• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    sliding element, in particular piston ring having a shell, and process for producing a sliding element. a sliding member, in particular piston ring, has on at least one sliding surface, from the inside out, a coating having a metal-containing adhesive layer and a ta-c type dlc layer at least 10 µm thick. > m
    公开号:BR112012016440B1
    申请号:R112012016440-6
    申请日:2011-10-13
    公开日:2019-10-15
    发明作者:Marcus Kennedy
    申请人:Federal-Mogul Burscheid Gmbh；
    IPC主号:
    专利说明:

    “SLIDING ELEMENT, IN PARTICULAR PISTON RING, HAVING A COATING, AND PROCESS FOR PRODUCTION OF A SLIDING ELEMENT”
    Technique field
    The invention relates to a sliding element, in particular a piston ring, having a coating on at least one bearing surface, and a process for producing a sliding element.
    Sliding elements, such as, for example, piston rings, pistons or cylinder liners, in combustion engines, must work for a long period of life and also with as little friction as possible and little wear. Friction, which in combustion engines is directly associated with fuel consumption, can be kept low by means of DLC (diamond-like carbon) coatings. In addition, layer thicknesses of up to 40 pm can be achieved in principle. However, with layer thicknesses greater than 5 pm there is a problem that the layer properties, for example, with respect to the structure and composition of the layer, change in a way that the required service life is not achieved. This is also true for layer thicknesses below 5 pm.
    The objective of the present invention is to provide a sliding element having an adhesive layer containing metal, as well as a DLC type ta-C coating with suitable layer thickness, in order to ensure minimal losses of frictional power over the entire life of the component.
    State of the art
    Diamond-like layers (DLC) is a metastable form of amorphous carbon with a significant proportion of hybridized sp 3 carbon. The supply of diamond-like layers on various substrates in order to develop new components is carried out today through different processes. The most well-known processes, by means of which sliding elements capable of being mass-produced can be coated, are PA-CVD, cathodic deposition and arc vapor deposition process under vacuum (DE4006456). The layer systems that can be provided through these conventionally contain hydrogen in the case of PA-CVD and are free of hydrogen in the case of processes
    2/8 cathodic deposition and arc vapor deposition under vacuum. A summary of possible DLC layer systems can be found on the VDI Guideline 2840 Carbon films.
    Table 1 lists the documents that contribute to the state of the art 5 within the context of this patent application. A distinction should be made in this list between publications that are relevant to the process and those that are relevant to the product.
    Number Year Type Important features DE 3901401 1989Method for controlling an arc vapor deposition process under vacuum DE 4006456 nineteen ninetyProcess to control vacuum arc discharge DE 10240337 2002 Production ofDLC / process Device for separating particles, in which the absorption electrode is placed in the shadow of the plasma that is produced and a magnetic (electro) field is generated in order to accelerate magnetic charge chargers. DE 19850217 /US 6558757 1998Vacuum coating process in which material is ionized from a target by means of a laser and reacts with a gas that is stored in the pores and is subsequently deposited on a substrate EP 1829986 2010Process for machining surfaces having a hard carbon coating EP 0724023 1996Amorphous, hard, hydrogen-free carbon layer (<0.5 at% H,
    3/8
    modulus of elasticity> 400 GPa, hardness> 40GPa, maximum layer thickness: a few pm, produced by a vacuum arc shaft. IN102005063123B3 2005Sliding element having wear protection and bearing layer, where the bearing layer contains hydrogen and nanocrystalline carbide phases. Number Year Type Important features IN102008016864B3 2008Piston ring having a DLC coating with a 3-layer system: adhesive layer, amorphous carbon layer containing metal, amorphous metal-free carbon layer, resistance> 5000 ohms US 6231956 1997Wear-resistant layer system consisting of a titanium alloy substrate, an intermediate layer and an amorphous carbon layer. DE 19735962 1997DLC inner liner bushing containing hydrogen. DE 19850218 1998Device and process for coating substrates in a vacuum with a special absorption electrode that is arranged so that particles do not deposit directly on the substrate. WO 2006125683 Al 2006Piston ring having 3 system
    4/8
    layers consisting of a first layer of the IVB, VB or VIB group (<1 pm), a second layer of a diamond-like nanocomposite (<5 pm) and a third diamond-like layer (layer thickness 0.1 pm to 10 pm) DE 102008022039 2008Anti-wear coating of amorphous carbon layer having oxygen content of 0.5 to% to 25 to%.
    EP 0724023 is known as a hydrogen-free DLC coating (<0.5 at%) having a frictional performance under non-lubricated conditions, as well as with reduced use of lubricant. This layer has a hardness of> 40 GPa and an elastic modulus of> 400 GPa with a maximum thickness of a few pm.
    DE 10 2005 063 123 B3 has a sliding element having a DLC coating with good operating performance. Due to the fact that the service life is very short, permanently low friction cannot be ensured over the entire life of the sliding element.
    DE 10 2008 016 864 B3 refers to a sliding element having a multilayer coating that comprises, from the inside out, an adhesive layer, a DLC layer containing metal and hydrogen and a DLC layer containing metal-free hydrogen.
    DE 197 35 962 A1 describes a guide bush and a process for forming a hard carbon film on the inner surface of the guide bush, in which a hydrogenated hard amorphous carbon film is formed on the inner surface by means of the CVD plasma process.
    WO 2006/125683 A1 describes a piston ring that comprises, from the inside out, a layer containing an element of the group IVB, VB or VIB, an intermediate layer having a diamond-like nanocomposite DLC layer.
    5/8
    It is known that good wear values are achieved when the content of hybridized sp 3 carbon atoms is as high as possible, in particular greater than 60 to%. Such layers are referred to as ta-C layers and can be produced by conventional cathodic bombardment processes or by so-called vacuum arc processes (see documents DE 40 40 456 Cl and DE 198 50 218 Cl in Table 1 in this regard). Hydrogen-free ta-C coatings can be produced with a thickness of a few micrometers as layers containing oxygen (see in this respect the teachings of DE 10 2008 022 039 Al from table 1) and layers free of oxygen and hydrogen (see this EP 0 724 023 A1).
    In this context, PVD coatings based on hard material are also known, which most often contain chromium nitride. Although these layers have the required wear resistance, they do not have the necessary low friction.
    Description of the Invention
    Against these grounds, the main objective of the invention is to provide a sliding element that is further improved with respect to the combination of friction coefficients and wear properties. A process for producing such a sliding element is also provided.
    Consequently, the sliding element according to the invention has at least one sliding surface, from inside to outside, a coating having an adhesive layer containing metal, and a DLC layer of the type ta-C with a thickness of at least 10 pm . the adhesive layer containing metal advantageously ensures not only the adhesion of the DLC layer, but also equalizes the internal stresses that occur in this layer. The minimum layer thickness of 10 pm ensures that the required wear resistance is obtained and additionally allows good friction values over the entire life of the engine. In particular, the wear behavior can be adapted both to the sliding element, in particular the piston ring itself, and to the sliding partner, for example, the piston jacket. The productivity of the coating according to the invention is ensured by the process steps described below, in particular the cleaning of the surface to be coated through a cathodic bombardment process, as well as the production process
    6/8 described for the adhesive layer and the DLC layer. Consequently, a significantly improved sliding element can be provided.
    One of the central requirements for the sliding element, especially the piston ring, is to provide a coating that lasts for the life of the element in order to ensure minimal losses of frictional power throughout the operation. In research on an engine it was found that, although the wear achieved by the piston ring coated with the AISi taC system / raceway was approximately 60% lower compared to piston rings with DLC coating containing hydrogen, a layer thickness of at least 10 pm is required depending on usage and sliding contact surfaces. The thickness of the coating as a whole is preferably greater than 20 µm.
    Preferred embodiments will be found in the other claims.
    In order to ensure sufficient layer adhesion, particularly in the case of ta-C layer thicknesses greater than a few pm, it is still necessary to provide an adhesive layer containing metal between the substrate and the DLC layer. Currently, based on the initial findings, it is preferable that the adhesive layer contains at least the following materials: chromium, titanium, chromium nitride and tungsten.
    The thickness of 0.1 pm to 1.0 pm was also found to be advantageous for the adhesive layer.
    Particularly good properties were still found when the DLC layer is substantially free of oxygen and / or hydrogen, which means that it contains a content of each of these elements of less than 0.5 to%.
    The hardness and modulus of elasticity of the DLC layer also affect the tribological behavior of the piston ring. During tests, the surface hardness of not more than 55 GPa with an elastic modulus of not more than 550 GPa was found to be advantageous for the coating.
    In contrast to the state of the art, it was also found, in research outside and inside the engine, that particularly good wear values were achieved when the DLC layer has a sp 3 hybridized carbon atoms content of at least 40 at%.
    A purposeful reduction in the sp 3 content at 1 pm to 3 pm outside the layer close to the edges leads to a reduction in friction in operation and in the operating period itself. In preliminary tests outside the engine, it was found that a
    7/8 another embodiment in which the outside 1 pm to 3 pm close to the edge were doped resulted in further improvement in terms of heat resistance and combustion mark behavior under insufficient lubrication conditions at maximum housings up to 700N.
    The outer region of the DLC layer close to the edge having a thickness from 1 pm to 3 pm can advantageously be doped with elements such as boron, oxygen, and / or silicon.
    In order, in particular, to ensure low friction value, the bearing surface of the sliding element must be as smooth as possible. The DLC layer provided here preferably has a roughness depth of Rz <6 pm in the coated state and in the finished state a roughness depth of Rz <2 pm, particularly <1 pm, as well as a reduced peak depth Rpk <0.3 pm, particularly 0.1 pm. In this regard, the measures of EP 1 829 986 A1 and DE 198 50 218 are included in the subject of the present application.
    Cast iron or steel, which can be nitrided for particular uses, are preferred for the substrate and base material of the sliding element to be coated. With respect to the molten material as a base material, the preferred forms are:
    - non-tempered cast iron, without alloys with lamellar graphite
    - gray cast iron, with carbides, with alloy, heat treated or not
    - spheroidal cast iron, tempered
    - vermicular graphite cast iron, not tempered
    - cast iron (at least 11% chromium by weight, martensitic structure incorporated with special carbides, nitrided or non-nitrided)
    With regard to steel as a base material, the preferred forms are:
    - chrome steel, at least 11% by weight of chrome, nitrided or non-nitrided
    - chromic silicic carbon steel
    Tests on an engine have shown that a particularly good oil scraping action of the piston ring with DLC type ta-C layer according to the invention is achieved on very small, “sharp” lower sliding edges. Therefore it is further preferred that the bottom sliding surface edge of the piston ring according to the invention has a radius of not more than 0.2 mm, preferably less than 0.1 mm.
    8/8
    The aforementioned objective is further achieved by the process described in claim 14 for the production of a sliding element, in particular a piston ring, in which coating is carried out with an adhesive layer containing metal and a DLC layer of the type ta-C with a thickness of at least 10 pm. The process of producing the vacuum laser arc process, which has been described previously in several documents (see table 1), has been refined within the context of this invention for the production of ta-C layers> 10 pm, in which a layer Optimized adhesive in terms of material choice and layer thickness was used and the process parameters ensure process stability over the entire coating period. Preferred measures and the advantages that are achieved by the process are evident, on the one hand, from the previous description of the sliding element according to the invention. It is further mentioned at this point that all the characteristics described below in relation to the process can be applied in relation to the sliding element according to the invention.
    On the other hand, it is mentioned that the adhesive layer can be formed in a particularly reliable way through a cathodic bombardment process, thermal vapor deposition process, or an electrical vapor deposition process, such as, for example, arc process .
    As mentioned above, particular advantages are achieved in terms of adhesion of the adhesive layer to the substrate of the sliding element if the surface to be coated is cleaned by a process of cathodic bombardment with metal ion.
    The roughness of the coating can be advantageously reduced by cutting, polishing with a belt and / or brush.
    权利要求:
    Claims (11)
    [1]
    1. Sliding element, in particular piston ring, which has at least one sliding surface, from inside to outside, a coating having an adhesive layer containing metal and a DLC layer of the type ta-C with a thickness of at least 10 pm, where the ta-C layer has a sp 3 content of hybridized carbon atoms of at least 40 at% (atomic percentage), characterized by the ta-C layer containing a hydrogen content less than 0.5 at% ( atomic percentage) and the sp 3 content is reduced in the range of 1 pm to 3 pm outside the layer.
    [2]
    2. Sliding element according to claim 1, characterized in that the adhesive layer contains at least one of the following materials: chromium, titanium, chromium nitride and / or tungsten.
    [3]
    Sliding element according to any one of claims 1 and 2, characterized in that the adhesive layer has a thickness of 0.1 pm to 1.0 pm.
    4. Element sliding, in wake up with any an of claims previous , characterized by the layer ta-C contain oxygen in a content smaller of that 0.5 at% (atomic percentage).5. Element sliding, in wake up with any an of claims previous , characterized by hardness no be greater than 55 GPa and the module elasticity no to be greater than 550 GPa.6. Element sliding, in wake up with any an of claims previous, characterized by the interval of 1 pm to 3 pm outer layer will be doped. 7. Element sliding, in wake up with any an
    of the preceding claims, characterized in that the interval from 1 pm to 3 pm outside the ta-C layer is doped with at least
    Petition 870190030484, of 03/29/2019, p. 6/8
    2/3 minus one of the following elements: boron, oxygen and / or silicon.
    [4]
    Sliding element according to any one of the preceding claims, characterized in that the coating has a roughness depth of Rz less than 6 gm, preferably less than 2 gm, particularly less than 1 gm.
    [5]
    Sliding element according to any one of the preceding claims, characterized in that the coating has a reduced peak depth Rpk less than 0.3 gm, preferably less than 0.1 gm.
    [6]
    Sliding element according to any one of the preceding claims, characterized in that the base material is cast iron or steel.
    [7]
    Sliding element according to claim 10, characterized in that the piston ring has a radius of the edge of the sliding surface less than 0.2 mm and preferably less than 0.1 mm.
    [8]
    12. Process for producing a sliding element, as defined in any one of claims 1 to 12, characterized by a coating
    with a layer adhesive containing metal and an DLC layer of like ta-C to be carried out in a thickness in at least 10 gm. 13. Process, according to claim 13, featured by the adhesive layer being formed by one process in cathodic bombing, one process in deposition per thermal evaporation or one process in deposition per electrical evaporation, such as, for example, a process of bow.
    [9]
    Process according to any one of claims 12 and 13, characterized in that the ta-C layer is formed by means of a vacuum laser arc process.
    [10]
    15. Process according to any one of claims 12 to 14, characterized by the surface to be
    Petition 870190030484, of 03/29/2019, p. 7/8
    3/3 coated to be cleaned through a metal ion bombardment process.
    [11]
    16. Process according to any one of claims 12 to 15, characterized in that the coating is smoothed by lapidation, polishing by means of a belt and / or brush, after it has been formed.
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-01-29| B06T| Formal requirements before examination [chapter 6.20 patent gazette]|
    2019-08-27| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-10-15| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/10/2011, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/10/2011, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102011003254.1|2011-01-27|
    DE201110003254|DE102011003254A1|2011-01-27|2011-01-27|Sliding element, in particular piston ring, with a coating and method for producing a sliding element|
    PCT/EP2011/067885|WO2012100847A1|2011-01-27|2011-10-13|Sliding element, in particular piston ring, having a coating and process for producing a sliding element|
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