EP0147484B1 - Verfahren zur Herstellung einer Schutzschicht für Oberflächen die mechanischem und thermischem Verschleiss unterworfen sind - Google Patents

Verfahren zur Herstellung einer Schutzschicht für Oberflächen die mechanischem und thermischem Verschleiss unterworfen sind Download PDF

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Publication number
EP0147484B1
EP0147484B1 EP83113249A EP83113249A EP0147484B1 EP 0147484 B1 EP0147484 B1 EP 0147484B1 EP 83113249 A EP83113249 A EP 83113249A EP 83113249 A EP83113249 A EP 83113249A EP 0147484 B1 EP0147484 B1 EP 0147484B1
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Prior art keywords
layer
electro
deposition
phase
lying
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EP83113249A
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English (en)
French (fr)
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EP0147484A1 (de
Inventor
Paolo Filomeni
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INDUSTRIALE Srl
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INDUSTRIALE Srl
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Priority to DE8383113249T priority Critical patent/DE3380965D1/de
Priority to AT83113249T priority patent/ATE48659T1/de
Priority to EP83113249A priority patent/EP0147484B1/de
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    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/625—Discontinuous layers, e.g. microcracked layers
    • 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
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • 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
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/623—Porosity of the layers
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B77/00—Component parts, details or accessories, not otherwise provided for
    • F02B77/02—Surface coverings of combustion-gas-swept parts
    • 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
    • F05C2201/0403—Refractory metals, e.g. V, W
    • F05C2201/0406—Chromium

Definitions

  • the present invention relates to a process for obtaining a protective coating for metallic surfaces subjected to both thermal and mechanical wear, for example, subjected simultaneously to wear by sliding and friction and to oxidation, such as the surfaces of elements comprising the combustion chamber of a heat engine, for example, the cylinders, valve stems, piston crowns and, above all, piston rings.
  • the invention further relates to a protective coating obtained by the process.
  • Know electro-deposition processes are not entirety free from disadvantages. In particular they permit coating layers of only a small thickness which are not suitable to ensure a long life of the elements treated, which is necessary, on the other hand to be able to extend the maintenance intervals of the engines fitted with such elements. Further, there is a tendency these days, for reasons of economy, to use inferior fuels, rich in sulphur and other corrosive elements and which therefore cause a rapid corrosive wear of the protective layers, whether obtained by electro-deposition methods or with other methods, and of the elements potected thereby.
  • An object of the present invention is that of providing a process for obtaining a protective coating for surfaces subjected to wear, which will be free from the described disadvantages an in particular of geater thickness and resistance to chemical corrosion so as to be able effectively to protect the surfaces to which they are applied.
  • Another object of the present invention is that of providing such a protective coating by utilising electro-deposited coating layers.
  • the said objects are achieved by the present invention in that it relates to a process for obtaining a protective coating for metallic surfaces subjected to wear by sliding and oxidation, in particularfor metallic surfaces of elements of heat engines, comprising a first electro-deposition phase depositing onto the said surfaces a first layer of hard chrome, and a second electro-deposition phase depositing onto the said first layer of hard chrome a second layer of hard chrome, characterized in that said first electro-deposition phase is carried out in an aqueous electrolytic bath containing Cr0 3 and chromic acid having such a composition to ensure a final hardness (Vickers) of said first layer lying between 400 and 600 kg/mm 2 , said first electro-deposition phase being carried out with a current density of substantially 30 Ampere/dm 2 associated with a deposition speed comprised between 5 and 15 um/ h and with a voltage between the electrodes of between 4 and 10 volts until a thickness of said first layer lying between 20 and 40 pm is reached; and being further characterized in that said second electro-
  • the present invention further relates to a protective coating for covering metallic surfaces subjected to thermal and mechanical wear of elements of heat engines, in particular for elements constituting the combustion chamber of a diesel engine and particularly for piston rings and piston sealing rings of reciprocating engines, said coating comprising a first layer of electro- deposited hard chrome, and a second layer of electro-deposited hard chrome, superimposed to said first layer, characterized in that said first layer has a thickness comprised between 20 and 40 Jl m and a hardness lying between 400 and 600 HV, and is substantially compact; in combination with such characteristics said second layer having a hardness of at least 1000 HV and a maximum thickness of 1.2 mm, said second layer being further provided with a plurality of micro-cracks dispersed uniformly therein and having dimensions lying between 5 and 30 pm and a distribution frequency in the sid second layer of at least about 200 micro-cracks per linear cm.
  • an element of a combustion chamber for a heat engine is generally indicated 1, this being constituted, in the illustrated example, by a sealing ring for a diesel engine piston.
  • the element 1, of which, for simplicity, only an outer portion of the radial section is illustrated, has a surface 2, in the illustrated example the outer side surface, subjected to wear both by sliding and oxidation, being intended to form a sliding seal between piston and the side wall of the cylinder of an engine in operating conditions.
  • the surface 2 is provided with a protective coating 3 which acts to protect it both from mechanical wear and from thermal wear due to chemical and electro-chemical attack at high temperature by the combustion products.
  • the protective coating 3, in the illustrated example, comprises two superimposed layers, electro-deposited onto the surface 2; a first layer 4 of hard chrome, having a Vickers hardness of 536 Kg/mm 2 and a thickness of 35 pm (0.035 mm) deposited immediately in contact with the surface 2 of the element 1, which is made of cast iron; and a second layer 5 of hard chrome, having a Vickers hardness of 1073 Kg/mm 2 (1073 HV) and of thickness equal to 1.05 mm, deposited over the layer 4.
  • the layer 4 is compacted, substantially free from cracks, micro-cracks and porosity, and adheres perfectly to the cast iron of the element 1.
  • the layer 5 is perfectly adherent to the layer 4, free from blow holes and cracks, well formed and having instead a plurality of micro-cracks 6 of very small dimensions (Figure 3) lying between about 5 and 30 micron, uniformly distributed in the layer 5 itself.
  • the protective coating 3 formed according to the invention can be applied to any surface subject to thermal and mechanical wear, and in the field of engines not only the piston rings, but also the valve stems and the cylinder sleeves, and the piston crowns or cavities can be covered with this coating.
  • the coating 3 can be made with a number of different variants, depending on technical requirements of the various applications, and therefore the layer 4 has a thickness lying between 20 and 40 pm and a hardness lying between 400 and 600 HV, while the layer 5 can have a hardness equal to or greater than 1000 HV and a maximum thickness equal to 1.2 mm.
  • the coating 3 further comprises a third electro-deposited layer for running in made of hard chrome deposited over the layer 5, of a hardness lying between about 650 and 800 HV and having a thickness such as to be completely worn away, leaving the layer 5 exposed, during the running-in phase of the engine the elements of which have had the coating 3 applied thereto.
  • the coating 3 has the dual function of constituting a protective layer for the surface 2 with regard to oxidising and chemically aggressive agents in general, and constitutes a consumable anti-wear layer for the surface 2. According to the invention this dual function is performed separately by the two layers 4 and 5.
  • the layer 4 thanks to its high compactedness and excellent adhesion to the base material, whether it be cast iron or steel, guarantees the anti-corrosive and anti-oxidative protection even in the presence of high temperatures (such as, for example, those in the combustion chambers of super-charged engines) and aggressive fuels such as heavy diesel having a high sulphur content. Thanks to its high thermal stability and to its capacity for rapid passivation, in fact, the chrome layer 4 prevents the formation of local electro-chemical corrosion pairs and the penetration of corrosive agents towards the base material.
  • the layer 5, serves to be slowly consumed during the operating life of the element 1 in such a way as to prevent direct sliding of the surface 2 and consequent possible gripping or seizure. Thanks to the great thickness (more than three times the normal thickness of electro-deposited chrome protective layers) it allows about three times the operating life of the element 1 permitting the maintenance intervals of the engines on which the elements provided with protective coatings 3 are fitted to be extended.
  • This layer 5, as well as its thickness, is represented by the presence of the micro-cracks 6.
  • the protective coating 3 previously described is obtained with the following process.
  • the layer 4 After having proceeded with an accurate cleaning of the element 1 to be coated, there is deposited on the surface 2, by means of electro-deposition treatment, the layer 4 by operating in an electrolytic vessel with lead anodes and cathodes constituted by the elements to be coated, in an electrolytic bath containing chrome in solution, preferably as Cr0 3 , and chromic acid and with a voltage between the electrodes of between 4 and 10 volts.
  • the hardness and thickness of the layer 4 can instead be chosen in dependence on the single coating requirements, by varying in a known way the duration of the deposition operation and the percentage composition of chrome in the bath; these must however remain between the following values:
  • a washing operation is performed and then a second electro-deposition operation, this time utilising an aqueous electrolytic bath containing Cr0 3 and a mixture of acids based on sulphuric acid (H Z S0 4 ) mixed with hydrofluoric acid (HF) and possibly with other mineral acids.
  • H Z S0 4 sulphuric acid
  • HF hydrofluoric acid
  • the chrome layer 5 is deposited after the layer 4, acting in vessels with lead anodes and cathodes constituted by the elements to be treated and a voltage between the electrodes of about 5-15 volts.
  • the hardness of the deposit which must be greater than or equal to 1000 Kg/mm 2 (Vickers) can be determined.
  • the maximum economic thickness of the layer 5 is of the order of 1.2 mm.
  • a further electro-deposition operation can subsequently be performed by depositing on the layer 5 a further hard chrome layer of Vickers hardness lying between 650 and 800 Kg/ mm 2 by working with a cathode current density of about 30-40 Ampere and a speed of deposition equal to that used in the deposition phase of the layer 5.
  • This produces a layer having characteristics similar to those of the layer 5 but somewhat softer, which can be used as a running-in layer.
  • Micro-cracks 6 can also be obtained in this layer.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electronic Switches (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Laminated Bodies (AREA)
  • Physical Vapour Deposition (AREA)

Claims (4)

1. Verfahren zum Herstellen eines Schutzüberzuges (3) für Metallflächen (2), die durch Gleiten und Oxidation Abnutzung unterliegen, insbesondere für Metallflächen (2) von Elementen (1) von Wärmekraftmaschinen, umfassend eine erste elektrolytische Fällungsphase, die auf diesen Oberflächen (2) eine erste Schicht (4) aus Hartchrom abscheidet, und eine zweite elektrolytische Fällungsphase, die auf diese erste Schicht (4) aus Hartchrom eine zweite Schicht (5) aus Hartchrom abscheidet, dadurch gekennzeichnet, daß die erste Elektrolytische Fällungsphase in einem wässerigen Elektrolysebad enthaltend Cr03 und Chromsäure mit einer solchen Zusammensetzung, daß eine Endhärte (Vickers) der ersten Schicht zwischen 400 und 600 kg/mm2 gewährleistet ist, durchgeführt wird, wobei die erste elektrolytische Fällungsphase mit einer Stromdichte von im wesentlichen 30 Ampere/dm2 in Verbindung mit einer Abscheidungsgeschwindigkeit von 5 bis 15 pm/h und mit einer Spannung zwischen den Elektroden von 4 bis 10 Volt durchgeführt wird, bis eine Dicke der ersten Schicht zwischen 20 und 40 um erreicht ist, und weiter dadurch gekennzeichnet, daß die zweite elektrolytische Fällungsphase in einem wässerigen Elektrolysebad, das Cr03 und eine Mischung von Schwefel- und Fluorwasserstoffsäure enthält, mit einer derartigen Zusammensetzung, daß eine Endhärte (Vickers) der zweiten Schicht (5) gleich oder größer als 1000 kg/mm2 gewährleistet ist, durchgeführt wird, wobei die zweite elektrolytische Fällungsphase mit einer Stromdichte von 40 bis 70 Ampere/dm2 in Verbindung mit einer Abscheidungsgeschwindigkeit, die vier- bis zehnmal höher ist als die Geschwindigkeit der Abscheidung des Chroms in der ersten Phase, durchgeführt wird, wobei die Spannung zwischen den Elektroden 5 bis 15 Volt beträgt, welche zweite elektrolytische Fällungsphase durchgeführt wird, bis eine maximale Dicke der zweiten Schicht von 1,2 mm erreicht ist.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß es weiters eine dritte Phase anschließend an diese zweite Phase aufweist, die die elektrolytische Fällung einer dritten Schicht aus Hartchrom mit einer Vickers-Härte von etwa 650 bis 800 kg/mm2 unfaßt, wobei die dritte Schicht auf die zweiste Schicht (5) abgeschieden wird und wobie wie in der genannten elektrolytischen Fällungsphase, jedoch mit einer Stromdichte zwischen 30 und 40 Ampere/dm2 gearbeitet wird.
3. Schutzüberzug (3) zum Überziehen von Metallflächen (2), die thermischer und mechanischer Abnutzung von Elementen (1) von Wärmekraftmaschinen unterliegen, insbesondere für Elemente (1), die die Verbrennungskammer eines Dieselmotors bilden, und insbesondere für Kolbenringe und Kolbendichtungsringe von Kolbenkraftmaschinen, welcher Überzug (3) eine erste Schicht (14) aus elektrolytisch gefälltem Hartchrom und eine zweite Schicht aus elektrolytisch gefälltem Hartchrom, die auf die erste Schicht (4) aufgebracht ist, umfaßt, dadurch gekennzeichnet, daß die erste Schicht (4) eine Dicke von 20 bis 40 pm und eine Härte von 400 bis 600 HV aufweist und im wesentlichen kompakt ist, wobei in Kombination mit derartigen Merkmalen die zweite Schicht (5) eine Härte von mindestens 1000 HV und eine maximale Dicke von 1,2 mm aufweist, welche zweite Schicht (5) weiters mit einer Vielzahl von gleichförmig darin verteilten Mikrorissen mit Dimensionen von 5 bis 30 pm und einer Vertielungsfrequenz in dieser zweiten Schicht von mindestens etwa 200 Mikrorissen pro linearem cm versehen ist.
4. Überzug (3) nach Anspruch 3, dadurch gekennzeichnet, daß er weiters eine dritte Schicht aus Hartchrom aufweist, die über der zweiten Schicht (5) liegt, mit einer Härte von etwa 650 bis 800 HV und einer derartigen Dicke, daß sie während der Einlaufphase der Wärmekraftmaschinen vollständig abgerieben wird.
EP83113249A 1983-12-30 1983-12-30 Verfahren zur Herstellung einer Schutzschicht für Oberflächen die mechanischem und thermischem Verschleiss unterworfen sind Expired EP0147484B1 (de)

Priority Applications (3)

Application Number Priority Date Filing Date Title
DE8383113249T DE3380965D1 (de) 1983-12-30 1983-12-30 Verfahren zur herstellung einer schutzschicht fuer oberflaechen die mechanischem und thermischem verschleiss unterworfen sind.
AT83113249T ATE48659T1 (de) 1983-12-30 1983-12-30 Verfahren zur herstellung einer schutzschicht fuer oberflaechen die mechanischem und thermischem verschleiss unterworfen sind.
EP83113249A EP0147484B1 (de) 1983-12-30 1983-12-30 Verfahren zur Herstellung einer Schutzschicht für Oberflächen die mechanischem und thermischem Verschleiss unterworfen sind

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP83113249A EP0147484B1 (de) 1983-12-30 1983-12-30 Verfahren zur Herstellung einer Schutzschicht für Oberflächen die mechanischem und thermischem Verschleiss unterworfen sind

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EP0147484A1 EP0147484A1 (de) 1985-07-10
EP0147484B1 true EP0147484B1 (de) 1989-12-13

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EP83113249A Expired EP0147484B1 (de) 1983-12-30 1983-12-30 Verfahren zur Herstellung einer Schutzschicht für Oberflächen die mechanischem und thermischem Verschleiss unterworfen sind

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EP (1) EP0147484B1 (de)
AT (1) ATE48659T1 (de)
DE (1) DE3380965D1 (de)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000017482A (ja) * 1998-06-26 2000-01-18 Nippon Piston Ring Co Ltd 耐摩耗性、疲労強度に優れた積層構造を有するクロムめっき皮膜
US7726121B2 (en) * 2004-08-06 2010-06-01 Yamaha Hatsudoki Kabushiki Kaisha Engine part
FR3032725B1 (fr) * 2015-02-12 2019-04-12 Safran Aircraft Engines Procede de depot d'un revetement de protection contre l'erosion sur une piece metallique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1301720A (fr) * 1961-09-26 1962-08-17 Procédé pour le dépôt électrolytique de chrome dur poreux sur l'aluminium ou ses alliages
DE1521079A1 (de) * 1963-12-04 1970-05-14 Volkswagenwerk Ag Verfahren zum Abscheiden von glaenzenden mikrorissigen Chromueberzuegen mittels Doppelverchromung
DE1496809A1 (de) * 1966-05-05 1969-07-17 Goetzewerke Verfahren zum Verchromen insbesondere von Kolbenringen

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EP0147484A1 (de) 1985-07-10
DE3380965D1 (de) 1990-01-18
ATE48659T1 (de) 1989-12-15

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