WO1998020186A1 - Composition et procede de revetement par conversion a phosphate - Google Patents

Composition et procede de revetement par conversion a phosphate Download PDF

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Publication number
WO1998020186A1
WO1998020186A1 PCT/US1997/019313 US9719313W WO9820186A1 WO 1998020186 A1 WO1998020186 A1 WO 1998020186A1 US 9719313 W US9719313 W US 9719313W WO 9820186 A1 WO9820186 A1 WO 9820186A1
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WO
WIPO (PCT)
Prior art keywords
component
amount
range
ratio
water soluble
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.)
Ceased
Application number
PCT/US1997/019313
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English (en)
Inventor
Mervet S. Boulos
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Henkel Corp
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Henkel Corp
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Filing date
Publication date
Application filed by Henkel Corp filed Critical Henkel Corp
Priority to AU50877/98A priority Critical patent/AU5087798A/en
Priority to CA002269455A priority patent/CA2269455A1/fr
Publication of WO1998020186A1 publication Critical patent/WO1998020186A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C23C22/34—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
    • 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
    • C23C22/361—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 titanium, zirconium or hafnium compounds
    • 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
    • C23C22/40—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 molybdates, tungstates or vanadates
    • C23C22/44—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 molybdates, tungstates or vanadates containing also fluorides or complex fluorides

Definitions

  • This invention relates to a composition and process for forming a phosphate conversion coating on active metal surfaces in order to increase the corrosion resistance of the surfaces, either as treated or after subsequent conventional overcoating of the conversion coating layer formed by an organic based protective coating such as a paint or lacquer.
  • a composition according to this invention is well adapted to treating any of a variety of base metals, including at least steel and galvanized steel, zinc and zinc based alloys, alum- inum and aluminum based alloys, and magnesium and magnesium based alloys.
  • the composition and method of the invention are therefore especially well adapted to treating objects having surfaces including more than one type of active metal to be protected against corrosion.
  • the major object of this invention is to achieve equally satisfactory phosphating quality as in U. S. Patent 5,143,562 with reduced amounts of sludge compared to the examples in that patent.
  • a composition according to this invention is an aqueous liquid composition comprising, or preferably consisting essentially of, still more preferably consisting of, water and:
  • a water soluble component providing in aqueous solution dissolved oxidizing agents selected from the group consisting of (i) nitroaromatic organic compounds and (ii) water soluble salts of molybdic acids; and, optionally, one or more of the following components: (G) a component including one or more surfactants to promote cleaning of the metal surface to be treated; (H) a hydrotrope component to increase the solubility of the constituents of component (G); and (J) a component of antifoam agent or agents, wherein, in said aqueous liquid composition: 5 - the ratio by weight of component (A) to component (B) is in the range from
  • ppt parts per thousand by weight
  • ppt parts per thousand by weight
  • the ratio of ppt of component (C) to ppt of component (D) is in the range from 0.010:1.0 to 6.0:1.0
  • the ratio by weight of component (D) to component (E) is in the range from 0.05:1.0 to 5.0:1.0
  • s - the ratio of the concentration in ppt of component (E) to the concentration in gram-moles per kilogram (hereinafter usually abbreviated as "M' ) of component (F) is in the range from 2000:1.0 to 20,000:1.0 if component (F) is made up of water soluble salts of molybdic acids or mixtures thereof and is in the range from 400:
  • a process according to this invention comprises at a minimum a step of contacting a metal surface to be treated with a composition according to the invention for a suffi- 5 cient time to form on the metal surface a detectable conversion coating.
  • the compositions according to this invention when they contain adequate amounts and types of surfactant component (G) as is usually preferred, are especially well suited to treating metal surfaces that have not been subjected to any prior chemical cleaning or conventional "activation" (e.g., contact with a suitably prepared aqueous dispersion of colloidal titanium o compounds), but conventional metal surface cleaning and/or activation steps before contact between the metal to be treated and the compositions according to the invention may be used if desired as part of a process according to this invention.
  • G surfactant component
  • a process according to the invention also may, and usually preferably does, include conventional steps subsequent to the contact between the metal surface to be 5 treated and the compositions according to the invention. These subsequent steps, e.g., may include rinsing with water, using reactive post treatments, such as with compositions according to the teachings of U. S. Patent 4,963,596 or with chromate containing solutions, and painting or otherwise protecting the surface with an outer coating of an organic based solid material.
  • compositions according to the invention contain no more than 4, 0.9, 0.5, 0.2, 0.07, or 0.01 grams per liter (hereinafter "g/L") of cations selected from the group consisting of Zn +2 , Ni *2 , n +2 , Co +2 , Cu +2 , Fe +2 , Ca +2 , Mg +2 , and all metal cations with a valence of 3 or higher.
  • g/L grams per liter
  • Preferred sources for component (A) as described above are the acids and the alkali metal and ammonium salts having the anions noted.
  • the concentration of component (A), calculated as the anion(s) present be in the range from 0.05 to 1.0, 0.10 to 0.70, or 0.30 to 0.50 ppt.
  • a concentrated composition according to the invention that is suitable for dilution with water, optionally with addition of acid or base for pH control at the same time as dilution of the concentrated composition, to prepare, at the point of use, a working composition with a concentra- tion of component (A) in the range given above and of other components in the ranges given below.
  • the concentrations of all components except water preferably are in the range from 5 to 100, more preferably from 12 to 50, or still more preferably from 20 to 25, times the concentrations of the same components in a working composition.
  • the most preferred source is hydrofluoric acid, and ammonium and alkali metal fluorides and bifluorides are otherwise preferred among other acceptable sources.
  • concentration of component (B) calculated as its stoichiometric equivalent of fluorine atoms, be in the range from 0.1 to 2.0, 0.2 to 0.8, or 0.4 to 0.7 ppt.
  • citric acid and/or its salts are used.
  • the total concentration of citric acid and/or its stoichiometric equivalent for any citrate salts present be at least, with increasing preference in the order given, 0.0010, 0.0015, 0.0025, 0.0050, 0.010, 0.020, 0.030, 0.040, 0.050, 0.060, 0.070, 0.080, 0.090, or 0.097 ppt and independently preferably be not more than, with increasing preference in the order given, 0.45, 0.40, 0.35, 0.30, 0.25, 0.20, 0.17, 0.15, 0.13, or 0.11 ppt of the total composition.
  • component (D) the most preferred source is hydroxylamine sulfate (briefly denoted hereinafter as "HAS”), but many other sources are satisfactory.
  • HAS hydroxylamine sulfate
  • concentration of component (D) calculated as its stoichiometric equivalent of hydroxylamine (H 2 NOH)
  • H 2 NOH stoichiometric equivalent of hydroxylamine
  • component (E) the most preferred source is orthophosphoric acid (H 3 P0 4 ) and/or its alkali metal and ammonium salts.
  • the acid itself and all anions produced by its partial or total ionization in aqueous solution are considered part of component (E) as described herein.
  • the concentration of component (E), calculated as its stoichiometric equivalent as phosphoric acid (H 3 P0 4 ) be in the range from 3 to 30, 7 to 15, or 5 to 12, g/L.
  • the most preferred sources of component (F) are water soluble salts of one of the molybdic acids, most preferably of H 2 Mo0 4 .
  • This component provides a dark blue colored conversion coating that is easy to detect visually and gives good corrosion protection, adequate for many purposes.
  • This embodiment is generally preferred by users who do not wish to quantitatively monitor the thickness of the coating produced.
  • the total concentration of (F) be in the range from 0.00002 to 0.02, 0.0002 to 0.02, or 0.002 to 0.02 M of total molybdate salts.
  • paranitrobenzene sulfonic acid and/or its water soluble salts, especially the sodium salt are the most preferred source of component (F).
  • the conversion coating layer produced by this embodiment is often difficult to detect visually, but the thickness of the coating can be readily determined by the quantitative methods known to those skilled in the art, which generally involve weighing a sample of the coating before and after using an appropriate stripping solution composition to remove the conversion coating.
  • concentration of component (F) be in the range from 0.0001 to 0.1 , 0.001 to 0.1, or 0.01 to 0.1 M.
  • component (G) In a working composition, it is preferred, with increasing preference in the order given, that the concentration of component (G) be in the range from 0 to 5.0, 1.5 to 3.0, or 1.5 to 2.0, g L.
  • Preferred chemical types for component (G) are polyethoxylated alcohols with about 12 - 22 carbon atoms in the alcohol portion, other modified polyethers of the aliphatic or aromatic types, and salts of complex organic phosphate esters.
  • a hydrotrope is defined generally as a substance that increases the solubility in water of another material that is only partially soluble. Hydrotrope component (H) is needed in the compositions according to this invention only if the amount of component (G) desired in the compositions is so large as to exceed the limit of ready solubility in the absence of a hydrotrope. In such cases, adequate solubility to produce an optically clear and homogeneous composition as preferred can generally be achieved by use of a hydrotrope.
  • a hydrotrope for this invention is preferably an ammonium or alkali metal salt of a sulfonate of toluene, xylene, or cumene, or a mixture of two or more such salts.
  • hydrotrope sodium xylene sulfonate.
  • a water soluble complex organo- phosphate ester or acid ester may often be advantageously added as an auxiliary hy- drotrope.
  • concentration of component (H) be in the range from 0 to 2.0, 0.4 to 1.2, or 0.6 to 0.8, g/L.
  • component (J) Preferred chemical types for component (J) are (i) aliphatic petroleum distillates modified with hydrophobic silica and/or (ii) polyethoxylated alcohols. Block copolymers of ethylene oxide and propylene oxide may also be used. The amount used, if needed, should be sufficient to reduce the foaming of the composition to an acceptable level.
  • the concentration of free acid be in the range from 0.0 to 2.0, 0.0 to 1.0, or 0.2 to 1.0, "points” and that the concentration of total acid be in the range from 3 to 12, 5 to 10, or 6.0 to 9.0, “points”.
  • “Points” are defined for this purpose as the number of millilit- ers (hereinafter "ml") of 0.1 N NaOH solution required to titrate a 10 ml sample of the composition, to a phenolphthalein end point for total acid and a bromthymol blue end point for free acid.
  • the pH value of a working composition according to the invention be in the range from 3.0 to 7.0, 4.2 to 5.9, or 4.5 to 5.5.
  • the ratio by weight of component (A) to the stoichiometric equivalent as fluoride ions of component (B) be in the range from 0.3:1.0 to 1.6:1.0, from 0.5:1.0 to
  • the components are to be measured in the same manner and units as described above for measuring the concentrations of the same components in working solutions.
  • contact between the metal surface to be treated and a composition according to the invention may be accomplished by spraying, dipping, or any other convenient method or combination of methods.
  • the temperature during contact between the metal treated and the composition according to the invention preferably is, with increasing preference in the order given, in the range from 21 to 85, 25 to 70, or 30 to 65, °C.
  • the time of contact preferably is, with increasing preference in the order given, in the range from 5 sec to 15 minutes (hereinafter "min"), 15 sec to 10 min, or 30 sec to 5 min.
  • the add-on mass of the phosphate coating formed preferably is, with increasing preference in the order given, in the range from 12 to 1600, 98 to 975, or 285 to 700, milligrams per square meter (hereinafter sometimes abbreviated as "mg/m 2 ) of surface treated.
  • mg/m 2 milligrams per square meter
  • compositions were prepared containing the following components
  • Variable ion sequestering agent - see table below 35 40 % sodium xylene sulfonate
  • ANTAROXTM LF-330 was commercially obtained from Rh ⁇ ne-Poulenc and is re- ported by its supplier to be a modified linear aliphatic polyether detergent and wetting agent with low foaming tendency.
  • TRITONTM DF-16 was commercially obtained from Union Carbide Corp. and is reported by its supplier to be a modified polyethoxylated straight chain alcohol nonionic low foaming detergent.
  • RHODAFACTM RP-710 was commercially obtained from Rh ⁇ ne-Poulenc and is reported by its supplier to be a complex organic phosphate anionic detergent and emulsifier with hydrotropic effect on low foaming nonionic surfactants.
  • the sodium hydroxide was added to about 90 % of the amount of water expected to be finally needed; the phosphoric acid was added next, with cooling until the temperature of the mixture fell to 43 °C or below. Then the sequestering agent, the principal hydrotrope, and the three surfactants were added in rapid succession and the mixture stirred until clear (about 15 min). The hydroxylamine sulfate and p-nitrobenzene sulfonic acid were then added, and 30 minutes of additional mixing was performed. Subsequently, the last two named ingredients were added, followed by another 30 minutes of mixing. The remaining water was then added, to the ex- tent necessary to achieve a total of 1000 parts by weight.
  • the concentrated compositions as described above were diluted with water to produce a working composition containing 50 grams of the concentrated composition per liter of the working composition.
  • Each working composition had a pH value of 4.8 and a total acidity as shown in Table 1 below.

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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)

Abstract

L'invention concerne une combinaison aqueuse liquide de fluorure, d'acide citrique et/ou de ses sels, d'ions phosphate, d'une source d'hydroxylamine, d'un agent oxydant choisi parmi des composés organiques nitro-aromatiques hydrosolubles, de molybdates et de tungstates simples ou complexes. Cette combinaison permet d'obtenir des revêtements protecteurs par conversion à phosphate de bonne qualité pour des surfaces métalliques en fer, zinc, en aluminium, en magnésium et en alliage de magnésium, sans besoin de cations métalliques bivalents ou à valence supérieure, tels que ceux qui sont généralement utilisés pour produire des revêtements par conversion à phosphate de bonne qualité. Ces combinaisons renfermant de l'acide citrique produisent moins de résidu que d'autres combinaisons similaires, dans lesquelles l'acide gluconique est utilisé à la place de l'acide citrique. Si la combinaison comprend des tensioactifs adéquats, aucun nettoyage chimique préalable du métal destiné à être revêtu n'est nécessaire pour obtenir un résultat satisfaisant.
PCT/US1997/019313 1996-11-06 1997-11-04 Composition et procede de revetement par conversion a phosphate Ceased WO1998020186A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
AU50877/98A AU5087798A (en) 1996-11-06 1997-11-04 Phosphate conversion coating composition and process
CA002269455A CA2269455A1 (fr) 1996-11-06 1997-11-04 Composition et procede de revetement par conversion a phosphate

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US2955796P 1996-11-06 1996-11-06
US60/029,557 1996-11-06

Publications (1)

Publication Number Publication Date
WO1998020186A1 true WO1998020186A1 (fr) 1998-05-14

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PCT/US1997/019313 Ceased WO1998020186A1 (fr) 1996-11-06 1997-11-04 Composition et procede de revetement par conversion a phosphate

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CA (1) CA2269455A1 (fr)
WO (1) WO1998020186A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001006035A1 (fr) * 1999-07-15 2001-01-25 Henkel Kommanditgesellschaft Auf Aktien Procede de traitement contre la corrosion ou de traitement posterieur de surfaces metalliques
EP1338678A3 (fr) * 2002-02-11 2004-10-06 United Technologies Corporation Revêtement par conversion sans chromate, résistant à la corrosion pour les alliages de magnésium
US6881355B2 (en) 2002-08-02 2005-04-19 Clariant Gmbh Antifreeze
WO2006108655A1 (fr) * 2005-04-14 2006-10-19 Chemetall Gmbh Procede de formation d'une couche de conversion sans chromate, bien visible, pour magnesium et alliages de magnesium
WO2006108108A3 (fr) * 2005-04-06 2008-01-17 Rem Technologies Superfinition de carbures de densite elevee
ITMI20100094A1 (it) * 2010-01-26 2011-07-27 Np Coil Dexter Ind Srl Processi di pretrattamento alla verniciatura, a basso impatto ambientale, alternativi ai trattamenti tradizionali di fosfatazione
CN102782187B (zh) * 2010-01-26 2016-11-30 Np线圈德克斯特工业公司 作为常规磷酸盐化处理的替代方案的低环境影响的涂装预处理方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927472A (en) * 1987-10-13 1990-05-22 Nihon Parkerizing Co., Ltd. Conversion coating solution for treating metal surfaces
US5143562A (en) * 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4927472A (en) * 1987-10-13 1990-05-22 Nihon Parkerizing Co., Ltd. Conversion coating solution for treating metal surfaces
US5143562A (en) * 1991-11-01 1992-09-01 Henkel Corporation Broadly applicable phosphate conversion coating composition and process

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001006035A1 (fr) * 1999-07-15 2001-01-25 Henkel Kommanditgesellschaft Auf Aktien Procede de traitement contre la corrosion ou de traitement posterieur de surfaces metalliques
EP1338678A3 (fr) * 2002-02-11 2004-10-06 United Technologies Corporation Revêtement par conversion sans chromate, résistant à la corrosion pour les alliages de magnésium
US6881355B2 (en) 2002-08-02 2005-04-19 Clariant Gmbh Antifreeze
WO2006108108A3 (fr) * 2005-04-06 2008-01-17 Rem Technologies Superfinition de carbures de densite elevee
US7641744B2 (en) 2005-04-06 2010-01-05 Rem Technologies, Inc. Superfinishing of high density carbides
WO2006108655A1 (fr) * 2005-04-14 2006-10-19 Chemetall Gmbh Procede de formation d'une couche de conversion sans chromate, bien visible, pour magnesium et alliages de magnesium
ITMI20100094A1 (it) * 2010-01-26 2011-07-27 Np Coil Dexter Ind Srl Processi di pretrattamento alla verniciatura, a basso impatto ambientale, alternativi ai trattamenti tradizionali di fosfatazione
WO2011092079A1 (fr) 2010-01-26 2011-08-04 Np Coil Dexter Industries S.R.L. Procédés de prétraitement de phosphatation à faible impact sur l'environnement comme alternative aux traitements de phosphatation classiques
CN102782187A (zh) * 2010-01-26 2012-11-14 Np线圈德克斯特工业公司 作为常规磷酸盐化处理的替代方案的低环境影响的涂装预处理方法
CN102782187B (zh) * 2010-01-26 2016-11-30 Np线圈德克斯特工业公司 作为常规磷酸盐化处理的替代方案的低环境影响的涂装预处理方法
US10378110B2 (en) 2010-01-26 2019-08-13 Quaker Chemical S.r.l. Painting pre-treatment processes with low environments impact, as an alternative to conventional phosphating treatments

Also Published As

Publication number Publication date
CA2269455A1 (fr) 1998-05-14
AU5087798A (en) 1998-05-29

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