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EP2280095A2 - Procédé de revêtement électrochimique d'une pièce usinée - Google Patents

Procédé de revêtement électrochimique d'une pièce usinée Download PDF

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Publication number
EP2280095A2
EP2280095A2 EP10170258A EP10170258A EP2280095A2 EP 2280095 A2 EP2280095 A2 EP 2280095A2 EP 10170258 A EP10170258 A EP 10170258A EP 10170258 A EP10170258 A EP 10170258A EP 2280095 A2 EP2280095 A2 EP 2280095A2
Authority
EP
European Patent Office
Prior art keywords
particles
ionic liquid
metal layer
kurzname
short name
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.)
Withdrawn
Application number
EP10170258A
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German (de)
English (en)
Other versions
EP2280095A3 (fr
Inventor
Gerhard Reusmann
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.)
Ewald Doerken AG
Original Assignee
Ewald Doerken 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 Ewald Doerken AG filed Critical Ewald Doerken AG
Publication of EP2280095A2 publication Critical patent/EP2280095A2/fr
Publication of EP2280095A3 publication Critical patent/EP2280095A3/fr
Withdrawn legal-status Critical Current

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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
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/66—Electroplating: Baths therefor from melts
    • C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D15/00—Electrolytic or electrophoretic production of coatings containing embedded materials, e.g. particles, whiskers, wires

Definitions

  • the invention relates to a method for the electrochemical coating of a workpiece.
  • Electrochemical processes are one of the most important ways of providing workpieces with metallic coatings.
  • the workpiece is introduced into a coating liquid containing metal ions.
  • the liquid may be a melt of a salt of the corresponding metal, but often it consists of a suitable solvent in which ions are dissolved.
  • the coating liquid is contained in a coating container during coating. Furthermore, an electrode for contacting the workpiece as well as a counterelectrode dip into the coating liquid within the container. For coating, a voltage is applied between the workpiece and the counter electrode.
  • the metal ions in the coating liquid are electrolytically discharged at the surface of the workpiece, whereby a metal layer is deposited on the surface. In this case, the workpiece forms a cathode, at which the metal cations are reduced.
  • a coating with aluminum is particularly advantageous.
  • an aluminum surface has an attractive appearance, and on the other because aluminum forms stable oxide layers, so that an aluminum coating can protect an underlying metal from oxidation and corrosion.
  • ionic liquids These are salts whose melting point is below 100 ° C, sometimes even below room temperature.
  • Typical ionic liquids used for electrochemical coating processes with aluminum are combinations of certain organic cations with halide ions, for example 1-ethyl-3-methylimidazoliumehlorid. In such a liquid, for example, aluminum chloride can be dissolved at room temperature. The solution can be used for electrochemical deposition of aluminum.
  • a coating based on an organic or inorganic binder to the aluminum layer, either as a powdered or liquid paint.
  • a coating in turn can protect the aluminum layer.
  • lubricants such as polytetrafluoroethylene, which are added to the paint, adjust the tribological properties of the surface.
  • the DE 10 2008 031 003 discloses producing a CNT-rich coating on workpieces.
  • the WO 2009/016189 is concerned with creating extra thick layers deposited from ionic liquids on workpiece surfaces. The thickness of the layer should provide protection against stress.
  • the object of the invention is therefore to propose measures that allow an improvement in the surface properties of an aluminum-coated workpiece.
  • the object is achieved by a method according to claim 1, a coating for a workpiece according to claim 15, a workpiece according to claim 16, an ionic liquid according to claim 17 and a method according to claim 18 or 19.
  • an aluminum-containing layer of an ionic liquid comprising aluminum ions is deposited on the surface of the workpiece.
  • An example of such an ionic liquid is the already mentioned solution of aluminum chloride in 1-ethyl-3-methylimidazolium chloride (EMIMCl).
  • EMIMCl 1-ethyl-3-methylimidazolium chloride
  • all ionic liquids known from the prior art for the deposition of aluminum can be used.
  • the available or suitable ionic liquids include, inter alia, salts of 3-methylimidazolium with one of the following side chains
  • OMIM 3-methyl-octylimidazolium
  • OMIM Cl chloride
  • OMIM BF4 tetrafluoroborate
  • metallic includes all metals and alloys, in particular all types of steels. It will be understood by those skilled in the art that a prior art alloy may include metals as well as metals or non-metals, for example silicon or carbon. It is also conceivable that it is a workpiece, that already has a metal layer, that is, for example, has been electrochemically coated in advance. In addition to metallic surfaces, non-metallic surfaces are also suitable, provided they are conductive. For example, conductive plastics and so-called organic semiconductors are known from the prior art, which have sufficient conductivity to allow an electrochemical coating.
  • the ionic liquid contains particles.
  • particles here means, according to the accepted view, small solids whose maximum extent is at most 1 mm.
  • the particles may take a variety of forms, e.g. spherical or lamellar, lenticular, polyhedral or acicular.
  • the composition of the particles can be arbitrary, but those materials are preferred which show no decomposition in ionic liquids, in particular are not soluble in these. Preferred materials and sizes of the particles are discussed below.
  • the ionic liquid used in the present invention can be provided by adding particles to an ionic liquid comprising aluminum ions.
  • an ionic liquid may be provided to which particles are added, after which aluminum ions are dissolved in the ionic liquid.
  • the particles should preferably be added in a pure form (ie, not as a paste or the like).
  • the particles should be cleaned by drying adhering air humidity. The addition of the particles can be done on site, immediately before coating, or it is done in advance in the factory, with which a ready-to-use coating bath can be provided.
  • the particles are suspended in the liquid, i. they do not sink but float in it.
  • the particles are incorporated in the aluminum-containing metal layer during the deposition process.
  • the exact mechanism of storage may vary.
  • the deposited metal can act as a kind of "binder" by which particles are randomly attached to them in the immediate vicinity of the surface of the workpiece.
  • particles also migrate electrostatically through the electrical field prevailing during the deposition to the surface of the workpiece, where they are connected by the deposited metal.
  • the subject of the present invention is independent of the mechanisms underlying the incorporation.
  • the metal layer deposited on the workpiece forms a kind of matrix into which the particles are bound.
  • the incorporation may be incomplete, ie, for example, particles may protrude from the surface of the metal layer, which are thus incorporated only in part.
  • the incorporation of particles according to the invention makes it possible to design the surface properties of the metal layer flexibly. More specifically, by incorporating the particles, a surface property of the metal layer is adjusted. It is thus possible to act on the surface property as planned and targeted. This is due to the fact that normally a part of the particles protrudes from the surface of the metal layer. On the other hand, particles completely embedded in the layer can also have an influence on the surface properties, in particular if a near-surface incorporation takes place. Also, particles that are initially close to the surface of the metal layer can be exposed by abrasion during use of the workpiece and thus affect the properties of the surface afterwards. Preferred possibilities of surface design will be explained below.
  • the storage during the deposition process ensures an optimal binding of the particles to the metal layer and thus to the surface of the workpiece.
  • Another advantage is the possibility that the surface design is possible through a single layer. This eliminates the need for an additional coating step and it is generally possible to make the coating thinner than conventional methods in which at least one further layer must be applied. This saves time, money and material. It should also be noted that any problems of adhesion of an additional layer to the metal layer are avoided.
  • the process is particularly suitable for incorporation of the hard material particles mentioned below.
  • a higher effective hardness of the coating is set by the embedded particles.
  • the aluminum layer which forms the matrix for the particles, becomes effective protected against abrasion. This results from the fact that - either from the beginning or after abrasion of the overlying aluminum - hard material particles protrude from the surface of the aluminum layer. External abrasive effects primarily affect the particles, thereby protecting the aluminum layer and thus also the underlying substrate.
  • the wear resistance and the abrasion resistance of the coating can be increased much better in this way, even for thin layers than by increasing the layer thickness.
  • Such particles typically have a Mohs hardness of at least 5, preferably at least 7, more preferably at least 9.
  • the particles are selected from silicic acid, alumina, titania, silica, zirconia, tungsten carbide, chromium carbide, boron carbide, silicon nitride, silicon carbide and diamond particles, as well as microbubbles or a mixture thereof.
  • Advantageous titanium oxide particles of the rutile or anatase type form radicals by photocatalysis on light, e.g. OH radicals from water, which decompose organic substances.
  • a thus coated workpiece thus has a self-cleaning ability, which contributes to the protection of the surface.
  • particles which comprise lubricants.
  • Such particles can consist entirely of lubricant or even partially, e.g. comprise an alumina core coated with lubricant.
  • lubricant here refers to those substances which are at the temperatures typical of the process, e.g. between o ° C and 100 ° C, are solid.
  • the use of lubricant particles can firstly be used to set a given friction coefficient for workpieces such as e.g. Screws are used.
  • lubricants can prevent mechanical damage to the workpiece or increased abrasion, as this friction forces, which are often the cause of damage, can be reduced.
  • the use of lubricants shows greater effect here than an increase in the layer thickness of the surface coating.
  • Suitable lubricants are all known from the prior art materials in question, such.
  • halogenated hydrocarbons in particular polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), perfluoroalkoxy copolymer (PFA), copolymer of tetrafluoroethylene with perfluorinated propylene and perfluoroalkyl vinyl ether (EPE), copolymer of tetrafluoroethylene and perfluoromethyl vinyl ether (MFA), MoS 2 , boron nitride, graphite, fluorinated graphite , Carnauba wax, polysulfones, polyolefin resins, especially polyethylene (PE) and polypropylene (PP), mixtures thereof or a combination thereof.
  • PTFE polytetrafluoroethylene
  • PVDF polyvinylid
  • the present process uses particles comprising graphene and / or fullerenes.
  • the carbon modifications mentioned can positively influence the surface properties of the metal layer in various ways. So they can e.g. Due to their high mechanical stability, the metal layer is protected against abrasion.
  • a workpiece can be e.g. be protected by the combined storage of hard particles and lubricant particles particularly effective from abrasion.
  • the size of the particles used can be varied within a relatively wide range. It should be noted, however, that too large particles can not be well integrated into the metal layers, which are typically a few micrometers thick, while particles that are too small can be ineffective for adjusting the surface properties. Therefore, it is advantageous if particles are used which have a maximum extent of between 10 nm and 10 ⁇ m, preferably between 50 nm and 5 ⁇ m, more preferably between 100 nm and 2 ⁇ m, particularly preferably between 500 nm and 1 ⁇ m.
  • the thickness of the coating is generally 1 micron to 5 microns, preferably 1 micron to 3 microns.
  • nanoparticles are used, ie particles whose size is well below 1 ⁇ m, they are preferably also used in ionically stabilized form.
  • the mass fraction of the particles is between 0.1% and 10%, preferably between 1% and 8%, more preferably between 2% and 5%, based on a reactive component contained in the ionic liquid.
  • reactive component the part of the ionic liquid involved in the deposition. If, for example, a melt of EMIMCl is present in which aluminum chloride is dissolved, the aluminum chloride is the reactive component.
  • Lower or higher particle levels within the ionic liquid can adversely affect the proportion of particles within the deposited metal layer. In order not to weaken the structural integrity of the metal layer, the proportion of particles in the layer should not be too large. On the other hand, too low a proportion may cause the particles to no longer sufficiently influence the surface properties.
  • the ionic liquids used in the present process are subject to a settling behavior that results in the formation of an inhomogeneous concentration of the metal ions to be deposited. This can adversely affect the deposition result.
  • the particles do not remain homogeneously suspended in the ionic liquid, but settle down or float, depending on whether their density is greater or smaller than that of the ionic liquid. Both effects generally oppose a controlled storage process. In order to counteract these effects, it is preferred that a mixing of the ionic liquid takes place before, during and / or after deposition. Thereby, the ionic liquid and in particular the distribution of the particles within it can be effectively homogenized.
  • Mixing before and after deposition offers the advantage that the electric field-induced ion currents that support the deposition process are not superimposed by movement of the liquid. Also, mixing during the deposition process may result in particles becoming less well attached to the surface, as they are ripped away before attachment by the deposited metal.
  • the particles are relatively large and their density significantly exceeds that of the ionic liquid, it may be advantageous to perform a mixing even during the deposition in order to keep the particle concentration reasonably homogeneous. It is of course possible to interrupt the separation process for this purpose.
  • Mixing can be carried out, for example, by mechanical stirrers, by magnetic stirrers or by sound, in particular ultrasound. It is also conceivable that the entire coating container, in which the ionic liquid is located, is rotated (for example in the manner of a concrete mixer) or oscillated back and forth in order to achieve thorough mixing of the ionic liquid. Also, the workpiece located in the ionic liquid itself can be moved for this purpose.
  • a mass fraction, a volume fraction and / or a number of particles in the ionic liquid is monitored. Since many ionic liquids are transparent, such monitoring may e.g. be performed with a nephelometer. Here, the fact is exploited that the scattering of light irradiated into the ionic liquid is changed by the number of particles suspended in it. Alternatively or additionally, sample counts of the particles can also be carried out in a small partial volume of the liquid. In this case it is also possible, e.g. to identify spectroscopically the composition of individual particles, so as to carry out a separate monitoring for the individual species separately when using different types of particles. In addition, other methods for measuring the number of particles are known, which are known in the art.
  • the monitoring can be done manually in the simplest case. However, automatic monitoring is preferred. In this case, the monitoring can also be used for automatic adjustment of the volume fraction or the number of particles, as will be explained below. It is also conceivable parallel monitoring for different areas of the ionic liquid. This makes it possible to determine whether the distribution of the particles is too inhomogeneous and thus a thorough mixing is necessary.
  • the ionic liquid loses particles by incorporation into the metal layer
  • the addition of the particles may be based on calculations or empirical values. However, it is carried out particularly advantageously dynamically as a function of the results of the monitoring of volume fraction or number of particles. In this case, monitoring and supplementing the particles form parts of a control loop.
  • the ionic liquid comprises ions of at least one further element selected from the group consisting of silicon, iron, copper, manganese, magnesium, chromium, nickel, zinc, lead and titanium.
  • the metal layer in addition to aluminum contains at least one of said elements.
  • the aluminum alloy preferably contains at least 60% by weight, more preferably at least 70% by weight, particularly preferably at least 80% by weight, advantageously at least 90% by weight of aluminum.
  • the aluminum-containing metal layer can be aftertreated, in particular by dyeing, sealing or applying a topcoate.
  • Steel screws 100 are provided for coating with aluminum, wherein the surface of the aluminum layer is to be protected by the incorporation of silicon carbide particles 11 from abrasion.
  • the screws 100 are sandblasted and degreased hot alkaline. This is followed by rinsing with tap water, followed by subsequent drying by means of hot air.
  • the screws 100 are introduced into an airtight sealable coating chamber within which there is a nitrogen atmosphere with a relative residual moisture of less than 0.1%.
  • the in Fig. 1 This comprises a container 2 made of ceramic material which is insensitive to ionic liquids.
  • the container 2 In the operating state, the container 2 is filled with a coating liquid 10 which consists of a mixture of 1.5: 1 of EMIMCl and aluminum chloride.
  • a receiving device 3 for the screws 100 is arranged in the container 2.
  • the receiving device 3 is cylindrical-cup-shaped with a perforated wall. It can be moved vertically, besides it can be rotated about its symmetry axis, whose position can also be adjusted to the vertical.
  • the receiving device 3 has a plurality of electrodes (not shown) for contacting the screws 100. These electrodes are connected via a voltage source (also not shown) with a counter electrode 4 made of high-purity aluminum, which is surrounded by the coating liquid 10.
  • the coating liquid 10 a plurality of silicon carbide particles 11 are suspended.
  • the approximately spherical particles 11 have an average diameter of about 500 nm.
  • the coating liquid 10 is continuously mixed by means of a magnetic stirrer 5.
  • the mass fraction of the particles 11 based on the reactive component contained in the coating liquid 10 is 2%.
  • Fig. Shows the state of the device during the coating process.
  • the screws 100 are located in the receiving device 3, which has been moved into the coating liquid 10 and whose axis is adjusted approximately 45 ° relative to the vertical.
  • the recording device 3 is rotated about its axis of symmetry at about 5 rpm. As a result, there is a circulation of the screws 100, whereby uniform contact points between the screws 100 are avoided.
  • a voltage is applied by means of the voltage source between the electrodes in the wall and the aluminum electrode 4, which generates a current density of 20 mA / cm 2 , wherein the aluminum electrode 4 acts as an anode.
  • the aluminum electrode 4 acts as an anode.
  • the power source is turned off and rotation of the pickup 3 is stopped.
  • the receiving device 3 is moved vertically out of the coating liquid 10 and tilted by changing its inclination in a basket (not shown).
  • the screws 100 now have an anticorrosive aluminum layer, which is protected against abrasion, since a plurality of silicon carbide particles 11 protrude from the surface of the aluminum layer and thus provide for increased effective hardness.
  • the screws 100 can subsequently be aftertreated in various ways.
  • a batch of steel screws 100 is provided for coating with aluminum.
  • the surface of the steel screws should be adjusted to a uniform coefficient of friction.
  • 1% PTFE particles with a diameter of 500 nm are dispersed in the coating liquid.
  • the coating is carried out as explained in Example 1.
  • the applied coating has a layer thickness of 3 ⁇ m.
  • the surface has a uniform coefficient of friction.

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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)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
EP10170258.7A 2009-07-30 2010-07-21 Procédé de revêtement électrochimique d'une pièce usinée Withdrawn EP2280095A3 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102009035660A DE102009035660A1 (de) 2009-07-30 2009-07-30 Verfahren zur elektrochemischen Beschichtung eines Werkstücks

Publications (2)

Publication Number Publication Date
EP2280095A2 true EP2280095A2 (fr) 2011-02-02
EP2280095A3 EP2280095A3 (fr) 2013-07-24

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US (1) US20110024299A1 (fr)
EP (1) EP2280095A3 (fr)
DE (1) DE102009035660A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102560606A (zh) * 2012-03-01 2012-07-11 梅河口市兴业精密钢管有限公司 纳米金刚石微粉复合镀铬的泵筒、生产工艺及生产装置
CN105152653A (zh) * 2015-07-09 2015-12-16 浙江长兴银兴窑业有限公司 一种抗腐蚀碳化硅棚板及其制备方法
EP3006605A1 (fr) * 2014-10-08 2016-04-13 The Swatch Group Research and Development Ltd. Revêtement composite auto-lubrifiant
CN104641022B (zh) * 2012-09-18 2016-12-07 住友电气工业株式会社 铝膜的制造方法
CN108417404A (zh) * 2016-08-26 2018-08-17 重庆文理学院 一种超级电容器电极材料的制备方法
WO2019007556A1 (fr) * 2017-07-04 2019-01-10 Linde Aktiengesellschaft Liquide ionique associé à un lubrifiant sec
CN109468675A (zh) * 2018-11-21 2019-03-15 山东大学 一种制备硬质合金粉末表面金刚石涂层材料的方法

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US8778163B2 (en) 2011-09-22 2014-07-15 Sikorsky Aircraft Corporation Protection of magnesium alloys by aluminum plating from ionic liquids
WO2014130451A1 (fr) * 2013-02-19 2014-08-28 Alumiplate, Inc. Films d'aluminium comprenant des particules durcissantes
CN103132119B (zh) * 2013-02-26 2015-06-17 四川农业大学 一种石墨烯/TiO2花状纳米簇的制备方法
WO2014150508A1 (fr) * 2013-03-15 2014-09-25 United Technologies Corporation Revêtement sacrificiel et procédure de dépôt électrolytique d'aluminium sur des alliages d'aluminium
US10006141B2 (en) 2013-06-20 2018-06-26 Baker Hughes, A Ge Company, Llc Method to produce metal matrix nanocomposite
US10669635B2 (en) * 2014-09-18 2020-06-02 Baker Hughes, A Ge Company, Llc Methods of coating substrates with composite coatings of diamond nanoparticles and metal
CN104355596B (zh) * 2014-10-17 2016-04-06 安徽永旭照明科技有限公司 一种含有石墨烯微片的led灯座组合物
US9873827B2 (en) 2014-10-21 2018-01-23 Baker Hughes Incorporated Methods of recovering hydrocarbons using suspensions for enhanced hydrocarbon recovery
US10167392B2 (en) 2014-10-31 2019-01-01 Baker Hughes Incorporated Compositions of coated diamond nanoparticles, methods of forming coated diamond nanoparticles, and methods of forming coatings
US10155899B2 (en) 2015-06-19 2018-12-18 Baker Hughes Incorporated Methods of forming suspensions and methods for recovery of hydrocarbon material from subterranean formations
CN106283140B (zh) * 2016-10-27 2019-02-05 安徽工业大学 一种基于甜菜碱-尿素-水低共熔溶剂的电镀镍磷合金方法
US10954600B2 (en) * 2016-12-16 2021-03-23 Hamilton Sundstrand Corporation Electroplating systems and methods
CN108385138B (zh) * 2018-03-19 2019-07-12 广州超邦化工有限公司 一种适用于海洋强腐蚀环境下的金属表面镀层结构的制备方法
CN108950455A (zh) * 2018-07-18 2018-12-07 合肥市新开创不锈钢设备有限公司 一种提高奥氏体不锈钢耐磨性和自润滑性的方法
CN111778541B (zh) * 2020-07-30 2022-01-11 山东大学 一种电镀金刚石线锯制作装置

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WO2009016189A1 (fr) 2007-08-02 2009-02-05 Akzo Nobel N.V. Procédé pour électrodéposer des métaux à l'aide de liquides ioniques en présence d'un additif
DE102008031003A1 (de) 2008-06-30 2009-12-31 Siemens Aktiengesellschaft Verfahren zum Erzeugen einer CNT enthaltenen Schicht aus einer ionischen Flüssigkeit

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JP2007070689A (ja) * 2005-09-07 2007-03-22 Nissan Motor Co Ltd ナノカーボン／アルミニウム複合材、その製造方法及びこれに用いるめっき液
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WO2009016189A1 (fr) 2007-08-02 2009-02-05 Akzo Nobel N.V. Procédé pour électrodéposer des métaux à l'aide de liquides ioniques en présence d'un additif
DE102008031003A1 (de) 2008-06-30 2009-12-31 Siemens Aktiengesellschaft Verfahren zum Erzeugen einer CNT enthaltenen Schicht aus einer ionischen Flüssigkeit

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102560606A (zh) * 2012-03-01 2012-07-11 梅河口市兴业精密钢管有限公司 纳米金刚石微粉复合镀铬的泵筒、生产工艺及生产装置
CN104641022B (zh) * 2012-09-18 2016-12-07 住友电气工业株式会社 铝膜的制造方法
EP3006605A1 (fr) * 2014-10-08 2016-04-13 The Swatch Group Research and Development Ltd. Revêtement composite auto-lubrifiant
WO2016055409A1 (fr) * 2014-10-08 2016-04-14 The Swatch Group Research And Development Ltd Revetement composite auto-lubrifiant
CN106795640A (zh) * 2014-10-08 2017-05-31 斯沃奇集团研究和开发有限公司 自润滑复合涂层
US10047450B2 (en) 2014-10-08 2018-08-14 The Swatch Group Research And Development Ltd Self-lubricating composite coating
CN106795640B (zh) * 2014-10-08 2019-03-08 斯沃奇集团研究和开发有限公司 自润滑复合涂层
CN105152653A (zh) * 2015-07-09 2015-12-16 浙江长兴银兴窑业有限公司 一种抗腐蚀碳化硅棚板及其制备方法
CN108417404A (zh) * 2016-08-26 2018-08-17 重庆文理学院 一种超级电容器电极材料的制备方法
WO2019007556A1 (fr) * 2017-07-04 2019-01-10 Linde Aktiengesellschaft Liquide ionique associé à un lubrifiant sec
CN109468675A (zh) * 2018-11-21 2019-03-15 山东大学 一种制备硬质合金粉末表面金刚石涂层材料的方法

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Publication number Publication date
US20110024299A1 (en) 2011-02-03
EP2280095A3 (fr) 2013-07-24
DE102009035660A1 (de) 2011-02-03

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