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EP2245213B1 - Agents de passivation, agents de traitement de surfaces, agents de pulvérisation pour traitement de surfaces, et procédé de traitement de surfaces métalliques de pièces ou de moules de coulée - Google Patents

Agents de passivation, agents de traitement de surfaces, agents de pulvérisation pour traitement de surfaces, et procédé de traitement de surfaces métalliques de pièces ou de moules de coulée Download PDF

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Publication number
EP2245213B1
EP2245213B1 EP09704705.4A EP09704705A EP2245213B1 EP 2245213 B1 EP2245213 B1 EP 2245213B1 EP 09704705 A EP09704705 A EP 09704705A EP 2245213 B1 EP2245213 B1 EP 2245213B1
Authority
EP
European Patent Office
Prior art keywords
surface treatment
weight
agent
metallic surfaces
recited
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.)
Not-in-force
Application number
EP09704705.4A
Other languages
German (de)
English (en)
Other versions
EP2245213A1 (fr
Inventor
Manfred Laudenklos
Stephan Beer
Matthias Reihmann
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.)
Gelita AG
KS Huayu Alutech GmbH
Original Assignee
Gelita AG
KS Huayu Alutech GmbH
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 Gelita AG, KS Huayu Alutech GmbH filed Critical Gelita AG
Publication of EP2245213A1 publication Critical patent/EP2245213A1/fr
Application granted granted Critical
Publication of EP2245213B1 publication Critical patent/EP2245213B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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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
    • C23C22/73—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 characterised by the process
    • C23C22/74—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 characterised by the process for obtaining burned-in conversion coatings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22C—FOUNDRY MOULDING
    • B22C3/00—Selection of compositions for coating the surfaces of moulds, cores, or patterns
    • 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

Definitions

  • the present invention relates to a passivation agent for metallic surfaces of workpieces or molds with an aqueous phosphate solution with metal ions, a surface treatment agent and a surface treatment spray for cleaning and passivation of metallic surfaces of workpieces or molds with such a passivating agent and a method for treating metallic surfaces of workpieces or molds with such a surface treatment agent or surface treatment spray.
  • Molds used in low pressure, gravity, squeeze casting or die casting are usually made from hot work steels because their recrystallization and / or transformation temperatures are well above those of the molten light metal materials.
  • the liquid melt for example in the form of a light metal alloy, especially an aluminum alloy, not adhere to the surface of the casting mold.
  • release agents or sizes are applied to the surfaces of the molds, which are intended to prevent adhesion of the molten metal to the mold.
  • Such a release agent which contains no toxic substances for example, from DE 10 2005 042 475 A1 known. To ensure that the release agent or sizing on the tool surfaces must be previously cleaned and passivated if necessary.
  • the passivation creates a non-metallic protective layer on the metallic material, which should slow or prevent corrosion as much as possible.
  • the passivation by phosphating is a widely used method of surface technology in which a conversion layer of firmly adhering metal phosphates is formed by a chemical reaction between the metallic workpiece surface and an aqueous phosphate solution.
  • the phosphating serves to protect against corrosion and forms a diffusion barrier.
  • the adhesion can be improved, for example, subsequently applied sizing and reduce wear.
  • the cleaning takes place for example by means of a high-pressure water jet, which is directed via a rotary nozzle with a pressure of 1750 to 3000 bar to the workpiece.
  • a high-pressure water jet which is directed via a rotary nozzle with a pressure of 1750 to 3000 bar to the workpiece.
  • the disadvantage of this is that caused by the water contact of the cleaned workpiece corrosion and organic and inorganic residues from the jet water remain on the surface.
  • the high pressures lead to high wear of the piston and valves of the blasting system and thus to increased costs.
  • a rust removing agent for metals which consists of a mixture of a fat solvent, a rust solvent such as phosphoric acid, a buffering agent, especially aluminum hydroxide, a phosphating agent consisting of zinc phosphate, potassium aluminum phosphate and gelatin as a thickening agent, and water.
  • the mold or the workpiece is immersed in a pickling bath to remove organic residues and oxides at temperatures of 40-90 ° C by means of inorganic acids and suitable surfactants. Subsequently, a deep cleaning in the bath by means of ultrasound, whereupon the workpiece or the mold is immersed in another bath for rinsing and neutralizing. Thereafter, the workpiece must be dried and activated in a further process step in the bath, before the phosphating, for example, by means of zinc phosphate at 40 - 70 ° C or manganese phosphate at 70 - 90 ° C. Finally, the workpiece or the mold is neutralized and dried.
  • the high-pressure cleaning is followed by a pickling bath and then rinsing and neutralizing with a suitable spray solution.
  • spray activation is carried out at elevated temperature before phosphating by means of a heated spray solution at 40-70 ° C for zinc phosphate and 70-90 ° C for manganese phosphate.
  • the neutralization and drying of the workpiece or of the casting mold follows as further steps.
  • the energy expenditure for achieving the necessary temperatures is relatively high, even in the case of correspondingly large mass ratios, even during the spray treatment, so that the process is uneconomical becomes.
  • the components treated with known passivating agents often have inadequate thermal shock resistance, which arises in particular from defects in the structure of the passivation layer.
  • a passivating agent which consists of an aqueous solution of aluminum hydrogen phosphate and organic polymers which form a film under the action of temperature.
  • organic polymers in this case acrylic or epoxy resins are used. When heated, however, these coatings lose their organic components.
  • the disadvantage of this agent is, in particular, that defects occur during repeated casting, whereby welding can occur with a cast component. Furthermore, there is still insufficient thermal shock resistance.
  • a passivation agent which according to the invention comprises a gelatin whose redox potential is adjusted so that the gold number of the gelatin is less than 50 ⁇ mol Au / g gelatin.
  • the phosphates cause in a known manner that formed with the base material iron phosphate in combination with the metallic ions of the phosphate system at the free lattice sites or grain boundaries in the treatment of steel components or molds Forming protective layer on the surface, which serves as corrosion protection and adhesion promoter for applied sizing, the gelatin acts in such an agent as a dispersant and equipotential bonding system and improves in a previously unknown manner, the diffusion barrier.
  • the electrochemical reaction is influenced by the gelatin in such a way that the phosphating proceeds at room temperature. This significantly reduces the energy required for phosphating. It has been found that with these gelatins particularly good results can be achieved with regard to the adhesion of the passivation layer and the thermal shock resistance of a component treated therewith.
  • the aqueous phosphate solution with the metal ions is an aqueous orthophosphate solution, wherein the orthophosphates consist of one or more of the compounds zinc phosphate, aluminum phosphate, manganese phosphate, titanium phosphate, calcium phosphate, boron phosphate or iron phosphate. These compounds have proven to be particularly effective at achieving phosphating in achieving smooth surfaces.
  • the passivating agent has the following composition: 0.1% by weight to 5% by weight gelatin, 5% by weight to 50% by weight orthophosphates and the remainder water.
  • a composition 0.1% by weight to 5% by weight gelatin, 5% by weight to 50% by weight orthophosphates and the remainder water.
  • a surface treatment agent with such a passivating agent which additionally comprises nonionic surfactants, lactic acid and a citric acid monohydrate.
  • Previous cleaning steps can be completely or at least partially dispensed with when using such a surface treatment agent, since even at room temperature rust and organic components such as fat, dirt, organic organics etc., are detached from the surface.
  • Non-ionic surfactants reduce the surface tension and, in combination with the organic acids, infiltrate impurities on the surface, so that these impurities are dissolved or dissolved, so that a particularly good and largely defect-free connection of the phosphate system to the metallic surface can take place.
  • the agent can be made by immersing the workpiece or the mold in a corresponding bath at room temperature.
  • the surface treatment agent additionally comprises molybdenum disulfide and / or bismuth.
  • molybdenum disulfide and / or bismuth Particularly advantageous is an added amount of 0.01 to 5 wt.%, Preferably 0.02 to 0.04 wt.% Molybdenum disulfide and / or 0.01 to 5 wt.%, Preferably 0.02 to 0.04 wt % Bismuth.
  • the molybdenum sulfide or bismuth becomes chemically bound in the matrix of the surface upon passivation. As a result, the heat resistance and abrasion resistance of the mold or the workpiece can be further increased and the lubricating effect can be improved.
  • a surface treatment spray in which the surface treatment agent according to the invention additionally comprises up to 60% by weight of a thickening agent.
  • a sprayability resulting in the elaborate Cleaning various baths can be dispensed with. Impurities of the surface treatment agent, such as may occur during treatment in baths are excluded.
  • the object of providing a simplified and more cost-effective compared to the prior art method is achieved by a method in which the workpiece or the mold is immersed in a bath of the surface treatment agent according to the invention or the surface treatment spray according to the invention on the surface of the workpiece or the Mold is sprayed on.
  • the surfaces treated in this way are cleaned absolutely residue-free and at the same time passivated, so that any further surface application can be applied uniformly and permanently. For example, release agents, sizes or lacquers can be applied to the surface cleaned and passivated in this way.
  • the cleaning and passivation according to the invention thus increases the service life and the functionality of the workpieces and molds treated in this way.
  • a size is applied to the cleaned and passivated surface of the casting mold after immersion in the surface treatment agent or after spraying the surface treatment spray agent.
  • the sizing may be, for example, a sodium or potassium water glass sizing applied to the tool surface which makes the surface smoother and protects it from thermal stress.
  • the size is applied at a mold temperature of 250 ° C.
  • the heating required for the application of the size leads to the polycondensation of the phosphate system and its organic components.
  • the gelatin of the surface treatment agent is incorporated into the chemical bonding of the metal with the phosphate system, whereby the adhesive strength is further increased. A separate heating of the surface treatment agent is therefore not necessary.
  • the workpiece used in the first embodiment was a non-prepurified, non-de-frosted and non-degreased test sheet of hot-work steel.
  • 1% GELITA NOVOTEC (R) gelatin FP200 was dissolved in advance in 14% distilled water.
  • the gelatin was first swollen at room temperature in distilled water for about twenty minutes and then dissolved at a temperature of 60 ° C. At this temperature, 0.03% molybdenum disulfide was dispersed in the medium.
  • the test panel was sprayed vertically standing with the surface treatment spray. After a short exposure time of 10 minutes, the plate was washed with water and dried. The sheet after cleaning had a closed black layer consisting of manganese phosphate and molybdenum disulfide. An additional heating of the sheet was not required. The sheet metal was largely free of defects, so that a high corrosion resistance was achieved.
  • a die casting mold was cleaned and passivated with a surface treatment spray of the invention.
  • 1% GELITA NOVOTEC (R) gelatin FP200 was pre-dissolved in 14% distilled water.
  • the gelatin was first swollen at room temperature in distilled water for about twenty minutes and then dissolved at a temperature of 60 ° C. At this temperature, 0.03% molybdenum disulfide was dispersed in the medium.
  • citric acid (0.7%), lactic acid (0.7%), phosphoric acid (1.4%) and a Brünofix GAM 5624 aqueous manganese phosphate solution (36%) were mixed and added to the suspension.
  • the flowability of the surface treatment spray of the invention was again adjusted with a nearly equivalent amount of a thickener of the Ardrox 6085 type, which in turn contains nonionic surfactants. This gave rise to a surface treatment spray according to the invention.
  • the mold was treated at room temperature by spraying the surface treatment spray. After a contact time of ten Minutes, the cleaning residues were washed off. Again, a uniform layer of manganese phosphate and molybdenum sulfide formed. Subsequently, the casting mold was tempered for four hours at 200 ° C. in the preheating phase and the leveling-out phase in the casting machine. It formed a closed layer of manganese phosphate and molybdenum disulfide
  • a low pressure die was treated with a surface treatment spray according to the invention.
  • 1% GELITA NOVOTEC (R) Gelatin FP200 was pre-dissolved in 14% distilled water to prepare this surface treatment spray.
  • the gelatin was first swollen again at room temperature in distilled water for about twenty minutes and then dissolved at a temperature of 60 ° C. Then, citric acid (0.7%), lactic acid (0.7%), phosphoric acid (1.4%) and Brünofix Z 5526 (36%), an aqueous zinc phosphate solution, were mixed and added to the suspension.
  • the flowability of the surface treatment spray was also adjusted in this example with the Ardrox 6085 thickener containing almost equivalent amount of nonionic surfactants.
  • the mold was treated at room temperature by spraying the surface treatment spray. After a reaction time of ten minutes, the cleaning residues were washed off. The mold was then tempered for four hours at 250 ° C to apply a waterglass bound sizing.
  • a squeeze-cast mold was sprayed with a surface treatment spray according to the invention.
  • 1% GELITA NOVOTEC (R) Gelatin FP200 was pre-dissolved in 14% distilled water.
  • the gelatin was first swollen at room temperature in distilled water for about twenty minutes and then dissolved at a temperature of 60 ° C. At this temperature, 0.03% molybdenum disulfide was dispersed in the medium.
  • citric acid (0.7%), lactic acid (0.7%), phosphoric acid (1.4%) and a Brünofix GAM 5624 aqueous manganese phosphate solution (36%) were mixed and added to the suspension.
  • the flowability of the surface treatment spray of the invention was again adjusted with a nearly equivalent amount of non-ionic surfactant-containing thickener of the Ardrox 6085 type.
  • the mold was treated at room temperature by spraying the cleaner. After a reaction time of ten minutes, the cleaning residues were washed off. The mold was tempered for four hours at 200 ° C in the preheating and balancing phase in the caster.
  • the invention is not limited to the described embodiments.
  • the same effects occur when using appropriately formulated surface treatment agents in cleaning and passivating the molds and workpieces in the dipping bath.
  • a pure passivation with a passivation agent according to the invention with previous cleaning is possible.
  • Such a surface treatment leads to an increase in the effect of the metal phosphate layer as a primer and diffusion barrier. This is done in particular by the firm connection of the phosphate system to the metallic surface by the action of gelatin as a dispersant and equipotential bonding system and by the occupancy of defects.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Claims (12)

  1. Agent de passivation pour surfaces métalliques de pièces ou de moules de coulée comprenant une solution de phosphate aqueuse contenant des ions métalliques,
    caractérisé en ce que
    l'agent de passivation comprend une gélatine, dont le potentiel rédox est ajusté de sorte que l'indice d'or de la gélatine est inférieur à 50 µmol Au/g de gélatine.
  2. Agent de passivation pour surfaces métalliques de pièces ou de moules de coulée selon la revendication 1, caractérisé en ce que la solution de phosphate aqueuse contenant des ions métalliques est une solution d'orthophosphate aqueuse, les orthophosphates étant constitués par une ou plusieurs des composés phosphate de zinc, phosphate d'aluminium, phosphate de manganèse, phosphate de titane, phosphate de calcium, phosphate de bore ou phosphate de fer.
  3. Agent de passivation pour surfaces métalliques de pièces ou de moules de coulée selon une des revendications précédentes, caractérisé en ce que l'agent de passivation est composé comme suit:
    0,1 % en poids à 5 % en poids de gélatine
    5 % en poids à 50 % en poids d'orthophosphates
    l'équilibre en eau.
  4. Agent de traitement de surfaces pour le nettoyage et la passivation de surfaces métalliques de pièces ou de moules de coulée avec un agent de passivation selon l'une des revendications 1 à 3, dans lequel l'agent de traitement de surfaces comprend, en outre, des agents tensioactifs non-ioniques, de l'acide lactique et un acide citrique monohydraté.
  5. Agent de traitement de surfaces pour le nettoyage et la passivation de surfaces métalliques de pièces ou de moules de coulée selon la revendication 4, caractérisé en ce que l'agent de traitement de surfaces est composé comme suit:
    0,1 à 5 % en poids, de préférence 0,41 à 1 % en poids de gélatine
    5 à 50 % en poids, de préférence 5 à 10 % en poids d'orthophosphates
    0,5 à 5 % en poids, de préférence 0,5 à 2,5 % en poids d'acide lactique
    0,5 à 5 % en poids, de préférence 0,5 à 2,5 % en poids d'acide citrique monohydraté
    0,1 à 3 % en poids, de préférence 0,5 à 2 % en poids d'agents tensioactifs non-ioniques
    l'équilibre en eau distillée.
  6. Agent de traitement de surfaces pour le nettoyage et la passivation de surfaces métalliques de pièces ou de moules de coulée selon la revendication 4 ou 5, caractérisé en ce que l'agent de traitement de surfaces comprend, en outre, de sulfure de molybdène et/ou de bismuth.
  7. Agent de traitement de surfaces pour le nettoyage et la passivation de surfaces métalliques de pièces ou de moules de coulée selon la revendication 6, caractérisé en ce que l'agent de traitement de surfaces comprend, en outre, 0,01 à 5 % en poids, de préférence 0,02 à 0,04 % en poids de sulfure de molybdène et/ou 0,01 à 5 % en poids, de préférence 0,02 à 0,04 % en poids de bismuth.
  8. Agent pulvérisé de traitement de surfaces pour le nettoyage et la passivation de surfaces métalliques de pièces ou de moules de coulée, caractérisé en ce que l'agent pulvérisé de traitement de surfaces contient l'agent de traitement de surfaces selon l'une des revendications 5 à 7 et jusqu'à 60% en poids d'un agent épaississant.
  9. Procédé de traitement de surfaces métalliques de pièces ou de moules de coulée, caractérisé en ce que la pièce ou le moule de coulée est immergé dans un bain de l'agent de traitement de surfaces selon l'une des revendications 5 à 7, ou l'agent pulvérisé de traitement de surfaces selon la revendication 8 est pulvérisé sur la surface de la pièce ou du moule de coulée.
  10. Procédé de traitement de surfaces métalliques de pièces ou de moules de coulée selon la revendication 9, caractérisé en ce que la pièce ou le moule de coulée est ensuite chauffé à 200°C.
  11. Procédé de traitement de surfaces métalliques de moules de coulée à basse pression selon la revendication 10, caractérisé en ce qu'après l'immersion dans l'agent de traitement de surfaces ou après la pulvérisation de l'agent pulvérisé de traitement de surfaces sur la surface nettoyée et passivée du moule de coulée, l'on applique un enrobage.
  12. Procédé de traitement de surfaces métalliques de moules de coulée selon la revendication 11, caractérisé en ce que l'enrobage est appliqué à une température du moule de coulée à basse pression de 250°C.
EP09704705.4A 2008-01-26 2009-01-26 Agents de passivation, agents de traitement de surfaces, agents de pulvérisation pour traitement de surfaces, et procédé de traitement de surfaces métalliques de pièces ou de moules de coulée Not-in-force EP2245213B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008006147A DE102008006147A1 (de) 2008-01-26 2008-01-26 Reinigungssystem für metallische und keramische Oberflächen
PCT/EP2009/050846 WO2009092817A1 (fr) 2008-01-26 2009-01-26 Agents de passivation, agents de traitement de surfaces, agents de pulvérisation pour traitement de surfaces, et procédé de traitement de surfaces métalliques de pièces ou de moules de coulée

Publications (2)

Publication Number Publication Date
EP2245213A1 EP2245213A1 (fr) 2010-11-03
EP2245213B1 true EP2245213B1 (fr) 2016-01-20

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EP09704705.4A Not-in-force EP2245213B1 (fr) 2008-01-26 2009-01-26 Agents de passivation, agents de traitement de surfaces, agents de pulvérisation pour traitement de surfaces, et procédé de traitement de surfaces métalliques de pièces ou de moules de coulée

Country Status (5)

Country Link
US (1) US8512484B2 (fr)
EP (1) EP2245213B1 (fr)
CN (1) CN101970722B (fr)
DE (1) DE102008006147A1 (fr)
WO (1) WO2009092817A1 (fr)

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WO2012117881A1 (fr) * 2011-02-28 2012-09-07 株式会社棚澤八光社 Outil de moulage et procédé de fabrication de cet outil, et procédé pour obtenir un brillant uniforme
DE102011113157A1 (de) * 2011-06-22 2012-12-27 Doncasters Precision Castings-Bochum Gmbh Verfahren und Vorrichtung zur Behandlung eines gerichtet erstarrten oder einkristallinen Gussteils
HUE043123T2 (hu) * 2014-12-25 2019-08-28 Lang Yuzer Otomotiv Yan Sanayi Ve Ticaret Anonim Sirketi Eljárás jármûvek gumiabroncsainak teljes öntõformáinak tiszítására
DE102016100245A1 (de) * 2016-01-08 2017-07-13 Staku Anlagenbau Gmbh Selbstschmierende elektrolytisch abgeschiedene Phosphatierungsbeschichtung
DE102016107681A1 (de) * 2016-04-26 2017-10-26 Kerona Gmbh Substanz zum Lösen von Korrosionsschichten
US20220364018A1 (en) 2021-05-14 2022-11-17 Ecolab Usa Inc. Neutralizing instrument reprocessing

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CH320338A (de) 1952-06-26 1957-03-31 Metallgesellschaft Ag Verfahren zur Bildung von nichtmetallischen Überzügen auf Metallen
DE3403660C2 (de) 1984-02-03 1995-06-14 Joachim Dr Marx Mittel zur Herstellung von Schutzschichten
CN1115794A (zh) 1994-07-27 1996-01-31 徐琐平 一种钢铁除锈磷化液
CN1132802A (zh) 1995-04-04 1996-10-09 李诗录 金属除锈、防锈液
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DE102005042475A1 (de) 2005-09-07 2007-03-08 Ks Aluminium-Technologie Ag Formtrennschicht für das Gießen von Nichteisenmetallen

Also Published As

Publication number Publication date
CN101970722B (zh) 2012-12-05
US20100297344A1 (en) 2010-11-25
DE102008006147A1 (de) 2009-09-10
CN101970722A (zh) 2011-02-09
EP2245213A1 (fr) 2010-11-03
US8512484B2 (en) 2013-08-20
WO2009092817A1 (fr) 2009-07-30

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