US3749598A - Surface treated steel for the use of forming operation - Google Patents

Surface treated steel for the use of forming operation Download PDF

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Publication number
US3749598A
US3749598A US3749598DA US3749598A US 3749598 A US3749598 A US 3749598A US 3749598D A US3749598D A US 3749598DA US 3749598 A US3749598 A US 3749598A
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Prior art keywords
steel sheet
coating
fatty acid
amine
film
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K Kushima
K Yahano
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Nippon Steel Corp
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Nippon Steel Corp
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
    • C10M2207/125—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms having hydrocarbon chains of eight up to twenty-nine carbon atoms, i.e. fatty acids
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    • C10M2207/10—Carboxylix acids; Neutral salts thereof
    • C10M2207/12—Carboxylix acids; Neutral salts thereof having carboxyl groups bound to acyclic or cycloaliphatic carbon atoms
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    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/27—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.]
    • Y10T428/273—Web or sheet containing structurally defined element or component, the element or component having a specified weight per unit area [e.g., gms/sq cm, lbs/sq ft, etc.] of coating
    • Y—GENERAL 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
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
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    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal

Definitions

  • This invention relates to a surface treated steel sheet use in a forming operation having a preliminary lubricant film comprising a fatty acid, an amine and a plasticizer on the surface of the steel sheet.
  • a lubricant is generally required to diminish the friction and to prevent the formation of burning and press defects when a steel sheet is subjected to a forming operation such as press forming.
  • a lubricant for this purpose liquid types, such as, oily products, and emulsion type have hitherto been used.
  • a solid lubricant film preliminary on the steel sheet surface in order to improve the lubricity as well as the workability.
  • a metallic soap based lubricant and a plastic film are used for such a preliminary lubricant. While a metallic soap based lubricant forms a solid film having an excellent lubricating ability, it has certain disadvantages.
  • a steel sheet having a coating film which is solid at ambient temperature, comprising a higher fatty acid with a suitable amount of an amine as a main constituent, can eliminate the problem in manufacturing encountered by using a steel sheet coated with said metallic soap based lubricant or with said plastic.
  • this preliminary lubricant film has many advantages such that the film has an excellent lubricating ability, even when only a small amount is used, comparable to that of the commercial high grade press oil, such that the film has an excellent rust preventing ability and is easily removed, morover, the film can be applied on the steel sheet surface with simple equipment.
  • said preliminary lubricant is squeezed out and deposits as a white powder on the surface of the forming die in the press work, thereby making inferior goods and decreasing the productivity.
  • the present inventors investigated the reason for the deposition of the white powder, and found that the powdery white crystals are formed when the composition comprising a higher fatty acid and an amine is cooled in the presence of water (including water vapour). This is because the fatty acid and its amine salt are insoluble in water.
  • a plasticizer having both hydrophilic and lipophilic radicals for instance, a coupling agent having a oxyethylene radical
  • the action of the coupling agent is to disperse water uniformly in the lubricant film comprizing a fatty acid and an amine, and to give plasticity to the film obtained, thus preventing the deposition of white powder in the film as well as the adhesion and accumulation thereof on the surface of the die during the press forming.
  • the essential point of the invention is a surface treated steel sheet having a coated layer of a composition, soild at ambient temperature, comprising 95-60 weight percent of a composition consisting of 60 mol percent of a higher fatty acid and 10-40 mol percent of an amine, and 5-40 weight percent of a coupling agent having both hydrophilic and lipophilic radicals, particularly the oxyethylene or oxypropylene radical, on the surface of the steel sheet.
  • Said steel sheet possesses excellent properties for the use in a forming operation.
  • the lubricant film in this invention is considered to of a salt formed by the reaction between a higher fatty acid and an amine, free higher fatty acid remaining unreacted in excess, and a coupling agent.
  • the lubricating action in the steel sheet of this invention may be due to the following reasons. Namely, in the range where the interface pressure is low, the coating layer itself has a fluid lubricating action, the layer acting as a very viscous fluid; and, on the other hand, when the contact pressure becomes high, the metallic soap, which is formed on the surface of the steel sheet by the reaction between the surface part of the steel sheet and free higher fatty acid, acts as a boundary film, decreasing the friction.
  • the metallic soap which is formed between the surface of steel sheet substrate and higher fatty acid as above-mentioned, orientates regularly and is combined firmly on the surface of the steel sheet substrate, and consequently possesses excellent properties as a boundary film. It is considered further that, even when a part of the boundary film is broken due to a high contact pressure, free fatty acid in the film remaining in excess repairs the boundary film at once. For these reasons, an excellent lubricating eifect can be obtained with only a very thin coating.
  • Steel sheet substrates for this invention are, for example, hot rolled medium plate, hot rolled thin sheet, cold rolled steel sheet, blue sheet and various kinds of plated steel sheet. They will be called in a general term simply as steel sheet hereinafter.
  • Higher fatty acid in this invention means fatty acid whose carbon number is more than 10.
  • those solid at ambient temperature and used in this invention include, for instance, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid and arachic acid.
  • a mixture of these fatty acids is also included.
  • Those containing a mixture of these fatty acids and corresponding unsaturated fatty acids as a main constituent, such as tallow fatty acid, hydrogenated fatty acid, hydrogenated castor oil fatty acid and naphthenic acid may also be applied. While said higher fatty acids are usually obtained commercially as a mixture, they belong naturally within the scope of the object of this invention.
  • Amines used in this invention include, for instance, primary amines such as octylamine and cyclohexylamine, secondary amines such as diisopropylamine and dicyclohexylamine, tertiary amines such as triethylamine and triethanolamine, oxazines, imidazoles, and mixtures thereof.
  • the coupling agent used in this invention means a plasticizer having both hydrophilic and lipophilic radicals, particularly the oxyethylene radical, -CH CH O, or oxypropylene radical, CH CH CH O-, in its molecule and whose hydrophile-lipophile balance value, (HLB- value),
  • the higher fatty acid takes charge of the lubricating action in the forming operation, and its effect differs depending on the mixing ratio with the amine.
  • the amine is added for the purpose of improving the rust preventing ability, easiness for degreasing and the ease of coating.
  • the content of the amine is less than 10 mol percent, the effect of the coating him in improving the rust preventing ability is insufiicient, and the ease degreasing (or removing) the film is also insufficient, thus requiring a long period for degreasing.
  • the coupling agent is added for the purpose of preventing the deposition of white powder in the film in both cases when the lubricant film is applied on the surface of steel sheet on which a trace of water is remaining, and when the steel sheet coated with a lubricating film is stored at lower temperatures.
  • Plasticizers having both hydrophilic and lipophilic properties are most excellent for the coupling agent.
  • the content of the coupling agent is smaller than 5% in Weight, the prevention of said deposition is not observed; and when the content exceeds 40% in weight, the composition is not a solid at ambient temperature as said coupling agents are liquid at ambient temperature, and the characteristic in lubricity of solid substance at ambient temperature and one of the features of this invention is lost. Therefore, the content of the coupling agent is desirously 540% in weight.
  • the preliminary lubricant may also be applied on the surface of the blank or forming die just before pressing as in the case of common press Working oil.
  • the composition may be made molten by heating and applied by means of a roll coater and the like, or the composition is dissolved in an organic solvent and the liquid so obtained is applied by roller coating, spray coating, electrostatic coating, brush coating or flow coating.
  • the coating operation becomes much easier.
  • the solid composition of this invention may also be applied directly as fine particles to adhere on the surface of the steel sheet by spraying etc., and then made molten by heating with, for instance, the use of an infrared beam, hot air or heating roller to form a uniform coating film.
  • composition of this invention is effective even when the amount coated is very smallffoninstance' about 0.1
  • the practical upper limit of the coating amount is g./m.
  • the coating film can easily be removed by an alkaline degreaser or an organic solvent. As the coating amount is small, pollution of the degreaser liquid is minimal.
  • the steel sheet of this invention shows, with only a small amount of the coating material, for instance with an amount of 0.1 g./m. a rust preventing property equal to or more than the same property the steel sheet coated with a common rust preventing oil. There is no need for coating with an additional rust preventing oil in transporting the steel sheet of this invention, and the rust preventing ability after press-forming is also excellent.
  • EXAMPLE 1 Various coating materials relating to this invention as shown in Table 1 were applied on cold rolled rimmed steel sheet with a thickness of 0.8 mm., and their lubricating ability, rust preventing ability and easiness of removing of the coating film were tested. Samples No. 1-8 differ in the mixing ratio of fatty acid and amine, including the compositions without the scope of this invention, samples No. 9-16 show the effect of various kinds of fatty acid under the addition of definite amounts of amine and coupling agent. As a comparison, commercial rust preventing oils (No. 17-18) and commercial mineral press oil (No. 19-20) were also tested. The results were as shown in Table 2.
  • fatty acids having a carbon number of more than 10 are advantageous. Namely compositions which are solid at ambient temperature sh'oW excellent lubricity. Among them, palmitic acid, stearic acid and a mixture of these show particularly excellent effects. As for the ratio of fatty acid and amine, it is adequate that the amount of fatty acid is more than the stoichiometrical equivalent.
  • the rust preventing ability when the content of amine in the lubricant component is less than 10 mol percent, the rust preventing ability in open air is insufficient, and when said content exceeds 40 mol percent, the rust preventing ability in moist atmosphere becomes insufficient.
  • the ratio of fatty acid and amine in the lubricant component is: fatty acid 90-60 mol percent and amine 10-40 mol percent.
  • Conical cup test Only the die side of blank was treated.
  • the conical cup value is obtained from a test wherein a. lubricated test pieceis placed in a conical die. A punch presses the test piece into the die, thus shaping the test piece into a conical cup. At the point where the bottom of the cup has at least a 0.05 mm. break, the maximum and minimum outerydiameters of the upper edge of the conical cup are determined.
  • the conical cup value is the arithmeticalmean of the maximum and minimum outer diameters expressed in millimeters. The conical cup test is described in Sheet Metal Industries, 44, 21 (1967).
  • a cold rolled steel sheet was degreased, washed with water, dried, coatedwith a composition with different mixing ratio of the lubricant component and the coupling agent, audstor'ed in a room at 10 C. for 2 weeks.
  • the surface condition was observed, and the accumulation of coating composition on the'pressing die was investigated in pressing the sheet-to obtain an outer part of an automobileffor riding; The results were as shown in Table 3.
  • composition of this invention is a composition of this invention.
  • composition of this invention exhibits an excellent lubricating ability as well for the zinc plated steel sheet.
  • the plated steel sheets it is possible to diminish the content of amine as compared with the case for bare steel sheet.
  • a surface treated steel sheet for use in a forming operation having a coating layer of a composition which is a solid at ambient temperature, comprising 95-60 weight percent of a lubricant component consisting of -60 mol percent of a higher fatty acid having more than 10 carbon atoms, 10-40 mol percent of an amine selected from the group consisting of octylamine, cyclohexylamine, diisopropylamine, dicyclohexylamine, triethylamine, triethanolamine, oxazine, imidazol, and mixtures thereof, and 5-40 weight percent of a coupling agent consisting of a plasticizer having oxyethylene or oxypropylene radicals on the surface of the steel sheet.

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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)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Laminated Bodies (AREA)
US3749598D 1970-07-30 1971-04-29 Surface treated steel for the use of forming operation Expired - Lifetime US3749598A (en)

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JP (1) JPS5014233B1 (fr)
CA (1) CA984818A (fr)
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101328A (en) * 1976-07-09 1978-07-18 A. F. Industries, Inc. White rust inhibitor
WO1979000297A1 (fr) * 1977-11-16 1979-05-31 Nat Can Corp Methode de formation de boites sans couture
US4445813A (en) * 1977-11-16 1984-05-01 National Can Corporation Method of forming seamless container
US4506533A (en) * 1980-05-14 1985-03-26 William Hessel Method of forming seamless drawn and ironed containers of aluminum stock
US5139700A (en) * 1988-08-23 1992-08-18 Cortec Corporation Vapor phase corrosion inhibitor material
US5209869A (en) * 1988-08-23 1993-05-11 Cortec Corporation Vapor phase corrosion inhibitor-dessiccant material
US5320778A (en) * 1988-08-23 1994-06-14 Cortec Corporation Vapor phase corrosion inhibitor-desiccant material
US5332525A (en) * 1988-08-23 1994-07-26 Cortec Corporation Vapor phase corrosion inhibitor-desiccant material
US5344589A (en) * 1988-08-23 1994-09-06 Cortec Corporation Vapor phase corrosion inhibitor-desiccant material

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2920857A1 (de) * 1978-06-12 1979-12-20 Akad Wissenschaften Ddr Verfahren zur kaltumformung metallischer werkstoffe
US4370244A (en) * 1978-12-21 1983-01-25 Akademie Der Wissenschaften Der Ddr Process for cold mechanical working of metallic materials
US5801128A (en) * 1995-10-23 1998-09-01 International Refining And Manufacturing Company Hot melt lubricant and method of application

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4101328A (en) * 1976-07-09 1978-07-18 A. F. Industries, Inc. White rust inhibitor
WO1979000297A1 (fr) * 1977-11-16 1979-05-31 Nat Can Corp Methode de formation de boites sans couture
US4445813A (en) * 1977-11-16 1984-05-01 National Can Corporation Method of forming seamless container
US4506533A (en) * 1980-05-14 1985-03-26 William Hessel Method of forming seamless drawn and ironed containers of aluminum stock
US5139700A (en) * 1988-08-23 1992-08-18 Cortec Corporation Vapor phase corrosion inhibitor material
US5209869A (en) * 1988-08-23 1993-05-11 Cortec Corporation Vapor phase corrosion inhibitor-dessiccant material
US5320778A (en) * 1988-08-23 1994-06-14 Cortec Corporation Vapor phase corrosion inhibitor-desiccant material
US5332525A (en) * 1988-08-23 1994-07-26 Cortec Corporation Vapor phase corrosion inhibitor-desiccant material
US5344589A (en) * 1988-08-23 1994-09-06 Cortec Corporation Vapor phase corrosion inhibitor-desiccant material
US5393457A (en) * 1988-08-23 1995-02-28 Miksic; Boris A. Vapor phase corrosion inhibitor-desiccant material
US5422187A (en) * 1988-08-23 1995-06-06 Cortec Corporation Vapor phase corrosion inhibitor-desiccant material

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Publication number Publication date
JPS5014233B1 (fr) 1975-05-26
FR2099675A1 (fr) 1972-03-17
FR2099675B1 (fr) 1974-08-23
DE2129207A1 (de) 1972-02-03
NL7109596A (fr) 1972-02-01
GB1319907A (en) 1973-06-13
CA984818A (en) 1976-03-02

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