EP0668375B1 - Procédé pour former un dépÔt électrochimique composite de chrome dur et revêtement résistant à l'usure ainsi obtenu - Google Patents

Procédé pour former un dépÔt électrochimique composite de chrome dur et revêtement résistant à l'usure ainsi obtenu Download PDF

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Publication number
EP0668375B1
EP0668375B1 EP95102258A EP95102258A EP0668375B1 EP 0668375 B1 EP0668375 B1 EP 0668375B1 EP 95102258 A EP95102258 A EP 95102258A EP 95102258 A EP95102258 A EP 95102258A EP 0668375 B1 EP0668375 B1 EP 0668375B1
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Prior art keywords
microcracks
layer
particles
matrix
chromium
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Expired - Lifetime
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EP95102258A
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German (de)
English (en)
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EP0668375A1 (fr
Inventor
Giulio Capezzuoli
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Koncentra Holding AB
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INDUSTRIALE Srl
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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
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02—Combined electrolytic and electrophoretic processes with charged materials

Definitions

  • the present invention relates to a process for forming, on a substrate, a composite hard chromium coating comprising a disperse phase consisting of nonmetal particles; and to a wear-resistant coating formed using such a process and particularly suitable for mechanical components subjected to high-temperature chafing, such as internal combustion engine piston rings and components.
  • US Patent n. 4,846,940 relates to galvanic hard chromium coatings characterized by a Cr matrix with a large number of micro- and macrocracks combined with a disperse phase, in the matrix, consisting of hard particles embedded in the micro- and macrocracks of the matrix.
  • Such coatings are formed by means of a galvanic electrodeposition process characterized by comprising a current inversion step, i.e. by alternately switching the substrate from cathode to anode potential and vice versa.
  • Such coatings present a small amount of incorporated hydrogen, a large number of even relatively large cracks, and a large number of particle inclusions in the cracks, which make them highly susceptible to corrosion. Moreover, depositing the coating by inverting the polarity of the electrodes poses practical problems which complicate the fabrication process.
  • a process for forming, on a substrate, a composite hard chromium coating comprising a disperse phase and particularly suitable for mechanical components subjected to high-temperature chafing comprising the step of galvanically depositing at least one layer of hard chromium in a chromium plating bath of the type forming microcracks and in which is dispersed in suspension a predetermined concentration of given sized particles of a nonmetal insoluble in the bath; characterized in that, in the course of said deposition step, the substrate is maintained permanently at cathode potential; and a pulsating cathode current, varying cyclically in time between a minimum and maximum value, is supplied to achieve a chromium layer comprising a matrix with microcracks of a given distribution, and a disperse phase consisting of said nonmetal particles, some of which are included in the microcracks, and some of which are directly embedded in the matrix, said chromium plat
  • This provides for achieving a so-called "disperse chromium" coating comprising a Cr matrix containing dispersing agents, which is extremely hard (over 1,000 Vickers), includes dispersing agents in the form of nonmetal particles of hard materials such as oxides, carbides and nitrides of very low thermal conductivity and high thermal stability, and which, combined with a low hydrogen content, presents a high degree of thermal stability characterized by a reduced loss in hardness alongside an increase in temperature, and a small amount of incorporated hydrogen in the Cr matrix.
  • variation of the cathode current may be achieved easily using known facilities, and fully automatically by means of appropriate programming, thus enabling troublefree, low-cost formation of the coating according to the present invention.
  • the above deposition step is preferably preceded by the step of depositing on the substrate a continuous hard chromium base layer with substantially no microcracks or porosity, which covers the whole of the substrate, and which is formed, preferably to a thickness of roughly 50 ⁇ m, by galvanically depositing chromium in a chromium plating bath of the type forming no microcracks and containing no particles in suspension.
  • a number of said "disperse" layers comprising a microcracked Cr matrix and including hard particles are then deposited successively on the continuous base layer.
  • the substrate-coating interface thus presents a fairly thick layer (in relation to the total thickness of the coating, which is roughly 500 ⁇ m) with absolutely no cracks or dispersing agent particles (at least none detectable by standard metallographic techniques), and which prevents the microcracks in the upper layers of the coating from propagating towards the substrate, thus ensuring absolute protection of the substrate and greatly enhancing the corrosion resistance of both the substrate and the coating.
  • the cathode current is supplied according to a cycle comprising the following steps:
  • the cathode current is varied in a square wave pattern; and in said first and third steps, it is varied in steps.
  • the "disperse chromium" layers are therefore formed with the microcracks of one layer offset, depthwise of the coating, in relation to those of the adjacent "disperse” layers, so that any depthwise propagation of the microcracks in one layer (due to mechanical stress in the layer) is prevented from being transmitted to those of the adjacent underlying layer, thus preventing the formation of macrocracks as in galvanic Cr coatings formed using known processes.
  • This provides for obtaining a much more stable coating, and for further improving the corrosion resistance of the substrate, without, however, affecting the in-service lubricant collecting and distribution function of the microcracks.
  • nonmetal dispersing agent particles substantially consisting of oxides (e.g. aluminium oxide - Al 2 O 3 ) and/or carbides (tungsten, chromium, silicon, boron) and/or nitrides (silicon, boron), i.e. extremely hard compounds, and both included inside the microcracks and embedded directly in the chromium matrix, provides for obtaining a coating which is extremely resistant to wear caused by abrasion or adhesion typical of high-temperature, mutually sliding metal surfaces.
  • oxides e.g. aluminium oxide - Al 2 O 3
  • carbides tungsten, chromium, silicon, boron
  • nitrides silicon, boron
  • the coating according to the present invention therefore comprises a layer comprising a microcracked hard chromium matrix and a disperse phase, in the matrix, consisting of a number of particles of a nonmetal material; a first number of said particles being included in the microcracks of the matrix, and a second number of said particles being embedded directly in parts of the matrix with no microcracks; characterized in that it comprises a first hard chromium layer with substantially no microcracks or porosity and without said particles; and, deposited on the first layer, a number of said layers comprising a microcracked matrix and a disperse phase consisting of said particles; the superimposed layers, deposited on the first layer, presenting the microcracks offset depthwise in relation to those of the adjacent layers.
  • the first layer presents a thickness of at least 50 ⁇ m; the width of the microcracks, measured parallel to the layer, is at least 1 ⁇ m; the density of the microcracks ranges from 100 to 300 per centimeter; and the size of the nonmetal particles embedded in the matrix ranges from 0.1 to 20 ⁇ m.
  • cylinder liners such as the piston rings of four- and two-stroke engines or piston pumps
  • the cylinder liners are normally made of lamellar, nodular or vermicular cast iron, either natural or hardened (e.g. laser quenched) or nitrided (e.g. using the TENIFER (registered trade mark) process or similar), or present surfaces with hot spray coatings such as FK1008 formed using the HVOF process (both registered trade marks).
  • Number 1 in Figure 1 indicates a wear-resistant coating formed according to the present invention on a substrate 2, e.g. any known mechanical component made of cast iron.
  • Coating 1 comprises a first layer 3, preferably no more than 50 ⁇ m deep, formed of hard Cr, and characterized by being continuous, i.e. by presenting no detectable microcracks or porosity, and no inclusions of any sort.
  • layer 3 On top of layer 3, there are deposited a given number (four in the example) of substantially identical layers 5a, 5b, 5c, 5d, each comprising a hard chromium matrix 6 in which are formed a number of microcracks 7 extending radially depthwise of layer 5 towards substrate 2, and a disperse phase in matrix 6 and consisting of a number of particles 8 of any hard nonmetal material.
  • a first number of particles 8 is included in microcracks 7 of matrix 6, and a second number of particles 8 is embedded directly inside parts of matrix 6 with no microcracks 7; and the microcracks 7 of layers 5 deposited on first layer 3 are offset depthwise in relation to those of the adjacent layers 5.
  • microcracks 7 of layer 5b extend depthwise towards underlying layer 5a and substantially towards the portions between microcracks 7 of layer 5a, i.e. towards matrix 6 portions of layer 5a presenting no microcracks.
  • the microcracks 7 of each layer 5 present a "spiderweb" pattern along the interface surface 9 of each layer 5, as shown in Figure 5.
  • the width of the microcracks, measured parallel to each layer 5, is at least 1 ⁇ m; the microcrack density measured at surfaces 9 ranges from 100 to 300 microcracks per centimeter of surface; and the size of nonmetal particles 8 ranges from 0.1 to 20 ⁇ m.
  • a coating as described above may be formed electrolytically; layer 3 being formed by galvanically depositing Cr in known manner using any known chromium plating bath of the type resulting in no microcracks and containing no particles in suspension, or operating accordingly with a bath containing particles in suspension; and layers 5 being formed using known chromium plating baths of the type for forming microcracks and containing particles 8 in suspension.
  • a further precaution to ensure layer 3 presents no microcracks is to limit its thickness, and to use such operating parameters (current cycles and density, etc.) as to limit the formation of stress within the layer due to excessive energy supply.
  • the baths for forming layers 5 and containing particles 8 in suspension are preferably agitated at all times, e.g. by means of mechanical, fluidodynamics, energetic agitators, or by air injection.
  • the nonmetal particles 8 included in the coating must be insoluble in the baths which present a chromic acid, sulphuric acid and catalyst base, are maintained at a temperature of about 55°C, and present a 20 to 400 gr/liter concentration of particles 8 (ranging in size between 0.1 and 20 micron).
  • Particles 8 therefore consist of one or more materials in the group comprising: tungsten carbide, silicon carbide, chromium carbide, aluminium oxide, silicon nitride, boron carbide, diamond, graphite, hexagonal boron nitride.
  • Each layer 5 may of course include particles 8 all of the same material or of different materials, and likewise from one layer to another.
  • the cathode current supply cycle comprises the following steps:
  • a bath with the following composition is prepared: CrO 3 250.0 gr/lt; FeSiF 6 1.5 gr/lt; H 2 SO 4 2.5 gr/lt SiC 50.0 gr/lt;
  • Lead anodes and a cathode consisting of rings of lamellar cast iron are immersed in the bath, and a chromium coating is deposited, agitating the bath by recirculating roughly 300 lt/min and injecting air at roughly 5 bar pressure, and operating with a potential difference of 15 volts and a continuous cathode current of a mean density of 70 A per square decimeter, which is varied during deposition according to the following cycle:

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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)
  • Electroplating Methods And Accessories (AREA)

Claims (10)

  1. Procédé pour former sur un substrat, un revêtement composite de chrome dur comprenant une phase dispersée et particulièrement convenable pour des composants mécaniques soumis à une usure à des températures élevées, le procédé comprenant l'étape de dépôt électrolytique d'au moins une couche de chrome dur dans un bain de placage de chrome du type formant des microfissures et dans lequel est dispersée en suspension une concentration prédéterminée de particules non métalliques de dimensions données insolubles dans le bain,
       caractérisé en ce que, en combinaison :
    (i) au cours de cette étape de dépôt, le substrat est maintenu en permanence au potentiel de la cathode, et un courant de cathode pulsé, variant de façon cyclique dans le temps entre une valeur minimale et une valeur maximale, est fourni pour former une couche de chrome comprenant une matrice avec des microfissures selon une distribution donnée, et une phase dispersée consistant en ces particules non métalliques, dont certaines sont incluses dans les microfissures, et dont certaines sont directement noyées dans la matrice;
    (ii) ce bain de placage de chrome est un bain à base d'acide chromique, contenant en solution du chrome principalement hexavalent.
  2. Procédé suivant la revendication 1, caractérisé en ce que cette étape de dépôt est précédée de l'étape de dépôt sur le substrat d'une couche de base continue de chrome dur n'ayant pratiquement pas de microfissures ou de porosité et qui recouvre la totalité du substrat, cette couche de base étant formée par dépôt électrolytique de chrome dans un bain de placage de chrome du type qui ne forme pas de microfissures.
  3. Procédé suivant la revendication 2, caractérisé en ce que, sur cette couche de base, il est déposé par voie électrolytique un certain nombre de couches de chrome dur, comprenant chacune une matrice microfissurée et une phase dispersée, ces couches étant formées de telle sorte que les microfissures de chaque couche sont décalées dans le sens de la profondeur par rapport aux microfissures des couches adjacentes.
  4. Procédé suivant l'une des revendications précédentes, caractérisé en ce que ces particules non métalliques insolubles dans le bain consistent en un ou plusieurs matériaux du groupe consistant en carbure de tungstène, carbure de silicium, carbure de chrome, oxyde d'aluminium, nitrure de silicium, carbure de bore, diamant, graphite et nitrure de bore hexagonal.
  5. Procédé suivant l'une des revendications précédentes, caractérisé en ce que, pendant l'étape de dépôt électrolytique de chaque couche de chrome dur comprenant une matrice microfissurée et une phase dispersée consistant en ces particules noyées dans la couche, le courant de cathode est fourni selon un cycle comprenant les étapes suivantes :
    une première étape dans laquelle le courant de cathode est amené et maintenu pendant une première période de temps prédéterminée à une première valeur de seuil autre que zéro;
    une deuxième étape, superposée à la première, dans laquelle le courant de cathode est modifié de façon alternative, selon un motif d'onde et pendant une deuxième période de temps prédéterminée entre cette première valeur de seuil et une deuxième valeur de seuil supérieure à la première; et
    une troisième étape dans laquelle le courant de cathode est mis à zéro et maintenu à zéro pendant une troisième période de temps prédéterminée.
  6. Procédé suivant la revendication 5, caractérisé en ce que, dans ladeuxième étape, le courant de cathode est modifié selon un motif d'onde carrée, et dans ces première et troisième étapes, le courant de cathode est modifié par étapes.
  7. Revêtement de chrome dur résistant à l'usure, caractérisé en ce qu'il est formé par le procédé suivant l'une des revendications précédentes 1 à 6, de façon à présenter une teneur en hydrogène relativement basse.
  8. Revêtement de chrome dur résistant à l'usure formé par voie électrolytique, comprenant une couche comprenant respectivement une matrice microfissurée de chrome dur et une phase dispersée, dans la matrice, consistant en un certain nombre de particules de matériau non métallique, et particulièrement convenable pour des composants mécaniques soumis à une usure à des températures élevées, un premier nombre de ces particules étant incluses dans les microfissures de la matrice, et un second nombre de ces particules étant noyées directement dans des parties de la matrice n'ayant pas de microfissures,
       caractérisé en ce que, en combinaison :
    (i) il comprend une première couche de chrome dur n'ayant pratiquement pas de microfissures ou de porosité et dépourvue de telles particules, et déposé sur cette première couche, un certain nombre de ces couches comprenant une matrice microfissurée et une phase dispersée consistant en ces particules;
    (ii) les microfissures de ces couches déposées sur la première couche étant formées de façon à être décalées dans le sens de la profondeur par rapport aux microfissures des couches adjacentes.
  9. Revêtement de chrome dur résistant à l'usure suivant la revendication 8, caractérisé en ce que la première couche présente une épaisseur d'au moins 50 µm.
  10. Revêtement de chrome dur résistant à l'usure suivant les revendications 8 ou 9, caractérisé en ce que la largeur des microfissures, mesurée parallèlement à la couche, est d'au moins 1 µm, la densité des microfissures est comprise dans la gamme de 100 à 300 microfissures par cm et la dimension de ces particules non métalliques est comprise dans la gamme de 0,1 à 20 µm.
EP95102258A 1994-02-18 1995-02-17 Procédé pour former un dépÔt électrochimique composite de chrome dur et revêtement résistant à l'usure ainsi obtenu Expired - Lifetime EP0668375B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT94TO000101A IT1267394B1 (it) 1994-02-18 1994-02-18 Procedimento per la realizzazione di riporti galvanici compositi in cromo duro con una fase dispersa e riporto anti-usura realizzato con
ITTO940101 1994-02-18

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EP0668375A1 EP0668375A1 (fr) 1995-08-23
EP0668375B1 true EP0668375B1 (fr) 1999-01-13

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19931829A1 (de) * 1999-07-08 2001-01-18 Federal Mogul Burscheid Gmbh Galvanische Hartchromschicht
DE102007050811A1 (de) * 2007-10-24 2009-04-30 Robert Bosch Gmbh Verschleißschutzschicht sowie Verfahren zu ihrer Herstellung
CN1764745B (zh) * 2004-01-30 2012-01-11 株式会社理研 复合铬电镀膜及具有该膜的滑动件以及该滑动件的制备方法
KR101589892B1 (ko) 2008-04-04 2016-01-27 페데랄-모굴 부르샤이트 게엠베하 구조화된 크롬 고체 입자들 층 및 이의 제조 방법

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0841413B1 (fr) * 1996-11-11 2001-09-26 Teikoku Piston Ring Co., LTd. Revêtement galvanique composite à base de chrome et élément de glissement revêtu avec celui-ci
DE69704752T3 (de) † 1996-11-11 2005-08-04 Teikoku Piston Ring Co., Ltd. Galvanische Komposit-Chrom-Beschichtung und damit beschichtetes Gleitteil
DE19745811C2 (de) * 1997-10-16 2002-06-13 Federal Mogul Burscheid Gmbh Galvanische Hartchromschicht, Verwendung und Verfahren zu deren Herstellung
SE514700C2 (sv) 1999-03-19 2001-04-02 Daros Holding Ab Elektrolytisk beläggning av ett substrat med ett keramkromskikt, keramkromskikt samt kolvring
EP1253220A4 (fr) * 1999-12-27 2006-03-22 Nippon Piston Ring Co Ltd Element coulissant
JP4059621B2 (ja) * 2000-09-29 2008-03-12 日本ピストンリング株式会社 クロムめっき摺動部材及びその製造方法
SE521471C2 (sv) 2001-03-27 2003-11-04 Koncentra Holding Ab Kolvring och beläggning på en kolvring innefattande ett kompositmaterial av en keram och en intermetallisk förening
DE10255853A1 (de) 2002-11-29 2004-06-17 Federal-Mogul Burscheid Gmbh Herstellung strukturierter Hartchromschichten
DE102004019370B3 (de) 2004-04-21 2005-09-01 Federal-Mogul Burscheid Gmbh Herstellung einer strukturierten Hartchromschicht und Herstellung einer Beschichtung
DE102005023627B4 (de) * 2005-05-21 2010-05-06 Federal-Mogul Burscheid Gmbh Stahlkolbering
DE102007037778A1 (de) * 2007-08-10 2009-02-12 Mahle International Gmbh Hartchromschicht, beschichtetes Substrat und tribologisches System
JP5885207B2 (ja) 2010-12-27 2016-03-15 日本ピストンリング株式会社 複合クロムめっき皮膜及びこの皮膜を用いた摺動部材

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3531410A1 (de) * 1985-09-03 1987-03-05 Goetze Ag Galvanische hartchromschicht
DE3933896C1 (fr) * 1989-10-11 1990-10-11 Lpw-Chemie Gmbh, 4040 Neuss, De

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19931829A1 (de) * 1999-07-08 2001-01-18 Federal Mogul Burscheid Gmbh Galvanische Hartchromschicht
CN1764745B (zh) * 2004-01-30 2012-01-11 株式会社理研 复合铬电镀膜及具有该膜的滑动件以及该滑动件的制备方法
DE102007050811A1 (de) * 2007-10-24 2009-04-30 Robert Bosch Gmbh Verschleißschutzschicht sowie Verfahren zu ihrer Herstellung
KR101589892B1 (ko) 2008-04-04 2016-01-27 페데랄-모굴 부르샤이트 게엠베하 구조화된 크롬 고체 입자들 층 및 이의 제조 방법

Also Published As

Publication number Publication date
IT1267394B1 (it) 1997-02-05
ITTO940101A1 (it) 1995-08-18
DE69507172D1 (de) 1999-02-25
EP0668375A1 (fr) 1995-08-23
DE69507172T2 (de) 1999-07-22
ITTO940101A0 (it) 1994-02-18

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