EP0668375A1 - Verfahren zur Herstellung galvanischer Dispersionsüberzüge von Hartchrom sowie auf diese Weise hergestellte verschleissfeste Überzüge - Google Patents

Verfahren zur Herstellung galvanischer Dispersionsüberzüge von Hartchrom sowie auf diese Weise hergestellte verschleissfeste Überzüge Download PDF

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Publication number
EP0668375A1
EP0668375A1 EP95102258A EP95102258A EP0668375A1 EP 0668375 A1 EP0668375 A1 EP 0668375A1 EP 95102258 A EP95102258 A EP 95102258A EP 95102258 A EP95102258 A EP 95102258A EP 0668375 A1 EP0668375 A1 EP 0668375A1
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EP
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Prior art keywords
microcracks
layer
particles
matrix
hard chromium
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EP95102258A
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English (en)
French (fr)
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EP0668375B1 (de
Inventor
Giulio Capezzuoli
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Koncentra Holding AB
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INDUSTRIALE Srl
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires
    • C25D15/02Combined 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;
  • 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.
  • 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 /1.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 /1.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 - A1 2 0 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 - A1 2 0 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, and is characterized by a first number of said particles being included in the microcracks of the matrix, and by a second number of said particles being embedded directly in parts of the matrix with no microcracks.
  • the wear-resistant coating according to the present invention 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 first layer presenting a thickness of at least 50 /1.m; the superimposed layers, deposited on the first layer, presenting the microcracks offset depthwise in relation to those of the adjacent layers; the width of the microcracks, measured parallel to the layer, being at least 1 ⁇ m; the density of the microcracks ranging from 100 to 300 per centimeter; and the size of the nonmetal particles embedded in the matrix ranging from 0.1 to 20 /1.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 /1.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 /1.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:
  • 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 It/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)
EP95102258A 1994-02-18 1995-02-17 Verfahren zur Herstellung galvanischer Dispersionsüberzüge von Hartchrom sowie auf diese Weise hergestellte verschleissfeste Überzüge Expired - Lifetime EP0668375B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITTO940101 1994-02-18
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

Publications (2)

Publication Number Publication Date
EP0668375A1 true EP0668375A1 (de) 1995-08-23
EP0668375B1 EP0668375B1 (de) 1999-01-13

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EP (1) EP0668375B1 (de)
DE (1) DE69507172T2 (de)
IT (1) IT1267394B1 (de)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0841413A1 (de) * 1996-11-11 1998-05-13 Teikoku Piston Ring Co., LTd. Galvanische Komposit-Chrom-Beschichtung und damit beschichtetes Gleitteil
EP0909839A1 (de) * 1997-10-16 1999-04-21 Federal-Mogul Burscheid GmbH Galvanische Hartchromschicht
WO2000056953A1 (en) * 1999-03-19 2000-09-28 Koncentra Verkstads Ab Process for electrolytic coating of a substrate
WO2001004386A1 (de) * 1999-07-08 2001-01-18 Federal Mogul Burscheid Gmbh Galvanische hartchromschicht
EP1253220A1 (de) * 1999-12-27 2002-10-30 Nippon Piston Ring Co., Ltd. Gleitelement
US6596410B2 (en) * 2000-09-29 2003-07-22 Nippon Piston Ring Co., Ltd. Chrome-plated sliding member and manufacturing method thereof
US6838196B2 (en) 2001-03-27 2005-01-04 Koncentra Holding Ab Nickel-aluminide based wear resistant material for piston rings
EP1719827A1 (de) * 2004-01-30 2006-11-08 Kabushiki Kaisha Riken Verbund-verchromungsschicht und damit versehenes gleitelement sowie deren herstellungsverfahren
DE102005023627A1 (de) * 2005-05-21 2006-11-30 Federal-Mogul Burscheid Gmbh Stahlkolbering
WO2009021494A1 (de) * 2007-08-10 2009-02-19 Mahle International Gmbh Hartchromschicht, beschichtetes substrat und tribologisches system
WO2009121443A1 (de) * 2008-04-04 2009-10-08 Federal-Mogul Burscheid Gmbh Strukturierte chrom-feststoffpartikel-schicht und verfahren zu deren herstellung
US8110087B2 (en) 2004-04-21 2012-02-07 Federal-Mogul Burscheid Gmbh Production of a structured hard chromium layer and production of a coating
US8277953B2 (en) 2002-11-29 2012-10-02 Federal-Mogul Burscheid Gmbh Production of structured hard chrome layers
EP2660362B1 (de) 2010-12-27 2019-06-26 Nippon Piston Ring Co., Ltd. Verbundverchromungsfilm und gleitelement mit diesem film

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0841414B2 (de) 1996-11-11 2005-03-02 Teikoku Piston Ring Co., LTd. Galvanische Komposit-Chrom-Beschichtung und damit beschichtetes Gleitteil
DE102007050811A1 (de) * 2007-10-24 2009-04-30 Robert Bosch Gmbh Verschleißschutzschicht sowie Verfahren zu ihrer Herstellung

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0217126A1 (de) * 1985-09-03 1987-04-08 Goetze Ag Galvanische Hartchromschicht
DE3933896C1 (de) * 1989-10-11 1990-10-11 Lpw-Chemie Gmbh, 4040 Neuss, De

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0217126A1 (de) * 1985-09-03 1987-04-08 Goetze Ag Galvanische Hartchromschicht
DE3933896C1 (de) * 1989-10-11 1990-10-11 Lpw-Chemie Gmbh, 4040 Neuss, De

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
TAKAYA: "trivalent chromium composite coatings containing silicon carbide or diamond particles", PLATING & SURFACE FINISHING, vol. 74, no. 9, September 1987 (1987-09-01), USA, pages 70 - 72 *

Cited By (27)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6013380A (en) * 1996-11-11 2000-01-11 Teiko Piston Ring Co., Ltd. Composite chromium plating film and sliding member covered thereof
EP0841413A1 (de) * 1996-11-11 1998-05-13 Teikoku Piston Ring Co., LTd. Galvanische Komposit-Chrom-Beschichtung und damit beschichtetes Gleitteil
EP0909839A1 (de) * 1997-10-16 1999-04-21 Federal-Mogul Burscheid GmbH Galvanische Hartchromschicht
DE19745811A1 (de) * 1997-10-16 1999-04-22 Federal Mogul Burscheid Gmbh Galvanische Hartchromschicht
DE19745811C2 (de) * 1997-10-16 2002-06-13 Federal Mogul Burscheid Gmbh Galvanische Hartchromschicht, Verwendung und Verfahren zu deren Herstellung
US6703145B1 (en) 1999-03-19 2004-03-09 Koncentra Holding Ab Process for electrolytic coating of a substrate and product produced
WO2000056953A1 (en) * 1999-03-19 2000-09-28 Koncentra Verkstads Ab Process for electrolytic coating of a substrate
WO2001004386A1 (de) * 1999-07-08 2001-01-18 Federal Mogul Burscheid Gmbh Galvanische hartchromschicht
US6503642B1 (en) 1999-07-08 2003-01-07 Federal Mogul Burscheid Gmbh Hard-chrome plated layer
EP1253220A4 (de) * 1999-12-27 2006-03-22 Nippon Piston Ring Co Ltd Gleitelement
EP1253220A1 (de) * 1999-12-27 2002-10-30 Nippon Piston Ring Co., Ltd. Gleitelement
US6596410B2 (en) * 2000-09-29 2003-07-22 Nippon Piston Ring Co., Ltd. Chrome-plated sliding member and manufacturing method thereof
US7144017B2 (en) 2001-03-27 2006-12-05 Koncentra Marine & Power Ab Piston ring having wear resistant composition
US6838196B2 (en) 2001-03-27 2005-01-04 Koncentra Holding Ab Nickel-aluminide based wear resistant material for piston rings
US7052018B2 (en) 2001-03-27 2006-05-30 Koncentra Marine & Power Ab Piston ring having wear resistant composition
US8277953B2 (en) 2002-11-29 2012-10-02 Federal-Mogul Burscheid Gmbh Production of structured hard chrome layers
US7318963B2 (en) * 2004-01-30 2008-01-15 Kabushiki Kaisha Riken Composite chromium plating film and sliding member having the same and method for manufacture thereof
EP1719827A4 (de) * 2004-01-30 2007-05-02 Riken Kk Verbund-verchromungsschicht und damit versehenes gleitelement sowie deren herstellungsverfahren
EP1719827A1 (de) * 2004-01-30 2006-11-08 Kabushiki Kaisha Riken Verbund-verchromungsschicht und damit versehenes gleitelement sowie deren herstellungsverfahren
US8110087B2 (en) 2004-04-21 2012-02-07 Federal-Mogul Burscheid Gmbh Production of a structured hard chromium layer and production of a coating
DE102005023627A1 (de) * 2005-05-21 2006-11-30 Federal-Mogul Burscheid Gmbh Stahlkolbering
DE102005023627B4 (de) * 2005-05-21 2010-05-06 Federal-Mogul Burscheid Gmbh Stahlkolbering
WO2009021494A1 (de) * 2007-08-10 2009-02-19 Mahle International Gmbh Hartchromschicht, beschichtetes substrat und tribologisches system
WO2009121443A1 (de) * 2008-04-04 2009-10-08 Federal-Mogul Burscheid Gmbh Strukturierte chrom-feststoffpartikel-schicht und verfahren zu deren herstellung
KR20110008027A (ko) * 2008-04-04 2011-01-25 페데랄-모굴 부르샤이드 게엠베하 구조화된 크롬 고체 입자들 층 및 이의 제조 방법
US8337687B2 (en) 2008-04-04 2012-12-25 Federal-Mogul Burscheid Gmbh Structured chrome solid particle layer and method for the production thereof
EP2660362B1 (de) 2010-12-27 2019-06-26 Nippon Piston Ring Co., Ltd. Verbundverchromungsfilm und gleitelement mit diesem film

Also Published As

Publication number Publication date
DE69507172T2 (de) 1999-07-22
EP0668375B1 (de) 1999-01-13
ITTO940101A0 (it) 1994-02-18
IT1267394B1 (it) 1997-02-05
ITTO940101A1 (it) 1995-08-18
DE69507172D1 (de) 1999-02-25

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