EP0469011B1 - Procede sans chlorate ni nitrite pour produire des couches de phosphate de zinc contenant du nickel et du manganese - Google Patents

Procede sans chlorate ni nitrite pour produire des couches de phosphate de zinc contenant du nickel et du manganese Download PDF

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Publication number
EP0469011B1
EP0469011B1 EP19900906149 EP90906149A EP0469011B1 EP 0469011 B1 EP0469011 B1 EP 0469011B1 EP 19900906149 EP19900906149 EP 19900906149 EP 90906149 A EP90906149 A EP 90906149A EP 0469011 B1 EP0469011 B1 EP 0469011B1
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EP
European Patent Office
Prior art keywords
zinc
iron
nickel
manganese
aqueous solution
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
EP19900906149
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German (de)
English (en)
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EP0469011A1 (fr
Inventor
Jörg Riesop
Kurt Hosemann
Karl-Heinz Gottwald
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.)
Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C23C22/05—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
    • C23C22/18—Orthophosphates containing manganese cations
    • C23C22/182—Orthophosphates containing manganese cations containing also zinc cations
    • C23C22/184—Orthophosphates containing manganese cations containing also zinc cations containing also nickel cations

Definitions

  • the present invention relates to a method for phosphating metal surfaces, in particular a method for producing manganese and nickel-containing zinc phosphate layers on steel, zinc and / or their alloys. These nickel and manganese-containing zinc phosphate layers are applied by spraying, splash-dipping and dipping with aqueous solutions.
  • Zinc phosphating baths can contain, for example, monozinc phosphate, free phosphoric acid, zinc nitrate and oxidizing agents as main components.
  • the pH of such solutions is usually in the range between 2.8 and 3.4.
  • the process consists essentially of two reactions: the pickling reaction and the formation of a zinc phosphate layer on the surface to be phosphated.
  • manganese-modified zinc phosphate coatings are known as a basis of liability for modern coatings.
  • the use of manganese ions in addition to zinc and nickel ions in Low-zinc phosphating processes have been shown to improve corrosion protection, especially when using surface-coated sheet metal.
  • the incorporation of manganese into the zinc phosphate coatings leads to smaller and more compact crystals with increased stability to alkali.
  • the working range of phosphating baths is increased; Aluminum can also be phosphated in combination with steel and galvanized steel to form a layer, whereby the generally achieved quality standard is guaranteed.
  • the object of the present invention was to provide a phosphating process which is free of both nitrite and chlorate and which, in particular, does not cause so-called “specks”. This means, on the one hand, growths of zinc salts, which are called “white staining” in English and are caused by the cleaning solution. On the other hand, during the phosphating process, crater-shaped openings are created, which are known in English as "nubbing".
  • the commonly used systems contain chlorate, bromate, nitrate, nitrite, peroxide and / or organic accelerators Nitro compounds such as 3-nitrobenzenesulfonate.
  • 3-nitrobenzenesulfonate has hitherto generally been used together with chlorate and / or nitrite accelerators according to the prior art.
  • the 3-nitrobenzenesulfonic acid / chlorate system usually used produces the abovementioned specks in the presence of nitrate on electrolytically galvanized steel, so that it is usually necessary to work without nitrates.
  • the above-mentioned object is achieved by a chlorate- and nitrite-free process for the production of nickel and manganese-containing zinc phosphate layers on steel, zinc and / or their alloys by spraying, spray-immersion and / or immersion with an aqueous solution 0.3 to 1.5 g / l zinc (II), 0.01 to 2.0 g / 1 manganese (II), 0.01 to 0.8 g / l iron (II), 0.3 to 2.0 g / l nickel (II), 10.0 to 20.0 g / l phosphate ions, 2.0 to 10.0 g / l nitrate ions and 0.1 to 2.0 g / 1 of an organic oxidizing agent, wherein the aqueous solution has a free acid content of 0.5 to 1.8 points and a total acid content of 15 to 35 points and Na+ is present in the amount necessary to adjust the free acid.
  • a low-zinc process which has a defined iron (II) content.
  • iron (II) is oxidized to iron (II) and removed from the system as iron phosphate sludge.
  • the desired iron (II) value can be added to the sludge elimination system by adding hydrogen peroxide and / or potassium permanganate Iron (II) can be adjusted to iron (II).
  • the advantage of the process according to the invention is, in particular, that if the above limits for iron (II) are observed and if a single accelerator, namely an organic oxidizing agent, is used, no nitrous gases are formed.
  • a single accelerator namely an organic oxidizing agent
  • the iron (II) concentration is determined continuously and / or discontinuously.
  • Such analytical determinations are known to the person skilled in the art.
  • an excessively high iron (II) concentration can be changed so that iron (III) is formed.
  • the precise control of the iron (II) content is an extremely essential point of the present invention.
  • the present invention is therefore a zinc phosphating process which can be used in particular in the low zinc range. With the help of this process, phosphate layers are created which contain cations and iron as well as nickel and manganese.
  • the organic oxidizing agent to be used is selected according to the invention in such a way that it does not contribute or makes little contribution to the oxidation of iron (II) to iron (II). This is mainly used to depolarize the nascent hydrogen.
  • the chlorate- and nitrite-free process for producing zinc phosphate layers on steel, zinc and / or their alloys is modified by dipping, spray-dipping and / or dipping with an aqueous solution in such a way that an aqueous solution is obtained 0.8 to 1.0 g / l zinc (II), 0.8 to 1.0 g / l manganese (II), 0.2 to 0.4 g / l iron (II), 0.5 to 0.7 g / l nickel (II), 12.0 to 16.0 g / l phosphate ions, 3.0 to 6.0 g / l nitrate ions and 0.3 to 0.8 g / l of an organic oxidizing agent starts.
  • the free acid content as well as the total acid content corresponds to the above as does the amount of sodium.
  • 3-nitrobenzenesulfonic acid is used as the organic oxidizing agent.
  • a preferred embodiment of the present invention consists in limiting the upper limit of the concentration of iron (II) in the aqueous solution to less than or equal to 0.3 g / l.
  • Atmospheric oxygen is primarily used for this. In principle, however, other oxidizing agents, such as hydrogen peroxide, oxygen and / or potassium permanganate, can also be used.
  • the sodium salt of 3-nitrobenzenesulfonic acid is used as the preferred organic oxidizing agent.
  • the iron (II) content in the bath solution was determined using oxidizing agents such as hydrogen peroxide, potassium and / or sodium permanganate, ozone, oxygen, and / or atmospheric oxygen, which was continuous or were added batchwise in the amounts required to adjust the iron (II) concentration, below the values given in Table 1.
  • oxidizing agents such as hydrogen peroxide, potassium and / or sodium permanganate, ozone, oxygen, and / or atmospheric oxygen
  • Steel sheets of quality St. 1405 treated according to application type B show the following layer composition: 52% hopeit (including Zn2Mn (PO4) 2 x 4 H2O) 48% phosphophyllite.
  • Corrosion tests in an alternating climate according to VW standard P 1210 were carried out with the test sheet using the application types (B) spray-immersion and (C) immersion with a test time of 30/60 days: (The standard KET primer FT 85 7042, Manufacturer BASF Paints and Varnishes, related) Application type B 30 days 60 days CRS 1) Z 2) ZE 3) CRS Z.
  • blistering that occurs in paints is defined by specifying the degree of blistering.
  • the degree of bubbles according to this standard is a measure of the formation of bubbles on a coating according to the frequency of the bubbles per unit area and the size of the bubbles.
  • the degree of bubbles is indicated by a code letter and a code number for the frequency of the bubbles per unit area as well as a code letter and a code number for the size of the bubbles.
  • the code letter and the code m0 mean no bubbles, while m5 defines a certain frequency of bubbles per unit area according to the degree of bubbles according to DIN 53 209.
  • the size of the bubbles is given the code letter g and the code number in the range from 0 to 5.
  • Code letter and code number g0 has the meaning - no bubbles - while g5 is shown according to the size of the bubbles according to the degree of bubbles in DIN 53 209.
  • the degree of blistering is determined, the image of which is most similar to the appearance of the coating.
  • the salt spray test according to this standard is used to determine the behavior of paints, coatings and similar coatings when exposed to sprayed sodium chloride solution. If the coating has weak points, pores or injuries, the coating preferably infiltrates from there. This leads to a reduction in adhesion or to loss of adhesion and corrosion of the metallic surface.
  • the salt spray test is used so that such errors can be recognized and the infiltration can be determined.
  • the VW standard P-VW 1210 is an alternating test that consists of a combination of different standardized test methods.
  • a test cycle is maintained which consists of 4 h salt spray test according to DIN 50 021, 4 h rest at room temperature and 16 h condensation constant climate according to DIN 50 017.
  • test bone is bombarded with a defined amount of steel shot with a certain grain size distribution. After the test period has expired, a key figure is assigned to the degree of corrosion.
  • the key figure 1 denotes an invisible corrosion, while with a key figure 10 practically the entire surface is corroded.

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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)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Cosmetics (AREA)

Claims (6)

  1. Procédé sans chlorate ni nitrite pour produire des couches de phosphate de zinc contenant du nickel et du manganèse sur de l'acier, du zinc et/ou leurs alliages par projection, projection et immersion et/ou immersion avec une solution aqueuse contenant :
       0,3 à 1,5 g/l de zinc (II)
       0,01 à 2,0 g/l de manganèse (II),
       0,01 à 0,8 g/l de fer (II),
       0,3 à 2,0 g/l de nickel (II),
       10,0 à 20,0 g/l d'ions phosphate
       2,0 à 10,0 g/l d'ions nitrate et
       0,1 à 2,0 g/l d'un agent d'oxydation organique,
    la solution aqueuse ayant une teneur en acide libre de 0,5 à 1,8 points et une teneur en acide total de 15 à 35 points de Na⁺ étant présent dans la quantité nécessaire à l'ajustage de l'acide libre.
  2. Procédé selon la revendication 1, caractérisé en ce que la solution aqueuse comprend :
       de 0,8 à 1,0 g/l de zinc (II)
       de 0,8 à 1,0 g/l de manganèse (II)
       de 0,2 à 0,4 g/l de fer (II)
       de 0,5 à 0,7 g/l de nickel (II)
       de 12,0 à 16,0 g/1 d'ions phosphate
       de 3,0 à 6,0 g/l d'ions nitrate et
       de 0,3 à 0,8 g/l d'un agent d'oxydation organique.
  3. Procédé selon les revendications 1 ou 2, caractérisé en ce que comme agent d'oxydation organique on met en oeuvre de l'acide 3-nitrobenzène-sulfonique.
  4. Procédé selon les revendications 1 à 3, caractérisé en ce que la solution aqueuse contient une quantité inférieure ou égale à 0,3 g/l de fer (II).
  5. Procédé selon une des revendications 3 à 4, caractérisé en ce qu'on met en oeuvre le sel de sodium de l'acide 3-nitrobenzène-sulfonique.
  6. Procédé selon une des revendications 1 à 5, caractérisé en ce qu'on ajuste la teneur en fer (II) par des agents d'oxydation, qui sont choisis parmi l'oxygène de l'air, l'oxygène, le peroxyde d'hydrogène et/ou le permanganate de potassium.
EP19900906149 1989-04-21 1990-04-14 Procede sans chlorate ni nitrite pour produire des couches de phosphate de zinc contenant du nickel et du manganese Expired - Lifetime EP0469011B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3913089 1989-04-21
DE3913089A DE3913089A1 (de) 1989-04-21 1989-04-21 Chlorat- und nitritfreies verfahren zur herstellung von nickel- und manganhaltigen zinkphosphatschichten
PCT/EP1990/000592 WO1990012901A1 (fr) 1989-04-21 1990-04-14 Procede sans chlorate ni nitrite pour produire des couches de phosphate de zinc contenant du nickel et du manganese

Publications (2)

Publication Number Publication Date
EP0469011A1 EP0469011A1 (fr) 1992-02-05
EP0469011B1 true EP0469011B1 (fr) 1995-01-04

Family

ID=6379116

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900906149 Expired - Lifetime EP0469011B1 (fr) 1989-04-21 1990-04-14 Procede sans chlorate ni nitrite pour produire des couches de phosphate de zinc contenant du nickel et du manganese

Country Status (9)

Country Link
US (1) US5312492A (fr)
EP (1) EP0469011B1 (fr)
JP (1) JPH04504881A (fr)
AT (1) ATE116693T1 (fr)
BR (1) BR9007301A (fr)
CA (1) CA2053244A1 (fr)
DE (2) DE3913089A1 (fr)
ES (1) ES2066200T3 (fr)
WO (1) WO1990012901A1 (fr)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1041001C (zh) * 1993-09-06 1998-12-02 汉克尔股份两合公司 无镍的磷酸盐化处理金属表面的方法
CN1093891C (zh) * 1994-12-06 2002-11-06 日本帕卡濑精株式会社 含水磷酸锌化学转化处理液及处理金属材料的方法
US5932292A (en) * 1994-12-06 1999-08-03 Henkel Corporation Zinc phosphate conversion coating composition and process
ES2183891T3 (es) * 1994-12-06 2003-04-01 Henkel Corp Composicion y proceso de rebvestimiento por conversion de fosfato de cinc.
CA2214834A1 (fr) * 1995-03-07 1996-09-12 Yasuhiko Nagashima Composition permettant de nettoyer et de revetir par conversion des surfaces de metaux et procede correspondant
WO1996027692A1 (fr) * 1995-03-07 1996-09-12 Henkel Corporation Composition servant a former une couche intermediaire de peinture sur des metaux et procede correspondant
US5888315A (en) * 1995-03-07 1999-03-30 Henkel Corporation Composition and process for forming an underpaint coating on metals
US6231688B1 (en) * 1995-12-06 2001-05-15 Henkel Corporation Composition and process for zinc phosphate conversion coating
WO1997020964A1 (fr) * 1995-12-06 1997-06-12 Henkel Corporation Composition et procede de revetement par conversion de phosphate de zinc
BRPI0811201A2 (pt) * 2007-06-07 2014-10-29 Henkel Ag & Co Kgaa Composição de matéria líquida útil para a formação de um revestimento de conversão de fosfato sobre um substrato metálico, processo para a produção de um revestimento de conversão de fosfato sobre um substrato metálico, e, artigo de fabricação.
KR20110054009A (ko) * 2008-09-17 2011-05-24 호덴 세이미츠 카코 켄쿄쇼 컴퍼니 리미티드 아연 또는 아연 합금 표면의 흑색화 화성 처리용 수용액과 그 처리용 수용액을 이용하는 흑색화 방청 피막 형성 방법

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1258855A (fr) * 1960-02-18 1961-04-21 Parker Ste Continentale Procédé perfectionné de phosphatation de surfaces métalliques
DE3101866A1 (de) * 1981-01-22 1982-08-26 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen
JPS57152472A (en) * 1981-03-16 1982-09-20 Nippon Paint Co Ltd Phosphating method for metallic surface for cation type electrodeposition painting
DE3118375A1 (de) * 1981-05-09 1982-11-25 Metallgesellschaft Ag, 6000 Frankfurt Verfahren zur phosphatierung von metallen sowie dessen anwendung zur vorbehandlung fuer die elektrotauchlackierung
GB8329250D0 (en) * 1983-11-02 1983-12-07 Pyrene Chemical Services Ltd Phosphating processes
SG52645A1 (en) * 1985-08-27 1998-09-28 Henkel Corp A process for phosphate-coating metal surfaces
DE3630246A1 (de) * 1986-09-05 1988-03-10 Metallgesellschaft Ag Verfahren zur erzeugung von phosphatueberzuegen sowie dessen anwendung
DE3712339A1 (de) * 1987-04-11 1988-10-20 Metallgesellschaft Ag Verfahren zur phosphatierung vor der elektrotauchlackierung
DE3742634A1 (de) * 1987-12-16 1989-06-29 Collardin Gmbh Gerhard Verfahren zur entschlammung von phosphatierungsbaedern und vorrichtung fuer dieses verfahren
EP0327153B1 (fr) * 1988-02-03 1993-08-04 Metallgesellschaft Ag Procédé pour former des couches de phosphates sur des métaux

Also Published As

Publication number Publication date
CA2053244A1 (fr) 1990-10-22
WO1990012901A1 (fr) 1990-11-01
ATE116693T1 (de) 1995-01-15
JPH04504881A (ja) 1992-08-27
ES2066200T3 (es) 1995-03-01
US5312492A (en) 1994-05-17
BR9007301A (pt) 1991-12-10
EP0469011A1 (fr) 1992-02-05
DE59008202D1 (de) 1995-02-16
DE3913089A1 (de) 1990-10-25

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