EP1521863B1 - Verfahren zur beschichtung von metallischen oberflächen - Google Patents

Verfahren zur beschichtung von metallischen oberflächen Download PDF

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Publication number
EP1521863B1
EP1521863B1 EP03763755A EP03763755A EP1521863B1 EP 1521863 B1 EP1521863 B1 EP 1521863B1 EP 03763755 A EP03763755 A EP 03763755A EP 03763755 A EP03763755 A EP 03763755A EP 1521863 B1 EP1521863 B1 EP 1521863B1
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EP
European Patent Office
Prior art keywords
concentration range
range
phosphating solution
process according
virtually none
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
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EP03763755A
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German (de)
English (en)
French (fr)
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EP1521863A2 (de
Inventor
Jürgen SPECHT
Peter Schubach
Rüdiger Rein
Peter Claude
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Chemetall GmbH
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Chemetall GmbH
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Filing date
Publication date
Priority claimed from DE2002131279 external-priority patent/DE10231279B3/de
Priority claimed from DE2002136526 external-priority patent/DE10236526A1/de
Application filed by Chemetall GmbH filed Critical Chemetall GmbH
Publication of EP1521863A2 publication Critical patent/EP1521863A2/de
Application granted granted Critical
Publication of EP1521863B1 publication Critical patent/EP1521863B1/de
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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
    • C23C22/34—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
    • 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
    • C23C22/362—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 zinc cations

Definitions

  • the invention relates to a process for coating metallic surfaces by zinc phosphating and to the use of the substrates coated by the process according to the invention.
  • the coating of metallic surfaces with phosphate layers can be done in many ways. Often zinc, manganese or / and nickel-containing phosphating solutions are used here. Some of the metallic substrates to be coated in the baths or installations on their surface also have a proportion of aluminum or aluminum alloys, which can possibly lead to problems.
  • the phosphate layer (s) should usually have a good corrosion protection and a good paint adhesion together with at least one subsequently applied lacquer layer or lacquer-like coating.
  • the simultaneous phosphating of substrates with different metallic surface has increased in importance. In particular, the proportion of aluminum-containing surfaces in such systems is increasing, so that problems with phosphating in such systems are more likely and more frequent than before.
  • an Al-F complex can form, which is dissolved in the solution, but which can also lead to a precipitate with monovalent ions such as sodium and / or potassium.
  • the precipitate can collect in the bath tank as sludge and be removed from there, but can also cause disruptive precipitation on the aluminum-containing metallic surfaces.
  • EP-A1-0 452 638 teaches a method of phosphating steel, galvanized steel surfaces together with surface portions containing aluminum with a phosphating solution having a total content of sodium ions in the range of at least 2 g / L, a content of sodium and potassium ions together of 2 to 15 g / L and having a manganese ion content of at least 1 g / L.
  • EP-A2-0 434 358 describes a process for phosphating metallic surfaces in the presence of aluminum, in which the phosphating solution contains not only zinc but also at least one complex fluoride and a so-called simple fluoride in which the molar ratio of complex fluoride to simple fluoride ranges from 0.01 to 0.5 lies.
  • a simple fluoride is a dissociated and undissociated hydrofluoric acid.
  • at least one separate treatment tank or a separate precipitation tank is used.
  • This publication leads No specific measures on monovalent cations that will allow the avoidance of cryolite precipitation except by using additional separate containers.
  • the value of the free acid FA should be 0.5 to 2 points, but was determined without KCI addition and would correspond to about 0.3 to 1.5 points FS-KCI. Very similar teaches EP-A2-0 454 361 ,
  • DE-A1-100 26 850 protects a phosphating process in which the precipitation of interfering cryolite deposits in the area of the metallic surfaces to be coated is avoided by limiting the aluminum content of the phosphating solution and by using an additional separate precipitation vessel through which the phosphating solution must circulate.
  • the phosphate layer should be closed, of good, fine-grained crystallinity, of sufficiently high corrosion resistance, and of sufficiently good paint adhesion. The procedure should be as simple, safe and cost-effective as possible.
  • pretreatment is intended to mean that at least one essential coating, for example at least one layer of a lacquer or / and of a lacquer-like material, is applied to the pretreatment layer.
  • At least 8% of these surfaces are made of aluminum or / and at least one aluminum alloy, more preferably at least 12%, at least 18%, at least 24%, at least 30%, at least 40%, at least 50%, at least 60%, at least 75% or at least 90%.
  • the dissolved contents of many ionic species can often coexist in a non-complexed and complexed state.
  • the content of sodium and potassium together, calculated as sodium is 0.3 to 1.8 g / L, in particular up to 1.6 g / L.
  • the content of zinc is particularly preferably 0.3 to 3 g / L, of phosphate 6 to 40 g / L, of free fluoride of at least 0.08 g / L or up to 0.3 g / L or / and of the total Fluoride 0.3 to 3 g / L, especially at least 0.4 g / L or up to 2.5 g / L of total fluoride.
  • the content of sodium, potassium and optionally further alkali metal ions, of ammonium and nitrate ions is kept as low as possible, in particular if only an addition of up to 1 g / L or virtually zero is used , preferably each optionally up to 0.5 g / L or up to 0.2 g / L, with an addition of nitrate advantageously at least 0.4 g / L, but not more than 6 g / L , Particularly advantageous only up to 4 g / L, most preferably only up to 3.5 or 3 or 2.5 or 2 g / L is maintained.
  • cryolite or / and related Al-F-containing compounds which can lead to paint defects of the subsequent coating.
  • no bifluoride of sodium or / and potassium is added.
  • the content of dissolved and complexed zinc may be in particular from 0.4 to 2.5 g / L, more preferably from 0.5 to 2.2 g / L, wherein a content in the application of the phosphating solution in the dipping at 0.5 to 2.5 g / L and in particular from 0.7 to 2.0 g / L or when applied by spraying at 0.3 to 2 g / L and in particular at 0.5 to 1.5 g / L is preferred ,
  • the content of phosphate can be in particular 6 to 40 g / L PO 4 , especially at least 8 g / L or up to 36 g / L.
  • the phosphate layer applied with the phosphating solution according to claim 1 can either directly on a metallic surface, on an activated metallic surface such as by activation based on titanium phosphate or on at least one previously applied precoating such as on a first phosphate layer which does not or not Activation alone serves, and / or at least one other way chemically composite layer such as applied to a complex fluoride, silane or / and polymer-containing layer.
  • a sample of the surface of an Al-containing surface is optionally placed after their comminution in a suitably suitable sample format in a scanning electron microscope and there by means of energy dispersive or wavelength dispersive analysis on the Presence of sodium or potassium, which are usually not incorporated into the crystal lattice of zinc phosphates, representative of the other alkali or alkaline earth metals or ammonium, which could be precipitated in parallel thereto with the sodium and potassium, tested.
  • the contents of dissolved aluminum in the phosphating solution may preferably be in the concentration range of 0.002 to 1 g / L, in particular of at least 0.005 g / L, particularly preferably 0.008 to 0.7 g / L, especially 0.01 to 0.4 g / L lie.
  • a higher aluminum content than 0.1 g / L is not detrimental to the process of the invention.
  • the total content of silicon complex fluoride and boron complex fluoride together in the phosphating solution may preferably be 0.01 to 8 g / L, optionally converted to SiF 6 on a molar basis, whereby both groups of fluoride complexes need not occur simultaneously.
  • the sum of the contents of complexed fluoride to silicon complex fluoride and boron complex fluoride is preferably 0.01 to 8 g / L, particularly preferably 0.02 to 5.3 g / L, very particularly preferably 0.02 to 4 g / L, in particular less than 3 or 2 g / L or even not more than 1 , 8 g / L. It is particularly preferred if the content of silicon complex fluoride is not more than 1.8 g / L.
  • the contents of complexed fluoride in the phosphating solution may preferably be 0.01 to 8 g / L, calculated as SiF 6 , being converted to molar basis.
  • the zinc content of the phosphating solution is greater than its manganese content.
  • the phosphating solution particularly preferably contains at least some nitrate content as accelerator, although it is advantageous to add at least one further accelerator.
  • the content of each compound is preferably in the case of m-nitrobenzenesulfonate 0.01 to 2 g / l, in the case of nitrite 0.001 to 0.400 g / l or in the case of nitroguanidine 0.01 to 3.5 g / l.
  • the content based on chlorate is preferably practically zero or in the range of 0.05 to 4 g / L or more preferably in the range of 0.1 to 3 g / L or of 0.15 to 1.8 g / L.
  • the content based on hydroxylamine is preferably virtually zero or in the range of 0.05 to 2 g / L or particularly preferably in the range of 0.2 to 1.5 g / L.
  • the content based on m-nitrobenzenesulfonate is preferably virtually zero or in the range of 0.05 to 1.5 g / L or particularly preferably in the range of 0.15 to 1 g / L.
  • the content based on nitrite is preferably virtually zero or in the range of 0.005 to 0.350 g / L or particularly preferably in the range of 0.010 to 0.300 g / L.
  • the content based on nitroguanidine is preferably virtually zero or in the range of 0.1 to 3 g / L or particularly preferably in the range of 0.3 to 2.5 g / L.
  • the content based on peroxide including water-soluble organic peroxide is preferably virtually zero or in the range of 0.003 to 0.150 g / L or more preferably in the range of 0.005 to 0.100 g / L.
  • the total content of all accelerators is less than 5 g / L, more preferably less than 4 g / L, in particular less than 3.5 g / L, less than 3 g / L or less than 2.5 g / L ,
  • the total content of all cations in the phosphating solution may preferably be in the concentration range of 0.35 to 80 g / L calculated on a mole basis as Zn and may be the total content of all anions without accelerator but including nitrate in the concentration range of 4 to 120 g / L calculated on a molar basis as PO 4 preferably.
  • at least one other than the abovementioned accelerators, in particular based on a nitro compound such as based on nitrobenzoate and / or nitrophenol, are used.
  • the phosphating solution contains no accelerator based on hydroxylamine.
  • the content of magnesium in the phosphating solution may preferably be not more than 1 g / L, more preferably less than 0.5 g / L, most preferably not more than 0.15 g / L.
  • no or virtually no precipitation product based on aluminum fluorocomplexes of ammonium, alkali or / and alkaline earth metal on the metallic surface, under the phosphate layer or / and between the zinc phosphate crystals is formed on the surfaces of aluminum and / or at least one aluminum alloy phosphated in this way deposited in the phosphate layer - at least their amounts should be limited so that the precipitation does not give rise to paint defects in the subsequent painting.
  • impurities, pickling reactions and carryover most likely to lead to such levels in small quantities Preferably also - in many cases - no copper is added.
  • electroless work is carried out; however, it is basically possible to use the phosphating solution electrolytic use, where appropriate, the content of accelerators can be reduced or even avoided.
  • the so-called S value is obtained by dividing the value of the free acid KCl by the value of the total acid according to Fischer.
  • the total acid diluted (GS diluted ) is the sum of the divalent cations present as well as free and bound phosphoric acids (the latter being phosphates). It is determined by the consumption of 0.1 molar sodium hydroxide solution using the indicator phenolphthalein diluted to 10 ml of phosphating solution with 200 ml of demineralized water. This consumption of 0.1 M NaOH in ml corresponds to the total acid score.
  • the content of free acid KCl may preferably be in the range of 0.3 to 6 points, the content of total acid preferably in the range of 8 to 70 points or / and the content of total acid Fischer preferably in the range of 4 to 50 Points are.
  • the range of free acid KCl is 0.4 to 5.5 points, especially 0.6 to 5 points.
  • the range of total acid is diluted at 12 to 50 points, especially at 18 to 44 points.
  • the range of the total acid Fischer is 7 to 42 points, in particular 10 to 30 points.
  • the S value as the ratio of the number of free acid KCI points to that of the total Fischer acid is preferably in the range of 0.01 to 0.40 points, especially in the range of 0.03 to 0.35 points, especially in the range from 0.05 to 0.30 points.
  • the pH of the phosphating solution may be in the range of 1 to 4, preferably in the range of 2.2 to 3.6, more preferably in the range of 2.8 to 3.3.
  • the coating method according to the invention can be coated with a predominantly aluminum, iron, copper, tin or zinc-containing metallic surface with the phosphating substrate, wherein always a minimum content of aluminum and / or at least one aluminum alloy occurs, in particular surfaces of at least one of the materials Base aluminum, iron, copper, steel, zinc or / and alloys containing aluminum, iron, copper, magnesium, tin or zinc.
  • these are usually strips of aluminum or / and of at least one aluminum alloy.
  • the phosphating solution can be applied to the surface of the substrates by flooding, Lance application, roll coating, spraying, spraying, brushing, dipping, misting, rolling, wherein individual process steps can be combined with each other - in particular spraying, spraying and dipping, in particular the spraying and squeezing or the spraying and squeezing on the belt can be used.
  • a slow-moving belt with an aluminum-containing surface can be coated according to the invention, e.g. also in the no-rinse procedure.
  • the phosphating solution is applied to the belt by roll coating, spraying, spraying, dipping and / or squeezing.
  • the phosphate coating may preferably be applied at a temperature in the range of 20 to 70 ° C, in particular in the range of 32 to 65 ° C, particularly preferably in the range of 40 to 60 ° C.
  • the metallic substrates may be coated in a time of up to 20 minutes, preferably by coating tape in a time of 0.1 to 120 seconds, and more preferably in a time of 0.3 to 60 seconds, and preferably parts be coated in a time of 1 to 12 minutes, and more preferably in a time of 2 to 8 minutes.
  • the layer weight of the coating according to the invention is preferably in the range from 0.9 to 9 g / m 2 , more preferably at least 1.2 g / m 2 or at least 1.6 g / m 2 or at most 8 g / m 2 , at most 7.2 g / m 2 , at most 6 g / m 2 or at most 5 g / m 2 .
  • phosphating is carried out in a so-called "layer-forming" manner (see Werner Rausch: The phosphating of metals, Saulgau 1988 ), because then a closed, with the naked eye well visible phosphate layer is formed.
  • the coated according to the inventive substrates can be used in the tape or in the parts production, for the production of components or body parts or preassembled elements in the automotive or aerospace industry, in the construction industry, in the furniture industry, for the production of Equipment and installations, in particular household appliances, measuring apparatus, control equipment, testing equipment, construction elements, cladding and small parts; as a wire, wire winding, wire mesh, sheet metal, cladding, shielding, body or part of a body, as part of a vehicle, trailer, motorhome or missile, as an electronic or microelectronic component, as a cover, housing, lamp, lamp, traffic light element, furniture or furniture element , Element of a household appliance, frame, profile, molded part of complicated geometry, crash barrier, radiator or fence element, bumper, part of or with at least one pipe and / or profile, window, door or bicycle frame or as a small part such as a screw, nut, flange, spring or spectacle frame.
  • composition of the respective phosphating solution is shown in Table 1.
  • the phosphate layers of the examples according to the invention were sufficiently finely crystalline and sufficiently closed. Their corrosion resistance and adhesive strength corresponded to typical quality standards of similar zinc phosphate coatings. All the sheets according to the invention, unlike the sheets of the comparative examples, did not show a precipitate of cryolite or chemically related phases. In the case of the metal sheets of the comparative examples, the precipitates on the phosphate layer or between the zinc phosphate crystals in the phosphate layer resulted in a different surface finish compared with the metal sheets coated according to the invention. The surface finish of the coated substrates of the comparative examples can lead to painting defects such as unacceptably rough paint surfaces or bubbles in the paint layer and thus, inevitably, to reworking, for example by grinding the painted surface. With the method according to the invention it was not necessary to use a separate area in the container of the phosphating solution for the precipitation or even not necessary to use a separate, additional precipitation container.
  • Table 2 Results of the outdoor weathering test according to VDA standard 621-414 on overcoated sheets of AA6016 in correlation with the Na and F free ⁇ / sub> content Examples / Comparative Examples Na content K content Free content Infiltration in mm according to VDA standard 621-414 g / L g / L g / L after 6 months after 9 months B 1 0.1 0 0.1 0 0 B 2 1.0 0 0.1 0 0 B 3 1.8 0 0.1 0 0 VB 4 5.0 0 0.1 1.5 2.5 B 9 0.1 0 0.1 0 0 B 10 1.0 0 1.0 0 0 VB 11 3.0 0 3.0 2.0 3.0 VB 12 5.0 0 5.0 2.5 3.5 B 16 1.8 0 0.25 0 0 VB 17 3.0 0 0.25 2.5 3.0 VB 27 0.5 4.0 0.2 2.5 3.5 B 28 1.9 0 0.25 0 0 VB 29 3.5 0 0.25 1.5 2.5 VB 30 3.0 0 0.25 2.5

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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)
  • Chemically Coating (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
EP03763755A 2002-07-10 2003-07-09 Verfahren zur beschichtung von metallischen oberflächen Expired - Lifetime EP1521863B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE2002131279 DE10231279B3 (de) 2002-07-10 2002-07-10 Verfahren zur Beschichtung von metallischen Oberflächen und Verwendung der derart beschichteten Substrate
DE10231279 2002-07-10
DE10236526 2002-08-09
DE2002136526 DE10236526A1 (de) 2002-08-09 2002-08-09 Verfahren zur Beschichtung von metallischen Oberflächen
PCT/EP2003/007359 WO2004007799A2 (de) 2002-07-10 2003-07-09 Verfahren zur beschichtung von metallischen oberflächen

Publications (2)

Publication Number Publication Date
EP1521863A2 EP1521863A2 (de) 2005-04-13
EP1521863B1 true EP1521863B1 (de) 2008-06-25

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Application Number Title Priority Date Filing Date
EP03763755A Expired - Lifetime EP1521863B1 (de) 2002-07-10 2003-07-09 Verfahren zur beschichtung von metallischen oberflächen

Country Status (11)

Country Link
US (2) US20050205166A1 (enExample)
EP (1) EP1521863B1 (enExample)
JP (1) JP4233565B2 (enExample)
CN (1) CN100374620C (enExample)
AT (1) ATE399218T1 (enExample)
AU (1) AU2003250917A1 (enExample)
CA (1) CA2494559C (enExample)
DE (1) DE50310042D1 (enExample)
ES (1) ES2309349T3 (enExample)
PT (1) PT1521863E (enExample)
WO (1) WO2004007799A2 (enExample)

Cited By (1)

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DE102022106091A1 (de) 2022-03-16 2023-09-21 Thyssenkrupp Steel Europe Ag Verfahren zum Modifizieren einer Oberfläche eines beschichteten Stahlblechs

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DE102008000600B4 (de) * 2008-03-11 2010-05-12 Chemetall Gmbh Verfahren zur Beschichtung von metallischen Oberflächen mit einem Passivierungsmittel, das Passivierungsmittel, die hiermit erzeugte Beschichtung und ihre Verwendung
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DE102011100974A1 (de) * 2011-05-09 2012-11-15 Knorr-Bremse Systeme für Schienenfahrzeuge GmbH Schienenrad und Verfahren zur Herstellung eines Schienenrades
CN105331966B (zh) 2015-11-30 2018-04-27 宝山钢铁股份有限公司 一种无铬表面处理镀锡板、其生产方法及表面处理剂
KR20190043155A (ko) 2016-08-24 2019-04-25 피피지 인더스트리즈 오하이오 인코포레이티드 금속 기판을 처리하기 위한 알칼리성 조성물
EP3392375B1 (de) 2017-04-21 2019-11-06 Henkel AG & Co. KGaA Verfahren zur schlammfreien schichtbildenden zinkphosphatierung von metallischen bauteilen in serie
EP3392376A1 (de) 2017-04-21 2018-10-24 Henkel AG & Co. KGaA Verfahren zur schichtbildenden zinkphosphatierung von metallischen bauteilen in serie
WO2019115395A1 (de) * 2017-12-12 2019-06-20 Chemetall Gmbh Borsäurefreie zusammensetzung zur entfernung von kryolithhaltigen ablagerungen
WO2019158508A1 (de) * 2018-02-19 2019-08-22 Chemetall Gmbh Verfahren zur selektiven phosphatierung einer verbundmetallkonstruktion
CN112442699A (zh) * 2019-08-29 2021-03-05 晟通科技集团有限公司 表面清洗剂
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Publication number Priority date Publication date Assignee Title
DE102022106091A1 (de) 2022-03-16 2023-09-21 Thyssenkrupp Steel Europe Ag Verfahren zum Modifizieren einer Oberfläche eines beschichteten Stahlblechs

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ES2309349T3 (es) 2008-12-16
CN100374620C (zh) 2008-03-12
US20110198000A1 (en) 2011-08-18
DE50310042D1 (de) 2008-08-07
ATE399218T1 (de) 2008-07-15
JP2006501372A (ja) 2006-01-12
CA2494559C (en) 2011-09-20
CN1665957A (zh) 2005-09-07
WO2004007799A3 (de) 2004-04-08
US8349092B2 (en) 2013-01-08
AU2003250917A8 (en) 2004-02-02
CA2494559A1 (en) 2004-01-22
EP1521863A2 (de) 2005-04-13
PT1521863E (pt) 2008-09-19
JP4233565B2 (ja) 2009-03-04
AU2003250917A1 (en) 2004-02-02
WO2004007799A2 (de) 2004-01-22

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