EP2245213A1 - Passiviermittel, oberflächenbehandlungsmittel, oberflächenbehandlungssprühmittel sowie verfahren zum behandeln von metallischen oberflächen von werkstücken oder gussformen - Google Patents
Passiviermittel, oberflächenbehandlungsmittel, oberflächenbehandlungssprühmittel sowie verfahren zum behandeln von metallischen oberflächen von werkstücken oder gussformenInfo
- Publication number
- EP2245213A1 EP2245213A1 EP09704705A EP09704705A EP2245213A1 EP 2245213 A1 EP2245213 A1 EP 2245213A1 EP 09704705 A EP09704705 A EP 09704705A EP 09704705 A EP09704705 A EP 09704705A EP 2245213 A1 EP2245213 A1 EP 2245213A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- surface treatment
- workpieces
- molds
- metallic surfaces
- treatment agent
- 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
Links
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
- Passivation agents surface treatment agents, surface treatment sprays and methods for treating metallic surfaces of workpieces or molds
- the present invention relates to a passivation agent for metallic surfaces of workpieces or molds having an aqueous phosphate solution with metal ions, a surface treatment agent and a surface treatment spray for cleaning and passivating metallic surfaces of workpieces or molds with such a passivating agent, and a method of 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 significantly higher than 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.
- 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 This 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 is carried out, for example, by means of a high-pressure water jet, which is directed onto the workpiece via a rotary nozzle at a pressure of 1750 to 3000 bar.
- a high-pressure water jet which is directed onto the workpiece via a rotary nozzle at a pressure of 1750 to 3000 bar.
- 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.
- 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. The workpiece then has to 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 becomes uneconomical.
- 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 passivation agent is described in DE-34 03 660 A1, which consists of an aqueous solution of aluminum hydrogen phosphate and organic polymers, which under temperature make a movie.
- acrylic or epoxy resins are used as organic polymers.
- 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 passivating agent which according to the invention comprises a 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 forms a protective layer on the surface, which serves as corrosion protection and adhesion promoter for serves to be 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.
- gelatins whose redox potential is adjusted so that the gold number of the gelatin is less than 50 .mu.mol Au / g gelatin. It has been shown that these gelatins give particularly good results. the adhesion of the passivation layer and the thermal shock resistance of a component treated therewith can be achieved.
- 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 phosphatization to achieve 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.
- 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.
- the nonionic surfactants present in the surface treatment agent reduce the surface tension and, in combination with the organic acids, infiltrate impurities on the surface, so that these impurities are dissolved or dissolved and 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 has the following composition:
- nonionic surfactants 0.1 to 3% by weight, preferably 0.5 to 2% by weight, of nonionic surfactants
- 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. This results in a sprayability, which can be dispensed with the complex cleaning of various baths. Impurities of the surface treatment agent, such as may occur during treatment in baths are excluded.
- the object to provide a simplified compared to the prior art and more cost-effective 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 is sprayed onto the surface of the workpiece or the casting mold.
- 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 size may be a sodium or potassium waterglass size that is applied to the tool surface, thereby smoothing the surface and further protecting it from thermal stress.
- the size is applied at a mold temperature of 250 0 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 bond of the metal with the phosphate system, whereby the adhesive strength is additionally 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 0 C. At this temperature, 0.03% molybdenum disulfide was dispersed in the medium.
- Embodiment 2 is a diagrammatic representation of Embodiment 1:
- 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 0 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 reaction time of ten minutes, the cleaning residues were washed off. Again, a uniform layer of manganese phosphate and molybdenum sulfide formed. Subsequently, the mold was tempered in the preheating and balancing phase in the casting machine for four hours at 200 0 C. It formed a closed layer of manganese phosphate and molybdenum disulfide To test the thermal shock resistance, similarly coated test panels of the same material as the casting mold were heated at 800 ° C. for one hour and then quenched in water at room temperature. There were no defects on the phosphate layer. An extremely good adhesion of the layer to the casting mold has been demonstrated and thus an unusually good thermal shock resistance has been achieved.
- 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 0 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 shape after sizing was annealed for four hours at 250 0 C for the application of a water glass-bonded.
- 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 0 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 heated in the preheating and balancing phase in the casting machine for four hours at 200 0 C.
- 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 passivating agent according to the invention is possible with prior cleaning.
- 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.
Landscapes
- 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)
Abstract
Description
Claims
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 (de) | 2008-01-26 | 2009-01-26 | Passiviermittel, oberflächenbehandlungsmittel, oberflächenbehandlungssprühmittel sowie verfahren zum behandeln von metallischen oberflächen von werkstücken oder gussformen |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2245213A1 true EP2245213A1 (de) | 2010-11-03 |
EP2245213B1 EP2245213B1 (de) | 2016-01-20 |
Family
ID=40577969
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09704705.4A Not-in-force EP2245213B1 (de) | 2008-01-26 | 2009-01-26 | Passiviermittel, oberflächenbehandlungsmittel, oberflächenbehandlungssprühmittel sowie verfahren zum behandeln von metallischen oberflächen von werkstücken oder gussformen |
Country Status (5)
Country | Link |
---|---|
US (1) | US8512484B2 (de) |
EP (1) | EP2245213B1 (de) |
CN (1) | CN101970722B (de) |
DE (1) | DE102008006147A1 (de) |
WO (1) | WO2009092817A1 (de) |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101990939B1 (ko) * | 2011-02-28 | 2019-06-19 | 가부시끼가이샤 다나자와 핫꼬오샤 | 성형용 금형 및 그 제조 방법, 및 광택도를 합치시키는 방법 |
DE102011113157A1 (de) * | 2011-06-22 | 2012-12-27 | Doncasters Precision Castings-Bochum Gmbh | Verfahren und Vorrichtung zur Behandlung eines gerichtet erstarrten oder einkristallinen Gussteils |
JP6659722B2 (ja) * | 2014-12-25 | 2020-03-04 | ラング ユザー オートモティヴ ヤン サナイ ヴェ ティカレット アノニム シレケッティLang Yuzer Otomotiv Yan Sanayi Ve Ticaret Anonim Sirketi | 車両用タイヤのフルモールドの洗浄のための方法 |
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 |
Family Cites Families (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
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 |
PL331923A1 (en) * | 1996-08-30 | 1999-08-16 | Solutia Inc | Novel water-soluble fluids for use in metal machining operations |
DE10012492A1 (de) * | 2000-03-15 | 2001-09-27 | Henkel Kgaa | Reinigungsmittel |
US20020045010A1 (en) * | 2000-06-14 | 2002-04-18 | The Procter & Gamble Company | Coating compositions for modifying hard surfaces |
DE10346192B4 (de) | 2003-10-02 | 2009-08-06 | Thyssenkrupp Presta Teccenter Ag | Verfahren zum Entrosten von Formteilen und Verwendung des Verfahrens |
DE102005042474A1 (de) | 2005-09-07 | 2007-03-08 | Ks Aluminium-Technologie Ag | Beschichtung eines thermisch und erosiv belasteten Funktionsbauteil, sowie ein Trennmittel und ein Verfahren zur Herstellung der Beschichtung |
DE102005042475A1 (de) | 2005-09-07 | 2007-03-08 | Ks Aluminium-Technologie Ag | Formtrennschicht für das Gießen von Nichteisenmetallen |
-
2008
- 2008-01-26 DE DE102008006147A patent/DE102008006147A1/de not_active Withdrawn
-
2009
- 2009-01-26 CN CN200980103112.7A patent/CN101970722B/zh not_active Expired - Fee Related
- 2009-01-26 US US12/864,237 patent/US8512484B2/en not_active Expired - Fee Related
- 2009-01-26 EP EP09704705.4A patent/EP2245213B1/de not_active Not-in-force
- 2009-01-26 WO PCT/EP2009/050846 patent/WO2009092817A1/de active Application Filing
Non-Patent Citations (1)
Title |
---|
See references of WO2009092817A1 * |
Also Published As
Publication number | Publication date |
---|---|
US20100297344A1 (en) | 2010-11-25 |
CN101970722A (zh) | 2011-02-09 |
WO2009092817A1 (de) | 2009-07-30 |
DE102008006147A1 (de) | 2009-09-10 |
CN101970722B (zh) | 2012-12-05 |
EP2245213B1 (de) | 2016-01-20 |
US8512484B2 (en) | 2013-08-20 |
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