EP0558724A4 - Surface finishes and methods for the production thereof - Google Patents

Surface finishes and methods for the production thereof

Info

Publication number
EP0558724A4
EP0558724A4 EP92919372A EP92919372A EP0558724A4 EP 0558724 A4 EP0558724 A4 EP 0558724A4 EP 92919372 A EP92919372 A EP 92919372A EP 92919372 A EP92919372 A EP 92919372A EP 0558724 A4 EP0558724 A4 EP 0558724A4
Authority
EP
European Patent Office
Prior art keywords
substrate
tetrafluoroethylene
molecular weight
product
fluorocarbon polymer
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Withdrawn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
EP92919372A
Other languages
English (en)
French (fr)
Other versions
EP0558724A1 (en
Inventor
Gary E Huggins
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.)
Eeonyx Corp
Original Assignee
Eeonyx Corp
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 Eeonyx Corp filed Critical Eeonyx Corp
Publication of EP0558724A1 publication Critical patent/EP0558724A1/en
Publication of EP0558724A4 publication Critical patent/EP0558724A4/en
Withdrawn legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M111/00—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential
    • C10M111/04—Lubrication compositions characterised by the base-material being a mixture of two or more compounds covered by more than one of the main groups C10M101/00 - C10M109/00, each of these compounds being essential at least one of them being a macromolecular organic compound
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/02—Carbon; Graphite
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    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/06—Metal compounds
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    • C10M107/00—Lubricating compositions characterised by the base-material being a macromolecular compound
    • C10M107/38—Lubricating compositions characterised by the base-material being a macromolecular compound containing halogen
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/04—Elements
    • C10M2201/041—Carbon; Graphite; Carbon black
    • C10M2201/0413—Carbon; Graphite; Carbon black used as base material
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    • C10M2201/042—Carbon; Graphite; Carbon black halogenated, i.e. graphite fluoride
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    • C10M2201/1006—Compounds containing silicon used as base material
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    • C10N2080/00—Special pretreatment of the material to be lubricated, e.g. phosphatising or chromatising of a metal

Definitions

  • This invention relates to surface finishes which impart nonabradable and nonetchable, durable dry lubricity, corrosion resistance and improved wet film entrapment characteristics to a substrate and to methods for applying such surface finishes to a substrate.
  • the metallic substrates employed herein may range from very hard metals having a hardness factor measured on the Rockwell C scale of greater than 40 to soft metals having hardness values measured on the Rockwell B scale.
  • 3,754,976 discloses a coating process wherein shot and powdered metal are peened against the surface of a work piece which has previously been cleaned with a gentle stream of peening particles in the absence of the coating material.
  • U.S. Patent No. 4,228,670 discloses a process wherein steel or glass shot is co-mingled with lubricant and blasted against a work piece in order to apply the lubricant to the work piece surface.
  • U.S. Patent No. 4,312,900 discloses a process wherein the work piece surface is initially pitted by shot blasting using abrasive materials such as glass or sand followed by buffing dry molybdenum disulfide into the pits created in the surface of the work piece by the shot blasting.
  • Patent No. 4,552,784 discloses a further process for applying a metal powder to the surface of a work piece by a peening technique.
  • a process is taught wherein a thin film coating of molybdenum disulfide is applied to a substrate surface by a peening action in order to adhere the molybdenum disulfide to the surface of the substrate as a coating thereon.
  • none of the prior disclosures have provided products demonstrating the combination of characteristics and properties which are achieved by the products of the present invention nor do they provide processes for producing such products.
  • the processes of the present invention achieve surface modification whereby plural polymers are bonded with the surface of the treated work piece or substrate.
  • bond or bonded will apply to either physical or chemical bonds which result in products demonstrating the desired characteristics.
  • the surface finishes of this invention are not coatings but are permanently bonded with the substrate and can only be removed by grinding away the substrate surface itself. Accordingly, the surface-finishing processes of the present invention result in products with permanent finishes having a degree of long lasting, durable dry lubricity and corrosion resistance which has not been achieved heretofore.
  • the present invention overcomes many of the known shortcomings of the prior art.
  • the invention comprises preparing a particulate mixture of a sulfur containing metallic compound such as molybdenum disulfide or tungsten disulfide and a fluorocarbon polymer such as tetrafluoroethylene, preferably in a ratio of about 1:1 to about 10:1 parts fluorocarbon polymer to sulfur containing metallic compound (on a weight percentage basis) .
  • a pressurized stream of the particulate mixture is impacted onto the surface of a substrate at a sufficient pressure and for a sufficient period of time to cause surface modification whereby the particulate mixture interacts with the substrate.
  • surface finishes have been found to provide a relatively thin, impermeable, surface hardened exterior on the surface of the substrate or work piece. These surface finishes have been found to be sufficiently thin so that the finishes do not interfere with critical tolerances of any processed parts or components.
  • Another object is to provide corrosion-resistant surface finishes demonstrating long lasting, durable dry lubricity characteristics as well as providing an impermeable, surface hardened outer surface on a substrate.
  • a further object is to provide methods for producing corrosion-resistant, long lasting, durable dry lubricant surface finishes on substrates.
  • a further object is to provide a surface finished product having a high degree of permanent dry lubricity.
  • Another object is to provide a metal surface exhibiting long lasting, durable dry lubricity and high resistance to temperature extremes.
  • a still further object is to provide methods for producing thin surface finishes which exhibit long lasting, durable dry lubricity; corrosion and heat resistance as well as improved thin film entrapment (or retention) properties.
  • yet another object is to provide methods for relatively easy and inexpensive application of the surface finishes of this invention to substrate surfaces.
  • Fig. 1 is a schematic flow diagram illustrating the method of the present invention employed to apply a dry lubricating, corrosion-resistant finish to the surface of a substrate.
  • the drawing is a schematic flow diagram showing an embodiment of the methods of the present invention for applying surface finishes to a substrate.
  • a multistep process is illustrated wherein a substrate surface is first subjected to an optional solvent precleaning step in order to remove any loose surface contamination such as hydrocarbons and other physical and chemical debris from the substrate prior to further processing.
  • This precleaning step is employed in order to reduce contamination which may be encountered and which may thereby interfere with the blast application of the surface finish onto the substrate.
  • the appropriate solvent to be used for this precleaning is somewhat substrate specific. For example, very dirty, greasy substrates will require a Stoddard solvent to be employed to clean the substrate surface.
  • 1,1,1 trichloroethane or equivalent solvent may be employed in an ultrasonic cleaning procedure.
  • a Branson IS solvent is employed in an ultrasonic cleaning procedure.
  • a metallic substrate was brush scrubbed in Stoddard solvent with Hurri-Safe Special Formula Degreaser at a 1:4 dilution in a Hurri-Kleen cold part washing machine and the substrate was then air dried. Thereafter, the material was cleaned in either Branson IS Formulated Cleaning Solution, 1:10 dilution or 1,1,1 trichloroethane precleaner (sold by Brownells) utilizing an indirect method in a Branson 8200 Ultrasonic Cleaner filled with Branson IS Formulated Cleaning Solution, 1:10 dilution. Cleaning time was about 15 minutes at 40° C.
  • the substrate is then subjected to an abrasive cleaning/surface disruption step to create a sufficient and appropriate amount of disrupted surface area on the surface of the substrate in order to interact with the surface finish material to be applied thereafter.
  • an abrasive cleaning/surface disruption step to create a sufficient and appropriate amount of disrupted surface area on the surface of the substrate in order to interact with the surface finish material to be applied thereafter.
  • this abrasive cleaning step any oxidation or contamination from the substrate material which was not removed in the precleaning step is removed.
  • This abrasive cleaning/surface disruption step may be performed in a blast cabinet environment in accordance with the procedures disclosed for precleaning in U.S. Patent No. 4,753,094 (the disclosure of which is incorporated herein by reference) .
  • the specific parameters of treatment within this step of the process are subject to choice, depending on the substrate material and its intended end use.
  • the delivery pressure/velocity, temperature, angle of delivery, duration of blasting and like parameters of the process are subject to choice and will vary depending on whether final treatment of the substrate is intended to increase dry lubricity, wear resistance, quick release (i.e., non-sticking effect) , operative temperature range and/or corrosion resistance.
  • blast materials to be used for this abrasive cleaning/surface disruption step it has been found that for softer, nonferrous metals and alloys, (e.g., aluminum, copper, lead, magnesium, zinc, beryllium, gold, tin, bronze, brass, etc.); glass beads, nylon or plastic particles or aluminum shot may be employed for blast cleaning the surface of the substrate.
  • metals and alloys e.g., aluminum, copper, lead, magnesium, zinc, beryllium, gold, tin, bronze, brass, etc.
  • glass beads, nylon or plastic particles or aluminum shot may be employed for blast cleaning the surface of the substrate.
  • nonferrous metals e.g., nickel
  • ferrous metals and alloys e.g., iron, molybdenum, chromium, tungsten, vanadium, steels and stainless steel
  • aluminum oxide particles, silicon carbide particles, glass beads, sand particles, steel shot and the like may be used to provide the peening action in cleansing the surface of the substrate.
  • less aggressive media e.g., glass beads
  • more aggressive media such as aluminum oxide or silicon carbide are preferred for use in applications where end product characteristics such as increased wear resistance or dry lubricity are desired.
  • the delivery pressures to be employed for performing this abrasive cleaning step it is believed that pressures up to 250 psi may be employed for hard and very hard substrates such as chrome/molybdenum steels and tungsten carbides, whereas lower delivery pressures of as low as about 20 psi may be used in other applications.
  • delivery pressure is defined as the blast pressure applied to a substrate at a distance of two inches from the nozzle of the delivery device.
  • the temperature range to be employed in performing this abrasive cleaning step appears to be a matter of selection and not to be determinative of the quality of the surface treatment achieved. However, it has been found that temperatures ranging between ambient temperatures and about 50° C are suitable for this cleaning step.
  • substrates which were to be cleaned/disrupted with aluminum oxide utilized a Techni Blast Model 36 Cleaning Machine, sold under the trademark "SURFGARD” at 58 cubic feet per minute at 100 pounds pressure. This cleaning machine was equipped with a 3/16 inch blast gun with a ceramic nozzle.
  • substrates which were to be cleaned/disrupted with glass beads were blasted utilizing a Trinco Direct Pressure Cabinet Model 36X30/PC equipped with a 1/4 inch nozzle I.D.
  • the substrate was blasted at 60-120 psi (preferably about 80-100 psi) at a distance of between about 2 inches and 12 inches (preferably about 6-8 inches) at an angle of about 20° - 90° (preferably about 30° - 60°) until a uniformly disrupted surface was obtained and all surface contamination was removed.
  • step three illustrated in the drawing the substrate is air cleaned with dry, compressed air to remove any residual cleaning/disrupting media thereby avoiding any possible cross-contamination with different media.
  • a pressurized stream of a particulate mixture of a sulfur containing metallic compound and a fluorocarbon polymer is directed in a pressurized stream to impact against the surface of a substrate at a sufficient pressure and for a sufficient period of time to cause the particulate mixture to interact with the substrate and to provide a surprisingly thin, impermeable, surface hardened, corrosion-resistant, durable, dry lubricant finish on the surface of the substrate.
  • the substrate surface to be treated is preferably a metallic surface.
  • the substrate may be any suitable ferrous or nonferrous metal or alloy of a metal or a ceramic composition.
  • suitable peening media having suitable shot sizes should be employed for purposes of conveying the mixture to the previously disrupted surface of the substrate.
  • Another purpose of the peening media in addition to providing a carrier for the surface finish particulate material is to surface harden the substrate through the peening process.
  • a suitable peening medium for purposes of use in the present process is chosen as a function of its compatibility with the substrate and its affinity for the particulate surface finish material which it is carrying. in addition, the size and hardness of the peening media have been found to influence the effective transfer of the surface finish material to the cleansed, disrupted substrate surface.
  • shot sizes ranging from SAE Size No. S70 to about S780 may suitably be employed in the processes of this invention.
  • SAE Size No. S70 and S230 preferably about Size No. S70 and S230; most preferably about Size S170
  • softer metal substrates such as those on the Rockwell B scale or on the Rockwell C scale ratings of 40 and below
  • larger size shot such as about SAE Size No. 170 and above
  • harder metals Rockwell C scale ratings of 40 and above
  • SAE No. S170 and above is likewise preferred for purposes of achieving continuous surface coverage.
  • smaller size shot may also be employed in certain applications to avoid surface asperities.
  • suitable peening media which may be used herein are steel shot, stainless steel shot, aluminum shot, plastic shot and the like having sufficient structural integrity to withstand impact on the substrate surface.
  • the surface finish composition of this invention is a particulate mixture of solid lubricants formulated to provide dry lubrication and/or corrosion resistance and/or non-stick properties desired for purposes of the end use of the product.
  • Suitable solid lubricants for use in the particulate mixtures of the present invention include fluorocarbon polymers and carrier or binder polymers.
  • Suitable fluorocarbon polymers are homogenates or mixtures of finely-divided fluorocarbon resins having fully fluorinated carbon backbones such as tetrafluoroethylene homopolymer (TFE) , hexafluoropropylene (HFP) , perfluoroalkoxyvinyl ether (PPVE) , copolymers of TFE and HFP, copolymers of TFE and PPVE.
  • TFE tetrafluoroethylene homopolymer
  • HFP hexafluoropropylene
  • PPVE perfluoroalkoxyvinyl ether
  • fluorocarbon polymers are fluoropolymer resins which are not fully fluorinated such as ethylenetetrafluoroethylene (ETFE) , polyvinylidene fluoride (PVDF) , ethylene- chlorotrifluoroethylene (ECTFE) , copolymers of ethylene and TFE such as products sold under the trademark "Tefzel” by E.I. Du Pont de Nemours & Co. (Inc.).
  • the molecular weight of the fluorocarbon polymers to be used herein may vary over a relatively wide range although molecular weights of from about 800 to about 2000 are preferred and, particularly about 1000-1800.
  • mixtures of fluorocarbon polymers of varying molecular weights may be advantageously employed herein as, for example, mixtures of tetrafluoroethylenes having molecular weights of 1100 and 1300.
  • the fluorocarbon polymers are chosen for their ability to impart their individual characteristics to the substrate and for their affinity to the substrate, the peening media employed, and/or the other solid lubricant material chosen.
  • suitable fluorocarbon polymers for use herein are impermeable and chemically unreactive to water and other solids, UV radiation and gases.
  • the polymers are highly thermally stable and will withstand high upper surface temperatures (i.e., about 204° C - 260° C) as a result of their high C-F and C-C bond strengths and the resulting non-polar nature of the linear polymer.
  • These resins have a low coefficient of friction and a low dielectric constant and dissipation factor. They exhibit a high degree of linear flexibility and are flame resistant.
  • the other solid lubricant component of the particulate mixture employed herein is a sulfur containing metallic compound which acts as a carrier or binder molecule herein.
  • Suitable metal sulfides for purposes of the present invention possess anti-friction/dry lubrication capabilities, can withstand increased operating temperatures and/or demonstrate high affinity towards metals such as those employed as the substrates herein or the peening media utilized herein as well as demonstrating high affinity toward the fluorocarbon polymers selected as part of the surface treatment mixture.
  • sulfur containing metallic compounds for use herein are sulfides of molybdenum, tungsten, lead, tin, copper, calcium, titanium, zinc, chromium, iron, antimony, bismuth, silver, cadmium and alloys and mixtures thereof.
  • molybdenum disulfide is employed as the sulfur containing metal compound in the particulate mixtures employed.
  • Molybdenum disulfide has a high affinity to steel and other base metals and has the ability to increase surface hardness, corrosion resistance, elevated temperature strength and dry lubricity. It also has a high affinity to fluorocarbon micropowders which may be employed advantageously herein. Thus, it has been found that use of molybdenum disulfide herein provides the dual function of a dry lubricant additive as well as a carrier/binder molecule for the fluorocarbon polymer to promote coating of the peening media.
  • the amount of fluorocarbon polymer to be incorporated in the particulate mixture to provide the requisite surface finish is determined by the amount of such polymer required to saturate the carrier or binder molecule such as molybdenum disulfide.
  • the total amount of the particulate mixture to be employed for applying the surface finish to the substrate via a peening action in a blast cabinet is determined by the amount of material required to keep the peening medium completely coated during the blasting operation in the cabinet.
  • a Techni Blast Model 36 SURFGARD Peen Plating Machine 70 cubic feet per minute at 100 pounds pressure, 3/16 inch Suction Blast Gun with Ceramic Nozzle was employed for directing the particulate mixture against the surface of a substrate in a blast cabinet.
  • the cabinet was loaded with 500 ml. (by volume) molybdenum disulfide (Super Fine Grade, Lot #510DS, Climax Molybdenum Co.); 500 ml. (by volume) tetrafluoroethylene having a molecular weight of about 1100 (Teflon Fluoroadditive Type MP1100, Lot #BMAB40D002, Du Pont); 500 ml.
  • tetrafluoroethylene having a molecular weight of about 1300 (Teflon Fluoroadditive Type MP1300, Lot #68-86, Du Pont) and 200 pounds of S70 steel shot (Techni Blast) .
  • the blast cabinet temperature was maintained at about 50° C and the delivery pressure at the nozzle of the peen plating machine was 80 psi.
  • the particulate mixture with the peening medium was blasted at a 45° angle at a distance of about 6-8 inches until a uniform, void-free surface treatment had been achieved.
  • step five in the drawing the substrates having the inventive surface finish applied therein are cleaned with dry, compressed air to remove any residual surface treatment particles. Thereafter, the substrate is washed with a cleaning solution and preserved with an oil that is compatible with the end use of the material, if so desired.
  • a surface finish is produced in the surface of a two inch by two inch square, 1/4 inch thick chrome/molybdenum steel sample.
  • the hardness of the chrome/molybdenum steel sample was 53 as measured on the Rockwell C scale.
  • the sample was subjected to an abrasive cleaning/surface disruption step in a cabinet wherein aluminum oxide shot was impacted onto the steel surface at 60 psi at an angle of about 45° under ambient temperature conditions.
  • the sample was introduced into a blast cabinet and a Techni Blast Model 36 SURFGARD Peen Plating Machine having a 3/16 inch Suction Blast Gun with Ceramic Nozzle was employed to direct a particulate mixture against the surface of this sample.
  • the particulate mixture was prepared by mixing 22 ounces (by weight) tetrafluoroethylene having a molecular weight of about
  • the contents of the two containers were then mixed together and an additional 24.3 ounces (by weight) of tetrafluoroethylene (MP1500J) was added to the mixture.
  • the combined mixture contained 60.8 ounces (by weight) tetrafluoroethylene, approximately 30 ounces (by weight) molybdenum disulfide and about 200 lbs. SAE No. S170 steel shot.
  • the resulting combined mixture contained a ratio by weight of tetrafluoroethylene to molybdenum disulfide of about 2:1.
  • the blast cabinet temperature was maintained at about 50° C and the delivery pressure at the nozzle of the peen plating machine was 80 psi.
  • the steel shot peening medium having the particulate mixture intimately coated on the surface of the shot was blasted onto the precleaned, disrupted surface of the sample at an angle of about 45° at a distance of about 4 inches for a period of about 15 seconds to form a uniform, void-free surface on the surface of the chrome/molybdenum steel sample.
  • the sample was subjected to a post-treatment cleaning step by subjecting the sample to Stoddard solvent in a Hurri-Kleen Station. This cleaning step was followed by subsequent cleaning of the resulting product in 1,1,1 - trichloroethylene in a 1000 ml. beaker and the resulting cleaned surface finish product was subjected to air drying before evaluation.
  • the resulting product was found to have a nonabradable, nonetchable surface which was durable, corrosion resistant and demonstrated dry lubricity and exceptional wet film entrapment characteristics.
  • the surface finished product demonstrates permanent dry lubricity and is highly resistant to temperature extremes. Furthermore, the surface finished product provides a natural barrier to normal oxidation and corrosion since it is chemically inert. In addition, the finish in the treated substrate surface exhibits exceptional durability and is extremely thin, being measured as low as about 0.5 micron thickness as opposed to prior art coatings wherein the coat is measured in mils such as the industry standard electroless nickel coatings which have a thickness of 3/8 mil when submerged in nickel plating solution for 45 minutes at 90.5° C. Still further, the surface finishes of the present invention are applied relatively easily even at relatively low temperatures and inexpensively in order to provide the desired surface modification herein.
  • the products produced in accordance with this invention have a multiplicity of uses in a variety of industries and in products containing metal on metal friction points or which are subject to metal surface corrosion.
  • Exemplary of the scope of the utilization of the present invention are applications within the automotive industry, fuel handling systems, power tools and equipment, fasteners, ball bearings, rollers and other anti-friction components, consumer products including cookware, houseware and razor blades, turbines, gears and other intermeshing machinery as well as a variety of other potential uses.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Paints Or Removers (AREA)
  • Laminated Bodies (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Polymerisation Methods In General (AREA)
  • Materials Applied To Surfaces To Minimize Adherence Of Mist Or Water (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Detergent Compositions (AREA)
  • Adornments (AREA)
  • Materials For Medical Uses (AREA)
EP92919372A 1991-08-26 1992-08-21 Surface finishes and methods for the production thereof Withdrawn EP0558724A4 (en)

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CN1091787C (zh) * 1995-07-13 2002-10-02 纳幕尔杜邦公司 四氟乙烯共聚物涂布组合物
MX9800350A (es) * 1995-07-13 1998-03-31 Du Pont Composicion dispersante de polimero de tetrafluoroetileno.
JPH10140144A (ja) * 1996-09-09 1998-05-26 Tokyo Silicone Kk 基材表面の改質方法
GB2377658B (en) * 2001-06-29 2004-05-05 Mohammed Nazim Khan Non-stick coating material having corrosion resistance to a wide range of solvents and mineral acids
FR2827869B1 (fr) * 2001-07-26 2007-04-13 Seb Sa Revetement anti-adhesif presentant une resistance amelioree a la rayure et a l'abrasion
US20070134468A1 (en) * 2004-07-14 2007-06-14 Buehler Jane E Enhanced friction reducing surface and method of making the same
US8814861B2 (en) 2005-05-12 2014-08-26 Innovatech, Llc Electrosurgical electrode and method of manufacturing same
US8603628B2 (en) 2007-04-30 2013-12-10 Saint-Gobain Performance Plastics Corporation Turbine blade protective barrier
CN101733237B (zh) * 2008-11-05 2012-07-25 中国航空工业标准件制造有限责任公司 干膜润滑剂的涂覆方法和设备
CN103060063B (zh) * 2012-12-16 2015-06-10 青岛文创科技有限公司 一种润滑剂
WO2017180159A1 (en) 2016-04-15 2017-10-19 Hewlett-Packard Development Company, L.P. Coating part precursors
CN108300006A (zh) * 2016-08-30 2018-07-20 石家庄嘉祥精密机械有限公司 轨道交通无油活塞压缩机活塞表面处理方法及专用喷涂液
CN106826571A (zh) * 2017-02-22 2017-06-13 河北工业大学 一种齿轮表面复合强化的方法
CN110936302A (zh) * 2019-10-26 2020-03-31 江苏亿达铸造机械有限公司 一种耐腐蚀性切丸及其加工方法
SE545195C2 (en) * 2021-09-29 2023-05-09 Tribonex Ab Induced formation of solid lubricant

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EP0539585A1 (en) * 1991-04-22 1993-05-05 Takata Corporation Surface-coated member

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EP0539585A1 (en) * 1991-04-22 1993-05-05 Takata Corporation Surface-coated member

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PL298943A1 (en) 1994-01-10
FI931869A (fi) 1993-04-26
WO1993003921A1 (en) 1993-03-04
CZ81693A3 (en) 1994-02-16
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HUT67752A (en) 1995-04-28
AU2515392A (en) 1993-03-16
EP0574556A1 (en) 1993-12-22
BR9205401A (pt) 1994-03-08
SK44993A3 (en) 1993-09-09
NO931446D0 (no) 1993-04-20
CA2094395A1 (en) 1993-02-27
CA2094396A1 (en) 1993-02-27
NO931445L (no) 1993-04-20
WO1993003919A1 (en) 1993-03-04
JPH06501051A (ja) 1994-01-27
SK45093A3 (en) 1993-09-09
CZ81593A3 (en) 1994-02-16
EP0558724A1 (en) 1993-09-08
FI931868A0 (fi) 1993-04-26
HU9301210D0 (en) 1993-09-28

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