EP0201841B1 - Verfahren zur Phosphatierung von Metalloberflächen - Google Patents

Verfahren zur Phosphatierung von Metalloberflächen Download PDF

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Publication number
EP0201841B1
EP0201841B1 EP86106161A EP86106161A EP0201841B1 EP 0201841 B1 EP0201841 B1 EP 0201841B1 EP 86106161 A EP86106161 A EP 86106161A EP 86106161 A EP86106161 A EP 86106161A EP 0201841 B1 EP0201841 B1 EP 0201841B1
Authority
EP
European Patent Office
Prior art keywords
metal surfaces
phosphate
rinse
bath
layer
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
EP86106161A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0201841A2 (de
EP0201841A3 (en
Inventor
Atsunori Nihon Parkerizing Co. Ltd. Yoshida
Toshi Nihon Parkerizing Co. Ltd. Miyawaki
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
Priority to AT86106161T priority Critical patent/ATE68532T1/de
Publication of EP0201841A2 publication Critical patent/EP0201841A2/de
Publication of EP0201841A3 publication Critical patent/EP0201841A3/de
Application granted granted Critical
Publication of EP0201841B1 publication Critical patent/EP0201841B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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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
    • C23C22/78—Pretreatment of the material to be coated
    • C23C22/80—Pretreatment of the material to be coated with solutions containing titanium or zirconium compounds

Definitions

  • the invention relates to a method for phosphating metal surfaces, in which the metal surfaces are brought into contact with an aqueous pre-rinse bath containing titanium, phosphate and pyrophosphate as activating agent before they are phosphated.
  • Activation of a metal surface before phosphating means contacting this surface with an aqueous pre-rinse bath in which an activating agent is extremely finely dispersed as a solid phase.
  • an activating agent is extremely finely dispersed as a solid phase.
  • the effectiveness of the activation extends both to the phosphating of iron and steel and to that of non-ferrous metals, for example zinc, zinc alloys, metals coated with zinc and zinc alloys, aluminum, aluminum alloys and metals coated with aluminum and its alloys.
  • the object of the invention is to provide a method for phosphating metal surfaces by pretreatment to be provided by means of a pre-rinse bath which does not have the known, in particular the aforementioned disadvantages, or has them in a greatly reduced form, can be used without additional work and remains effective over a considerably extended period of time.
  • the object is achieved by designing the method of the type mentioned at the outset in accordance with the invention in such a way that the metal surfaces are brought into contact with a prewash bath which contains and has a pH of 8 to 9.5.
  • the phosphate layer produced becomes less dense. If the concentration is increased above 100 ppm, the phosphate layer remains as dense as in the range from 3 to 100 ppm, but no additional effect is obtained, so that such high concentrations are not recommended from an economic point of view.
  • the phosphate layer becomes less dense and its weight increases.
  • the well-known aging effect is noticeable.
  • the concentration exceeds 360 ppm, it becomes increasingly difficult to form a zinc phosphate type layer; instead, an iron phosphate layer is increasingly formed.
  • Layers with the desired density of the phosphate crystals and the desired low layer weight are obtained only in the range from 60 to 360 ppm, which should be explained by the suppression of the coagulation of the titanium colloids.
  • the fourth essential component of the pre-rinse bath - especially in connection with pyrophosphate - ensures that perfect layers are obtained even after relatively long periods of use.
  • the reason for this is likely to be that the coagulation of the titanium colloids responsible for aging is suppressed or the titanium colloids are stabilized. This stabilization could possibly also be achieved by correspondingly high amounts of pyrophosphate, but then the metal surfaces become inactive and the layer formation is inhibited.
  • the combined use of both bath components in the concentrations mentioned ensures that on the one hand the initially present stability of the titanium colloids and at the same time the activity of the metal surfaces is retained.
  • Compliance with the pH range is important insofar as there is a tendency for the titanium colloids to coagulate when the value falls below and the conditioning effect of the pre-rinse bath is lost when it is exceeded.
  • the metal surfaces are brought into contact with a pre-rinse bath whose water-soluble, anionic polymer is formed from the unsaturated carboxylic acid, acrylic acid, metacrylic acid and / or maleic acid.
  • the phosphate layers formed were evaluated according to the appearance with o for a dense and even layer, with x for an uneven and incomplete layer with rust film, based on the layer weight, determined from the weight difference before and after removal of the phosphate layer with 5% by weight chromic acid solution, according to the size of the crystals (measured with an electron microscope model ZSM-T100 from Nihon Denski KK)
  • Tables 1 and 2 The test results are summarized in Tables 1 and 2. This shows that the layers produced by the process according to the invention (Table 1 Examples 1 to 8; Table 2 Examples 1 to 8) are of excellent quality in terms of appearance, weight gain and crystal size, while the layers produced by the known process (Table 1 Comparative Example 1 and Table 2 Comparative Example 1) also show good results immediately after the preparation, but are unsatisfactory after a waiting period of 10 days.
  • Table 2 also shows the results obtained with essentially the same pre-rinse baths in Table 1. Only the water used had a specific conductivity of 150 ⁇ S / cm instead of 600 ⁇ S / cm. The effective bath components and their amounts were the same. From this it follows that the lower water quality has far less impact on the results obtained than in the known pre-rinse baths (cf. Experiment 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)
  • Laminated Bodies (AREA)
  • Catalysts (AREA)
  • Dental Preparations (AREA)
  • ing And Chemical Polishing (AREA)
EP86106161A 1985-05-10 1986-05-06 Verfahren zur Phosphatierung von Metalloberflächen Expired - Lifetime EP0201841B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT86106161T ATE68532T1 (de) 1985-05-10 1986-05-06 Verfahren zur phosphatierung von metalloberflaechen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP60099278A JPS61257481A (ja) 1985-05-10 1985-05-10 りん酸塩皮膜化成処理用水性表面調整液
JP99278/85 1985-05-10

Publications (3)

Publication Number Publication Date
EP0201841A2 EP0201841A2 (de) 1986-11-20
EP0201841A3 EP0201841A3 (en) 1988-08-10
EP0201841B1 true EP0201841B1 (de) 1991-10-16

Family

ID=14243197

Family Applications (1)

Application Number Title Priority Date Filing Date
EP86106161A Expired - Lifetime EP0201841B1 (de) 1985-05-10 1986-05-06 Verfahren zur Phosphatierung von Metalloberflächen

Country Status (7)

Country Link
EP (1) EP0201841B1 (enExample)
JP (1) JPS61257481A (enExample)
AT (1) ATE68532T1 (enExample)
AU (1) AU5672986A (enExample)
BR (1) BR8602096A (enExample)
DE (2) DE3615294A1 (enExample)
GB (1) GB2174719B (enExample)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0633465B2 (ja) * 1986-04-26 1994-05-02 日本パ−カライジング株式会社 りん酸塩処理した自動車車体の後処理方法
DE3814287A1 (de) * 1988-04-28 1989-11-09 Henkel Kgaa Polymere titanphosphate, verfahren zu ihrer herstellung und ihre verwendung zur aktivierung von metalloberflaechen vor einer zinkphosphatierung
DE3814334A1 (de) * 1988-04-28 1989-11-09 Henkel Kgaa Hartwasserstabilisierender zusatz zu aktivierungsmitteln fuer die zinkphosphatierung
DE4416619A1 (de) * 1994-05-11 1995-11-16 Henkel Kgaa Herstellung phosphathaltiger Aktiviermittel für die Phosphatierung unter Einsatz von Mikrowellen
EP0972862A3 (en) * 1998-07-01 2004-01-02 Nihon Parkerizing Co., Ltd. Method for forming a phosphate film on steel wires and apparatus used therefor
US8506728B2 (en) 2009-09-03 2013-08-13 Mazda Motor Corporation Surface treatment method of metal material
DE102014105226A1 (de) 2014-04-11 2015-10-15 Thyssenkrupp Ag Verfahren zur Aktivierung von zu phosphatierenden Metalloberflächen, vorzugsweise verzinktem Stahlblech

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3728163A (en) * 1970-05-25 1973-04-17 Balm Paints Ltd Alkaline liquids for cleaning metals
US3864139A (en) * 1970-12-04 1975-02-04 Amchem Prod Pretreatment compositions and use thereof in treating metal surfaces
GB1408702A (en) * 1973-02-09 1975-10-01 Pyrene Chemical Services Ltd Phosphate coating compositions and processes
JPS5855229B2 (ja) * 1981-01-19 1983-12-08 日本ペイント株式会社 リン酸亜鉛処理用表面調整剤
JPS5855229A (ja) * 1981-09-28 1983-04-01 Toyo Rubber Chem Ind Co Ltd ポリスチレン発泡体の製造方法
AU2448684A (en) * 1983-03-02 1984-09-06 Parker Chemical Company Metal treatment before phosphate coating

Also Published As

Publication number Publication date
GB2174719A (en) 1986-11-12
ATE68532T1 (de) 1991-11-15
JPH0338343B2 (enExample) 1991-06-10
GB2174719B (en) 1989-05-04
DE3615294A1 (de) 1986-11-13
DE3681958D1 (de) 1991-11-21
GB8611556D0 (en) 1986-06-18
EP0201841A2 (de) 1986-11-20
EP0201841A3 (en) 1988-08-10
JPS61257481A (ja) 1986-11-14
BR8602096A (pt) 1987-01-13
AU5672986A (en) 1986-11-13

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