US3923673A - Metal deforming process - Google Patents

Metal deforming process Download PDF

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Publication number
US3923673A
US3923673A US414488A US41448873A US3923673A US 3923673 A US3923673 A US 3923673A US 414488 A US414488 A US 414488A US 41448873 A US41448873 A US 41448873A US 3923673 A US3923673 A US 3923673A
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United States
Prior art keywords
metal
weight
process according
deforming
block copolymer
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Expired - Lifetime
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US414488A
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English (en)
Inventor
Henten Klaas Van
Cornelis Couvee
Jager Dirk De
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Shell USA Inc
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Shell Oil Co
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M1/00Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants
    • C10M1/08Liquid compositions essentially based on mineral lubricating oils or fatty oils; Their use as lubricants with additives
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/06Well-defined aromatic compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2203/00Organic non-macromolecular hydrocarbon compounds and hydrocarbon fractions as ingredients in lubricant compositions
    • C10M2203/10Petroleum or coal fractions, e.g. tars, solvents, bitumen
    • C10M2203/102Aliphatic fractions
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2205/00Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions
    • C10M2205/06Organic macromolecular hydrocarbon compounds or fractions, whether or not modified by oxidation as ingredients in lubricant compositions containing conjugated dienes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/042Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds between the nitrogen-containing monomer and an aldehyde or ketone
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2217/00Organic macromolecular compounds containing nitrogen as ingredients in lubricant compositions
    • C10M2217/04Macromolecular compounds from nitrogen-containing monomers obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2217/043Mannich bases
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/24Metal working without essential removal of material, e.g. forming, gorging, drawing, pressing, stamping, rolling or extruding; Punching metal
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/241Manufacturing joint-less pipes
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/242Hot working
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/243Cold working
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • C10N2040/245Soft metals, e.g. aluminum
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • C10N2040/246Iron or steel
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00Specified use or application for which the lubricating composition is intended
    • C10N2040/20Metal working
    • C10N2040/244Metal working of specific metals
    • C10N2040/247Stainless steel
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10NINDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2050/00Form in which the lubricant is applied to the material being lubricated
    • C10N2050/04Aerosols
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00Metal working
    • Y10T29/49Method of mechanical manufacture
    • Y10T29/4981Utilizing transitory attached element or associated separate material
    • Y10T29/49812Temporary protective coating, impregnation, or cast layer

Definitions

  • metal forming operations involves the storage period prior to such operations wherein the metal often is procured for periods up to several months, for example, prior to its use. During this storage period the metal surfaces are subjected to corroding influences including the action of water, oxygen, S H 5 and other acid forming gases or vapors.
  • the material applied to the metal surface to relieve the stress of the deforming operations can be referred to as a lubricant even though the material may be in fact a solid or polymeric substance.
  • the lubricants may be applied as or in oils, emulsions, solutions, or powders.
  • the lubricant so deposited does not immediately form a continuous film and therefore exposes a portion of the surface of the metal to the corroding influences referred to above.
  • one of the most critical limitations inherently possessed by most of the previously employed lubricants is their sensitivity to decomposition at the nearest point of contact between the metal surface and the shaping mechanism.
  • the unit pressures encountered even in shallow drawing of sheet steel are of the order of 1,000 psi, but may exceed 300,000 psi in bar drawing of high tensile'materials. Because of these extreme presssures, contact temperatures may be in the order of 600F or higher during such Common operations as wire drawing. It is evident, therefore, that many materials are subject to instantaneous decomposition at the point of contact and may lose their effectiveness at that time as metal lubricants. Furthermore, during the storage periods preceeding the deforming operations, some polymers may decompose and either expose the metal surface or result in relatively poor operation as lubricants during deforming operations.
  • oils have been employed as well as pigmented emulsions, extreme pressure compositions, soap films, sulfide or phosphate coatings, sulfurized oils, chlorinated oils, oxalate coatings solid powders such as graphite, products such as tallow and fats and a great variety of combinations of the same.
  • Certain polymers have been investigated for this purpose including polyolefins and hydrogenated polymers of conjugated dienes. However, each of these has been found to have limitations, particularly wherein extreme requirements are encountered as in deep drawing operations.
  • An ideal lubricant particularly in deep drawing oper ations, should be one capable of satisfactory lubricating both in the deformation in mill direction and, simulta-'.
  • a process for the deforming of metals comprises coating the metal with a lubricant comprising an oil-modified block copolymer havingat least one polymer block A of a monoalkenylarene and at least one polymer block B of a conjugated diene, and thereafter subjecting the coated metal to mechanical deformation.
  • the present invention is based upon the discovery that these non-hydrogenated block copolymers when modified with a petroleum lubricant provide an essentially ideal deforming lubricant and moreover provide a stable protective surface for the metal parts prior to and during the deforming operations.
  • the block copolymers used in this invention have the minimal structure A-B, and the preferred structure of A-B-A, but may utilize more complex structures which are either linear or branched.
  • Typical polymers are the following:
  • polystyrene-polyisoprene polystyrene-polybutadiene polystyrene-polybutadiene-polystyrene poly( a-methylstyrene )-polyisoprene-poly( a-methylstyrene).
  • the polymer blocks A are monoalkenylarene species 3 such as polystyrene, poly-(tert-butylstyrene) or poly( amethylstyrene).
  • the polymer blocks B are conjugated diene polymer blocks. While homopolymeric blocks are preferred, copolymeric blocks may be employed as long as blocks A on the one hand and b ocks B on the other predominate in the species referred to above.
  • Block molecular weights may vary over a wide range; thus, for example, the polymer blocks A may have number average molecular weights between about 4,000 and 100,000, preferably between about 10,000 and 50,000.
  • Polymer blocks B may have average molecular weights between about 20,000 and 1,000,000, preferably between about 25,000 and 150,000. The molecular weights referred to herein may be determined, for example, by tritium counting methods or osmotic pressure methods. V
  • the block copolymers are applied to the metal surfaces as oil dispersions which comprise 5 to 50% of the block copolymer and 50-95% by weight of an oil.
  • oil is of petroleum origin or other hydrocarbon source
  • a selection of the type of oil may be made with the. variables being the proportions of aromatic, naphthenic and paraffinic constituents. It is preferred that such oils contain no .more than about 30% by weight aromatic hydrocarbons.
  • the compositions of this type may be applied to the metal surface by painting or spraying. This may be a single operation or may entail multi-stage operations in which, for example, the
  • the oil-modified block copolymers may be applied to the metal surface as powders, melts, solutions in relatively volatile solvents, as oil dispersions or in emulsion form or colloidal dispersions.
  • the block copolymers may be used without further modification or may be compounded for specific purposes. The following lists illustrate the materials which may be utilized together with the block copolymers for the purposes of this invention.
  • Solid Inorganic Lubricants graphite molybdenum sulfide zinc phosphate borax plumbago wax
  • Polymeric Lubricants polysulfide rubbers Thiokols) polyvinyl chloride polychloroprenes nylon polyethylene polypropylene polytetrafluroethylene Extreme Pressure Agents tritolyl phosphate tributyl phosphate tricresyl phosphate trioctyl phosphate sulfurized fats soaps
  • Oils vegetable oils and their acids aliphatic diesters e.g., di-Z-ethylhexyl sebacate
  • polyalkylene oxides polyoxyalkylene glycols Resins A.
  • Adhesion of the block copolymers .to the metal surface is enhanced by utilizing certain primers which may be applied to the metal prior to application of the block copolymer or may form a part of the block copolymer. coating composition. Adhesion to the metal is also promoted by the placement of polar substituents on the block copolymer or on a fraction thereof, such as-by chlorosulfination, chlorination, hydroxylation or carboxylation.
  • Such derivatized block copolymers are included within the concept of the block copolymers forming the essential lubricant of this invention (as long as their polar substituents comprise no more than about 2% by weight of the block copolymer) or may constitute an additive which may be mixed with the otherwise unmodified block copolymers.
  • compositions of the block copolymer comprising compositions of the block copolymer, polyvinylchloride and trihydrocarbyl phosphates.
  • Polyvinylchlorides have only borderline compatibility with the block copolymers but form surprisingly satisfactory compositions with the latter when the phosphate is present as what may be referred to as a compatibilizing plasticizer.
  • a composition of this type comprises parts by weight of the block copolymer, 10-100 parts by weight of the polyvinylchloride and 5-150 parts by weight of the phosphate.
  • the lubricants of this invention provide nearly ideal lubrication, particularly in deep drawing operations as indicated by the point on the graph forming the figure and labeled thermoplastic rubber. The reason for this is obscure. It has been found, however, tht with many other types of polymers excessive lubrication may lead to wrinkling or buckling, while poor lubrication can cause tearing of the metal. The deforming problems become most serious when forming unsymmetrical parts which involve simultaneously drawing and stretching. Friction between the tools and the work piece predominates in reorganized areas and scoring may occur when less satisfactory lubricants are employed. Viscosity and lubricity may be factors qualifying the end result. In other systems, it has been indicated that lubricity improves with an increase in viscosity.
  • compositions found to be especially useful in this process comprise the block copolymers modified with petroleum waxes and sulfides or phosphates.
  • the latter may chemically react with the metal surface while the wax performs a function of lubrication which, however, is insufficient in the absence of the block copolymer.
  • compositions of this type comprise 100 parts by weight of the block copolymer, 10-100 parts by weight of petroleum wax and l-SO parts by weight of sulfides or phosphates such as those listed in the disclosure.
  • the metals contemplated for treatment in the process of this invention include particularly iron, steel, brass, aluminum, copper, titanium and the like.
  • the deforming operations considered here include cold or hot working, shallow or deep drawing of sheets or bars or other shapes as well as extrusion and stamping.
  • process for deforming metal which comprises applying to the surface of said metal a composition comprising 550% by weight of a non-hydrogenated block copolymer having at least one homo polymer block of a monoalkenylarene selected from the group consisting of styrene, alpha-methylstyrene and tertbutyl styrene, said block having an average molecular weight between about 4000 and 100,000 and at least one homo polymer block of a conjugated diene selected from the group consisting of butadiene and isoprene, said block having an average molecular weight between about 20,000 and 1,000,000, and 50-95% by weight of a hydrocarbon lubricant, said lubricant containing no more than about by weight of aromatic hydrocarbons and subjecting the metal so treated to deforming operations.
  • a composition comprising 550% by weight of a non-hydrogenated block copolymer having at least one homo polymer block of a monoalkenylarene selected from the group consisting of s
  • composition is applied to the metal surface as a hot melt.
  • block copolymer has the structure polystyrene-polybutadiene-polystyrene.
  • composition comprises 1030% of block copolymer and of a petroleum wax.
  • composition is applied to the metal in the form of a powder.
  • lubricant comprises a petroleum hydrocarbon lubricating oil.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Lubricants (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
US414488A 1973-03-09 1973-11-09 Metal deforming process Expired - Lifetime US3923673A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB1145573A GB1466261A (en) 1973-03-09 1973-03-09 Deep-drawing of metals coated with a thermoplastic rubber/oil dispersion

Publications (1)

Publication Number Publication Date
US3923673A true US3923673A (en) 1975-12-02

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Application Number Title Priority Date Filing Date
US414488A Expired - Lifetime US3923673A (en) 1973-03-09 1973-11-09 Metal deforming process

Country Status (11)

Country Link
US (1) US3923673A (xx)
JP (1) JPS5025601A (xx)
AU (1) AU6639774A (xx)
BE (1) BE811992A (xx)
CA (1) CA1045622A (xx)
DE (1) DE2411010A1 (xx)
FR (1) FR2220577B1 (xx)
GB (1) GB1466261A (xx)
IT (1) IT1013062B (xx)
NL (1) NL7403136A (xx)
SE (1) SE395472B (xx)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4688411A (en) * 1984-05-21 1987-08-25 Sumitomo Metal Industries, Inc. Method for continuous drawing of wire rod
USH1482H (en) * 1987-12-04 1995-09-05 Shell Oil Company Coatings for metals based on functionalized block copolymers
WO1995031297A1 (en) * 1994-05-13 1995-11-23 Henkel Corporation Aqueous metal coating composition and process with reduced staining and corrosion
US5650087A (en) * 1993-03-02 1997-07-22 Gram A/S Metal mould for making a frozen confectionary product and a method for making the mould
US6096435A (en) * 1997-03-06 2000-08-01 Kuraray Co., Ltd. Thermoplastic polymer composition having a thermoplastic elastic polymer and a block copolymer

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7297735B2 (en) 2003-03-05 2007-11-20 Eastman Chemical Company Polycarbonate compositions
DE60320035T2 (de) 2003-03-05 2009-05-14 Eastman Chemical Co., Kingsport Polymerblends

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3258319A (en) * 1962-11-23 1966-06-28 Du Pont Lubricant coated formable metal article
US3269943A (en) * 1961-06-12 1966-08-30 Horace T Potts Multi-layer lubrication utilizing encapsulating coating
US3370010A (en) * 1966-05-03 1968-02-20 Sinclair Research Inc Mineral lubricating oil containing polymer having anti-wear properties
US3515528A (en) * 1965-12-14 1970-06-02 Shell Oil Co Block copolymer strippable coatings of butadiene styrene block copolymer containing a fatty acid amide
US3568486A (en) * 1969-01-31 1971-03-09 Montgomery H A Co Preparation of metal for deforming operations

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3269943A (en) * 1961-06-12 1966-08-30 Horace T Potts Multi-layer lubrication utilizing encapsulating coating
US3258319A (en) * 1962-11-23 1966-06-28 Du Pont Lubricant coated formable metal article
US3515528A (en) * 1965-12-14 1970-06-02 Shell Oil Co Block copolymer strippable coatings of butadiene styrene block copolymer containing a fatty acid amide
US3370010A (en) * 1966-05-03 1968-02-20 Sinclair Research Inc Mineral lubricating oil containing polymer having anti-wear properties
US3568486A (en) * 1969-01-31 1971-03-09 Montgomery H A Co Preparation of metal for deforming operations

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4688411A (en) * 1984-05-21 1987-08-25 Sumitomo Metal Industries, Inc. Method for continuous drawing of wire rod
USH1482H (en) * 1987-12-04 1995-09-05 Shell Oil Company Coatings for metals based on functionalized block copolymers
US5650087A (en) * 1993-03-02 1997-07-22 Gram A/S Metal mould for making a frozen confectionary product and a method for making the mould
WO1995031297A1 (en) * 1994-05-13 1995-11-23 Henkel Corporation Aqueous metal coating composition and process with reduced staining and corrosion
US6248701B1 (en) * 1994-05-13 2001-06-19 Henkel Corporation Aqueous metal coating composition and process with reduced staining and corrosion
US6096435A (en) * 1997-03-06 2000-08-01 Kuraray Co., Ltd. Thermoplastic polymer composition having a thermoplastic elastic polymer and a block copolymer

Also Published As

Publication number Publication date
SE395472B (sv) 1977-08-15
DE2411010A1 (de) 1974-09-19
BE811992A (fr) 1974-09-09
CA1045622A (en) 1979-01-02
JPS5025601A (xx) 1975-03-18
IT1013062B (it) 1977-03-30
GB1466261A (en) 1977-03-02
FR2220577A1 (xx) 1974-10-04
FR2220577B1 (xx) 1978-07-07
NL7403136A (xx) 1974-09-11
AU6639774A (en) 1975-09-11

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