EP0725166A1 - Verfahren zur Beschichtung der Oberfläche eines Werkstücks aus Aluminium oder einer Aluminiumlegierung - Google Patents

Verfahren zur Beschichtung der Oberfläche eines Werkstücks aus Aluminium oder einer Aluminiumlegierung Download PDF

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Publication number
EP0725166A1
EP0725166A1 EP96420033A EP96420033A EP0725166A1 EP 0725166 A1 EP0725166 A1 EP 0725166A1 EP 96420033 A EP96420033 A EP 96420033A EP 96420033 A EP96420033 A EP 96420033A EP 0725166 A1 EP0725166 A1 EP 0725166A1
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EP
European Patent Office
Prior art keywords
grams
bath
nickel
electrolytic deposition
activation
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Granted
Application number
EP96420033A
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English (en)
French (fr)
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EP0725166B1 (de
Inventor
Mohamed Benmalek
Marc Santarini
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Rio Tinto France SAS
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Aluminium Pechiney SA
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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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
    • C25D5/44—Aluminium

Definitions

  • the invention relates to the field of aluminum or aluminum alloy parts having at least one face or surface subjected to high friction stresses, in particular molded or forged parts of motor vehicles. These are, for example, the liners which equip internal combustion engines of motor vehicles or else cylinders machined directly in the engine block.
  • the invention relates more precisely to the internal surface, or bore, of a jacket or of an engine block which is subjected, cold as hot, to high stresses of friction and is sensitive to wear.
  • Patent application FR-A-1,579,266 proposes a process for the galvanic deposition of a metal coating containing solid particles.
  • the deposition is carried out in two stages: a preparatory stage where a first layer of zinc is deposited by chemical means on the surface to be treated, and a second stage which is the actual electrolytic deposition, the part to be treated being the cathode , this deposition taking place in two stages: first deposition of a thin layer of almost pure nickel then deposition of the nickel loaded with solid particles.
  • This process is currently used widely on a large scale for both aluminum alloy engine blocks and cast iron engine blocks or liners, since the coating thus obtained not only increases the resistance to wear but also improves lubrication because it facilitates the retention of the lubricant thanks to the particles of silicon carbide which emerge from the nickel surface.
  • Patent application FR-A-2 159 179 provides an improvement to the initial process which consists of a mechanical preparation of the surface (shot blasting) followed by a sodium attack and finally a double zincing with intermediate nitric attack. Improving the adhesion of the deposited layer, it is used for mass production but has the disadvantage of producing a layer of irregular thickness.
  • Patent application EP-A-0 288 364 discloses a process for coating drums of cast iron engine blocks in which the initial deposit of zinc is replaced by an electrolytic sulfuric attack. This process allows better control of the thickness of the deposit but is not suitable for aluminum alloys.
  • the bore of a cylinder block is the seat of the piston stroke, so it must be performed within very tight dimensional tolerances.
  • the irregularity of the thickness of the deposited layer imposes in practice a final machining, generally by abrasion-grinding, long, delicate and expensive. Good geometrical precision of the deposit would make it possible to no longer provide for a resumption of machining and to aim straight away at the thickness corresponding to the maximum wear that can be expected from this coating.
  • these operations can be separated by rinsing with pure water and follow one another in a very short time, so that the surface to be coated does not dry between each step and without said surface having been exposed to air or any other environment causing its reactivity to drop.
  • an electrode with a shape close to that of the surface to be treated is placed near said surface.
  • said electrode having to be simply brought to a cathode polarity at the first stage, zero at the second and anodic at the third.
  • the first step according to the invention is an electrochemical activation phase in which the surface to be treated and the electrode are in a bath containing a halogenated acid salt of nickel.
  • this bath is an aqueous solution containing nickel chloride, a fluorinated compound and boric or fluoboric acid.
  • an aqueous solution will be used comprising, per liter of electrolyte, from 100 to 250 grams of nickel chloride, from 2 to 10 grams of ammonium bifluoride, and from 10 to 20 grams of fluoboric acid.
  • a direct current is applied between the part which acts as an anode and the electrode which acts as cathode.
  • the current density is between 10 and 50 A / dm 2 for 30 to 120 seconds, the bath being maintained at a temperature between 40 ° C and 60 ° C.
  • the second step according to the invention is an over-activation treatment whose purpose is to complete the depassivation of the surface to be coated and to dissolve the few residues resulting from the electrochemical treatment of the first step and liable to disturb the regularity and the homogeneity of the future deposit.
  • this overactivation treatment is carried out with a nitric fluoboric bath and more particularly an aqueous solution comprising between 20% and 50% by volume of concentrated nitric acid at 68% and between 20% and 75% by volume of concentrated fluoboric acid. at 50%.
  • the surface in contact with this bath is maintained for a period of 30 to 120 seconds at a temperature between 20 ° C and 40 ° C
  • the third step according to the invention is the phase of electrolytic deposition of the composite nickel.
  • the bath is a nickel-plating bath containing a filler composed of solid particles which may be either carbides, in particular silicon carbide, or else any other component hardening the coating and improving the wear resistance of the deposit (diamond for example), either a component reducing the coefficient of friction (graphite for example), or a mixture of components of these two categories intended to provide the best compromise between wear resistance and coefficient of friction corresponding to the intended use.
  • said nickel plating bath may comprise nickel sulfamate, nickel chloride, boric acid, saccharin and said charge of solid particles.
  • a nickel-plating bath comprising approximately, per liter of electrolyte, from 250 to 400 grams of nickel sulfamate, from 20 to 40 grams of nickel chloride, from 10 to 100 grams of boric acid and from 50 at 150 grams of charge.
  • the bath is maintained at a temperature between 40 ° C and 60 ° C, while its pH is maintained between 2 and 5, preferably between 2.5 and 3.5.
  • the bath also contains saccharin, which has the advantageous effect of reducing the residual stresses prevailing in the deposit. Its concentration is however limited because saccharin has the other effect of reducing the deposition rate.
  • one liter of nickel-plating bath contains between 0.5 and 4 grams of saccharin.
  • a direct or pulsed current is applied between the part which acts as a cathode and the electrode which acts as an anode.
  • the current density is between 20 and 50 A / dm 2 for the time necessary to reach the desired thickness.
  • the treatment lasts 15 minutes to obtain a layer of 45 ⁇ m at a temperature close to 50 ° C.
  • all of the particles of said filler according to the invention can reach a predominant size of between 0.5 ⁇ m and 5 ⁇ m.
  • particles of silicon carbide with a particle size of between 3 ⁇ m and 5 ⁇ m are introduced, that is to say sufficiently large to reduce the risks of seizure but not too much to avoid too strong wear of the other element in contact.
  • This same charge is enriched with graphite particles of finer particle size: 1 ⁇ m to 3 ⁇ m.
  • the combination of the electrochemical activation of the first stage according to the invention and the over-activation of the second stage according to the invention improves the deposition efficiency of the third stage so that there is no need to reach the bath concentrations of the prior art to obtain the same concentration of charge in the deposited layer.
  • This allows, at identical bath viscosity, to enrich the filler either with the same element to improve a given property, or with other elements to give it other properties; thus, for example, it is possible to add to the silicon carbide powder, which improves the wear resistance, graphite powder which reduces the friction at start-up and thus reduces the risks of seizure.
  • FIG. 1 represents the diagram of a preferred embodiment given solely by way of nonlimiting example. According to this embodiment, the operations are limited, the waiting time between the steps is minimal, the activation of the surface is not hampered by any oxidation or passivation.
  • the system is dynamic, that is to say that the treatment cell for the part 1 is not dismantled during the process and that all of the baths are successively introduced inside the said cell 1. required. This is possible thanks to circuit 2 which includes polypropylene pipes and a pump 3 allowing the circulation of fluids between their retention tank and the treatment cell.
  • the pump first drives the activation bath of the tank 5, the rinsing bath of the tank 6, the overactivation bath of the tank 7, a new rinsing bath, finally the nickel-plating bath of the tank 8.
  • FIG. 2 presents a block diagram of the cell for treating the part to be coated.
  • an engine block is particularly bulky and heavy to handle, we have simplified the part by replacing it with a cylindrical jacket 12 made of the AS5U3G alloy commonly used for engine blocks. This aluminum alloy contains approximately 5% silicon, 3% copper and 0.3% magnesium.
  • the electrode 10 is held by a support 11 covering the jacket 12.
  • the support of the jacket 13 has a centering means which makes it possible to make the electrode and the jacket concentric.
  • the electrode support 11 and the jacket support 13 hermetically surround the jacket and allow the various fluids coming from the circuit of FIG. 1 to pass through the cavities 14 of the jacket support 13 and 15 of the electrode support 11.
  • the electrochemical activation bath stored in the polypropylene tank 5 and maintained at the temperature of 50 ° C. has the following composition: NiCl 2 125 g / l NH 4 HF 2 5 g / l H 3 BO 3 12.5 g / l It is brought to the treatment cell 1 via the pump 3, the maximum flow rate of which is 100 liters / minute. For 30 seconds, using a 40V 300A generator, a current is passed in such a way that a current density of 28 A / dm 2 is established.
  • the nickel-plating bath used has the following composition: Ni (NH 2 SO 3 ) 2 300 g / l H 3 BO 3 30 g / l NiCl 2 30 g / l saccharin 2 g / l filler: silicon carbide 75 g / l, average particle size 2 micrometers
  • the deposit obtained is characterized by its adhesion, the regularity of the thickness deposited, homogeneity of the particle distribution and by friction and wear tests.
  • the adhesion tests used follow the recommendations of ASTM: B571-84 ⁇ 9 (thermal shock), the temperature of use target being set at 200 ° C and B571-84 ⁇ 7 (file test).
  • the lubricant used is decane
  • the frequency of the alternative displacement is 12 Hz
  • the test lasts 30 minutes.
  • the lubricant used is a neutral engine oil, that is to say uncharged, the frequency of the reciprocating movement is 16 Hz, the test lasts 120 minutes.
  • Table 1 the wear of the coating is characterized by a loss in weight expressed in milligrams.
  • the wear of the segments is given qualitatively according to the appearance of the contact surface of the segment at the end of the test and it is represented in the table by a number of crosses all the greater the greater .

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
  • Coating With Molten Metal (AREA)
EP96420033A 1995-02-02 1996-01-31 Verfahren zur Beschichtung der Oberfläche eines Werkstücks aus Aluminium oder einer Aluminiumlegierung Expired - Lifetime EP0725166B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9501405 1995-02-02
FR9501405A FR2730245B1 (fr) 1995-02-02 1995-02-02 Procede de revetement de pieces de vehicules automobiles en aluminium ou alliage d'aluminium

Publications (2)

Publication Number Publication Date
EP0725166A1 true EP0725166A1 (de) 1996-08-07
EP0725166B1 EP0725166B1 (de) 1998-04-29

Family

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EP96420033A Expired - Lifetime EP0725166B1 (de) 1995-02-02 1996-01-31 Verfahren zur Beschichtung der Oberfläche eines Werkstücks aus Aluminium oder einer Aluminiumlegierung

Country Status (12)

Country Link
US (1) US5643434A (de)
EP (1) EP0725166B1 (de)
JP (1) JPH08239793A (de)
CN (1) CN1144851A (de)
AT (1) ATE165632T1 (de)
BR (1) BR9600303A (de)
CA (1) CA2167767A1 (de)
DE (1) DE69600258T2 (de)
ES (1) ES2115419T3 (de)
FR (1) FR2730245B1 (de)
HK (1) HK1000650A1 (de)
TW (1) TW384319B (de)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2995617A1 (fr) * 2012-09-14 2014-03-21 Adolf Edelhoff Gmbh & Co Kg Procede de revetement de conducteurs electriques en aluminium
CN105506526A (zh) * 2015-12-08 2016-04-20 西北工业大学 铝合金表面Ni-SiC复合镀层的制备方法及其电镀液

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JP3296543B2 (ja) * 1996-10-30 2002-07-02 スズキ株式会社 めっき被覆アルミニウム合金、及びそのシリンダーブロック、めっき処理ライン、めっき方法
US6996549B2 (en) * 1998-05-01 2006-02-07 Health Discovery Corporation Computer-aided image analysis
AU744563B2 (en) 1998-08-28 2002-02-28 Arconic, Inc. Method for surface treating aluminum products
HUP0300706A2 (en) 2000-05-18 2003-07-28 Corus Aluminium Walzprod Gmbh Method of manufacturing an aluminium product
US6796484B2 (en) 2001-02-02 2004-09-28 Corus Aluminum Walzprodukte Gmbh Nickel-plated brazing product having improved corrosion performance
AU2002316865B2 (en) 2001-04-20 2006-07-20 Corus Aluminium Walzprodukte Gmbh Method of plating and pretreating aluminium workpieces
KR20030029350A (ko) * 2001-10-08 2003-04-14 현대자동차주식회사 디젤엔진용 실린더 라이너의 제조방법
US6815086B2 (en) 2001-11-21 2004-11-09 Dana Canada Corporation Methods for fluxless brazing
US7294411B2 (en) * 2002-01-31 2007-11-13 Aleris Aluminum Koblenz Gmbh Brazing product and method of its manufacture
US6994919B2 (en) * 2002-01-31 2006-02-07 Corus Aluminium Walzprodukte Gmbh Brazing product and method of manufacturing a brazing product
US7078111B2 (en) * 2002-12-13 2006-07-18 Corus Aluminium Walzprodukte Gmbh Brazing sheet product and method of its manufacture
US7056597B2 (en) * 2002-12-13 2006-06-06 Corus Aluminium Walzprodukte Gmbh Brazing sheet product and method of its manufacture
US6828660B2 (en) * 2003-01-17 2004-12-07 Texas Instruments Incorporated Semiconductor device with double nickel-plated leadframe
US20050067286A1 (en) * 2003-09-26 2005-03-31 The University Of Cincinnati Microfabricated structures and processes for manufacturing same
US20060157352A1 (en) * 2005-01-19 2006-07-20 Corus Aluminium Walzprodukte Gmbh Method of electroplating and pre-treating aluminium workpieces
FR2881146B1 (fr) * 2005-01-27 2007-10-19 Snecma Moteurs Sa Procede de reparation d'une surface de frottement d'une aube a calage variable de turbomachine
CN100336940C (zh) * 2005-02-24 2007-09-12 上海交通大学 纳米碳化硅颗粒增强镍基复合材料的复合电铸制备方法
CN101886282A (zh) * 2010-07-12 2010-11-17 江门朝扬精密制造有限公司 一种引擎汽缸的制作方法
WO2014130451A1 (en) * 2013-02-19 2014-08-28 Alumiplate, Inc. Aluminum films having hardening particles
JPWO2015133490A1 (ja) * 2014-03-04 2017-04-06 本田技研工業株式会社 内燃機関用シリンダブロック及びその製造方法
KR102471172B1 (ko) * 2016-06-03 2022-11-25 후루카와 덴끼고교 가부시키가이샤 표면 처리재 및 그 제조 방법 및 표면 처리재를 이용하여 형성한 부품
CN109623676B (zh) * 2018-12-30 2020-08-25 苏州赛尔科技有限公司 Pcb板用轮毂型金刚石超薄切割片及其应用
CN113895164B (zh) * 2021-09-01 2022-06-14 清远南方制版科技有限公司 一种无缝铝合金管制的辊筒及制备方法和在凹版印刷版辊中的应用

Citations (1)

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Publication number Priority date Publication date Assignee Title
JPS62238393A (ja) * 1986-04-07 1987-10-19 Nippon Light Metal Co Ltd アルミニウム材への電気めつき方法

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US3531379A (en) * 1965-07-28 1970-09-29 Micral Ind Inc Process of coating aluminum with other metals
JPS521172B2 (de) * 1972-09-13 1977-01-12
US5139586A (en) * 1991-02-11 1992-08-18 Coral International, Inc. Coating composition and method for the treatment of formed metal surfaces

Patent Citations (1)

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JPS62238393A (ja) * 1986-04-07 1987-10-19 Nippon Light Metal Co Ltd アルミニウム材への電気めつき方法

Non-Patent Citations (1)

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Title
CHEMICAL ABSTRACTS, vol. 108, no. 12, 21 March 1988, Columbus, Ohio, US; abstract no. 102985r, SATO: "electroplating on aluminium" page 565; *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2995617A1 (fr) * 2012-09-14 2014-03-21 Adolf Edelhoff Gmbh & Co Kg Procede de revetement de conducteurs electriques en aluminium
CN105506526A (zh) * 2015-12-08 2016-04-20 西北工业大学 铝合金表面Ni-SiC复合镀层的制备方法及其电镀液

Also Published As

Publication number Publication date
CA2167767A1 (fr) 1996-08-03
EP0725166B1 (de) 1998-04-29
HK1000650A1 (en) 2000-03-17
TW384319B (en) 2000-03-11
US5643434A (en) 1997-07-01
BR9600303A (pt) 1997-12-23
ATE165632T1 (de) 1998-05-15
ES2115419T3 (es) 1998-06-16
DE69600258D1 (de) 1998-06-04
CN1144851A (zh) 1997-03-12
FR2730245A1 (fr) 1996-08-09
FR2730245B1 (fr) 1997-03-14
DE69600258T2 (de) 1998-08-20
JPH08239793A (ja) 1996-09-17

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