EP3068928B1 - Verfahren zur herstellung einer beschichteten oberfläche eines tribologischen systems - Google Patents

Verfahren zur herstellung einer beschichteten oberfläche eines tribologischen systems Download PDF

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Publication number
EP3068928B1
EP3068928B1 EP14821488.5A EP14821488A EP3068928B1 EP 3068928 B1 EP3068928 B1 EP 3068928B1 EP 14821488 A EP14821488 A EP 14821488A EP 3068928 B1 EP3068928 B1 EP 3068928B1
Authority
EP
European Patent Office
Prior art keywords
coating
wear
honing
layer
producing
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.)
Not-in-force
Application number
EP14821488.5A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP3068928A1 (de
Inventor
Urban Morawitz
Clemens Verpoort
Christian Rosenkranz
Gerhard Flores
Andreas Wiens
Andreas Wagner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henkel AG and Co KGaA
Ford Werke GmbH
Original Assignee
Henkel AG and Co KGaA
Ford Werke 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
Publication date
Application filed by Henkel AG and Co KGaA, Ford Werke GmbH filed Critical Henkel AG and Co KGaA
Publication of EP3068928A1 publication Critical patent/EP3068928A1/de
Application granted granted Critical
Publication of EP3068928B1 publication Critical patent/EP3068928B1/de
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
    • C23G1/22—Light metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/022—Anodisation on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/026—Anodisation with spark discharge
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/06—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used
    • C25D11/08—Anodisation of aluminium or alloys based thereon characterised by the electrolytes used containing inorganic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/16—Pretreatment, e.g. desmutting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/06—Electrolytic coating other than with metals with inorganic materials by anodic processes
    • 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
    • F02F1/00—Cylinders; Cylinder heads 
    • F02F1/18—Other cylinders
    • F02F1/20—Other cylinders characterised by constructional features providing for lubrication

Definitions

  • the invention relates to a method for producing a coated surface of a friction- and wear-optimized cylinder liner and arose against the background of increasing demands for a reduction of CO 2 emissions in internal combustion engines of motor vehicles.
  • NiSiC nickel-silicon carbide dispersion layer
  • thermal coating methods are used (see for example the DE 10 2007 023 297 A1 or the US 5,691,004 ) in which the coating material is melted as an alloyed wire or as a heterogeneous powder and individual Schmetzpgreg be thrown at high speed on the cylinder wall and thus build up a thermal spray coating.
  • These layers are very expensive to produce and cause a high thermal load of the cylinder block. As a result, the cylinder block can warp, which is undesirable. Especially with weight-optimized and therefore thin-walled cylinders, this effect occurs.
  • the DE 195 06 656 A1 discloses a method for ceramizing light metal surfaces utilizing spark discharge of electrolytes, in particular for producing coatings of cylinder liners of internal combustion engines, further disclosed DE 195 06 656 A1 in that the coating can be applied by a plasma-chemical method. It is based on electrolyte compositions of DD 142 360 Referenced. Next goes the DE 195 06 656 A1 not on the plasma-chemical coating, the one referred to DD 142 360 relates to a process for the production of alpha-Al 2 O 3 -containing layers on aluminum metals and thus points only to a plasma-electrolytic oxidation PEO.
  • the object underlying the invention is to provide an economical and suitable for large-scale production process of aluminum workpieces, which leads to a wear-resistant surface; with good oil retention capacity.
  • a method comprising at least two process steps according to claim 1, which leads in the case of an aluminum cylinder block to a wear-resistant and friction-optimized topography of the cylinder bore.
  • Preferred embodiment of the method according to the invention are given in the dependent claims.
  • Starting point of the method according to the invention is a relatively coarse machined cylinder bore, which is present as a monolithic aluminum block or which is used as a wet or dry socket.
  • the surface to be machined is in any case made of an aluminum alloy, usually of hypoeutectic aluminum.
  • the surface is brought by honing or fine boring in the desired shape and processed to almost the final dimension.
  • the (still) untreated aluminum can be machined very well and economically. It is possible to produce a cylindrical shape by the pre-machining.
  • One suitable method is fine boring. As a result of the subsequent coating according to the invention, this desired shape is only insignificantly changed.
  • the pre-processing not only produces the desired shape, but also prepares the surface for the subsequent coating.
  • the roughness achieved in the first process step has an influence on the final quality after coating.
  • the surface is still degreased before the coating is produced.
  • the subsequently applied by electrolysis, ie by PED coating forms the pre-machined (nominal) form equidistant, so that the created by the first process step form is largely retained.
  • a wear-resistant coating is applied or produced by electrolysis, ie by PED. There is no distortion on the workpiece and the desired shape of the surface is not changed.
  • This layer has a high hardness and is therefore very resistant to wear.
  • the porosity of the layer can be adjusted specifically. Porosity improves oil retention, reduces sliding friction wear, and promotes hydrodynamic lubrication
  • the high hardness reduces the sliding friction in the mixed friction range at lower engine speeds and increases the service life.
  • An electrolytic process according to the invention is the so-called “plasma electrolytic deposition” which is carried out in the aqueous electrolyte and brings about both an inward edge change and a layer build-up to the outside.
  • a further advantage of the PED is that, in addition to the layers of aluminum oxide mentioned, it is also possible to produce other metal oxide layers, so that according to the invention titanium oxide layers (TiO 2 ) can be produced.
  • TiO 2 titanium oxide layers
  • such wear-resistant coatings are preferred, which are obtainable by means of PED from an acidic aqueous electrolyte containing water-soluble compounds of the element titanium, selected from fluoro complexes, when the workpiece is switched predominantly as the anode.
  • the workpiece is then predominantly connected as an anode if it has taken over a predominantly anodic amount of charge for all the time intervals during which the PED method is operated above the actual decomposition voltage of the electrolyte.
  • Coatings produced in this way consist essentially of oxides / hydroxides of the element titanium and have proven to be particularly resistant to wear.
  • the coatings produced in this way have an altered edge zone inwards with an invasion depth of z. B. 3 microns and a layer structure to the outside of z. B. 9 microns, so that in this case results in a layer thickness of 12 microns.
  • the typically used layer thicknesses are well below 70 microns, their hardness is up to 1500 HV.
  • the hardness and topography of the coating can be adjusted via the electrical process parameters of the electrolysis. The coating process takes place in the electrolytic bath.
  • the workpiece is largely masked, so that only the bore to be coated is in contact with the electrolyte and so a selective coating of the bore is possible
  • the masking is done, for example, with the aid of a lid, which - sealed with O-rings - closes the bore towards the crankcase.
  • the electrode is preferably designed as a cylinder, which has approximately the length of the cylinder bore to be machined and is dimensioned such that a radial gap of about 20-30 mm thickness arises between the electrode and the cylinder bore. Through this gap, the electrolyte flows at a flow rate of eg 20 L / min in a cylinder bore for a car engine, is deflected to the lid and flows again in the direction of the sealing surface for the cylinder head.
  • the electrode is poled cathodically, the workpiece anodic. Between the electrode and the cathode is a pulsed direct current with a voltage of 400-500 volts.
  • the electrolysis can also be done with unpulsed DC with or without superimposed AC component. It has proven current densities of about 10-30 A / dm 2 .
  • the coating time is about 2-10 minutes; The coating can be carried out simultaneously on all cylinders of a block by means of several electrodes. The layer thickness, the resulting layer roughness and the pore size are dependent on the applied electrical current, the voltage, the pulse program used and on the coating time,
  • the coating usually has a roughness of 2-3 microns Rz and a Rpk value of z.
  • B 1.0 - 2.0 microns with a pore size of 2-3 microns.
  • the depth of the edge zone change in the material of the workpiece is about 1/3 of the outwardly growing layer.
  • the edge zone change inwards z. B about 5 microns and about 15 microns layer structure out into the hole.
  • the specified roughness of the layer consists of a waviness, which is due to the pores and the structure of the layer.
  • the coating is therefore finished, if necessary, by a smoothing operation, in order to level the undulations which have arisen during the coating. If the ripple is small, the smoothing process can be omitted.
  • the smoothing can be done by honing or brushing. To level the waviness of the layer, you can work with conventional honing tools. However, it is recommended to minimize the removal and to change the (free) form of the surface only minimally to work with special Glätthhontechnikmaschinemaschineen. Their pendulum-suspended (hon) inguinal segments are relatively short, based on the length of the cylinder bore, but longer than the short-wave portions of the coating profile and thereby produce the desired smoothing, without significantly changing the geometry of the cylinder bore with minimal material removal.
  • honing brushes which also adapt to the waviness due to the flexibility.
  • These are brushes whose individual bristles consist, for example, of polyamide, in which abrasive hard materials, such as silicon carbide, corundum or diamond grain, are incorporated.
  • so-called flex-honing brushes can be used, which are equipped at the bristle end, for example, with ceramic-bound cutting tubers.
  • the finished smoothed layer topography is superimposed on the roughness before coating and on the layer-characteristic pores.
  • the roughness profile changes from the above values after coating to Rz values of 2.0-2.5 ⁇ m after smoothing.
  • a suitable Rpk value is 0.13 ⁇ m.
  • metal-bound diamond grains and ceramic-bound corundum or SiC grains have proven themselves.
  • a layer can be produced with the method according to the invention in a manner which can be easily controlled in terms of production, and which is particularly suitable for tribology because of its pore structure and high material hardness.
  • the heat removal from the combustion chamber via the layer is particularly effective because the layer has been applied quasi-galvanically and thus the best possible substrate connection is made.
  • the layer according to the invention does not influence the geometry of the cylinder bore, or does so only insignificantly, so that the desired shape can be completed even before coating.
  • the order resulting from the coating and the material removal resulting from the optional smoothing must be taken into account.
  • the method according to the invention can be realized in a compact production chain which is highly efficient both economically and technologically.
  • FIG. 1 is the surface line 2 of a pre-processed by honing (cylinder) hole shown.
  • the substrate is activated for the subsequent coating and has the desired nominal shape.
  • FIG. 2 the surface is shown after treatment by PED.
  • a thickness of the coating 9 to about a third represents a change in the edge zone of the substrate and about two-thirds (reference numeral 3) causes a layer structure to the outside.
  • Vorbearbeitungsw the bore (see the surface line 2) is designed so that the surface line 5 of the coating 9 is within the tolerance band of the finished bore.
  • FIG. 3 shows the smoothed generatrix 6, which, for example, by honing with in FIG. 4 shown tool has been achieved.
  • the surface line was smoothed so that a straight generatrix 6 is formed while maintaining the pores 8.
  • the smoothed surface line 6 is also in the tolerance band of the finished bore.
  • the surface of the smoothed generatrix is also in Figure 3.1 in the profile as well as in the SEM image Figure 3.2 shown.
  • FIG. 4 shows the principle of Glätthonens with a spring-mounted honing stone 7 at the beginning of Glätthonens.
  • About the radial force FR is the radial loading of the coating. Due to the springs of the honing stone 7 has the ability to reduce the short ripples of the coating without changing the desired shape of the cylinder bore. When smoothing, the pore structures are largely retained.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Cylinder Crankcases Of Internal Combustion Engines (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Electroplating Methods And Accessories (AREA)
EP14821488.5A 2013-11-12 2014-11-11 Verfahren zur herstellung einer beschichteten oberfläche eines tribologischen systems Not-in-force EP3068928B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE201310223011 DE102013223011A1 (de) 2013-11-12 2013-11-12 Verfahren zur Herstellung einer beschichteten Oberfläche eines tribologischen Systems
PCT/DE2014/000574 WO2015070833A1 (de) 2013-11-12 2014-11-11 Verfahren zur herstellung einer beschichteten oberfläche eines tribologischen systems

Publications (2)

Publication Number Publication Date
EP3068928A1 EP3068928A1 (de) 2016-09-21
EP3068928B1 true EP3068928B1 (de) 2018-11-07

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EP14821488.5A Not-in-force EP3068928B1 (de) 2013-11-12 2014-11-11 Verfahren zur herstellung einer beschichteten oberfläche eines tribologischen systems

Country Status (6)

Country Link
US (1) US9994966B2 (https=)
EP (1) EP3068928B1 (https=)
JP (1) JP2016540119A (https=)
KR (1) KR20160085261A (https=)
DE (1) DE102013223011A1 (https=)
WO (1) WO2015070833A1 (https=)

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DE102017206722B4 (de) 2016-04-26 2024-07-11 Ford Global Technologies, Llc Verfahren und Vorrichtung zur Herstellung einer beschichteten Oberfläche eines tribologischen Systems
US10106878B2 (en) * 2016-06-16 2018-10-23 GM Global Technologies Operations LLC Surface texture providing improved thermal spray adhesion
DE102016013932A1 (de) 2016-11-22 2018-05-24 Daimler Ag Verfahren zum Bearbeiten einer Lauffläche einer Zylinderlaufbuchse für eine Brennkraftmaschine
CN108441912B (zh) * 2018-03-16 2019-10-08 南京理工大学 铝合金表面Al3C4-Al2O3-ZrO2耐磨复合涂层的制备方法
JP7344460B2 (ja) * 2019-06-17 2023-09-14 スズキ株式会社 内燃機関用ピストン
CN110484949A (zh) * 2019-08-14 2019-11-22 江苏苏扬包装股份有限公司 采用等离子体液相电解沉积制备活塞环表面陶瓷膜的方法
CN111321444A (zh) * 2020-04-09 2020-06-23 宁波江丰电子材料股份有限公司 一种减少背板表面处理返修的方法

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Also Published As

Publication number Publication date
DE102013223011A1 (de) 2015-05-13
WO2015070833A1 (de) 2015-05-21
KR20160085261A (ko) 2016-07-15
JP2016540119A (ja) 2016-12-22
US9994966B2 (en) 2018-06-12
US20160289856A1 (en) 2016-10-06
EP3068928A1 (de) 2016-09-21

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