DE4035524A1 - Light metal cylinder for internal combustion engine piston - has electrolytically deposited wear resistant coating of nickel@ or iron@ dispersed with boron carbide - Google Patents

Light metal cylinder for internal combustion engine piston - has electrolytically deposited wear resistant coating of nickel@ or iron@ dispersed with boron carbide

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Publication number
DE4035524A1
DE4035524A1 DE19904035524 DE4035524A DE4035524A1 DE 4035524 A1 DE4035524 A1 DE 4035524A1 DE 19904035524 DE19904035524 DE 19904035524 DE 4035524 A DE4035524 A DE 4035524A DE 4035524 A1 DE4035524 A1 DE 4035524A1
Authority
DE
Germany
Prior art keywords
nickel
internal combustion
combustion engine
iron
light metal
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.)
Granted
Application number
DE19904035524
Other languages
German (de)
Other versions
DE4035524C2 (en
Inventor
Goetz Mielsch
Manfred Froehler
Werner Huber
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.)
Bayerische Motoren Werke AG
Original Assignee
Bayerische Motoren Werke AG
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 Bayerische Motoren Werke AG filed Critical Bayerische Motoren Werke AG
Priority to DE19904035524 priority Critical patent/DE4035524A1/en
Publication of DE4035524A1 publication Critical patent/DE4035524A1/en
Application granted granted Critical
Publication of DE4035524C2 publication Critical patent/DE4035524C2/de
Granted legal-status Critical Current

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Classifications

    • 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

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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)
  • Chemically Coating (AREA)
  • Pistons, Piston Rings, And Cylinders (AREA)

Abstract

Light metal cylinder of a piston engine has a wear-resistant coating of a Ni or Fe dispersion coating contg. tetra-B carbide. The coating is deposited electrolytically from a bath contg. the carbide. In use, the coating forms NiB2C at 350 deg.C and Ni3B from 450 deg.C or FeB and Fe2B. ADVANTAGE - Maximum resistance to wear.

Description

Die Erfindung betrifft einen Leichtmetallzylinder einer Hubkolben-Brennkraftmaschine mit einer carbidhaltigen Dispersions-Verschleißschutzschicht. Derartige Schutz­ schichten sind bekannt und üblicherweise als Nickel­ dispersionsschichten mit eingelagerten Siliziumcar­ bidteilchen ausgebildet.The invention relates to a light metal cylinder Reciprocating internal combustion engine with a carbide-containing one Dispersion wear protection layer. Such protection layers are known and commonly known as nickel dispersion layers with embedded silicon car formed bi-particle.

Es hat sich gezeigt, daß eine einfache Nickeldispersions­ beschichtung mit Siliziumcarbid als Dispergid unter ex­ tremen Randbedingungen, wie sie insbesondere im Feuer­ stegbereich von Zylindern von Hubkolben-Brennkraftmaschi­ nen auftreten, nicht beständig sind. Dort ist die Ver­ schleißschutzschicht nämlich nicht nur extrem hohen Tem­ peraturen ausgesetzt, sondern darüber hinaus auch aggres­ siven Reagenzien, die in den heißen Verbrennungsgasen ei­ ner Brennkraftmaschine enthalten sind. Da sich in diesem Bereich somit die Beschichtung auflöst, tritt dort nicht nur ein untolerierbarer Abbrand, sondern auch eine ver­ stärkte Korrosion auf, die zu einem raschen Zerbröckeln der Beschichtung führen kann.It has been shown that a simple nickel dispersion coating with silicon carbide as dispersant under ex treme boundary conditions, such as those in fire Bridge area of cylinders of reciprocating internal combustion engines occur, are not stable. There is the Ver wear protection layer namely not only extremely high temperature exposed to temperatures, but also aggres sive reagents in the hot combustion gases ner internal combustion engine are included. Because in this Area thus dissolves the coating does not occur there only an intolerable burn, but also a ver intensified corrosion which led to rapid crumbling the coating can lead.

Eine mögliche Abhilfemaßnahme hiergegen bestünde bei­ spielsweise im Einsatz von thermisch stabilen Dispergi­ den, wie beispielsweise Aluminiumoxid oder Chromdioxid. Diese Dispergide sind chemisch inert und lösen sich nicht auf, jedoch sind derartige Oxide unter tribologischen Ge­ sichtspunkten ungeeignet. Im Einsatz an einem Leichtme­ tallzylinder einer Hubkolben-Brennkraftmaschine würden derartige Schichten zum Fressen mit den Kolbenringen und den Kolben neigen.A possible remedial measure against this would exist at for example in the use of thermally stable dispersi  such as aluminum oxide or chromium dioxide. These dispersants are chemically inert and do not dissolve on, but such oxides are under tribological Ge viewpoints unsuitable. In use on a Leichtme Tall cylinder a reciprocating internal combustion engine would such layers to eat with the piston rings and tilt the piston.

Eine andere Abhilfemaßnahme ist in der DE 32 16 763 C1 beschrieben, wobei in eine galvanisch erzeugte Nickel­ dispersionsschicht mit Siliziumcarbid von der Oberfläche aus Zinn eindiffundiert wird, das sich über die ganze Schicht verteilt. Eine derartige zusätzliche Oberflächen­ behandlung ist jedoch äußerst aufwendig.Another remedial measure is in DE 32 16 763 C1 described, being in a galvanically generated nickel dispersion layer with silicon carbide from the surface is diffused out of tin, which is spread over the whole Layer distributed. Such additional surfaces however, treatment is extremely complex.

Aufgabe der Erfindung ist es daher, für einen Leichtme­ tallzylinder einer Hubkolben-Brennkraftmaschine mit einer carbidhaltigen Dispersions-Verschleißschutzschicht Maß­ nahmen aufzuzeigen, mit Hilfe derer auf einfache Weise auch unter den oben geschilderten harten Randbedingungen eine höchste Beständigkeit erzielt werden kann.The object of the invention is therefore for a Leichtme Tall cylinder a reciprocating internal combustion engine with a Carbide-containing dispersion wear protection layer dimension with the help of which in a simple way even under the harsh conditions outlined above the highest resistance can be achieved.

Zur Lösung dieser Aufgabe ist vorgesehen, daß die Ver­ schleißschutzschicht aus Tetraborcarbid gebildet ist. Zwar lösen sich auch diese Carbide unter den oben ge­ schilderten Randbedingungen teilweise auf, jedoch wird nach der Erfindung diese Auflösung in der Weise genutzt, daß sich hierbei wiederum eine resistente Verschleiß- Schutzschicht bildet. Besteht die Verschleiß-Schutz­ schicht aus einer Nickeldispersionsschicht (Merkmal des Patentanspruchs 2), so bilden sich mit dem Auflösen des Tetraborcarbids heißgaskorrosionsbeständige Nickel-Bor- Verbindungen. Diese durch thermische Umwandlungen aus dem Tetraborcarbid entstandenen Nickel-Bor-Verbindungen sind bis zu 900°C unter Abgasbedingungen völlig inert und füh­ ren zusätzlich zu einer Härtung der Beschichtung. Vor­ teilhafterweise ergaben Reibwertmessungen zusätzlich um ca. 10 bis 20% geringere Reibbeiwerte, als sie von her­ kömmlichen Nickelsiliziumcarbid-Schichten her bekannt sind.To solve this problem it is provided that the Ver wear protection layer is formed from tetraborecarbide. These carbides also dissolve under the ge above partially outlined boundary conditions, however according to the invention this resolution is used in such a way that there is again a resistant wear Protective layer forms. There is wear protection layer of a nickel dispersion layer (feature of Claim 2), form with the dissolution of the Tetraborcarbids hot gas corrosion resistant nickel boron Links. This through thermal transformations from the Tetraborcarbide are nickel-boron compounds completely inert up to 900 ° C under exhaust gas conditions in addition to hardening the coating. Before In some cases, friction coefficient measurements additionally resulted  approx. 10 to 20% lower friction coefficients than they used to be conventional nickel silicon carbide layers ago known are.

Besonders vorteilhaft ist der Einsatz von Tetraborcarbid jedoch bei einer Eisendispersions-Verschleißschutz­ schicht. Die gebildeten Eisenboride weisen nämlich eine nochmals erheblich höhere Härte auf, als die Nickel­ boride. Die sich somit im Betrieb der Brennkraftmaschine einstellende Stoffumwandlung in der Verschleißschutz­ schicht ist metallurgisch betrachtet somit dem bekannten Borieren von Stahllegierungen vergleichbar. Den dann stattfindenden Umwandlungsprozeß könnte man sozusagen als "internes Borieren" bezeichnen.The use of tetraborecarbide is particularly advantageous however with an iron dispersion wear protection layer. The iron borides formed have one hardness significantly higher than nickel boride. Which is thus in the operation of the internal combustion engine adjusting fabric conversion in wear protection From a metallurgical point of view, layer is thus the known one Boronizing of steel alloys comparable. Then that the conversion process taking place could be said to be Describe "internal boriding".

Die Herstellung erfindungsgemäßer Beschichtungen erfolgt auf galvanischem Wege in bekannter Weise wie z. B. die herkömmliche Nickeldispersionsbeschichtung. Im Beschich­ tungsbad wird lediglich das Siliziumcarbid gegen das Tetraborcarbid ausgetauscht. Dieser Austausch ist in be­ stehenden Anlagen ohne Änderungsmaßnahmen durchführbar.Coatings according to the invention are produced by galvanic means in a known manner such. B. the conventional nickel dispersion coating. In the Beschich only the silicon carbide against the Tetraboric carbide exchanged. This exchange is in be standing systems can be carried out without any change measures.

Für die Erzeugung einer Eisendispersionsschicht mit Tetraborcarbid werden hinsichtlich der Härte, der Bestän­ digkeit sowie der tribologischen Aspekte (Reibbeiwerte etc.) beste Ergebnisse mit einem Beschichtungsbad der folgenden Zusammensetzung erzielt:
500 g/l FeSO4 × 6 H2O
30 g/l H3BO3
0,0005-0,001 g/l NaBH4
20-40 g/l B4C,
wobei ein Toleranzband von +/-20% ebenfalls akzeptable Ergebnisse lieferte. Durch die Zugabe von Natriumbor­ hydrid wird beim Beschichtungsprozeß von Anfang an Bor in die Schicht eingebaut, so daß sich dieses nicht erst durch Auflösen des Tetrabors bilden muß. Die Folge ist eine sofortige Härtung der Verschleißschutzschicht. Vor­ teilhaft ist hierbei auch, daß bei der Oxidation von Bor­ hydrid als Reaktionsprodukt Borsäure entsteht. Borsäure ist jedoch ohnehin Bestandteil der oben angegebenen Bad­ zusammensetzung, und muß deshalb nicht entfernt werden.
For the production of an iron dispersion layer with tetrabor carbide, the best results are achieved with a coating bath of the following composition in terms of hardness, resistance and tribological aspects (friction coefficients, etc.):
500 g / l FeSO 4 × 6 H 2 O
30 g / l H 3 BO 3
0.0005-0.001 g / l NaBH 4
20-40 g / l B 4 C,
a tolerance band of +/- 20% also gave acceptable results. By adding sodium borohydride, boron is built into the layer from the start in the coating process, so that this does not have to be formed only by dissolving the tetrabor. The result is an immediate hardening of the wear protection layer. Before geous is also that boric acid is formed as a reaction product in the oxidation of boron hydride. However, boric acid is part of the bath composition given above and therefore does not have to be removed.

Als Resümee soll somit festgehalten werden, daß eine er­ findungsgemäße Verschleißschutzschicht abweichend von den üblichen Siliziumcarbid-Partikeln aus Tetraborcarbid ge­ bildet ist, wobei zwar auch diese Carbide im geschilder­ ten Einsatzfall zum Zerfall neigen, dabei jedoch wiederum beständige und die Aufgabe einer Verschleißschutzschicht optimal erfüllende Verbindungen entweder aus NiB2C bei 350°C und Ni3B ab 450°C bilden. Bei der Auflösung von Tetraborcarbid in der Eisenmatrix bildet sich FeB bzw. Fe2B.As a summary, it should be noted that he wear protection layer according to the invention is different from the usual silicon carbide particles of tetrabor carbide, although these carbides also tend to disintegrate in the case described, but in turn are stable and the task of a wear protection layer optimally fulfilling compounds either form NiB 2 C at 350 ° C and Ni 3 B from 450 ° C. When tetraborarbide is dissolved in the iron matrix, FeB or Fe 2 B forms.

Claims (3)

1. Leichtmetallzylinder einer Hubkolben-Brennkraftma­ schine mit einer carbidhaltigen Dispersions-Ver­ schleißschutzschicht, dadurch gekennzeichnet, daß die Verschleißschutz­ schicht aus Tetraborcarbid gebildet ist.1. Light alloy cylinder of a reciprocating internal combustion engine with a carbide-containing dispersion wear protection layer, characterized in that the wear protection layer is formed from tetraborecarbide. 2. Leichtmetallzylinder nach Anspruch 1 mit einer Nickeldispersionsschicht.2. Light metal cylinder according to claim 1 with a Nickel dispersion layer. 3. Leichtemtallzylinder nach Anspruch 1 mit einer Eisendispersionsschicht.3. Light alloy cylinder according to claim 1 with a Iron dispersion layer.
DE19904035524 1990-11-08 1990-11-08 Light metal cylinder for internal combustion engine piston - has electrolytically deposited wear resistant coating of nickel@ or iron@ dispersed with boron carbide Granted DE4035524A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
DE19904035524 DE4035524A1 (en) 1990-11-08 1990-11-08 Light metal cylinder for internal combustion engine piston - has electrolytically deposited wear resistant coating of nickel@ or iron@ dispersed with boron carbide

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19904035524 DE4035524A1 (en) 1990-11-08 1990-11-08 Light metal cylinder for internal combustion engine piston - has electrolytically deposited wear resistant coating of nickel@ or iron@ dispersed with boron carbide

Publications (2)

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DE4035524A1 true DE4035524A1 (en) 1992-05-14
DE4035524C2 DE4035524C2 (en) 1993-05-27

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008055826A1 (en) * 2006-11-07 2008-05-15 BSH Bosch und Siemens Hausgeräte GmbH Compressor comprising a compressed gas-assisted piston

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1621129A1 (en) * 1967-09-09 1971-05-19 Audi Nsu Auto Union Ag Method and device for the galvanic application of a metal coating containing solid particles to light metal workpieces
US3640799A (en) * 1967-09-09 1972-02-08 Nsu Motorenwerke Ag Process for producing a wear-resistant surface on a workpiece
DE2348362A1 (en) * 1973-09-26 1975-04-24 Daimler Benz Ag PROCESS FOR COATING COMPONENTS SUBJECT TO WEAR
DE3216763C1 (en) * 1982-05-05 1983-10-20 Mahle Gmbh, 7000 Stuttgart Electrically produced nickel dispersion layer as running surface protection for drive parts of internal combustion engines
DE3246323A1 (en) * 1982-12-15 1984-06-20 Franz Rieger Metallveredelung, 7924 Steinheim Nickel bath

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1621129A1 (en) * 1967-09-09 1971-05-19 Audi Nsu Auto Union Ag Method and device for the galvanic application of a metal coating containing solid particles to light metal workpieces
US3640799A (en) * 1967-09-09 1972-02-08 Nsu Motorenwerke Ag Process for producing a wear-resistant surface on a workpiece
DE2348362A1 (en) * 1973-09-26 1975-04-24 Daimler Benz Ag PROCESS FOR COATING COMPONENTS SUBJECT TO WEAR
DE3216763C1 (en) * 1982-05-05 1983-10-20 Mahle Gmbh, 7000 Stuttgart Electrically produced nickel dispersion layer as running surface protection for drive parts of internal combustion engines
DE3246323A1 (en) * 1982-12-15 1984-06-20 Franz Rieger Metallveredelung, 7924 Steinheim Nickel bath

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008055826A1 (en) * 2006-11-07 2008-05-15 BSH Bosch und Siemens Hausgeräte GmbH Compressor comprising a compressed gas-assisted piston

Also Published As

Publication number Publication date
DE4035524C2 (en) 1993-05-27

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