EP1451392B1 - Processus de traitement de surface pour l'enduction de materiaux en aluminium - Google Patents

Processus de traitement de surface pour l'enduction de materiaux en aluminium Download PDF

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Publication number
EP1451392B1
EP1451392B1 EP02785370A EP02785370A EP1451392B1 EP 1451392 B1 EP1451392 B1 EP 1451392B1 EP 02785370 A EP02785370 A EP 02785370A EP 02785370 A EP02785370 A EP 02785370A EP 1451392 B1 EP1451392 B1 EP 1451392B1
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EP
European Patent Office
Prior art keywords
component
electrolyte
functional layer
layer
added
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP02785370A
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German (de)
English (en)
Other versions
EP1451392A2 (fr
Inventor
Rudolf Linde
Wolfgang Stuckert
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Federal Mogul Burscheid GmbH
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Federal Mogul Burscheid 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
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Publication of EP1451392A2 publication Critical patent/EP1451392A2/fr
Application granted granted Critical
Publication of EP1451392B1 publication Critical patent/EP1451392B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02F—CYLINDERS, PISTONS OR CASINGS, FOR COMBUSTION ENGINES; ARRANGEMENTS OF SEALINGS IN COMBUSTION ENGINES
    • F02F3/00—Pistons 
    • F02F3/10—Pistons  having surface coverings
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44—Aluminium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/20—Electroplating: Baths therefor from solutions of iron
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2201/00—Metals
    • F05C2201/02—Light metals
    • F05C2201/021—Aluminium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2201/00—Metals
    • F05C2201/04—Heavy metals
    • F05C2201/0433—Iron group; Ferrous alloys, e.g. steel
    • F05C2201/0436—Iron
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2201/00—Metals
    • F05C2201/90—Alloys not otherwise provided for
    • F05C2201/903—Aluminium alloy, e.g. AlCuMgPb F34,37
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2253/00—Other material characteristics; Treatment of material
    • F05C2253/12—Coating

Definitions

  • Method for applying electrodeposited metal coatings to components made of aluminum or an aluminum alloy in which the surface of the component is cleaned in a suitable solution, in particular of oils, fats, emulsions, pigments, etc., and then the surface is etched in a suitable solution is so that a certain amount of the material or the near-surface alloying constituents are dissolved and that after cleaning and after dissolving rinsing is done by means of water.
  • a suitable solution in particular of oils, fats, emulsions, pigments, etc.
  • these components can be subjected to various measures. Measures to increase wear resistance include alloying, tempering and coating.
  • coating plays an important role in aluminum materials and their alloys, because it allows the positive properties of these materials to be combined with those of the coating.
  • piston and cylinder liner it has long been standard practice to produce these two elements from aluminum, since the efforts of engine manufacturers to reduce the weight of the elements.
  • the tribological system would fail and galling would occur at the contact surfaces.
  • a problem that arises in the coating of aluminum is the chemically very stable and naturally forming oxide layer on the surface of the aluminum.
  • oxide layer To improve the adhesion of coatings on the aluminum or even to allow the oxide layer must be broken and removed. So that the oxide layer, after removal and before a further coating, does not reform again, it is generally customary to apply an intermediate layer to the surface of the aluminum, which then makes it possible to deposit so-called functional layers.
  • a functional layer can be made of iron, for example, and serves inter alia wear resistance.
  • DE 19 15 762 discloses a method for applying electrodeposited metal coatings to aluminum and aluminum alloys.
  • the surface of the material is cleaned, then activated and provided with an adhesive intermediate layer and then with a coating material, in this case, the coating would be the functional layer, plated.
  • the intermediate layers used in this case can consist of zinc, nickel, tin or copper.
  • the parts to be metallized are immersed in a solution consisting of hydrochloric acid, copper-11-chloride and a metallic copper powder until an intermediate layer of monovalent copper has formed in this immersion bath on the surface of the aluminum.
  • a disadvantage of this method is the high aggressiveness of the chloride electrolyte, so that the use of this method costly and with great effort, z. B. in terms of safety at work, is connected.
  • a thin conductive intermediate layer is deposited, which prevents the reoxidation of the surface during the introduction into the coating bath and causes good adhesion to the coating (functional layer).
  • the further development of the process is aimed at replacing cyanide zinc stains with cyanide-free ones. This is done by using organic complexing agents instead of cyanide and iron instead of nickel and copper.
  • cyanide-free zincate stains a special complexing agent was developed. The metal ions are precisely complexed so that a uniform and controlled deposition with excellent adhesion. At the same time, the complexing agent allows a rapid ion exchange and thus ensures a rapid layer structure.
  • the components are cleaned and freed from interfering fats, oils, emulsions, pigments and similar impurities in the manufacturing process. After cleaning, a thorough rinse with water follows. Subsequently, the surface of the components is etched in a suitable solution, that is, a certain amount of aluminum, or near-surface alloying constituents, is dissolved. Thereafter, the component is again thoroughly rinsed with water.
  • a suitable solution that is, a certain amount of aluminum, or near-surface alloying constituents
  • the component is again thoroughly rinsed with water.
  • the commonly used electrolytes operate on a base of chloride, fluoroborate or ammonium sulfate. Chloride electrolytes have a high aggressiveness as described above, the fluoroborates have a high aggressiveness and toxidity, and the ammonium sulfate electrolytes have a poor sewage compatibility.
  • solid lubricants were added to the electrolyte, which were in a size of about 0.2 to 2.0 .mu.m.
  • Suitable solid lubricants include hexagonal boron nitride, colloid fluoride, graphite, molybdenum sulfide, Teflon, steel particles or oil-filled microcapsules. These solid lubricants can be used separately but also as a mixture or mixtures. The tests have shown that the solid lubricants have a very positive influence on the tribological system and that the coefficients of friction are more favorable. It formed a functional layer in which the solid lubricants finely distributed and submitted with a share of about 20Vol-%.
  • Example 4 a sulphate-based electrolyte according to the invention, with 300 g / l of iron II sulfate heptahydrate, a proportion of 5 ml / l of a hypophosphorous acid, z. B. H3PO2 added.
  • the functional layer formed by the method according to the invention then had a hardness of 700 HV 0.05. With the help of amounts of phosphorus in the electrolyte, it is thus possible to influence the hardness of the layer targeted.
  • Example 5 a hard material according to Example 1 was added to the phosphorus-containing electrolyte from Example 4.
  • the hardness of the layer produced was 750 HV 0.05, that is, the hardness could be further increased.
  • the wear tests gave similar values as in Example 1.
  • a solid lubricant according to Example 2 was added to the phosphorus-containing electrolyte of Example 4. Under these conditions, a functional layer was deposited as an iron layer, in which finely divided about 20% by volume of solid lubricants were included. The hardness of this layer was 650 HV 0.05. The results of the friction value tests were better than those of the layers without phosphorus content. The results of the wear tests were comparable.
  • the applied functional layers were characterized by an excellent bond to the base material of the component.
  • a coated according to the examples of the invention functional layer, as an iron layer showed in an adhesion test under extreme conditions, eg. As thermal shock test, glass bead test and scratch test, an excellent bond to the base material and the functional layers, which were applied with an adhesion-promoting intermediate layer based on zinc and copper comparable and in some areas even superior.
  • the functional layer has an excellent bond to the base material and at the same time serves as the basis for a further or several layers.
  • the coating materials are named, but they are only to be seen as examples. Since the functional layer is formed predominantly of iron, any layer material which has an affinity for iron can be applied to the component or to the functional layer. In particular, these are all metallic materials but also plastics and ceramics. Also in the choice of the coating method can be mentioned in the dependent claims only examples. Basically, any method is suitable with which iron materials can be coated. By way of example, electrochemical, with the inter alia, tin, copper, etc. can be deposited, thermal, with the inter alia molybdenum, etc., and reactive processes are mentioned. These include high-speed flame spraying, plasma spraying, PVD and CVD processes as well as screen printing or sprayed organic coatings.
  • FIG. 1 shows the cross section through a component 1 coated according to the invention.
  • the figure shows the base material 2 and the functional layer 3 applied thereon.
  • the functional layer 3 was deposited directly without intermediate layer by means of an electrolyte.
  • the functional layer 3 consists primarily of iron 5, here are finely divided hard materials 6 and solid lubricants 7 incorporated.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Claims (16)

  1. Procédé d'application par dépôt galvanique de couches fonctionnelles (3) composées de fer (5) sur des pièces (1) réalisées dans un alliage d'aluminium, dans lequel la surface (4) de la pièce est nettoyée dans une solution appropriée, en particulier, est débarrassée des huiles, graisses, émulsions, pigments, etc. et dans lequel la surface (4) est ensuite décapée dans une solution appropriée, de telle sorte qu'une certaine quantité du matériau, plus précisément des éléments d'alliage à proximité de la surface sont dissous, et dans lequel, après le nettoyage et après la dissolution, est réalisé un rinçage à l'eau, et dans lequel la surface (4) de la pièce (1) est activée directement après la dissolution des zones à proximité de la surface par branchement anodique de la pièce (1) dans une solution contenant des ions de fer, et dans lequel, sans rinçage intermédiaire, la couche fonctionnelle (3) est déposée par branchement cathodique de la pièce (1) dans le même électrolyte, caractérisé en ce que la pièce (1) contient au moins une proportion d'alliage de silicium comprise entre 3 et 22 % en poids et en ce que l'activation est réalisée dans une solution à base de sulfate contenant 50 à 500 g/l de sulfate ferreux heptahydrate, avec une valeur de pH comprise entre 0,5 et 2,5.
  2. Procédé selon la revendication 1, caractérisé en ce que l'activation de la pièce (1) est réalisée avec une durée d'exposition dans la solution comprise entre 5 secondes et 5 minutes.
  3. Procédé selon l'une des revendications 1 et 2, caractérisé en ce que l'activation de la surface (4) et le dépôt de la couche fonctionnelle sont réalisés avec une densité de courant de 2 à 20 A/dm2.
  4. Procédé selon l'une quelconque des revendications 1 à 3, caractérisé en ce que l'activation est réalisée dans une solution dans une fourchette de températures comprise entre 20°C et 95°C.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'au moins un matériau dur (6) est ajouté à l'électrolyte et en ce que les particules de matériau dur ont une dimension d'environ 0,2 µm à 5 µm, l'oxyde d'aluminium, le nitrure de silicium, le nitrure de chrome, le carbure de titane, le nitrure de bore cubique, ainsi que des particules de diamant étant prévus en tant que matériau dur (6).
  6. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce qu'au moins un matériau lubrifiant solide (7) est ajouté à l'électrolyte, le nitrure de bore hexagonal, le fluorure de carbone, le graphite, le bisulfure de molybdène, le téflon ou des microcapsules remplies d'huile étant prévus en tant que matériau lubrifiant solide (7), et en ce que les particules de matériau lubrifiant solide ont une dimension d'environ 0,2 µm à 5 µm.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce qu'au moins un matériau dur (6) et au moins un matériau lubrifiant solide (7) sont ajoutés à l'électrolyte.
  8. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que 0,25 à 5 ml/l d'un acide hypophosphorique, tel que H3PO2, de préférence l'acide H3PO2 à 50 % sont ajoutés à l'électrolyte.
  9. Procédé selon l'une quelconque des revendications 1 à 4 et 8, caractérisé en ce qu'au moins un matériau dur (6) est ajouté à l'électrolyte et en ce que les particules de matériau dur ont une dimension d'environ 0,2 µm à 5,0 µm, l'oxyde d'aluminium, le nitrure de silicium, le nitrure de chrome, le carbure de titane, le nitrure de bore cubique, ainsi que des particules de diamant étant prévus en tant que matériau dur (6).
  10. Procédé selon l'une quelconque des revendications 1 à 4 et 8, caractérisé en ce qu'au moins un matériau lubrifiant solide (7) est ajouté à l'électrolyte, le nitrure de bore hexagonal, le fluorure de carbone, le graphite, le bisulfure de molybdène, le téflon ou des microcapsules remplies d'huile étant prévus en tant que matériau lubrifiant solide (7), et en ce que les particules de matériau lubrifiant solide ont une dimension d'environ 0,2 µm à 5,0 µm.
  11. Procédé selon l'une quelconque des revendications 1 à 4 et 8, 9 et 10, caractérisé en ce qu'au moins un matériau dur (6) et au moins un matériau lubrifiant solide (7) sont ajoutés à l'électrolyte.
  12. Procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce qu'au moins une autre couche est déposée sur la couche fonctionnelle (3).
  13. Procédé selon l'une quelconque des revendications 1 à 12, caractérisé en ce qu'au moins une autre couche est déposée sur la couche fonctionnelle (3) et en ce que ladite autre couche est composée par au moins un des matériaux, tels que l'étain, le cuivre, le nickel, le chrome, par des matériaux céramiques ou céramiques métalliques, ainsi que par tous les matériaux et alliages qui présentent une affinité avec le fer (5) et forment des couches.
  14. Procédé selon l'une quelconque des revendications 1 à 13, caractérisé en ce qu'au moins une autre couche est déposée sur la couche fonctionnelle (3) et en ce que ladite autre couche est composée par au moins un des matériaux, tels que l'étain, le cuivre, le nickel, le chrome, par des matériaux céramiques ou céramiques métalliques, ainsi que par tous les matériaux et alliages qui présentent une affinité avec le fer (5) et forment des couches et en ce que la couche est déposée par voie électrochimique, thermique ou au moyen d'un procédé réactif, en particulier le procédé PVD ou le procédé CVD.
  15. Piston d'un moteur à combustion interne, réalisé selon l'une quelconque des revendications 1 à 14, caractérisé en ce que la couche fonctionnelle (3) est déposée directement sur la surface (4) de la pièce (1).
  16. Chemise de cylindre d'un moteur à combustion interne, réalisée selon l'une quelconque des revendications 1 à 14, caractérisée en ce que la couche fonctionnelle (3) est déposée directement sur la surface (4) de la pièce (1).
EP02785370A 2001-12-06 2002-11-07 Processus de traitement de surface pour l'enduction de materiaux en aluminium Expired - Lifetime EP1451392B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10159890A DE10159890B4 (de) 2001-12-06 2001-12-06 Verfahren für das Beschichten von Aluminiumwerkstoffen mit Funktionsschichten aus Eisen
DE10159890 2001-12-06
PCT/EP2002/012437 WO2003048427A2 (fr) 2001-12-06 2002-11-07 Processus de traitement de surface pour l'enduction de materiaux en aluminium

Publications (2)

Publication Number Publication Date
EP1451392A2 EP1451392A2 (fr) 2004-09-01
EP1451392B1 true EP1451392B1 (fr) 2006-07-05

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP02785370A Expired - Lifetime EP1451392B1 (fr) 2001-12-06 2002-11-07 Processus de traitement de surface pour l'enduction de materiaux en aluminium

Country Status (11)

Country Link
US (1) US20050067296A1 (fr)
EP (1) EP1451392B1 (fr)
JP (1) JP2005511898A (fr)
CN (1) CN1599809A (fr)
AT (1) ATE332401T1 (fr)
AU (1) AU2002350675A1 (fr)
BR (1) BR0212923A (fr)
DE (2) DE10159890B4 (fr)
ES (1) ES2264735T3 (fr)
PL (1) PL204301B1 (fr)
WO (1) WO2003048427A2 (fr)

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US20050249968A1 (en) * 2004-05-04 2005-11-10 Enthone Inc. Whisker inhibition in tin surfaces of electronic components
TW200530433A (en) * 2004-01-21 2005-09-16 Enthone Preserving solderability and inhibiting whisker growth in tin surfaces of electronic components
JP2011187226A (ja) * 2010-03-05 2011-09-22 Sumitomo Electric Ind Ltd 電池用負極前駆体材料の製造方法、電池用負極前駆体材料、及び電池
KR20130040781A (ko) 2010-04-06 2013-04-24 스미토모덴키고교가부시키가이샤 세퍼레이터 제조 방법, 용융염 전지의 제조 방법, 세퍼레이터 및 용융염 전지
CN103184457B (zh) * 2011-12-28 2015-06-10 北京有色金属研究总院 一种表面合金化强化方法
JP6444860B2 (ja) * 2012-06-08 2018-12-26 オンデルゾエクセントラム・フォー・アーンウェンディング・ファン・シュタール・エヌ・フェー 金属コーティングを作製するための方法
DE102012018159A1 (de) * 2012-09-14 2014-03-20 Feindrahtwerk Adolf Edelhoff Gmbh & Co. Kg Verfahren zum Beschichten von Aluminiumleitern
KR101574717B1 (ko) 2012-12-18 2015-12-04 포스코에너지 주식회사 고체 전해질 및 그 제조 방법
DE102012112723B4 (de) * 2012-12-20 2023-04-27 Dr. Ing. H.C. F. Porsche Aktiengesellschaft Kolben für eine Brennkraftmaschine sowie Verfahren zur Herstellung eines derartigen Kolbens
CN105445104B (zh) * 2015-12-17 2019-03-01 郑州磨料磨具磨削研究所有限公司 镀层强度检测试件及其制备方法

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JPS51126935A (en) * 1975-04-30 1976-11-05 Riken Piston Ring Ind Co Ltd Abrasionnresistant and antiiseizing surface layer for aluminum alloy sliding members
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DE10013298C2 (de) * 2000-03-09 2003-10-30 Atotech Deutschland Gmbh Verfahren zum Aufbringen einer Metallschicht auf Leichtmetalloberflächen und Anwendung des Verfahrens

Also Published As

Publication number Publication date
PL368710A1 (en) 2005-04-04
EP1451392A2 (fr) 2004-09-01
ATE332401T1 (de) 2006-07-15
DE50207452D1 (de) 2006-08-17
ES2264735T3 (es) 2007-01-16
WO2003048427A3 (fr) 2003-12-24
WO2003048427A2 (fr) 2003-06-12
JP2005511898A (ja) 2005-04-28
AU2002350675A1 (en) 2003-06-17
US20050067296A1 (en) 2005-03-31
PL204301B1 (pl) 2009-12-31
CN1599809A (zh) 2005-03-23
DE10159890A1 (de) 2003-07-24
DE10159890B4 (de) 2006-02-16
BR0212923A (pt) 2004-10-13

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