-07-25 Detrex Corporation Zinc phosphate coated metal and process of producing same
GB2137231A (en) * 1983-03-31 1984-10-03 Pyrene Chemical Services Ltd Phosphate coating processes
EP0154367A2 (en) * 1984-03-09 1985-09-11 Metallgesellschaft Ag Process for phosphatizing metals
GB2179680A (en) * 1985-08-26 1987-03-11 Parker Chemical Co Method of forming phosphate coatings on zinc
GB2196024A (en) * 1986-09-05 1988-04-20 Pyrene Chemical Services Ltd Process for producing phosphate coatings

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2223239A (en) * 1988-08-24 1990-04-04 Ardrox Pyrene Ltd Phosphating process
GB2223239B (en) * 1988-08-24 1992-09-23 Ardrox Pyrene Ltd Phosphating process
US5399208A (en) * 1989-12-19 1995-03-21 Nippon Paint Co., Ltd. Method for phosphating metal surface with zinc phosphate
DE4131382A1 (en) * 1990-09-21 1992-03-26 Kobe Steel Ltd Surface treated aluminium@ alloy sheet for motor car construction - used in making decorative coloured items, zinc phosphate layer having fine grained structure of uniform thickness
US5868874A (en) * 1995-12-14 1999-02-09 Ppg Industries, Inc. Zinc phosphate conversion coating compositions and process
US6413588B1 (en) 1999-01-11 2002-07-02 E. I. Du Pont De Nemours And Company Method of producing durable layered coatings

Also Published As

Publication number Publication date
ES2036666T3 (en) 1993-06-01
CA1333147C (en) 1994-11-22
ZA886167B (en) 1990-04-25
GB8819791D0 (en) 1988-09-21
EP0304108B1 (en) 1992-05-13
JPS6468481A (en) 1989-03-14
GB2208876B (en) 1991-08-14
EP0304108A1 (en) 1989-02-22
JP2680618B2 (en) 1997-11-19
DE3871031D1 (en) 1992-06-17

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