EP0759519A2 - Piston ring for internal combustion engine - Google Patents
Piston ring for internal combustion engine Download PDFInfo
- Publication number
- EP0759519A2 EP0759519A2 EP96112522A EP96112522A EP0759519A2 EP 0759519 A2 EP0759519 A2 EP 0759519A2 EP 96112522 A EP96112522 A EP 96112522A EP 96112522 A EP96112522 A EP 96112522A EP 0759519 A2 EP0759519 A2 EP 0759519A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- piston
- piston ring
- ring
- coated
- hard carbon
- 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
Links
- 238000002485 combustion reaction Methods 0.000 title claims description 6
- 229910021385 hard carbon Inorganic materials 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 16
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 229910000838 Al alloy Inorganic materials 0.000 claims abstract description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 7
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 6
- 239000010432 diamond Substances 0.000 claims abstract description 6
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 6
- 239000010959 steel Substances 0.000 claims abstract description 6
- 229910000831 Steel Inorganic materials 0.000 claims abstract description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005268 plasma chemical vapour deposition Methods 0.000 claims abstract description 4
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 4
- 229910000906 Bronze Inorganic materials 0.000 claims abstract description 3
- 229910034327 TiC Inorganic materials 0.000 claims abstract description 3
- 239000010974 bronze Substances 0.000 claims abstract description 3
- 239000000919 ceramic Substances 0.000 claims abstract description 3
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 3
- 229910003465 moissanite Inorganic materials 0.000 claims abstract description 3
- 229910052749 magnesium Inorganic materials 0.000 claims abstract 2
- 238000000034 method Methods 0.000 claims description 16
- 238000004519 manufacturing process Methods 0.000 claims description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 6
- 229910001060 Gray iron Inorganic materials 0.000 claims description 6
- 230000002093 peripheral effect Effects 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims 1
- 238000007796 conventional method Methods 0.000 claims 1
- 239000011777 magnesium Substances 0.000 claims 1
- 229910052710 silicon Inorganic materials 0.000 claims 1
- 239000010703 silicon Substances 0.000 claims 1
- 229910001018 Cast iron Inorganic materials 0.000 abstract description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 230000003746 surface roughness Effects 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 23
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 230000002787 reinforcement Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000969 carrier Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012791 sliding layer Substances 0.000 description 2
- 229910018566 Al—Si—Mg Inorganic materials 0.000 description 1
- 206010010904 Convulsion Diseases 0.000 description 1
- 229910001208 Crucible steel Inorganic materials 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002178 crystalline material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000010285 flame spraying Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 238000010849 ion bombardment Methods 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
- C22C21/02—Alloys based on aluminium with silicon as the next major constituent
Definitions
- the present invention relates to a method for producing piston rings for internal combustion engines and a piston with piston rings produced according to the invention.
- the piston rings inserted into the piston ring grooves in the head of pistons for internal combustion engines have the task of sealing the gap between the piston head and the cylinder wall with respect to the combustion chamber.
- the piston ring slides on the one hand with its outer circumferential surface in constant resilient contact against the cylinder wall, on the other hand the piston ring slides oscillating in its piston ring groove due to the tilting movements of the piston, its flanks, i.e. the top and bottom of the piston ring alternately rest on the upper or lower groove flank of the piston ring groove.
- sliding layers on a piston ring and a cylinder wall
- these sliding layers e.g. Nickel
- the particulate inclusions can consist of silicon carbide or diamond.
- a cast-in piston ring carrier which generally consists of austenitic gray cast iron (cf. on this, Nüral Piston Manual, edition 1983, pages 128 to 131, in particular Fig. 166).
- ring carriers solve the problem of groove wear satisfactorily and are therefore also used on a large scale.
- a ring carrier is also associated with a considerable disadvantage, since it increases the piston weight and requires complex manufacturing technology both when the piston is cast and when it is mechanically machined, which overall causes considerable additional costs.
- piston ring carriers occupy a space in the piston head that restricts the arrangement of cooling channels and does not permit them where they would be most desired, namely as close as possible to the uppermost ring groove.
- Alternatives to ring carrier castings which are also known from the prior art, are, for example, reinforcements of the uppermost ring groove by cladding or welding alloys of the groove flanks and surface layers applied by flame spraying.
- these processes also prepare large manufacturing technology Problems and very high costs so that they do not offer a satisfactory solution.
- a piston ring blank is first produced from a material customary for piston rings, for example gray cast iron or steel, machined in a known manner, provided on the outer peripheral surface with a suitable coating as a running layer opposite the cylinder liner and, if necessary, by final fine machining in brought a ready-to-install condition.
- a material customary for piston rings for example gray cast iron or steel
- the piston ring thus obtained is then coated in the plasma CVD process with a doped hard carbon layer, preferably with the formula a-C: H, where a denotes an amorphous material and C and H denote carbon and hydrogen as material constituents.
- Such a doped, super hard carbon layer is also offered under the trade name Dynamant (registered trademark) and is based on the contribution by Dr. Knut Enke "Known with modified super hard carbon against wear, corrosion and friction", which appeared in the year booktrentechnik Volume 45, 1989, of the metal publishing house. It is based on this state of the art expressly referenced with respect to the superhard, doped carbon layer and its content is considered to be part of the disclosure of this application. Ion bombardment creates a carbon modification that is neither pure graphite nor pure diamond, but rather lies between these two materials.
- the general formula aC: H means that it is an amorphous (“a”), ie non-crystalline material, which consists essentially of carbon, which contains an unspecified proportion of hydrogen.
- the hard carbon layer provided according to the invention serves primarily as a running layer opposite the groove flanks of the piston ring grooves and not necessarily as a running layer opposite the cylinder liner which is usually made of gray cast iron.
- the hard carbon layer can also be applied to the outer circumferential surface of the piston ring, since it does not interfere there, it does not bring any significant additional advantages to gray cast iron liners.
- the reinforcement of the piston ring according to the invention on its top and bottom sides, that is to say on the surfaces which come into contact with the groove flanks of the piston ring groove brings very considerable advantages.
- the hard carbon layer in the pairing of the piston ring and the piston ring groove protects both the piston ring flanks and the groove flanks in the piston material against inadmissibly high wear, even when used in highly loaded diesel engines.
- the piston rings produced according to the invention to dispense with reinforcement of the piston ring grooves, which significantly reduces the manufacturing costs of the pistons.
- a ring carrier insert for the uppermost piston ring groove can therefore be dispensed with, which makes it possible for the first time to bring the cooling channel in the piston head into the proximity to the uppermost ring groove desired from a thermal point of view. This lowers the operating temperature in the area of the uppermost ring groove and thus also contributed effectively to the operational safety of the uppermost ring groove.
- the hard carbon layer provided according to the invention also has extremely good dry running properties.
- the outer circumferential surface of the piston ring can be coated in a known manner with chromium, molybdenum, nickel, diamond or similar materials in order to reduce the wear on the circumferential running surface of the piston ring.
- the method according to the invention can be modified such that the coating of the outer peripheral surface with a special running layer is omitted, but the piston ring is coated on all sides with the hard carbon layer.
- a light metal cylinder liner i.e. for cylinder running surfaces made of aluminum alloys, for example.
- the piston rings should be coated with an end face running layer, the pairing of a piston ring coated with hard carbon on all sides, which has no further coating from the running layer on the outer circumferential surface, with a light metal cylinder liner also leads to satisfactory sliding behavior on the end face of the ring .
- nitrided steel rings can be provided without any previous end face allocation.
- an electroplated chrome coating of the end face can also be provided.
- this relates to a piston which produces at least one piston according to the invention Has piston ring.
- the piston can be made according to the invention from a heat-resistant aluminum alloy, which in particular has a composition according to claim 11.
- Such an alloy is known from DE 43 26 978 A1.
- a piston made of such an aluminum alloy which is combined with a piston ring produced according to the invention, has decisive advantages.
- the heat-resistant aluminum alloy for the piston material proposed according to the invention is advantageous not only in terms of frictional wear, but also in particular in terms of the striking stress on the ring groove flanks under the action of the oscillating in the groove with the motorized piston movement in the ring groove Piston ring.
- Other preferred heat-resistant aluminum alloys are Al-Si-Mg alloys with relatively high levels of heavy metals such as Ni, Cu, Mn and Fe. With piston alloys of this type, even the uppermost ring groove can be worked directly into the piston material when using the piston rings produced according to the invention.
- the combination according to the invention of the piston ring produced according to the invention, which is coated with hard carbon, with a piston made of a heat-resistant aluminum alloy, which has an unreinforced annular groove offers a simple, inexpensive and, in every respect, advantageous solution to the problem mentioned at the beginning.
- a piston ring blank is first produced from steel using known methods and the surface is nitrided.
- the outer circumferential surface of the piston ring is provided with a running layer opposite the cylinder liner, which consists, for example, of electroplated chrome.
- the piston ring thus obtained is machined to a roughness of Rz ⁇ 1 ⁇ m ready for installation.
- the piston ring In order to provide the piston ring thus obtained with the coating according to the invention, it is coated on all sides in the plasma CVD process with a doped hard carbon layer which has a thickness of 3 ⁇ 0.5 ⁇ m.
- This hard carbon layer which is known under the trade name Dynamant and is defined by the general formula a-C: H, makes the surfaces of the piston ring particularly slidable against the groove flanks of the respective piston ring groove with which the ring is engaged. This protects both the piston ring flanks and the groove flanks from excessive wear.
- the piston provided according to the invention is cast from a heat-resistant aluminum alloy as claimed in claim 11 and described in DE 43 26 978 A1. With regard to the alloy composition, this document is also made the subject of the disclosure of this application.
- the piston ring grooves are pierced directly into the material of the piston in the course of the usual mechanical processing, without special flank reinforcement being provided.
- the piston rings according to the invention are inserted into the piston ring grooves of the piston in a conventional manner.
- piston rings produced according to the present invention have been described above for pairing with unreinforced grooves in an aluminum piston alloy, they can also be used advantageously for pairings in grooves in ferrous materials, for example in built pistons with a light metal lower part and an upper part made of steel or cast iron.
- the piston rings produced according to the invention can also be used in pairs with grooves in the known ring carriers. Here, too, they can extend the service life of the equal surfaces under extreme loads.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Pistons, Piston Rings, And Cylinders (AREA)
Abstract
Description
Die vorliegende Erfindung betrifft ein Verfahren zum Herstellen von Kolbenringen für Verbrennungsmotoren sowie einen Kolben mit erfindungsgemäß hergestellten Kolbenringen.The present invention relates to a method for producing piston rings for internal combustion engines and a piston with piston rings produced according to the invention.
Die im Kopf von Kolben für Verbrennungsmotoren in die Kolbenringnuten eingesetzten Kolbenringe haben die Aufgabe, den zwischen Kolbenkopf und Zylinderwand vorhandenen Spalt gegenüber dem Brennraum abzudichten. Bei der Auf- und Abbewegung des Kolbens gleitet der Kolbenring einerseits mit seiner äußeren Umfangsfläche in ständiger federnder Anlage gegen die Zylinderwand, andererseits gleitet der Kolbenring oszillierend in seiner Kolbenringnut, bedingt durch die Kippbewegungen des Kolbens, wobei seine Flanken, d.h. die Ober- und Unterseite des Kolbenringes, wechselnd an der oberen oder unteren Nutenflanke der Kolbenringnut anliegen.The piston rings inserted into the piston ring grooves in the head of pistons for internal combustion engines have the task of sealing the gap between the piston head and the cylinder wall with respect to the combustion chamber. When the piston moves up and down, the piston ring slides on the one hand with its outer circumferential surface in constant resilient contact against the cylinder wall, on the other hand the piston ring slides oscillating in its piston ring groove due to the tilting movements of the piston, its flanks, i.e. the top and bottom of the piston ring alternately rest on the upper or lower groove flank of the piston ring groove.
Abhängig von den Materialeigenschaften der jeweils gegeneinander laufenden Gleitpartner tritt bei dem einen oder dem anderen der Gleitpartner mehr oder weniger starker Verschleiß auf, der bei einem Trockenlauf zu sogenannten Fressern, zu Riefenbildung und letztlich zu einer Motorzerstörung führen kann (vgl. hierzu auch Nüral Kolben-Handbuch der Alcan Aluminiumwerk Nürnberg GmbH, 1983, Seiten 146 bis 151).Depending on the material properties of the sliding partners running against each other, one or the other of the sliding partners experiences more or less heavy wear, which can lead to so-called seizures, scoring and ultimately engine destruction if run dry (see also Nüral Piston Manual of Alcan Aluminumwerk Nürnberg GmbH, 1983, pages 146 to 151).
Um das Gleitverhalten gegenüber der Zylinderwand zu verbessern, die in der Regel aus Grauguß besteht, sind im Stand der Technik zahlreiche Oberflächenbeschichtungen für die Umfangsfläche der Kolbenringe entwickelt worden. So ist in der DE-AS 17 51 573 ein chrombeschichteter Kolbenring beschrieben, der an seiner Umfangsfläche teilweise zusätzlich mit Molybdän beschichtet ist. In dem Kolbenring-Handbuch der Goetzewerke Friedrich Goetze AG, 3. Auflage 1977, Seite 28 ff. sind darüber hinaus verschleißmindernde Schichten als Laufflächenbewehrungen vorgesehen, die aus Chrom, Molybdän, Keramik, aus Bronzeeinlagen oder auch aus zusammengesetzten Schichten verschiedener Werkstoffe bestehen können.In order to improve the sliding behavior in relation to the cylinder wall, which generally consists of gray cast iron, numerous surface coatings have been developed in the prior art for the peripheral surface of the piston rings. For example, DE-AS 17 51 573 describes a chrome-coated piston ring which is partially additionally coated with molybdenum on its peripheral surface. In the piston ring manual of Goetzewerke Friedrich Goetze AG, 3rd edition 1977, page 28 ff., Wear-reducing layers are also provided as tread reinforcements, which can consist of chrome, molybdenum, ceramic, bronze inlays or composite layers of different materials.
Aus der DE-OS 21 56 127 ist ferner ein elektrolytisches Aufbringen von Gleitschichten auf einen Kolbenring und eine Zylinderwandung bekannt, wobei diese Gleitschichten, z.B. Nickel, durch harte suspendierte Partikel in ihrer Abriebsfestigkeit erhöht werden. Die partikelförmigen Einlagerungen können hierbei aus Siliciumcarbid oder Diamant bestehen.From DE-OS 21 56 127 an electrolytic application of sliding layers on a piston ring and a cylinder wall is also known, these sliding layers, e.g. Nickel, can be increased in their abrasion resistance by hard suspended particles. The particulate inclusions can consist of silicon carbide or diamond.
Jüngere Entwicklungen bei Kolbenringen nützen die Möglichkeit der Abscheidung dünner Schichten aus Plasma (Plasma-PVD oder -CVD-Verfahren) (vgl. JP-A-62 58050). In dieser Druckschrift wird das Aufbringen von superharten Beschichtungen aus CBN, TiC, SiC, Al2O3 oder Diamant auf den Außenumfang von Kolbenringen beschrieben. Die Dicke dieser Superhart-Schichten ist relativ groß und beträgt 15 µm. Darüber hinaus ist auf der Superhart-Werkstoffbeschichtung als oberste Beschichtung eine äußere Schicht aus TiN mit einer geringeren Dicke von 3 µm aufgebracht.Recent developments in piston rings make use of the possibility of depositing thin layers of plasma (plasma PVD or CVD processes) (cf. JP-A-62 58050). This publication describes the application of superhard coatings made of CBN, TiC, SiC, Al 2 O 3 or diamond to the outer circumference of piston rings. The thickness of these super hard layers is relatively large and is 15 µm. In addition, an outer layer of TiN with a smaller thickness of 3 µm is applied to the super hard material coating as the top coating.
Obwohl auf dem Gebiet der Kolbenringe vielfache Anstrengungen unternommen wurden, den Verschleiß der Nutenflanken bei Verwendung von Aluminiumkolben zu reduzieren, konnte dies durch die obenbeschriebenen Entwicklungen nicht erreicht werden. Es hat sich im Gegenteil herausgestellt, daß gerade sogenannte Superhart-Schichten zwar den Kolbenring selbst vor einem Verschleiß schützen, daß derartige Verschleißschutzschichten jedoch aufgrund ihrer Härte bei Aluminiumlegierungen als Gleitpartner einen stärkeren Verschleiß bewirken. Insbesondere hat das vielfach verwendete TiN nur unzureichende Trockenlaufeigenschaften, so daß derartige Beschichtungen bei einem Schmierölmangel in kürzester Zeit erhebliche Laufflächenschäden erzeugen.Although many efforts have been made in the area of piston rings to reduce the wear of the groove flanks when using aluminum pistons, this could not be achieved by the developments described above. On the contrary, it turned out that just so-called super hard layers protect the piston ring itself from wear, but such wear protective layers cause greater wear due to their hardness with aluminum alloys as sliding partners. In particular, the widely used TiN has inadequate dry-running properties, so that coatings of this type produce considerable tread damage in a very short time when there is a lack of lubricating oil.
Aufgrund der obenbeschriebenen Probleme werden im Stand der Technik, insbesondere bei hochbeanspruchten Dieselkolben, die dem Brennraum am nächsten liegenden Nuten, die folglich den höchsten thermischen und mechanischen Beanspruchungen ausgesetzt sind, durch einen eingegossenen Kolbenringträger armiert, der in der Regel aus austenitischem Grauguß besteht (vgl. hierzu Nüral Kolben-Handbuch, Ausgabe 1983, Seiten 128 bis 131, insbesondere Bild 166).Due to the problems described above, in the prior art, particularly in the case of highly stressed diesel pistons, the grooves closest to the combustion chamber, which are consequently exposed to the highest thermal and mechanical stresses, are reinforced by a cast-in piston ring carrier, which generally consists of austenitic gray cast iron (cf. on this, Nüral Piston Manual, edition 1983, pages 128 to 131, in particular Fig. 166).
Derartige Ringträger lösen zwar das Problem des Nutenverschleißes auf befriedigende Weise und werden deshalb auch in großem Umfang angewendet. Jedoch ist mit derartigen Ringträgern auch ein erheblicher Nachteil verbunden, da durch sie das Kolbengewicht erhöht wird und sowohl beim Gießen des Kolbens als auch bei dessen mechanischer Bearbeitung eine aufwendige Fertigungstechnologie erforderlich ist, was insgesamt erhebliche Mehrkosten verursacht. Kolbenringträger nehmen darüber hinaus im Kolbenkopf einen Raum ein, der die Anordnung von Kühlkanälen einschränkt und gerade dort nicht zuläßt, wo diese am meisten gewünscht wären, nämlich in möglichst großer Nähe zur obersten Ringnut. Aus dem Stand der Technik ebenfalls bekannte Alternativen zu Ringträgereingußteilen sind beispielsweise Armierungen der obersten Ringnut durch Auftragsschweißen oder schweißtechnische Auflegierungen der Nutenflanken sowie durch Flammspritzen aufgetragene Oberflächenschichten. Jedoch bereiten auch diese Verfahren große fertigungstechnische Probleme und sehr hohe Kosten, so daß diese keine befriedigende Lösung bieten.Such ring carriers solve the problem of groove wear satisfactorily and are therefore also used on a large scale. However, such a ring carrier is also associated with a considerable disadvantage, since it increases the piston weight and requires complex manufacturing technology both when the piston is cast and when it is mechanically machined, which overall causes considerable additional costs. In addition, piston ring carriers occupy a space in the piston head that restricts the arrangement of cooling channels and does not permit them where they would be most desired, namely as close as possible to the uppermost ring groove. Alternatives to ring carrier castings, which are also known from the prior art, are, for example, reinforcements of the uppermost ring groove by cladding or welding alloys of the groove flanks and surface layers applied by flame spraying. However, these processes also prepare large manufacturing technology Problems and very high costs so that they do not offer a satisfactory solution.
Es ist das der Erfindung zugrundeliegende Problem (Aufgabe), einen Kolbenring zu schaffen, der kostengünstig hergestellt werden kann, selber verschleißbeständig ist und insbesondere in der obersten Nut eines hochbelasteten Leichtmetall-Kolbens eingesetzt werden kann, ohne daß die Flanken der Nut einer besonderen Armierung bedürfen.It is the problem underlying the invention (task) to create a piston ring that can be manufactured inexpensively, is itself wear-resistant and can be used in particular in the uppermost groove of a highly loaded light metal piston without the flanks of the groove requiring special reinforcement .
Die Lösung dieser Aufgabe erfolgt durch einen Kolben, der gemäß Anspruch 1 hergestellt ist.This object is achieved by a piston which is produced according to claim 1.
Bei dem erfindungsgemäßen Herstellungsverfahren für Kolbenringe wird zunächst ein Kolbenringrohling aus einem für Kolbenringe gebräuchlichen Werkstoff, beispielsweise Grauguß oder Stahl, hergestellt, in bekannter Weise zerspanend bearbeitet, auf der äußeren Umfangsfläche mit einer geeigneten Beschichtung als Laufschicht gegenüber der Zylinderbüchse versehen und erforderlichenfalls durch abschließendes Feinstbearbeiten in einen einbaufertigen Zustand gebracht.In the production method for piston rings according to the invention, a piston ring blank is first produced from a material customary for piston rings, for example gray cast iron or steel, machined in a known manner, provided on the outer peripheral surface with a suitable coating as a running layer opposite the cylinder liner and, if necessary, by final fine machining in brought a ready-to-install condition.
Erfindungsgemäß erfolgt anschließend ein Beschichten des so erhaltenen Kolbenringes im Plasma-CVD-Verfahren mit einer dotierten Hartkohlenstoffschicht, vorzugsweise mit der Formel a-C:H, wobei a ein amorphes Material bezeichnet und C und H Kohlenstoff und Wasserstoff als Materialbestandteile bezeichnen.According to the invention, the piston ring thus obtained is then coated in the plasma CVD process with a doped hard carbon layer, preferably with the formula a-C: H, where a denotes an amorphous material and C and H denote carbon and hydrogen as material constituents.
Eine derartige dotierte, superharte Kohlenstoffschicht wird auch unter dem Handelsnamen Dynamant (eingetragene Marke) angeboten und ist aus dem Beitrag von Dr. Knut Enke "Mit modifiziertem superhartem Kohlenstoff gegen Verschleiß, Korrosion und Reibung" bekannt, der im Jahrbuch Oberflächentechnik Band 45, 1989, des Metall-Verlages erschienen ist. Auf diesen Stand der Technik wird hiermit hinsichtlich der superharten, dotierten Kohlenstoffschicht ausdrücklich Bezug genommen und dessen Inhalt wird als Bestandteil der Offenbarung dieser Anmeldung angesehen. Durch Ionenbeschuß entsteht hier eine Kohlenstoffmodifikation, die weder reiner Graphit noch reiner Diamant ist, sondern vielmehr zwischen diesen beiden Materialien liegt. Die allgemeine Formel a-C:H bedeutet, daß es sich um ein amorphes ("a") also nicht-kristallines Material handelt, das im wesentlichen aus Kohlenstoff besteht, der einen nicht näher angegebenen Anteil an Wasserstoff enthält.Such a doped, super hard carbon layer is also offered under the trade name Dynamant (registered trademark) and is based on the contribution by Dr. Knut Enke "Known with modified super hard carbon against wear, corrosion and friction", which appeared in the year book Oberflächentechnik Volume 45, 1989, of the metal publishing house. It is based on this state of the art expressly referenced with respect to the superhard, doped carbon layer and its content is considered to be part of the disclosure of this application. Ion bombardment creates a carbon modification that is neither pure graphite nor pure diamond, but rather lies between these two materials. The general formula aC: H means that it is an amorphous ("a"), ie non-crystalline material, which consists essentially of carbon, which contains an unspecified proportion of hydrogen.
Die erfindungsgemäß vorgesehene Hartkohlenstoffschicht dient in erster Linie als Laufschicht gegenüber den Nutenflanken der Kolbenringnuten und nicht notwendigerweise als Laufschicht gegenüber der üblicherweise aus Grauguß bestehenden Zylinderbüchse. Zwar kann die Hartkohlenstoffschicht auch auf die äußere Umfangsfläche des Kolbenringes aufgebracht werden, da sie dort nicht stört, jedoch bringt sie dort bei Laufbüchsen aus Grauguß keine wesentlichen zusätzlichen Vorteile. Andererseits bringt die erfindungsgemäße Bewehrung des Kolbenringes an seiner Oberseite und seiner Unterseite, d.h. an den Flächen, die mit den Nutenflanken der Kolbenringnut in Berührung treten, ganz erhebliche Vorteile. Die Hartkohlenstoffschicht schützt nämlich in der Paarung von Kolbenring und Kolbenringnut sowohl die Kolbenringflanken als auch die Nutenflanken im Kolbenwerkstoff vor unzulässig hohem Verschleiß, und dies selbst bei einem Einsatz in hochbelasteten Dieselmotoren. Hierbei ist es mit den erfindungsgemäß hergestellten Kolbenringen möglich, auf eine Bewehrung der Kolbenringnuten zu verzichten, was die Herstellungskosten der Kolben entscheidend verringert. Auf einen Ringträgereinsatz für die oberste Kolbenringnut kann demnach verzichtet werden, wodurch es erstmals möglich wird, den Kühlkanal im Kolbenkopf in die unter thermischen Gesichtspunkten gewünschte Nähe zur obersten Ringnut zu bringen. Hierdurch wird die Betriebstemperatur im Bereich der obersten Ringnut gesenkt und somit zusätzlich wirksam zur Betriebssicherheit der obersten Ringnut beigetragen. Schließlich besitzt die erfindungsgemäß vorgesehene Hartkohlenstoffschicht auch außerordentlich gute Trockenlaufeigenschaften.The hard carbon layer provided according to the invention serves primarily as a running layer opposite the groove flanks of the piston ring grooves and not necessarily as a running layer opposite the cylinder liner which is usually made of gray cast iron. Although the hard carbon layer can also be applied to the outer circumferential surface of the piston ring, since it does not interfere there, it does not bring any significant additional advantages to gray cast iron liners. On the other hand, the reinforcement of the piston ring according to the invention on its top and bottom sides, that is to say on the surfaces which come into contact with the groove flanks of the piston ring groove, brings very considerable advantages. The hard carbon layer in the pairing of the piston ring and the piston ring groove protects both the piston ring flanks and the groove flanks in the piston material against inadmissibly high wear, even when used in highly loaded diesel engines. Here it is possible with the piston rings produced according to the invention to dispense with reinforcement of the piston ring grooves, which significantly reduces the manufacturing costs of the pistons. A ring carrier insert for the uppermost piston ring groove can therefore be dispensed with, which makes it possible for the first time to bring the cooling channel in the piston head into the proximity to the uppermost ring groove desired from a thermal point of view. This lowers the operating temperature in the area of the uppermost ring groove and thus also contributed effectively to the operational safety of the uppermost ring groove. Finally, the hard carbon layer provided according to the invention also has extremely good dry running properties.
Vorteilhafte Ausführungsformen des erfindungsgemäßen Verfahrens sind durch die Unteransprüche 2 bis 8 gekennzeichnet.Advantageous embodiments of the method according to the invention are characterized by subclaims 2 to 8.
So kann das Beschichten der äußeren Umfangsfläche des Kolbenringes in bekannter Weise mit Chrom, Molybdän, Nickel, Diamant oder ähnlichen Materialien erfolgen, um den Verschleiß der Umfangslauffläche des Kolbenringes zu verringern.Thus, the outer circumferential surface of the piston ring can be coated in a known manner with chromium, molybdenum, nickel, diamond or similar materials in order to reduce the wear on the circumferential running surface of the piston ring.
Nach einer weiteren vorteilhaften Ausführungsform kann das erfindungsgemäße Verfahren so abgeändert werden, daß das Beschichten der äußeren Umfangsfläche mit einer speziellen Laufschicht weggelassen wird, jedoch der Kolbenring allseitig mit der Hartkohlenstoffschicht beschichtet wird. Eine derartige Ausführungsform eignet sich insbesondere bei Paarung mit einer Leichtmetallzylinderlaufbüchse, d.h. bei Zylinderlaufflächen aus beispielsweise Aluminiumlegierungen. Während bei den üblichen Grauguß-Zylinderbüchsen die Kolbenringe mit einer stirnseitigen Laufschicht beschichtet sein sollten, führt die Paarung eines allseitig hartkohlenstoffbeschichteten Kolbenringes, der keine weitere Beschichtung aus Laufschicht auf der äußeren Umfangsfläche aufweist, mit einer Leichtmetallzylinderlaufbüchse auch auf der Stirnseite des Ringes zu einem zufriedenstellenden Gleitverhalten. Hierbei können nitrierte Stahlringe ohne jede vorhergehende Stirnflächenbelegung vorgesehen werden. In Einzelfällen kann zusätzlich eine galvanische Chrombeschichtung der Stirnfläche vorgesehen werden.According to a further advantageous embodiment, the method according to the invention can be modified such that the coating of the outer peripheral surface with a special running layer is omitted, but the piston ring is coated on all sides with the hard carbon layer. Such an embodiment is particularly suitable when paired with a light metal cylinder liner, i.e. for cylinder running surfaces made of aluminum alloys, for example. While in conventional cast iron cylinder liners, the piston rings should be coated with an end face running layer, the pairing of a piston ring coated with hard carbon on all sides, which has no further coating from the running layer on the outer circumferential surface, with a light metal cylinder liner also leads to satisfactory sliding behavior on the end face of the ring . In this case, nitrided steel rings can be provided without any previous end face allocation. In individual cases, an electroplated chrome coating of the end face can also be provided.
Nach einem weiteren Aspekt der Erfindung betrifft diese einen Kolben, der mindestens einen erfindungsgemäß hergestellten Kolbenring aufweist. Hierbei kann der Kolben erfindungsgemäß aus einer warmfesten Aluminiumlegierung hergestellt sein, die insbesondere eine Zusammensetzung gemäß Anspruch 11 aufweist.According to a further aspect of the invention, this relates to a piston which produces at least one piston according to the invention Has piston ring. Here, the piston can be made according to the invention from a heat-resistant aluminum alloy, which in particular has a composition according to claim 11.
Eine derartige Legierung ist zwar aus der DE 43 26 978 A1 bekannt. Jedoch hat sich herausgestellt, daß ein Kolben aus einer derartigen Aluminiumlegierung, der mit einem erfindungsgemäß hergestellten Kolbenring kombiniert wird, entscheidende Vorteile bringt. Die erfindungsgemäß vorgeschlagene, warmfeste Aluminiumlegierung für den Kolbenwerkstoff ist nicht nur in Hinblick auf den Reibverschleiß vorteilhaft, sondern insbesondere auch in Hinblick auf die schlagende Beanspruchung der Ringnutenflanken unter der Einwirkung des sich in der Nut oszillierend mit der motorischen Kolbenbewegung in der Ringnut auf- und abbewegenden Kolbenringes. Andere bevorzugte, warmfeste Aluminiumlegierungen sind Al-Si-Mg-Legierungen mit relativ hohen Gehalten an Schwermetallen wie Ni, Cu, Mn und Fe. Bei derartigen Kolbenlegierungen kann bei Verwendung der erfindungsgemäß hergestellten Kolbenringe selbst die oberste Ringnut direkt in den Kolbenwerkstoff eingearbeitet werden. Somit bietet die erfindungsgemäße Kombination des erfindungsgemäß hergestellten Kolbenringes, der hartkohlenstoffbeschichtet ist, mit einem Kolben aus einer warmfesten Aluminiumlegierung, der eine unbewehrte Ringnut aufweist, eine einfache, kostengünstige und in jeder Hinsicht vorteilhafte Lösung des eingangs genannten Problemes.Such an alloy is known from DE 43 26 978 A1. However, it has been found that a piston made of such an aluminum alloy, which is combined with a piston ring produced according to the invention, has decisive advantages. The heat-resistant aluminum alloy for the piston material proposed according to the invention is advantageous not only in terms of frictional wear, but also in particular in terms of the striking stress on the ring groove flanks under the action of the oscillating in the groove with the motorized piston movement in the ring groove Piston ring. Other preferred heat-resistant aluminum alloys are Al-Si-Mg alloys with relatively high levels of heavy metals such as Ni, Cu, Mn and Fe. With piston alloys of this type, even the uppermost ring groove can be worked directly into the piston material when using the piston rings produced according to the invention. Thus, the combination according to the invention of the piston ring produced according to the invention, which is coated with hard carbon, with a piston made of a heat-resistant aluminum alloy, which has an unreinforced annular groove, offers a simple, inexpensive and, in every respect, advantageous solution to the problem mentioned at the beginning.
Nachfolgend wird die vorliegende Erfindung rein beispielhaft anhand einer vorteilhaften Ausführungsform beschrieben.The present invention is described below purely by way of example using an advantageous embodiment.
Zur Herstellung des erfindungsgemäßen Kolbenringes wird zunächst ein Kolbenringrohling nach bekannten Verfahren aus Stahl hergestellt und in seiner Oberfläche nitriert.To produce the piston ring according to the invention, a piston ring blank is first produced from steel using known methods and the surface is nitrided.
In einem nachfolgenden Schritt wird die äußere Umfangsfläche des Kolbenringes mit einer Laufschicht gegenüber der Zylinderbüchse versehen, die beispielsweise aus galvanisch aufgebrachtem Chrom besteht. Hierauf wird der so erhaltene Kolbenring auf eine Rauhigkeit von Rz ≤ 1 µm einbaufertig feinstbearbeitet.In a subsequent step, the outer circumferential surface of the piston ring is provided with a running layer opposite the cylinder liner, which consists, for example, of electroplated chrome. Thereupon the piston ring thus obtained is machined to a roughness of Rz ≤ 1 µm ready for installation.
Um den so erhaltenen Kolbenring mit der erfindungsgemäßen Beschichtung zu versehen, wird dieser allseitig im Plasma-CVD-Verfahren mit einer dotierten Hartkohlenstoffschicht überzogen, die eine Dicke von 3 ± 0,5 µm aufweist. Diese Hartkohlenstoffschicht, die unter dem Handelsnamen Dynamant bekannt und durch die allgemeine Formel a-C:H definiert ist, macht die Oberflächen des Kolbenringes in besonderer Weise gleitfähig gegenüber den Nutenflanken der jeweiligen Kolbenringnut, mit der der Ring in Eingriff steht. Hierdurch werden sowohl die Kolbenringflanken wie auch die Nutenflanken vor unzulässig hohem Verschleiß geschützt.In order to provide the piston ring thus obtained with the coating according to the invention, it is coated on all sides in the plasma CVD process with a doped hard carbon layer which has a thickness of 3 ± 0.5 μm. This hard carbon layer, which is known under the trade name Dynamant and is defined by the general formula a-C: H, makes the surfaces of the piston ring particularly slidable against the groove flanks of the respective piston ring groove with which the ring is engaged. This protects both the piston ring flanks and the groove flanks from excessive wear.
Der erfindungsgemäß vorgesehene Kolben wird aus einer warmfesten Aluminiumlegierung gegossen, wie sie in Anspruch 11 beansprucht und in der DE 43 26 978 A1 beschrieben ist. Hinsichtlich der Legierungszusammensetzung wird diese Druckschrift ebenfalls zum Gegenstand der Offenbarung dieser Anmeldung gemacht. Nach dem Gießen des Kolbens werden im Zuge der üblichen mechanischen Bearbeitung die Kolbenringnuten direkt in den Werkstoff des Kolbens eingestochen, ohne daß eine besondere Flankenarmierung vorgesehen wird. Die erfindungsgemäßen Kolbenringe werden auf herkömmliche Weise in die Kolbenringnuten des Kolbens eingesetzt.The piston provided according to the invention is cast from a heat-resistant aluminum alloy as claimed in claim 11 and described in DE 43 26 978 A1. With regard to the alloy composition, this document is also made the subject of the disclosure of this application. After casting the piston, the piston ring grooves are pierced directly into the material of the piston in the course of the usual mechanical processing, without special flank reinforcement being provided. The piston rings according to the invention are inserted into the piston ring grooves of the piston in a conventional manner.
Die gemäß der vorliegenden Erfindung hergestellten Kolbenringe wurden zwar vorstehend für eine Paarung mit unbewehrten Nuten in einer Aluminiumkolbenlegierung beschrieben, sie sind jedoch auch auf vorteilhafte Weise für Paarungen in Nuten in Eisenwerkstoffen einsetzbar, z.B. bei gebauten Kolben mit einem Leichtmetallunterteil und einem Oberteil aus Stahl oder Grauguß. Auch können die erfindungsgemäß hergestellten Kolbenringe in Paarungen mit Nuten in den bekannten Ringträgern eingesetzt werden. Auch hier können sie unter extremen Belastungen Standzeitverlängerungen der Gleichtflächen bewirken.Although the piston rings produced according to the present invention have been described above for pairing with unreinforced grooves in an aluminum piston alloy, they can also be used advantageously for pairings in grooves in ferrous materials, for example in built pistons with a light metal lower part and an upper part made of steel or cast iron. The piston rings produced according to the invention can also be used in pairs with grooves in the known ring carriers. Here, too, they can extend the service life of the equal surfaces under extreme loads.
Claims (16)
dadurch gekennzeichnet, daß
die dotierte Hartkohlenstoffschicht folgende Zusammensetzung aufweist:
a-C:H,
wobei
characterized in that
the doped hard carbon layer has the following composition:
Oh,
in which
dadurch gekennzeichnet, daß
das Beschichten des Kolbenringes mit einer Hartkohlenstoffschicht allseitig erfolgt.The method of claim 1 or 2,
characterized in that
the piston ring is coated on all sides with a hard carbon layer.
dadurch gekennzeichnet, daß
der Kolbenring vor dem Beschichten mit der Hartkohlenstoffschicht feinstbearbeitet wird, vorzugsweise auf eine Rauhigkeit ≤ 1 µm.Method according to one of the preceding claims,
characterized in that
the piston ring is finely machined before coating with the hard carbon layer, preferably to a roughness of ≤ 1 µm.
dadurch gekennzeichnet, daß
das Beschichten des Kolbenringes mit einer Schichtdicke von mindestens 2,5 µm, vorzugsweise von 3 ± 0,5 µm erfolgt.Method according to one of the preceding claims,
characterized in that
the piston ring is coated with a layer thickness of at least 2.5 μm, preferably 3 ± 0.5 μm.
dadurch gekennzeichnet, daß
der Kolbenring aus Grauguß und vorzugsweise aus Stahl hergestellt wird.Method according to one of the preceding claims,
characterized in that
the piston ring is made of gray cast iron and preferably steel.
dadurch gekennzeichnet, daß
die Oberfläche des Kolbenringes vor dem Beschichten nitriert wird.Method according to one of the preceding claims,
characterized in that
the surface of the piston ring is nitrided before coating.
dadurch gekennzeichnet, daß
zur Bildung einer Laufschicht das Beschichten der äußeren Umfangsfläche des Kolbenringes mit einem oder mehreren der folgenden Materialien erfolgt: Chrom, Molybdän, Keramik, Bronze, Nickel, SiC, TiC, Al2O3, oder Diamant.Method according to one of the preceding claims,
characterized in that
To form a running layer, the outer circumferential surface of the piston ring is coated with one or more of the following materials: chromium, molybdenum, ceramic, bronze, nickel, SiC, TiC, Al 2 O 3 , or diamond.
dadurch gekennzeichnet, daß
der Verfahrensschritt des Beschichtens der äußeren Umfangsfläche des Kolbenringes mit einer Laufschicht weggelassen wird.Method according to claim 3,
characterized in that
the step of coating the outer peripheral surface of the piston ring with a running layer is omitted.
dadurch gekennzeichnet, daß
die Aluminiumlegierung folgende Zusammensetzung aufweist:
characterized in that
the aluminum alloy has the following composition:
dadurch gekennzeichnet, daß
die Ringnut des Kolbens direkt in den Kolbenwerkstoff eingearbeitet ist.Piston according to one of the preceding claims 11 or 12,
characterized in that
the ring groove of the piston is machined directly into the piston material.
dadurch gekennzeichnet, daß
dieser keinen Kolbenring-Trägereinsatz aufweist.Piston according to one of the preceding claims 11 to 13,
characterized in that
this has no piston ring carrier insert.
dadurch gekennzeichnet, daß
dieser in der Nähe seiner obersten Ringnut einen Kühlkanal im Kolbenkopf aufweist.Piston according to claim 14,
characterized in that
this has a cooling channel in the piston head near its uppermost annular groove.
dadurch gekennzeichnet, daß
der engste Abstand zwischen Kühlkanalwand und dem Nutengrund der obersten Ringnut nicht mehr als 3 mm beträgt.Piston according to claim 15,
characterized in that
the closest distance between the cooling channel wall and the groove base of the uppermost ring groove is not more than 3 mm.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE19530511 | 1995-08-18 | ||
DE19530511A DE19530511C1 (en) | 1995-08-18 | 1995-08-18 | Pistons for internal combustion engines |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0759519A2 true EP0759519A2 (en) | 1997-02-26 |
EP0759519A3 EP0759519A3 (en) | 1997-03-12 |
EP0759519B1 EP0759519B1 (en) | 2002-10-23 |
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Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP96112522A Expired - Lifetime EP0759519B1 (en) | 1995-08-18 | 1996-08-02 | Piston ring for internal combustion engine |
Country Status (2)
Country | Link |
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EP (1) | EP0759519B1 (en) |
DE (2) | DE19530511C1 (en) |
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EP1136730A3 (en) * | 2000-03-23 | 2003-11-05 | Federal-Mogul Burscheid GmbH | Piston ring with a wear resistant layer and wear resistant layer for a piston ring |
US6726216B2 (en) * | 2001-06-01 | 2004-04-27 | Federal-Mogul Friedberg Gmbh | Piston ring with oxide-nitride composite layer |
EP1479946A3 (en) * | 2003-05-23 | 2005-01-12 | Nissan Motor Company, Limited | Piston for internal combustion engine |
CN1325822C (en) * | 2003-05-23 | 2007-07-11 | 日产自动车株式会社 | Piston for internal combustion engine |
US7406940B2 (en) | 2003-05-23 | 2008-08-05 | Nissan Motor Co., Ltd. | Piston for internal combustion engine |
US8206035B2 (en) | 2003-08-06 | 2012-06-26 | Nissan Motor Co., Ltd. | Low-friction sliding mechanism, low-friction agent composition and method of friction reduction |
US8575076B2 (en) | 2003-08-08 | 2013-11-05 | Nissan Motor Co., Ltd. | Sliding member and production process thereof |
US7650976B2 (en) | 2003-08-22 | 2010-01-26 | Nissan Motor Co., Ltd. | Low-friction sliding member in transmission, and transmission oil therefor |
Also Published As
Publication number | Publication date |
---|---|
DE19530511C1 (en) | 1997-02-20 |
EP0759519B1 (en) | 2002-10-23 |
EP0759519A3 (en) | 1997-03-12 |
DE59609811D1 (en) | 2002-11-28 |
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