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US20030130137A1 - Aqueous lubricant for plactic working of metallic material and method of lubricant film processing - Google Patents

Aqueous lubricant for plactic working of metallic material and method of lubricant film processing Download PDF

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Publication number
US20030130137A1
US20030130137A1 US10/360,482 US36048203A US2003130137A1 US 20030130137 A1 US20030130137 A1 US 20030130137A1 US 36048203 A US36048203 A US 36048203A US 2003130137 A1 US2003130137 A1 US 2003130137A1
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US
United States
Prior art keywords
lubricant
water
waterborne
wax
waxes
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.)
Abandoned
Application number
US10/360,482
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English (en)
Inventor
Yasuo Imai
Syuji Nagata
Masayuki Yoshida
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.)
Henkel AG and Co KGaA
Original Assignee
Henkel AG and Co KGaA
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 Henkel AG and Co KGaA filed Critical Henkel AG and Co KGaA
Assigned to HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN reassignment HENKEL KOMMANDITGESELLSCHAFT AUF AKTIEN ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IMAI, YASUO, NAGATA, SYUJI, YOSHIDA, MASAYUKI
Publication of US20030130137A1 publication Critical patent/US20030130137A1/en
Abandoned 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
    • C10M173/00—Lubricating compositions containing more than 10% water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C9/00—Cooling, heating or lubricating drawing material
    • B21C9/005—Cold application of the lubricant
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
    • B21C9/00—Cooling, heating or lubricating drawing material
    • B21C9/02—Selection of compositions therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21J—FORGING; HAMMERING; PRESSING METAL; RIVETING; FORGE FURNACES
    • B21J3/00—Lubricating during forging or pressing
    • 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
    • C—CHEMISTRY; METALLURGY
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    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/02—Carbon; Graphite
    • 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
    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/10—Metal oxides, hydroxides, carbonates or bicarbonates
    • C—CHEMISTRY; METALLURGY
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    • C10M125/00—Lubricating compositions characterised by the additive being an inorganic material
    • C10M125/22—Compounds containing sulfur, selenium or tellurium
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
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    • C10M2201/0663—Molybdenum sulfide used as base material
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    • C10M2201/08—Inorganic acids or salts thereof
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    • 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
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    • C10M2201/0873—Boron oxides, acids or salts used as base material
    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
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Definitions

  • This invention relates to a waterborne lubricant for the plastic working of metals, such as iron, steel, stainless steel, titanium, and aluminum, that imparts an excellent lubricity to the surface of the metal and that does so without the execution of a conversion treatment on the metal surface.
  • This invention also relates to a method for using said waterborne lubricant. More particularly, this invention relates to a waterborne lubricant for the plastic working of metals that forms, by a simple procedure and without the execution of a conversion treatment, a highly lubricating coating on the surface of a metal, such as iron, steel, stainless steel, titanium, or aluminum, that will be subjected to plastic working, such as forging, wire drawing, or tube drawing.
  • This invention also relates to a method for forming a lubricating coating on metals in which a lubricating coating is formed on a metal surface using the waterborne lubricant according to this invention.
  • a lubricating coating is usually formed on the surface of a metal, such as iron, steel, or stainless steel, that will be subjected to plastic working in order to prevent the scuffing and galling that would be produced by metal-to-metal contact between the workpiece and tool.
  • a metal such as iron, steel, or stainless steel
  • One type of lubricating coating that can be produced on the metal surface involves the physical attachment of lubricant to the metal surface.
  • Another type involves the application of lubricant after the production of a conversion coating on the metal surface by a chemical reaction. Physical attachment of the lubricant on the metal surface provides a poorer adherence than use of the lubricant on a conversion coating elaborated on the metal surface, and as a result the former type is usually employed with light working processes.
  • a phosphate coating or oxalate coating is produced on the metal surface when a conversion coating is used; this conversion coating functions as a carrier.
  • a sliding lubricant is applied after the production of this conversion coating.
  • the application of lubricant on an underlayer of a phosphate or oxalate coating is frequently used in particular in the severe working sector.
  • the lubricants applied on conversion coatings can also be broadly divided into two types depending on the method of application.
  • One type involves physical attachment of the lubricant on the conversion coating, while the other type involves a reactive attachment of the lubricant on the conversion coating.
  • the first type includes lubricants comprising an extreme-pressure agent added to a mineral, vegetable, or synthetic base oil.
  • the first type also includes lubricants comprising a solid lubricant (e.g., graphite or molybdenum disulfide) dissolved along with a binder component in water; these lubricants are attached by drying. Since these lubricants can be simply applied by spraying or immersion, they offer the advantage of making bath management almost unnecessary.
  • This invention relates to a waterborne lubricant for the cold plastic working of metals.
  • This waterborne lubricant comprises (A) water-soluble inorganic salt; (B) solid lubricant; (C) at least one oil component selected from mineral oils, animal and vegetable fats and oils, and synthetic oils; (D) surfactant; and (E) water.
  • the solid lubricant is present uniformly dispersed, while the oil is present uniformly emulsified.
  • the lubricant provided by this invention is not stable in industrial applications due to the presence of the oil component in emulsion form, and this lubricant therefore does not provide a high lubricity on a stable basis.
  • This invention relates to a lubricant composition for the plastic working of metals.
  • This lubricant composition contains (A) synthetic resin, (B) water-soluble inorganic salt, and water, wherein the solids weight ratio (B)/(A) is 0.25/1 to 9/1 and the synthetic resin is present dissolved or dispersed.
  • the lubricant provided by this invention does not generate an acceptable lubricity on a stable basis under severe working conditions due to its use of synthetic resin as a main component.
  • An object of this invention is to provide a waterborne lubricant for the plastic working of metals that can be applied to a variety of metals, enables a simple treatment, and takes global environmental protection into consideration.
  • Another object of this invention is to provide a method for forming lubricating coatings.
  • the inventive waterborne lubricant for the plastic working of metals characteristically contains (A) water-soluble inorganic salt, (B) at least one lubricating agent selected from molybdenum disulfide and graphite, and (C) wax, wherein these components are dissolved or dispersed in water, the (B)/(A) solids concentration ratio (as the weight ratio) is 1.0 to 5.0, and the (C)/(A) solids concentration ratio (as the weight ratio) is 0.1 to 1.0.
  • A water-soluble inorganic salt
  • B at least one lubricating agent selected from molybdenum disulfide and graphite
  • C wax
  • the water-soluble inorganic salt used in this invention is preferably at least one selection from the group consisting of sulfates, silicates, borates, molybdates, and tungstates.
  • the inorganic salt is selected from the group consisting of sodium sulfate, potassium sulfate, potassium silicate, sodium borate potassium borate, ammonium borate, ammonium molybdate, sodium molybdate, sodium tungstate and mixtures thereof.
  • graphite is used as the lubricating agent.
  • molybdenum disulfide is used as the lubricating agent.
  • the wax used in this invention is preferably a water-dispersed natural or synthetic wax having a melting point of 70 to 150° C.
  • preferred waxes include paraffin waxes, microcrystalline waxes, petrolatum waxes, Fischer-Tropsch waxes, polyethylene waxes, polypropylene waxes, carnauba wax, and montan wax.
  • the invention is also directed to a nonreactive method for forming a lubricating coating useful in the plastic working of metals on a metal surface comprising applying a waterborne lubricating coating at an add-on of at least 0.5 g/m2 to a conversion coating-free metal surface and drying the waterborne lubricating coating; said waterborne lubricating coating comprising (A) a component of water-soluble inorganic salt and (B) a component of at least one lubricating agent selected from molybdenum disulfide and graphite, and (C) a component of wax wherein these components are dissolved or dispersed in water, the (B)/(A) solids concentration ratio (as the weight ratio) is 1.0 to 5.0, and the (C)/(A) solids concentration ratio (as the weight ratio) is 0.1 to 1.0.
  • a preferred method for forming a lubricating coating on a metal is characterized by forming a lubricating coating at an add-on of 0.5 to 40 g/m2 on the surface of a metal by bringing the cleaned metal into contact with a lubricant as described above and then drying.
  • the metal is preferably cleaned using at least one selection from the group consisting of shotblasting, sandblasting, alkaline degreasing, and pickling.
  • Contact with the lubricant is preferably effected after the metal has been heated to 60-100° C. It is also preferred that the waterborne lubricant has a temperature of 50-90° C.
  • FIG. 1A shows test specimens of selected size and shape used in the backward punch test prior to forming into a cup shape.
  • FIG. 1B shows a sectional view of a test specimen in the punch and die according to the backward punch test as the test is being performed.
  • FIG. 1C shows test specimens after forming into a cup shape in the backward punch test.
  • FIG. 2A shows a test specimen in position on a die for the spike test.
  • FIG. 2B shows a test specimen during the spike test.
  • the water-soluble inorganic salt (A) used in the inventive waterborne lubricant functions to impart hardness and strength to the lubricating coating.
  • the selected water-soluble inorganic salt must therefore dissolve uniformly in the solution and must form a solid coating film upon drying.
  • Water-soluble inorganic salts with such properties preferably comprise at least one selection from the group consisting of the sulfates, silicates, borates, molybdates, and tungstates.
  • sodium borate e.g., sodium tetraborate
  • potassium borate e.g., potassium tetraborate
  • ammonium borate e.g., ammonium tetraborate
  • ammonium molybdate sodium molybdate
  • sodium molybdate sodium molybdate
  • sodium tungstate sodium tungstate
  • the at least one lubricating agent selected from molybdenum disulfide and graphite comprising the component (B) used by this invention functions to impart lubricity.
  • the lubricating agent used by this invention is present in dispersed form in the inventive waterborne lubricant.
  • a known surfactant can therefore be used as necessary or desired.
  • the lubrication performance is undesirably diminished when this ratio is less than 1.0, while a ratio in excess of 5.0 is undesirable due to the associated decline in the bath stability of the lubricant.
  • the wax (C) is not particularly restricted with regard to its structure and type, but the use of a natural or synthetic wax is preferred.
  • the wax component is added in order to enhance the sliding properties of the coating by melting upon exposure to the heat generated during the plastic working operation.
  • the wax should therefore have a melting point of 70 to 150° C. in order to manifest its activity in the initial working period, while the wax should also be stable in aqueous solution and should not impair the strength of the coating.
  • the wax can be exemplified by paraffin waxes, microcrystalline waxes, petrolatum waxes, Fischer-Tropsch waxes, polyethylene waxes, polypropylene waxes, carnauba wax, and montan wax.
  • the wax content preferably gives a value of 0.1 to 1.0 for the ratio (C)/(A) (solids weight ratio between the wax (C) and water-soluble inorganic salt (A)).
  • the more preferred range for this ratio is 0.2 to 0.8.
  • An oil and/or solid lubricant may also be added to the inventive waterborne lubricant as an auxiliary when the inventive waterborne lubricant will be used in severe working operations.
  • Nonionic surfactant, anionic surfactant, amphoteric surfactant, or cationic surfactant can be used in those cases where surfactant is required in order to disperse the above-described lubricating agent or wax.
  • the nonionic surfactant is not critical and can be exemplified by polyoxyethylene alkyl ethers, polyoxyalkylene (ethylene and/or propylene) alkylphenyl ethers, polyoxyethylene alkyl esters originating from polyethylene glycol (or ethylene oxide) and higher fatty acid (e.g., C12-C18), and polyoxyethylene sorbitan alkyl esters originating from sorbitan, polyethylene glycol, and higher fatty acid (e.g., C12-C18).
  • the anionic surfactant is also not critical and can be exemplified by the salts of fatty acids, sulfate ester salts, sulfonate salts, phosphate ester salts, and dithiophosphate ester salts.
  • the amphoteric surfactant is again not critical and can be exemplified by amino acid-type and betaine-type carboxylates, sulfate ester salts, sulfonate salts, and phosphate ester salts.
  • the cationic surfactant is also not critical and can be exemplified by the amine salts of fatty acids and by quaternary ammonium salts. These surfactants can in each case be used singly or in combinations of two or more selections.
  • the waterborne lubricant according to this invention can also be used as a cold plastic working lubricant (e.g., for wire drawing, tube drawing, forging, and so forth) on metal (e.g., iron, steel, stainless steel, copper, copper alloys, aluminum, aluminum alloys, titanium, titanium alloys, and so forth) already coated by a known method with a phosphate coating (zinc phosphate, manganese phosphate, iron phosphate, tin phosphate, etc.), oxalate coating (iron oxalate, etc.), cryolite, or calcium aluminate.
  • a phosphate coating zinc phosphate, manganese phosphate, iron phosphate, tin phosphate, etc.
  • oxalate coating iron oxalate, etc.
  • cryolite or calcium aluminate.
  • the shape of the metal is not critical, and one can contemplate application to the working of not only stock such as bar or block, but also shaped material (e.g., gears, shafts) after hot forging.
  • the inventive method for forming a lubricating coating on metals is a nonreactive method that is characterized by the formation of a lubricating coating at an add-on of 0.5 to 40 g/m2 on the surface of a metal by bringing the cleaned metal into contact with lubricant as described above and then drying.
  • the add-on of the lubricating coating formed on the metal surface should be adjusted as appropriate for the ensuing degree of working, but is preferably in the range of 0.5 to 40 g/m2 and more preferably is in the range of 2 to 20 g/m2.
  • the lubricity becomes unsatisfactory when this add-on is below 0.5 g/m2. While there are no problems with lubricity at above 40 g/m2, such values are undesirable because they result in clogging of the die by residues.
  • the add-on is calculated from the surface area and the weight difference of the metal before and after treatment.
  • the quantity of waterborne lubricant solids (concentration) should be suitably adjusted so as to control the add-on into the above-specified range.
  • a procedure frequently used in practical applications involves dilution of a concentrate of the lubricant and use of the resulting dilution.
  • the water used to make the dilution is not critical, but the use of deionized water or distilled water is preferred.
  • the procedure for cleaning the metal when the metal is to be submitted to application of the lubricating coating preferably is at least one selection from the group consisting of shotblasting, sandblasting, alkaline degreasing, and pickling.
  • the purpose of this cleaning step is to remove oxide scale that has grown during, for example, annealing, and to remove various other contaminants (e.g., oil).
  • the procedure for effecting contact between the inventive waterborne lubricant and the metal is not critical and procedures such as immersion, flow coating, and spraying can be used.
  • the coating time is also not critical as long as the surface becomes thoroughly coated with the waterborne lubricant.
  • the waterborne lubricant must be dried after application. While this drying can be carried out by standing at ambient temperature, it will ordinarily be best to carry out drying at 60 to 150° C. for 10 to 60 minutes.
  • the waterborne lubricant is preferably brought into contact with metal already heated to 60 to 100° C. Moreover, contact is preferably carried out using waterborne lubricant heated to 50 to 90° C. These tactics lead to a substantial improvement in drying performance and can even enable drying at ambient temperature as well as enabling a reduction in thermal energy losses.
  • Test material for the backward punch tests This was commercial spheroidized annealed S45C. The diameter was 30 mm ⁇ and the height was varied from 18 to 40 mm in steps of 2 mm.
  • Test material for the spike tests This was commercial spheroidized annealed S45C. The diameter was 25 mm ⁇ and the height was 30 mm.
  • FIG. 1A A series of cylindrical test specimens of selected dimension are shown in FIG. 1A.
  • Specimen 2 was molded with the punch 3 and die 1 of a 200-ton crank press as shown in FIG. 1B to fabricate a cup-shaped molding.
  • FIG. 1C A series of resulting cup-shaped moldings, resulting from the backward punch test on the series of cylindrical test specimens of FIG. 1A are shown in FIG. 1C.
  • This molding operation left 10 mm and produced a 50% cross section reduction.
  • the good punch depth (mm) was designated as the largest inside height of the test specimen cups at which the inner surface remained undamaged.
  • the material submitted to the backward punch tests was commercial spheroidized annealed S45C.
  • the test specimens had a diameter of 30 mm ⁇ and a height that was varied from 18 to 40 mm in steps of 2 mm.
  • the die was SKD11; the punch was HAP40; the land diameter was 21.21 mm ⁇ ; and the working rate was 30 strokes/minute.
  • This spike test was based on Japanese Laid-Open (Unexamined or Kokai or A) Patent Application Number Hei 5-7969 (7,969/1993).
  • a cylindrical specimen 2 is placed as shown in FIG. 2A on a die 1 that has a funnel-shaped inner surface and is placed under a load and the specimen is pressed into the die to carry out forming as shown in FIG. 2B.
  • the lubricity is evaluated based on the height (mm) of the resulting spike: a higher spike height is indicative of better lubricity.
  • the material used in this test was commercial spheroidized annealed S45C.
  • the diameter of the test specimen was 25 mm ⁇ and its height was 30 mm.
  • Treatment was carried out using sequence A and waterborne lubricant 1 as described below (1 weight % nonionic surfactant was added for dispersion).
  • Water-soluble inorganic salt sodium tetraborate
  • lubricating agent molybdenum disulfide
  • wax polyethylene wax
  • Treatment was carried out using sequence B and waterborne lubricant 2 as described below (1 weight % nonionic surfactant was added for dispersion).
  • water-soluble inorganic salt sodium tetraborate
  • lubricating agent graphite
  • wax polyethylene wax
  • Treatment was carried out using sequence A and waterborne lubricant 3 as described below (1 weight % nonionic surfactant was added for dispersion).
  • water-soluble inorganic salt sodium silicate
  • lubricating agent graphite
  • wax polyethylene wax
  • Treatment was carried out using sequence A and waterborne lubricant 4 as described below (1 weight % nonionic surfactant was added for dispersion).
  • water-soluble inorganic salt sodium tungstate
  • lubricating agent molybdenum disulfide
  • wax paraffin wax
  • Treatment was carried out using sequence B and waterborne lubricant 5 as described below (1 weight % nonionic surfactant was added for dispersion).
  • water-soluble inorganic salt potassium sulfate
  • lubricating agent molybdenum disulfide
  • wax paraffin wax
  • Treatment was carried out using sequence A and waterborne lubricant 6 as described below (1 weight % nonionic surfactant was added for dispersion).
  • water-soluble inorganic salt potassium sulfate
  • wax paraffin wax
  • Treatment was carried out using sequence B and waterborne lubricant 7 as described below.
  • water-soluble inorganic salt potassium sulfate
  • lubricating agent molybdenum disulfide
  • Treatment was carried out using sequence A and waterborne lubricant 8 as described below (1 weight % nonionic surfactant was added for dispersion).
  • water-soluble inorganic salt borax, 10%
  • solid lubricant calcium stearate, 10%
  • oil component palm oil, 0.5%
  • surfactant polyoxyethylene alkyl alcohol, 1%
  • Treatment was carried out using sequence A and waterborne lubricant 9 as described below (1 weight % nonionic surfactant was added for dispersion).
  • water-soluble inorganic salt sodium tetraborate
  • metal salt of fatty acid calcium stearate
  • coating weight g/m 2 : 10 TABLE 1 Results of evaluation no. of steps backward in treatment punch spike height, sequence Treatment depth, mm mm
  • Example 1 4 coating type 60 13.2
  • Example 2 4 coating type 60 13.2
  • Example 3 4 coating type 60 13.2
  • Example 4 4 coating type 60 13.1
  • Example 5 4 coating type 60 13.1 Comp. Ex. 1 4 coating type 40 11.6 Comp. Ex. 2 4 coating type 40 11.7 Comp. Ex. 3 6 reactive type/ 56 13.0 large amounts of waste Comp. Ex. 4 4 coating type 56 12.5 Comp. Ex. 5 4 coating type 56 12.6

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US10/360,482 2000-08-07 2003-02-07 Aqueous lubricant for plactic working of metallic material and method of lubricant film processing Abandoned US20030130137A1 (en)

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PCT/JP2001/003639 WO2002012419A1 (fr) 2000-08-07 2001-04-26 Lubrifiant aqueux pour le travail au plastique d'un materiau metallique et procede d'elaboration d'un film lubrifiant

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US20090048129A1 (en) * 2006-01-31 2009-02-19 Nissan Motor Co., Ltd. Nanoparticle-containing lubricating oil compositions
CN102092987A (zh) * 2010-12-02 2011-06-15 二重集团（德阳）重型装备股份有限公司 锻件模锻用保温粘接剂及其制备方法
US9192973B1 (en) 2013-03-13 2015-11-24 Meier Tool & Engineering, Inc. Drawing process for titanium
US9487732B2 (en) 2011-03-28 2016-11-08 Henkel Ag & Co. Kgaa Lubricating coating agent for plastic working and method for producing the same
CN108219912A (zh) * 2017-12-30 2018-06-29 常州市奥普泰科光电有限公司 一种水基金属切削液及其制备方法
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US20090018037A1 (en) * 2006-01-31 2009-01-15 Nissan Motor Co., Ltd. Nanoparticle-containing lubricating oil compositions
US20090048129A1 (en) * 2006-01-31 2009-02-19 Nissan Motor Co., Ltd. Nanoparticle-containing lubricating oil compositions
US9023771B2 (en) 2006-01-31 2015-05-05 Nissan Motor Co., Ltd. Nanoparticle-containing lubricating oil compositions
CN102092987A (zh) * 2010-12-02 2011-06-15 二重集团（德阳）重型装备股份有限公司 锻件模锻用保温粘接剂及其制备方法
US9487732B2 (en) 2011-03-28 2016-11-08 Henkel Ag & Co. Kgaa Lubricating coating agent for plastic working and method for producing the same
US9192973B1 (en) 2013-03-13 2015-11-24 Meier Tool & Engineering, Inc. Drawing process for titanium
CN108219912A (zh) * 2017-12-30 2018-06-29 常州市奥普泰科光电有限公司 一种水基金属切削液及其制备方法
CN113210448A (zh) * 2021-05-17 2021-08-06 西北有色金属研究院 一种带润滑涂层的tb9钛合金盘圆丝材冷拉拔制备方法

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CN1214095C (zh) 2005-08-10
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KR20030027002A (ko) 2003-04-03
CN1468294A (zh) 2004-01-14
JP3984158B2 (ja) 2007-10-03
KR100621693B1 (ko) 2006-09-08
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CA2418942A1 (en) 2003-02-07
WO2002012419A1 (fr) 2002-02-14

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