EP1924723A2 - Revetement d'element fonctionnel sollicite de maniere thermique et erosive, agent de separation et procede pour produire ledit revetement - Google Patents

Revetement d'element fonctionnel sollicite de maniere thermique et erosive, agent de separation et procede pour produire ledit revetement

Info

Publication number
EP1924723A2
EP1924723A2 EP06805667A EP06805667A EP1924723A2 EP 1924723 A2 EP1924723 A2 EP 1924723A2 EP 06805667 A EP06805667 A EP 06805667A EP 06805667 A EP06805667 A EP 06805667A EP 1924723 A2 EP1924723 A2 EP 1924723A2
Authority
EP
European Patent Office
Prior art keywords
release agent
functional component
phosphate
coating
proportion
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.)
Withdrawn
Application number
EP06805667A
Other languages
German (de)
English (en)
Inventor
Manfred Laudenklos
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
KS Aluminium Technologie 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 KS Aluminium Technologie GmbH filed Critical KS Aluminium Technologie GmbH
Publication of EP1924723A2 publication Critical patent/EP1924723A2/fr
Withdrawn legal-status Critical Current

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
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/18—Fireproof paints including high temperature resistant paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/68—Particle size between 100-1000 nm
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
    • C04B2111/0087—Uses not provided for elsewhere in C04B2111/00 for metallurgical applications
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/256—Heavy metal or aluminum or compound thereof
    • Y10T428/257—Iron oxide or aluminum oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
    • Y10T428/259—Silicic material

Definitions

  • the invention relates to a metallic functional component, which is exposed to a thermal or a thermal and erosive load and on which a coating is applied to at least one surface, wherein the coating of a binder phase, which consists at least largely of a phosphate, and one in the binder phase embedded material. Moreover, the invention relates to a release agent for producing a coating on a functional component and moreover relates to a method for producing a coating on a metallic surface of a functional component.
  • components that are subjected to thermal or thermal and erosive stress while flowing, pressurized, or exposed to a medium perform, for example, the function of a power transmission or a baffle. In this function, they are charged with flowing or expanding media. In many cases, it comes to strong temperature fluctuations, so that the components must meet the condition of temperature resistance. In many cases, components which are in contact with flowing media also lead to deposits, so that these components are usually provided with coatings.
  • Typical examples of such functional components are, for example, pistons, cylinder head calottes and the entire area of exhaust gas recirculation in the motor vehicle. In addition to the erosive loading of these components, these components are also inferior to high thermal loads and temperature fluctuations. To protect such functional components a variety of coatings and coating methods are known.
  • DE 101 24 434 A1 discloses a process for producing a coating and a coating for metals or metal alloys, such as steels, sintered metals or aluminum alloys from the fields of automobile construction and mechanical engineering.
  • the aim of this coating is to protect the materials mentioned against wear and corrosion.
  • the coating consists of an inorganic matrix phase, the at least largely consists of a phosphate and a material embedded therein.
  • the coating consists of an inorganic matrix phase of aluminum phosphate, in which materials such as alumina or graphite are embedded.
  • Such coatings are preferably applied to the substrate to be coated via water-based gels or dispersions of dissolved monoaluminum phosphate and powdered functional materials dispersed therein, dried and baked at typical temperatures of 150 ° C. to 500 ° C. in an oven.
  • the coating here refers to the surface of a piston skirt having a hard anodized coating and a composite polymer coating applied to the hard anodized coating.
  • the composite polymer coating comprises a variety of solid and lubricious particles in a heat-resistant polymer matrix that can withstand engine operating temperatures.
  • the known lubricant materials graphite, boron nitride, molybdenum et cetera are used.
  • the object of the present invention is to develop a coating of thermally or thermally and erosively loaded functional surfaces on components, which forms a chemical bond with the base material of the functional component and thus counteracts the erosive and thermal stresses on the functional components.
  • the coating should be easy to apply and have a high adhesion to the base material.
  • Another object of the invention is to provide a method capable of producing such a layer and which produces high adhesion between the binder and the base material.
  • the object according to the invention is achieved in relation to the functional component provided with a coating in that the binder phase is chemically bonded to the base material of the functional component and in that the binder phase consists of a polymer of polymerized monoaluminum phosphate and / or monozinc phosphate and / or monomagnesium phosphate and / or sodium phosphate and / or boron phosphate is formed and the functional component is part of an internal combustion engine, and the material embedded in the binder phase, a structural part of the form AI 2 O 3 and / or SiO 2 and / or TiO 2 and / or ZrO 2 in a fraction of 80 nm to 200 nm and embedded in the binder phase material of primary parts of the form AI 2 O 3 , SiO 2 , ZnO, ZrO 2 , CeO, TiO 2 in a fraction of 2nm to 80nm is formed, wherein the primary parts are embedded in the gaps between the structural parts and the primary parts and the structural parts are enclosed
  • the binder phase structural parts of the form AI 2 O 3 and / or SiO 2 and / or TiO 2 and / or ZrO 2 are involved.
  • the polymer chains enclose the structural parts and bind the structural parts to the base material.
  • the phosphate is either a chemical bond with an existing iron in the base material or a non-metal such as aluminum.
  • a firmly adhering layer is also produced by the binder diffusing into the base material. The degree of infiltration depends on the bulk density of the base material and on the degree of porosity present.
  • the functional component which forms a great security against erosive loads by means of a chemical bond with the base material and the inclusion of the structural elements in the polymer chains.
  • the hard structural parts which are present as oxides, as a wear carrier and the binder phase as a binder between the base material and structural element.
  • the structural parts are present in a fraction of 80nm to 200nm and form with up to 10 wt .-%, the largest proportion of particulate materials in the coating.
  • the structural parts have a relatively coarse surface structure, so that on the one hand the structural parts interlock with each other and at the same time ensure a good hold in the binder phase.
  • Advantageously and essential to the invention is a proportion of primary parts of the form AI 2 O 3 and / or SiO 2 and / or ZnO and / or TiO 2 and / or ZrO 2 and / or CeO in the binder phase.
  • the primary parts are integrated.
  • the primary parts are optimally suited to serve as fillers between the structural parts. This results in a very smooth surface, which in turn counteracts erosion and deposition of the soot particles acting on the functional part, for example contained in an exhaust gas of an exhaust gas recirculation channel.
  • the very smooth and resistant surface thus enables the advantage according to the invention that the functional components provided with a coating according to the invention have a long service life.
  • the primary parts are preferably present in proportions of 1 wt .-% to 3 wt .-% in the coating.
  • an organic and / or inorganic dispersant is also important.
  • a gelatine marketed under the brand name "Gelita” is used, the main components of which are calcium with a content of 3950 mg per kg and magnesium with a content of 1500 mg per kg, the remainder consisting of organic and inorganic components
  • Gelantine preferably has the task of making a coordinated contribution to balance the potential for dispersing and accelerating the reaction.
  • the Richardson-Ellingham diagram which is known on the one hand and on the other hand
  • Magnesium and calcium as main constituents of the gelatin serve to stabilize the structural parts and primary parts during the dissolution of the hot base material through the coating, so that a control of the binding of the coating to the Gr Material is possible.
  • the gelatin is present in proportions of 0.5 wt .-% to 5 wt .-% in the release agent and is thus detectable at least in trace amounts in the coating of the functional component
  • sliding parts of the form boron nitride and / or magnesium aluminum silicate and / or molybdenum sulfide and / or silicate minerals, for example mica, are incorporated into the binder phase.
  • the sliding parts are contained in the coating at levels of up to 5% by weight.
  • the much larger sliding parts with dimensions of 2 ⁇ m to 15 ⁇ m are also by the Polymer chains of polymerized phosphate held or lie between the structural parts in the coating.
  • Thicknesses between 1 .mu.m and 80 .mu.m are preferably provided as layer thicknesses.
  • a thickness of between 25 ⁇ m and 60 ⁇ m is built up on the surface of the functional component.
  • Functional components are for example components such as pistons, a cylinder head calotte, or parts of the exhaust gas recirculation in a motor vehicle.
  • the functional components are made of aluminum alloys or steel. It is also possible to form a coating according to the invention on a functional component made of cast iron, in particular a cast iron of the form GG 1 GGG, GGV.
  • the object according to the invention is achieved in relation to the release agent for producing a coating on a functional component such that the release agent is formed from a demineralized water and contains the following constituents:
  • organic and / or inorganic dispersant such as, for example, gelatin
  • the acid buffer By means of the acid buffer, it is possible according to the invention to adjust the acid content and thus the pH of the release agent and thus to control the reaction rate and formation of the polymers.
  • the acid buffer thus serves to delay the reaction and to ensure a uniform course of the reaction.
  • a pH of 4 to 5 is set in the release agent.
  • the release agent By using the release agent, it is now possible to produce a coating according to claim 1.
  • structural parts and primary parts are contained in the release agent, which are applied by means of spraying or dipping of the functional component on the surface of the material of the functional component. It is also advantageous in the release agent Sliding members of the form boron nitride and / or magnesium aluminum silicate and / or molybdenum disulfide bring.
  • the fractions of the structural parts lie between 80nm to 200nm of the primary parts between 2nm and 80nm and the sliding parts between 2 ⁇ m and 15 ⁇ m.
  • the advantage here is the gelatin, which forms nanoparticles on its own.
  • binder in a size proportion of up to 5 wt .-% are added to the release agent.
  • the structural parts are added with up to 10 wt .-%, the primary parts of up to 3 wt .-% and the sliding parts in an amount of up to 5 wt .-% of the release agent.
  • the release agent has a high level of liquidity and can be sprayed by simple means, for example, on the surface of the functional component.
  • the coating according to the invention is produced by first applying a release agent to the surface and then heating the functional component to a temperature of at least 200 ° C., so that a chemical bond of the phosphate with the base material and a polymerization of the binder takes place.
  • the heating is generated by means of a high-frequency electric field that, for example, is applied capacitively or inductively to the functional component.
  • Preferred frequency ranges for heating by means of a high-frequency electric field are in this case 100 kHz up to 10 MHz 1, wherein preferably about 4 MHz are used. With a heating at 4 MHz, this results in a penetration depth of the phosphate of 0.2 to 0.3 mm. It is thus produced a very good adhesion coating on the functional component.
  • the polymer chains serve on the one hand for the cohesion of the layer and on the other hand, they are advantageous because they grow under thermal stress and thus increase the elasticity of the layer. With cyclic thermal stress, therefore, no premature component failure occurs due to crack formation of the coating, since the coating according to the invention can elastically follow the expansions of the base material.
  • the inventive construction of the layer a temperature resistance can be achieved up to about 1300 0 C.
  • the phosphate binder systems used have a polymer temperature of about 220 0 C and a glazing temperature of 830 0 C.
  • the adhesion to the base material is hereby ensured even in almost glazed or glazed state by the chemical bond to the base material.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Nanotechnology (AREA)
  • Mechanical Engineering (AREA)
  • Structural Engineering (AREA)
  • Metallurgy (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Paints Or Removers (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Building Environments (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un élément fonctionnel métallique, qui est exposé à des sollicitations d'ordre thermique ou thermique et érosives et sur lequel est appliqué un revêtement sur au moins une surface. Ledit revêtement comprend une phase de liaison consistant au moins dans une large mesure en un phosphate et un matériau noyé dans la phase de liaison. L'invention concerne en outre un agent de séparation utilisé pour produire un revêtement de ce type, ainsi qu'un procédé pour appliquer ledit revêtement sur un élément fonctionnel.
EP06805667A 2005-09-07 2006-09-07 Revetement d'element fonctionnel sollicite de maniere thermique et erosive, agent de separation et procede pour produire ledit revetement Withdrawn EP1924723A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005042474A DE102005042474A1 (de) 2005-09-07 2005-09-07 Beschichtung eines thermisch und erosiv belasteten Funktionsbauteil, sowie ein Trennmittel und ein Verfahren zur Herstellung der Beschichtung
PCT/EP2006/008750 WO2007028621A2 (fr) 2005-09-07 2006-09-07 Revetement d'element fonctionnel sollicite de maniere thermique et erosive, agent de separation et procede pour produire ledit revetement

Publications (1)

Publication Number Publication Date
EP1924723A2 true EP1924723A2 (fr) 2008-05-28

Family

ID=37496451

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06805667A Withdrawn EP1924723A2 (fr) 2005-09-07 2006-09-07 Revetement d'element fonctionnel sollicite de maniere thermique et erosive, agent de separation et procede pour produire ledit revetement

Country Status (6)

Country Link
US (1) US8685155B2 (fr)
EP (1) EP1924723A2 (fr)
KR (1) KR100989882B1 (fr)
CN (1) CN101316948B (fr)
DE (1) DE102005042474A1 (fr)
WO (1) WO2007028621A2 (fr)

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CN116023157B (zh) * 2023-02-14 2023-09-19 武汉船用电力推进装置研究所(中国船舶集团有限公司第七一二研究所) 一种环保型防火耐高温石墨材料涂层及其制备方法与应用
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US8685155B2 (en) 2014-04-01
US20100304129A1 (en) 2010-12-02
WO2007028621A2 (fr) 2007-03-15
CN101316948B (zh) 2010-12-22
CN101316948A (zh) 2008-12-03
WO2007028621A3 (fr) 2007-06-21
KR100989882B1 (ko) 2010-10-26
KR20080088575A (ko) 2008-10-02
DE102005042474A1 (de) 2007-03-08

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