EP0073306B1 - Schmiermittel für die Kaltverformung und Verfahren zu deren Verwendung - Google Patents

Schmiermittel für die Kaltverformung und Verfahren zu deren Verwendung Download PDF

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Publication number
EP0073306B1
EP0073306B1 EP82105093A EP82105093A EP0073306B1 EP 0073306 B1 EP0073306 B1 EP 0073306B1 EP 82105093 A EP82105093 A EP 82105093A EP 82105093 A EP82105093 A EP 82105093A EP 0073306 B1 EP0073306 B1 EP 0073306B1
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EP
European Patent Office
Prior art keywords
coating
pigment
lubricant
fatty acids
free
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.)
Expired
Application number
EP82105093A
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English (en)
French (fr)
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EP0073306A1 (de
Inventor
Thomas C. Atkiss
Leo F. Corcoran
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.)
Pennwalt Corp
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Pennwalt Corp
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Publication date
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Publication of EP0073306A1 publication Critical patent/EP0073306A1/de
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Publication of EP0073306B1 publication Critical patent/EP0073306B1/de
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    • 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
    • C10M111/02—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 non-macromolecular organic compound
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
    • C10M105/08—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing oxygen
    • C10M105/22—Carboxylic acids or their salts
    • C10M105/24—Carboxylic acids or their salts having only one carboxyl group bound to an acyclic carbon atom, cycloaliphatic carbon atom or hydrogen
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    • C10M105/50—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound containing halogen
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    • C10M105/00—Lubricating compositions characterised by the base-material being a non-macromolecular organic compound
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/08—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-nitrogen bonds
    • C10M2223/083—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions having phosphorus-to-nitrogen bonds used as base material
    • 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
    • C10M2223/00—Organic non-macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2223/10—Phosphatides, e.g. lecithin, cephalin
    • C10M2223/103—Phosphatides, e.g. lecithin, cephalin used as base material
    • 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
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • 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
    • C10M2225/00—Organic macromolecular compounds containing phosphorus as ingredients in lubricant compositions
    • C10M2225/02—Macromolecular compounds from phosphorus-containg monomers, obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/02—Groups 1 or 11
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2010/00—Metal present as such or in compounds
    • C10N2010/04—Groups 2 or 12
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/24—Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/241—Manufacturing joint-less pipes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/242—Hot working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/243—Cold working
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/245—Soft metals, e.g. aluminum
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/246—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/20—Metal working
    • C10N2040/244—Metal working of specific metals
    • C10N2040/247—Stainless steel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00—Form in which the lubricant is applied to the material being lubricated
    • C10N2050/10—Semi-solids; greasy
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2070/00—Specific manufacturing methods for lubricant compositions

Definitions

  • This invention relates to a dry film lubricant system comprising a zinc phosphate coating on steel or aluminum. Moreover, the present invention relates to a process for cold forming ferrous and non-ferrous metals such as steel, stainless steel, copper and aluminum.
  • a current practice is to prepare the parts by applying a zinc phosphate coating to the parts and then applying a dry film lubricant or a reactive lubricant to the zinc phosphate coating.
  • Dry film lubricants are products containing soap and borax as their major constituents. Such lubricants are applied from an aqueous solution at high. temperatures (greater than 60°C to boiling) and then dried on the metal surface. Dry film lubricants generally are used for mild forming operations.
  • Reactive stearate lubricants are also applied from aqueous solution. They consist of solutions of sodium stearate which are controlled in such a way that they react with the zinc phosphate coating to form zinc stearate within the crystal lattice of the coating. This provides a tightly bonded lubricant system which performs well in many severe cold extrusion applications.
  • Both lubricant systems offer the advantage of a dry, hard film which is not easily physically removed from the metal surface. This leads to a cleaner and safer work environment because oils tend to run off treated parts and coat the work area. However, there are some severe cold forming applications where neither system will perform adequately. At such times the use of an additional lubricant (such as molybdenum disulfide) or additional processing steps are required, both of which lead to additional expense.
  • an additional lubricant such as molybdenum disulfide
  • GB-A-1 349 475 and FR-A-1 498 978 describe lubricating compositions comprising an aqueous pigment-free bath containing an alkali metal fatty acid with 8 to 22 carbon atoms and phosphate esters of polyethoxy ethers.
  • an alkali metal fatty acid with 8 to 22 carbon atoms
  • phosphate esters of polyethoxy ethers From US-A-3 983 044 it is known to use chlorinated or sulfurized fatty acids as extreme pressure additives in water based lubricants for the cold forming of metals.
  • a dry film lubricant system comprising a zinc phosphate coating on steel or aluminum which is characterized by the fact that the coating has been reacted with an alkali metal stearate and a compound selected from the group consisting of sulfurized fatty acids and chlorinated fatty acids, and mixtures thereof to provide a dry, pigment-free lubricant film.
  • a process for cold forming steel or aluminum is provided which is characterized by applying to a steel or aluminum billet a coating of zinc phosphate, applying to the zinc phosphate a second pigment-free coating which includes an alkali metal stearate and an additive selected from the group consisting of sulfurized fatty acids and chlorinated fatty acids, and mixtures thereof from an aqueous bath so as to form a dry pigment-free lubricant film including a zinc soap and then forming the billet using a die.
  • a process for cold forming metals which is characterized by applying to the metal billet a pigment-free coating which includes an alkali metal fatty acid soap and an additive selected from the group consisting of sulfurized fatty acids, chlorinated fatty acids, and mixtures thereof from an aqueous bath so as to form a dry, pigment-free lubricant film and then forming the billet using a die.
  • a pigment-free coating which includes an alkali metal fatty acid soap and an additive selected from the group consisting of sulfurized fatty acids, chlorinated fatty acids, and mixtures thereof from an aqueous bath so as to form a dry, pigment-free lubricant film and then forming the billet using a die.
  • the lubricant system and process of the invention are suitable for extreme cold forming operations where reductions of 35% or more are necessary in forming metal parts.
  • the metal parts are dipped in a heated aqueous lubricant bath for several minutes, removed and dried to provide a hard dry lubricant film.
  • ferrous or aluminum parts are first provided with a zinc phosphate coating having a coating weight of approximately 1.6 to 3.2 mg/cm 2 as is conventional.
  • the parts are next dipped in a reactive lubricant bath of the invention which contains an alkali metal stearate, for several minutes.
  • the zinc coating reacts with the bath and, upon drying, a hard, dry lubricant film is formed on the part.
  • the lubricant system of the present invention includes an alkali metal stearate and an additive compound selected from the group consisting of sulfurized fatty acids, chlorinated fatty acids, and mixtures thereof.
  • the sulfurized and chlorinated fatty acids are derived from unsaturated fatty acids and esters having 12 to 22 carbon atoms in the acid carbon chain, such as oleic, linderic, erucic, linoleic, linolenic, etc. acids by reacting the unsaturated bonds with sulfur or chlorine.
  • chlorinated and sulfurized fatty acids include esters thereof. Such materials are available from Keil Chemical Division, Ferro Corp.
  • the lubricant system may contain an phosphate ester of polyoxyethylene based non-ionic surfactants.
  • the phosphate esters are sold as extreme pressure lubricants and are available under the trademark Antara@ from GAF Corporation. They comprise a phosphate radical on a polyethyleneoxy non-ionic surfactant base.
  • the non-ionic surfactant base consists of a hydro- phobe and polyoxyethylene.
  • an important attribute of the additive material is that it has an acid group which can react with the zinc phosphate to form a water insoluble zinc soap which is chemically bonded to the surface of the metal.
  • the combination of these additives and the stearate provide a dry film with unique lubricating properties which permits the cold extrusion of certain metal parts. The forming temperatures are reduced so that the parts are not heat damaged and the lubricating system avoids various other operating problems such as sticking in the die.
  • the free acidity of the bath must be adjusted to assure reaction of the ingredients of the bath with the zinc phosphate coating when a phosphate precoat is used. The adjustment also is used to control the viscosity of the bath.
  • the "free fatty acid” is adjusted by adding a base such as NaOH so as to be within the range of ⁇ 1.0 with ⁇ 0.5 preferred. Free fatty acid is determined by placing 100 ml of 190 proof ethyl alcohol in a 250 ml. Erlenmeyer flask and adding five drops of phenolphthalein indicator. Sodium hydroxide (0.1 N) is added dropwise until a faint pink color develops. A 10 ml.
  • the amount of lubricant additive employed will depend upon the application and generally can range from about 1-30 parts by weight per 100 parts of the total combined weight of fatty acid soap and additive combined. A sufficient amount is used to provide the required lubrication for a given application. Amounts of additive above about 30 parts by weight make the lubricant coating film soft.
  • the solution concentration carf range from about 2 to 10% by weight and preferably 4 to 8% by weight "total fatty solids".
  • Total fatty solids are determined by pipetting a 20 ml sample of the bath into an 18 gram Babcock type test bottle. A 25 ml portion of concentrated sulfuric acid is then added and the bottle is shaken until the fatty matter separates. The liquid sample is diluted with 50% aqueous H 2 S0 4 until the volume of separated fatty matter can be read on the graduated neck of the bottle directly as percent fatty solids.
  • the bath of the invention is formed and maintained by adding the ingredients with mixing to hot water (71°C or above), otherwise the fatty acid portion will separate.
  • compositions and process of the invention are further illustrated by, but are not intended to be limited to, the following examples wherein parts are parts by weight unless otherwise indicated.
  • the billets were cylindrical tubes with a length of about 6.35 cm and a diameter of about 1.27 cm.
  • the billets were formed into hose couplings by cold forward extrusion where one end of the billet was reduced to provide a 17.8 cm long section of 2.54 cm in diameter with a wall thickness of about 0.32 cm extending from about a 2.54 cm long section of billet of the original dimensions.
  • a zinc phosphate coating was first formed on the billet and then the billets were dipped for 5 minutes in the reactive lubricant bath, which was at a temperature of about 71-77°C, removed and allowed to dry.
  • the bath compositions are given in Table I below:
  • Example 4 The composition of Example 4 was used to coat 400 steel billets for deep drawing steel grenades.
  • the billets were cleaned in a caustic solution, rinsed with water, dried, immersed in the lubricant bath at a temperature of 79.4 ⁇ 82.2°C for about 5 minutes and then removed from the bath and dried.
  • the bath had a total fatty solids content of 7 to 9% and a free fatty acid content of about 0.5 point.
  • the billets were subjected to four cold forming operations, with cleaning, annealing and lubricant application between each forming operation, to successfully form the grenades.
  • the acceptance rate was 96.5% which is slightly above the normal rate.
  • the process previously used a phosphoric acid reactive oil which was messy to use and corrosive to the skin.
  • Example 4 The composition of Example 4 was used to coat aluminum billets for forming fire extinguisher bottles by impact extrusion.
  • the aluminum billets were first cleaned in an alkaline solution, rinsed with water, alkaline etched, and rinsed with water.
  • a number of the billets were coated with zinc phosphate, rinsed with water and an alkaline solution, coated with the lubricant composition of Example 4 at a bath concentration of about 8 percent by weight total fatty solids at temperatures of about 75.6-82.2 * C and dried.
  • the remaining billets were coated with lubricant without applying the zinc phosphate coating. It was noted that a reaction of the lubricant with the aluminum surface occurred even in the absence of the zinc phosphate undercoat. Both groups of billets were successfully impact extruded. Some die pick up resulted from the phosphate coated parts which could be remedied by lowering the coating thicknesses by adjusting the bath concentrations.
  • the process previously used to form the bottles included a zinc phosphate undercoat and a
  • the process and compositions of the invention thus provide a non-oily, non-hygroscopic, dry, hard lubricant system which permits the severe cold forming of parts without die sticking and without damage or discoloration of the parts due to excessive temperature generation.
  • the lubricant system is so effective that, as illustrated above, the use of a phosphate precoating can be eliminated in certain severe applications which reduces process stops and the possibility of die pick up of the lubricant.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Lubricants (AREA)

Claims (6)

1. Trockenfilm-Schmiermittelsystem, umfassend einen Zinkphosphatüberzug auf Stahl oder Aluminium, dadurch gekennzeichnet, daß der Überzug mit einem Alkalimetallstearat und einer Verbindung, ausgewählt aus der Gruppe, bestehend aus sulfurisierten Fettsäuren und chlorierten Fettsäuren und Gemischen davon, umgesetzt worden ist, um einen trockenen, .pigmentfreien Schmiermittelfilm herzustellen.
2. Trockenfilm-Schmiermittelsystem nach Anspruch 1, dadurch gekennzeichnet, daß der Überzug zusätzlich mit einem Phosphatester eines nichtionogenen oberflächenaktiven Mittels auf Polyoxyethylenbasis umgesetzt worden ist.
3. Verfahren zur Kaltverformung von Stahl oder Aluminium, dadurch gekennzeichnet, daß man auf einen Stahl- oder Aluminiumbarren einen Überzug aus Zinkphosphat aufbringt, auf das Zinkphosphat aus einem wäßrigen Bad einen zweiten pigmentfreien Überzug aufbringt, der ein Alkalimetallstearat und ein Additiv, ausgewählt aus der Gruppe, bestehend aus sulfurisierten Fettsäuren und chlorierten Fettsäuren und Gemischen davon, einschließt, um einen trockenen pigmentfreien Schmiermittelfilm zu bilden, der eine Zinkseife einschließt, und daß man sodann den Barren unter Verwendung eines Preßgesenks verformt.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß der zweite pigmentfreie Überzug zusätzlich einen Phosphatester eines nichtionogenen oberflächenaktiven Mittels auf Polyoxyethylenbasis enthält.
5. Verfahren zur Kaltverformung von Metallen, dadurch gekennzeichnet, daß man auf den Metallbarren aus einem wäßrigen Bad einen pigmentfreien Überzug aufbringt, der eine Alkalimetallfettsäureseife und ein Additiv, ausgewählt aus der Gruppe, bestehend aus sulfurisierten Fettsäuren, chlorierten Fettsäuren und Gemischen davon, einschließt, um einen trockenen pigmentfreien Schmiermittelfilm zu bilden, und daß man sodann den Barren unter Verwendung eines Preßgesenks verformt.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß der pigmentfreie Überzug zusätzlich einen Phosphatester eines nichtionogenen oberflächenaktiven Mittels auf Polyoxyethylenbasis enthält.
EP82105093A 1981-08-19 1982-06-11 Schmiermittel für die Kaltverformung und Verfahren zu deren Verwendung Expired EP0073306B1 (de)

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US29425981A 1981-08-19 1981-08-19
US294259 1981-08-19
US33721982A 1982-01-06 1982-01-06
US337219 1982-01-06

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8950366B2 (en) 2013-05-07 2015-02-10 Ford Global Technologies, Llc Method for reducing valve recession in gaseous fuel engines
US9453465B2 (en) 2013-05-07 2016-09-27 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines
US9624872B2 (en) 2013-05-07 2017-04-18 Ford Global Technologies, Llc Method for reducing valve recession in gaseous fuel engines
US9777646B2 (en) 2013-05-07 2017-10-03 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines
US9909514B2 (en) 2013-05-07 2018-03-06 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61269929A (ja) * 1985-05-24 1986-11-29 Nippon Parkerizing Co Ltd 金属材料の潤滑処理方法
BR9408416A (pt) * 1993-12-24 1997-08-05 Castrol Kabushiki Kaisha Lubrificante para moldagem de alumínio ou liga de alumínio e placa de alumínio ou de liga de alumínio para processos de moldagem
US5706684A (en) * 1995-10-03 1998-01-13 Cincinnati Milacron Inc. Metalworking process
CN101677933B (zh) 2007-06-12 2013-07-17 罗迪亚公司 口腔护理制剂中的烷氧基化的磷酸一元醇酯、二元醇酯和多元醇酯及其使用方法
EP2152839B1 (de) 2007-06-12 2018-11-14 Solvay USA Inc. Waschmittelzusammensetzung mit schmutzlösenden hydrophilierungsmitteln und verfahren zur verwendung

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Publication number Priority date Publication date Assignee Title
US3372117A (en) * 1965-11-26 1968-03-05 Hooker Chemical Corp Cold forming lubricant
US3375193A (en) * 1966-07-05 1968-03-26 Chrysler Corp Metalworking lubricant
FR2086367A1 (de) * 1970-04-27 1971-12-31 Parker Ste Continentale
US3983044A (en) * 1974-04-01 1976-09-28 Sun Oil Company Of Pennsylvania Low smoking lubricating composition for cold heading operations

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8950366B2 (en) 2013-05-07 2015-02-10 Ford Global Technologies, Llc Method for reducing valve recession in gaseous fuel engines
US9453465B2 (en) 2013-05-07 2016-09-27 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines
US9624872B2 (en) 2013-05-07 2017-04-18 Ford Global Technologies, Llc Method for reducing valve recession in gaseous fuel engines
US9777646B2 (en) 2013-05-07 2017-10-03 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines
US9909514B2 (en) 2013-05-07 2018-03-06 Ford Global Technologies, Llc Direct injection of diluents or secondary fuels in gaseous fuel engines

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CA1182101A (en) 1985-02-05
AU8540682A (en) 1983-02-24
DE3270379D1 (en) 1986-05-15
DK370082A (da) 1983-02-20
AU547051B2 (en) 1985-10-03

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