EP0486576A1 - Procede pour la realisation de revetements de phosphate de zinc comportant du manganese sur de l'acier galvanise. - Google Patents

Procede pour la realisation de revetements de phosphate de zinc comportant du manganese sur de l'acier galvanise.

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Publication number
EP0486576A1
EP0486576A1 EP90912396A EP90912396A EP0486576A1 EP 0486576 A1 EP0486576 A1 EP 0486576A1 EP 90912396 A EP90912396 A EP 90912396A EP 90912396 A EP90912396 A EP 90912396A EP 0486576 A1 EP0486576 A1 EP 0486576A1
Authority
EP
European Patent Office
Prior art keywords
content
anions
phosphating
galvanized steel
cations
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.)
Granted
Application number
EP90912396A
Other languages
German (de)
English (en)
Other versions
EP0486576B1 (fr
Inventor
Joerg Riesop
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
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Publication of EP0486576A1 publication Critical patent/EP0486576A1/fr
Application granted granted Critical
Publication of EP0486576B1 publication Critical patent/EP0486576B1/fr
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
    • C23C22/05—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
    • 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
    • C23C22/364—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 also manganese cations
    • C23C22/365—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 also manganese cations containing also zinc and nickel cations

Definitions

  • the present invention relates to a method for phosphating electrolytically and / or hot-dip galvanized steel strip with the formation of zinc phosphate layers containing manganese and nickel. These manganese and nickel-containing zinc phosphate layers are applied by spraying, splash-dipping and / or dipping with aqueous solutions.
  • DE 32 45 411 A1 discloses a method for phosphating electrolytically galvanized metal products, in particular electrolytically galvanized steel strips, by short-term treatment with acid phosphating solutions which, in addition to zinc and phosphate ions, can contain further metal cations and / or anions of oxygen-containing acids with accelerating action.
  • acid phosphating solutions which, in addition to zinc and phosphate ions, can contain further metal cations and / or anions of oxygen-containing acids with accelerating action.
  • zinc phosphate layers with a mass per unit area of less than 2 g / m 2 are formed. It works with acid phosphating solutions, the content of Zn2 + cations is about 1 to 2.5 g / 1, while the free acid content in the range of 0.8 to 3 points and the total acid / free acid ratio in the range be kept from 5 to 10.
  • the duration of the treatment should not be significantly longer than 5 s.
  • the weight ratio of Zn2 + / N ⁇ 3 ⁇ in the range from 1: 1 to 1: 8 and the weight ratio of P043- / N03 "in the range from 1: 0.1 to 1: 2.5 is held.
  • EP 0 106 459 A1 discloses a phosphating process in which zinc phosphate coatings containing manganese and nickel are formed.
  • the presence of fluoride ions is regarded as essential, as is the upper limit of 10 g / l of nitrate anions.
  • a high nickel phosphating process is known from EP 0 112826 B1.
  • a molar ratio of nickel to zinc in the range from 5.2: 1 to 16: I is assumed.
  • a phosphating process is known from EP 0 175 606, in which the use of iron-containing phosphating baths in particular is used. Furthermore, as Accelerators used a number of organic substances, while the presence of manganese is not required. In addition, the setting of certain ratios of zinc to nickel and zinc to iron is required.
  • the object of the present invention was to avoid darkening of the zinc phosphate layers on electrolytically and / or hot-dip galvanized steel strip at treatment times of 2 to 30 s while maintaining the corrosion protection values.
  • the nickel content of processes known from the literature should be greatly reduced by substitution with manganese in order to Corrosion protection and paint adhesion as in the trication processes used in the automotive industry can also be achieved in continuous strip phosphating. It was, of course, imperative that dense, closed layers of the phosphate layer be formed during the treatment times mentioned and that the deformation properties also be satisfactory.
  • the term “electrolytically and / or hot-dip galvanized steel strip” also includes, of course, generally known zinc alloys (for example “Neuralyt”, ZNE electrolytically applied zinc alloy containing 10 to 13% Ni or “galvannealed”, ZFE electrolytic) applied zinc alloy containing Fe).
  • zinc alloys generally means those zinc alloys which contain at least 45% by weight of zinc.
  • the above-mentioned objects are achieved by using a method for phosphating electrolytically and / or hot-dip galvanized steel strip with the formation of manganese and nickel-containing zinc phosphate layers by brief treatment with acidic phosphating solutions, the duration of the treatment being 2 up to 30 s, the phosphating is carried out in the temperature range from 40 to 70 ° C and the phosphating solutions - at least at the beginning of the treatment - contain the following components or correspond to the following parameters:
  • Free acid content in the range from 1.6 to 3.0 points
  • Total acidity in the range of 12 to 40 points.
  • the weight ratio of Ni + cations to N03 " anions should be set in the range from 1:10 to 1:60 and the weight ratio of Mn + cations to N ⁇ 3" anions in the range from 1: 1 to 1:40 become.
  • the above-mentioned content of P ⁇ 43 ⁇ anions also includes HP04 "and H2 Ü4" anions present in the phosphating solutions as well as undissociated H3PO4 - in the form of the stoichiometric equivalent of P ⁇ 43 anions.
  • the free acid score is accordingly defined as the number of ml 0.1 N NaOH required to titrate 10 ml bath solution against dimethyl yellow, methyl orange or bromophenol blue.
  • the total acid score is calculated as the number of ml of 0.1 N NaOH required to titrate 10 ml of bath solution using phenolphthalein as an indicator until the first pink color.
  • the concentration of Zn 2+ cations is kept in a very low range. Small amounts of zinc ions are the Treatment bath added at the beginning to accelerate the adjustment of the cation balance.
  • the acidic phosphating solutions quickly remove zinc from the galvanized strip. If the zinc content of the phosphating solution before the start of phosphating is more than 0.75 g / 1, the adhesion of a lacquer applied subsequently can be significantly impaired. Under certain system conditions, a higher zinc content in the phosphating bath occurs in operation due to the usual entry of Zn 2+ cations through the galvanized steel strip, but this does not influence the process.
  • the manganese content in the zinc phosphate layer becomes so low that the adhesion between the substrate and the coating after the cataphoresis is insufficient.
  • the manganese content is more than 2.0 g / 1, no further improved effects can be obtained for the subsequent coating.
  • the manganese concentration is increased, precipitates separate from the phosphating solution, so that it is impossible to provide a stable solution.
  • the phosphating solutions preferably contain no strong oxidizing agents, such as nitrites, chlorates or hydrogen peroxide.
  • An essential component of the present invention is the weight ratio of nickel cations to nitrate anions and the weight ratio of manganese cations to nitrate anions.
  • nickel cations to nitrate anions
  • manganese cations to nitrate anions.
  • the coloring of this zinc phosphate layer does not play a major role in the automotive industry, but the color of the zinc phosphate layer is extremely important, for example, in the manufacture of household appliances due to the very thin layers of lacquer that are often applied in the following.
  • Another essential criterion of the present invention is the duration of the phosphating treatment. While times above 120 s are normally used for the phosphating in the automotive industry, a time below 1 min is in any case aimed for in the phosphating of galvanized steel strip. For the purposes of the present invention, the duration of the treatment will therefore be between 2 and 30 s. A duration of the treatment of 3 to 20 s is particularly preferred.
  • the main advantage of the present invention is that zinc phosphate coatings can be produced according to the invention on galvanized steel strip, which have a bright surface appearance. point, although they contain nickel. ⁇ At the same time the Ge could halt of nickel compared to the prior art by substitution with manganese without loss of corrosion protection value are significantly reduced. This is of ecological as well as economic importance, as it is the first time that a manganese-containing trication process has been described for the band sector.
  • the method for phosphating electrolytically and / or hot-dip galvanized steel strip is characterized in that the phosphating solutions contain - at least at the beginning of the treatment - the following constituents or correspond to the following parameters:
  • the weight ratio of nickel cations to nitrate anions is set in the range from 1:20 to 1:60.
  • the weight ratio of manganese cations to nitrate anions is set in the range from 1: 6 to 1:20. This can have a particularly positive influence on the wet paint adhesion.
  • the present process is that it can be replaced both for phosphating electrolytically and hot-dip galvanized steel strip. With electrolytically galvanized
  • phosphating solutions contain a fluoride anion content of 0.1 to 1.0 g / 1, preferably 0.4 to 0.6 g / 1. The corresponding.
  • the amount of fluoride anions is added to the phosphating solutions in the form of hydrofluoric acid or in the form of the sodium or potassium salts of this acid.
  • complex fluoride compounds such as fluoroborates or fluorosilicates can also be used.
  • the phosphating itself takes place at moderately elevated temperatures in the range from about 40 to 70 ° C.
  • the temperature range from 55 to 65 ° C. can be particularly suitable. Any technically useful way of applying the treatment solution is suitable. In particular, it is therefore possible to carry out the new method both by means of spraying technology and by immersion.
  • the electrolytically and / or hot-dip galvanized surface Before the phosphating solution is applied, the electrolytically and / or hot-dip galvanized surface must be completely water-wettable. This is usually the case in continuously operating conveyor systems. If the surface of the galvanized strip is oiled for storage and protection against corrosion, this oil must be removed before the phosphating with known known means and methods.
  • the water wettable the zinc-coated metal surface is then expediently subjected to a known, activating pretreatment prior to the application of the phosphating solution. Suitable pretreatment processes are described in particular in DE-OS 20 38 105 and DE-OS 20 43 085.
  • the metal surfaces to be phosphated subsequently are treated with solutions which contain, as activating agents, essentially titanium salts and sodium phosphate together with organic components such as, for example, alkyl phosphonates or polycarboxylic acids.
  • Soluble compounds of titanium such as potassium titanium fluoride and in particular titanyl sulfate can preferably be used as the titanium component.
  • Disodium orthophosphate is generally used as the sodium phosphate. Titanium-containing compounds and sodium phosphate are used in proportions such that the titanium content is at least 0.005% by weight, based on the weight of the titanium-containing compound and the sodium phosphate.
  • the process according to the invention produces zinc phosphate coatings with an area-related mass of the zinc phosphate layers of less than 2 g / m 2 , which have a closed, finely crystalline structure and which give the electrolytically and / or hot-dip galvanized steel strip a desired, uniform, light gray Give appearance.
  • a steel strip phosphated in this way can also be processed without subsequent coating.
  • the thin phosphate layers produced by the process according to the invention maintain themselves more favorably in many deformation processes than the phosphate layers of a higher mass per unit area produced with the previously customary processes. However, even subsequently applied organic coatings show significantly improved adhesion compared to the prior art, both during and after the deformation processes.
  • surface-based masses of the zinc phosphate layer in the range from 0.7 to 1.6 g / m 2 are produced when using electrolytically galvanized steel strip.
  • the production of a mass per unit area of the zinc phosphate layer in the range from 0.8 to 1.6 g / m 2 should be emphasized as particularly advantageous.
  • the method according to the invention allows the zinc and manganese-containing zinc phosphate layer to be applied by techniques known per se in the prior art, such as spraying, dipping and / or spray-dipping, in particular their combined methods.
  • the acid ratio is determined when using electrolytically galvanized steel strip, i.e. the quotient from “total acid” to “free acid” is set in the range from 25: 1 to 10: 1, preferably in the range from 15: 1 to 10: 1.
  • a further embodiment of the present invention is characterized in that the content of N03 "anions in the phosphating solutions is 1.0 to 30 g / l.
  • the surface layers produced with the aid of the method according to the invention can be used well in all fields in which phosphate coatings are used.
  • a particularly advantageous application is the preparation of the metal surfaces for painting, in particular electro-dip painting.
  • alkaline cleaning agents containing surfactants such as RID0LINE R C 72
  • spraying at 50 to 60 ° C. and treatment times of 5 to 20 s.
  • agents containing titanium salt such as FIX0DINE R 950
  • spraying at 20 to 40 ° C and treatment times of 2 to 4 s.
  • chrome-containing or chrome-free post-passivation agents such as DE0XYLYTE R 41B or DE0XYLYTE R 80
  • spraying or dipping at 20 to 50 ° C and treatment times of 2 to 6 s.
  • the tape dries after being squeezed by its own heat.
  • the surface treatment was carried out on electrolytically galvanized steel (coating on both sides 7.5 ⁇ m Zn) and hot-dip galvanized steel (coating on both sides 10 ⁇ m Zn).
  • a surface-related mass of 0.6 to 1.6 g / m 2 was obtained for electrolytically galvanized steel (ZE) and a surface-related mass of the phosphate layer of 0.8 to 1.6 g / m 2 for hot-dip galvanized steel (Z) manufactured.
  • Zn as oxide or nitrate
  • Mn as carbonate
  • Ni as nitrate or phosphate
  • F as hydrofluoric acid or sodium fluoride
  • PO4 as H3PO4 or nickel phosphate
  • NO3 as HNO3 or nickel nitrate.
  • the substrate to be phosphated was selected to be galvanized steel on both sides (7.5 / 7.5 ⁇ m zinc) for testing by means of VW-P 1210 alternating climate test and hot-dip galvanized steel (10/10 ⁇ m zinc) for the salt spray test .
  • the sheets obtained with the help of Examples 1, 3 and 4 and the comparative example were used to carry out corrosion tests with an alternating climate in accordance with VW standard P 1210 over a test period of 15 and 30 days, and corrosion tests in a salt spray test in accordance with DIN 50021 SS, 1008 h.
  • blistering that occurs in paints is defined by specifying the degree of blistering.
  • the degree of blistering according to this standard is a measure of a blistering that has occurred on a coating according to the frequency of the blisters per unit area and size of the blisters.
  • 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 mO mean no bubbles, while m5 defines a certain frequency of bubbles per unit area according to the bubble degree images 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 GO has the importance of freedom from bubbles, while g5 shows the size of the bubbles in accordance with the bubble degree images of DIN 53209.
  • the degree of bubbles is determined, the image of which is most similar to the appearance of the paint.
  • the salt spray test according to this standard serves 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 is preferably infiltrated from there. This leads to a reduction in adhesion or to loss of adhesion and corrosion of the metallic substrate.
  • the salt spray test is used so that such errors can be recognized and the infiltration can be determined.
  • the VW standard P 1210 defines an alternating test which consists of a combination of different, standardized test methods. So in During the course of - in the present case - 15 and 30 days a test cycle was followed, which consists of
  • the test sheet is bombarded with a defined amount of steel shot with a certain grain size distribution.
  • a key figure is assigned to the degree of corrosion.
  • the key figure 1 denotes invisible corrosion, while with a key figure 10 the entire surface is practically corroded.
  • the sample is bent for 1 to 2 s with various bending radii parallel to the rolling direction by 180 °, the coating being on the outside.
  • the smallest bending radius which allows the sample to bend without tearing, determines the adhesive power at a 180 ° bend.
  • test T0 the sheet is bent evenly through 180 ° within 1 to 2 s without an intermediate layer. The sheet is examined immediately after bending with a magnifying glass that magnifies ten times. The test procedure is made more difficult by firmly pressing an adhesive film onto the edge and tearing it off quickly. The amount of lacquer torn off is then assessed.

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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)
  • Coating With Molten Metal (AREA)

Abstract

Lors d'un procédé de phosphatation d'acier sous forme de feuillard par l'électrolyse et/ou par galvanisation à chaud, ledit feuillard est traité brièvement par des solutions de phosphatation acides comportant, en plus d'ions de zinc et de phosphate, des cations de manganèse et de nickel ainsi que des anions d'acides comportant de l'oxygène à effet accelérateur. Le rapport pondéral entre les cations de nickel et les anions de nitrate est ajusté à entre 1:10 et 1:60, le rapport pondéral entre les cations de manganèse et les anions de nitrate étant ajusté à entre 1:1 et 1:40.
EP90912396A 1989-08-17 1990-08-08 Procede pour la realisation de revetements de phosphate de zinc comportant du manganese sur de l'acier galvanise Expired - Lifetime EP0486576B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE3927131A DE3927131A1 (de) 1989-08-17 1989-08-17 Verfahren zur herstellung von manganhaltigen zinkphosphatschichten auf verzinktem stahl
DE3927131 1989-08-17
PCT/EP1990/001295 WO1991002829A2 (fr) 1989-08-17 1990-08-08 Procede pour la realisation de revetements de phosphate de zinc comportant du manganese sur de l'acier galvanise

Publications (2)

Publication Number Publication Date
EP0486576A1 true EP0486576A1 (fr) 1992-05-27
EP0486576B1 EP0486576B1 (fr) 1995-04-26

Family

ID=6387273

Family Applications (1)

Application Number Title Priority Date Filing Date
EP90912396A Expired - Lifetime EP0486576B1 (fr) 1989-08-17 1990-08-08 Procede pour la realisation de revetements de phosphate de zinc comportant du manganese sur de l'acier galvanise

Country Status (10)

Country Link
EP (1) EP0486576B1 (fr)
JP (1) JPH04507436A (fr)
CN (1) CN1034681C (fr)
AT (1) ATE121803T1 (fr)
AU (1) AU633135B2 (fr)
CA (1) CA2065004A1 (fr)
DE (2) DE3927131A1 (fr)
ES (1) ES2071110T3 (fr)
WO (1) WO1991002829A2 (fr)
ZA (1) ZA906507B (fr)

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4326388A1 (de) * 1993-08-06 1995-02-09 Metallgesellschaft Ag Verfahren zur phosphatierenden Behandlung von einseitig verzinktem Stahlband
DE4443882A1 (de) * 1994-12-09 1996-06-13 Metallgesellschaft Ag Verfahren zum Aufbringen von Phosphatüberzügen auf Metalloberflächen
DE19808755A1 (de) 1998-03-02 1999-09-09 Henkel Kgaa Schichtgewichtsteuerung bei Bandphosphatierung
RU2149829C1 (ru) * 1999-01-29 2000-05-27 Закрытое акционерное общество "ФК" Способ получения марганцевого фосфатирующего концентрата
DE10010355A1 (de) * 2000-03-07 2001-09-13 Chemetall Gmbh Verfahren zum Aufbringen eines Phosphatüberzuges und Verwendung der derart phosphatierten Metallteile
CN1297688C (zh) * 2000-05-30 2007-01-31 杰富意钢铁株式会社 具有有机涂层的钢板和其制造方法
JP4603502B2 (ja) * 2006-03-30 2010-12-22 新日本製鐵株式会社 被覆鋼材
CN101660164B (zh) * 2008-08-26 2011-12-28 宝山钢铁股份有限公司 一种润滑性电镀锌钢板及其生产方法
CN102677034A (zh) * 2012-05-25 2012-09-19 衡阳市金化科技有限公司 一种中温低渣锌系磷化液
AT516956B1 (de) * 2015-06-29 2016-10-15 Andritz Ag Maschf Vorrichtung und verfahren zur herstellung eines verzinkten stahlbandes
CN112195429B (zh) * 2020-09-25 2022-08-23 河钢股份有限公司承德分公司 一种无锌花900g/m2双面超厚锌层镀锌板的生产方法
CN112410768B (zh) * 2020-10-30 2023-06-23 马鞍山钢铁股份有限公司 一种镀锌钢板表面处理剂、表面处理剂的制备方法及自润滑镀锌钢板、钢板的制备方法

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Publication number Priority date Publication date Assignee Title
JPS57152472A (en) * 1981-03-16 1982-09-20 Nippon Paint Co Ltd Phosphating method for metallic surface for cation type electrodeposition painting
JPS5935681A (ja) * 1982-08-24 1984-02-27 Nippon Paint Co Ltd カチオン型電着塗装用金属表面のリン酸塩処理方法
DE3245411A1 (de) * 1982-12-08 1984-07-05 Gerhard Collardin GmbH, 5000 Köln Verfahren zur phosphatierung elektrolytisch verzinkter metallwaren
DE3689442T2 (de) * 1985-08-27 1994-06-16 Nippon Paint Co Ltd Saure, wässrige Phosphatüberzugslösungen für ein Verfahren zum Phosphatbeschichten metallischer Oberfläche.
DE3537108A1 (de) * 1985-10-18 1987-04-23 Collardin Gmbh Gerhard Verfahren zur phosphatierung elektrolytisch verzinkter metallwaren
DE3631759A1 (de) * 1986-09-18 1988-03-31 Metallgesellschaft Ag Verfahren zum erzeugen von phosphatueberzuegen auf metalloberflaechen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9102829A2 *

Also Published As

Publication number Publication date
AU6167590A (en) 1991-04-03
ATE121803T1 (de) 1995-05-15
ES2071110T3 (es) 1995-06-16
JPH04507436A (ja) 1992-12-24
CN1034681C (zh) 1997-04-23
AU633135B2 (en) 1993-01-21
WO1991002829A3 (fr) 1991-04-04
DE3927131A1 (de) 1991-02-21
WO1991002829A2 (fr) 1991-03-07
EP0486576B1 (fr) 1995-04-26
ZA906507B (en) 1991-04-24
DE59008978D1 (de) 1995-06-01
CA2065004A1 (fr) 1991-02-18
CN1049531A (zh) 1991-02-27

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