US3506413A - Surface treated steel sheet suitable for forming - Google Patents

Surface treated steel sheet suitable for forming Download PDF

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US3506413A
US3506413A US704496A US3506413DA US3506413A US 3506413 A US3506413 A US 3506413A US 704496 A US704496 A US 704496A US 3506413D A US3506413D A US 3506413DA US 3506413 A US3506413 A US 3506413A
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steel sheet
coating
acid
zinc
metallic
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Hiromu Uchida
Toshio Herai
Yasuyuki Taniguchi
Hideshi Sato
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Fuji Iron and Steel Co Ltd
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Fuji Iron and Steel Co Ltd
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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
    • C10M177/00—Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/934—Electrical process
    • Y10S428/935—Electroplating
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12542—More than one such component
    • Y10T428/12549—Adjacent to each other
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • Y10T428/12618—Plural oxides
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12701—Pb-base component
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12785—Group IIB metal-base component
    • Y10T428/12792—Zn-base component
    • Y10T428/12799—Next to Fe-base component [e.g., galvanized]
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12951—Fe-base component
    • Y10T428/12972—Containing 0.01-1.7% carbon [i.e., steel]

Definitions

  • the present invention relates to a surface treated steel sheet suitable for forming.
  • the surface treated steel sheet of this invention is obtained by coating a steel sheet with zinc, lead, zinc based alloy or lead based alloy (hereinafter called zinc or lead), and applying on the coated surface a layer of matter, solid at room temperatures, which comprises a higher carboxylic acid or a mixture thereof with a suitable amount of amine.
  • Lubricants are generally required when a steel sheet is subjected to a forming operation such as press forming. For this purpose oily products have been used. Recently attempts have been made to use metallic soap based lubricants as substitutes for the oil lubricants.
  • the metallic soap based lubricants have excellent lubricating ability as compared with the oil lubricants. Also, the steel sheet which is coated with such soap bases is easy to handle, since the coating layer is solid and not sticky and thus it can be advantageously used as a coating material for a pre-lubricated steel sheet. On the other hand, the metallic soap based lubricants have disadvantages.
  • the metallic surface of zinc, or lead present on the steel surface has a strong affinity with the higher carboxylic acid or its mixture with a suitable amount of amine (hereinafter called higher carboxylic acid based coating material).
  • higher carboxylic acid based coating material A thin layer of metallic-soap-like substance is formed 3,506,413 Patented Apr. 14, 1970 "ice by reaction of the metallic coating with the higher carboxylic acid based coating material at the interface therebetween.
  • the metallic-soap-like substance having a higher carboxylic acid radical is regularly oriented in respect to the steel sheet substrate and strongly bonded with the layer on the steel sheet substrate according to its formation history, thus giving a remarkable lubricating eifect.
  • FIG. 1 shows the results of measurement of kinetic friction coeificient in a bath of stearic acid obtained with Sodas type II penduram style tester, between a non-plated steel ball and three kinds of pins (1), (2) and (3).
  • Pin 1 is a non-plated steel pin.
  • Pin 2 is a steel pin which is coated with 10 g./m. of zinc by electroplating and
  • pin 3 is a steel pin which is coated with g./m. of lead-tin alloy (Sn: 20 wt. percent) by hot dipping. In the case of measurements below the melting point of the stearic acid, molten stearic acid was coated on the pin by hot dipping.
  • This coated pin was used and the measurements taken in a water bath.
  • the stearic acid used in the test contained a small amount of palmitic acid and had a melting point of 57 C.
  • the zinc stearate corresponding to this stearic acid has a melting point of above 100 C.
  • a metallic soap composed mainly of lead stearate also shows a melting point above 100 C. It should be noted from FIG. 1 that in both the zinc plated pin and the lead-zinc alloy plated pin, the kinetic friction coelficient tends to lower even above the melting point of the stearic acid and shows the minimum point at a temperature above 100 C.
  • the minimum point of kinetic friction coeflicient appears at the melting point of stearic acid, and the friction coefficient increases as the temperature increases beyond the melting point. From this it can be seen that the formation of iron based metallic soap does not easily progress even with increases in temperature. Further, the kinetic friction coefiicient near room temperatures shows a lower value in case of the zinc plated pin or the lead-tin alloy played pin.
  • the excellent lubricity of the present steel sheet is based on the presence of a thin layer of metallic-soap-like substance formed on the interface between the metallic coating of zinc or lead and the higher carboxylic acid based coating material. It should be noted that the excellent lubricity can be maintained under most severe forming conditions, such as those encountered in press forming works. This maintenance of excellent lubricity under severe forming conditions is considered to be based on the fact that in the present steel sheet, both the metallic coating and the higher carboxylic acid coating react only partially, and for the most part remain unreacted on the steel sheet surface.
  • the unreacted metallic coating and higher carboxylic acid react with each other to form an additional metallic-soap-like substance even when the aforesaid layer of metallic-soap-like substance is damaged by contact with the press forming tool and is thinned due to the dimensional increase of the steel sheet.
  • the above effects can be obtained only when the layer of higher carboxylic acid based coating is in the solid form at the ordinary temperatures.
  • the coating layer at portions on which heavy load is put during a severe forming work, namely at portions which require lubricant most, i squeezed out thus causing shortness of lubricant and a desirable maintenance of excellent lubricity as above cannot be obtained.
  • the layer of higher carboxylic acid based coating is limited to a solid form in the present invention.
  • FIG. 1 is a graph showing the relation between tem pertures and kinetic friction coefficient of a non-plated steel pin, an electrolytic zinc plated steel pin and a hotdip lead-tin alloy (tin: 20 wt. percent) plated steel pin respectively with a non-plated steel ball in stearic acid; and FIGS. 25 are graphs respectively showing results of Fukuis Conical Cup Test and Ericksen Test in the examples of the present invention.
  • metallic coatings applied on the steel sheet zinc coating, lead coating or alloy coatings composed mainly of zinc or lead applied by an ordinary electrolytic platings or by an ordinary hot-dip plating are useful. Further the metal coatings applied by the above method may be subjected to thermal treatment to allow the coating metal to diffuse into the steel sheet substrate and convert the surface of the steel sheet substrate to an alloy system containing iron. This also gives eflective metal coatings.
  • a thin layer of hydrated metal oxide such as hydrated chromium oxide and/or silicon oxide, may be applied on the above metal coatings by a chemical treatment and the like for the purpose of improving paint adherence or preventing rust formation with almost no deteriorating effects on the forming quality of the present steel sheet.
  • the coating material which is solid at room temperatures, for application on the steel sheet according to the present invention, is prepared by selecting higher carboxlic acids and adjusting the amount of amine to be added to the higher carboxylic acids as described hereinafter.
  • higher carboxylic acid used in the present invention means any carboxylic acid having eight or more carbon atoms, which includes, for example, saturated fatty acids having no fewer carbon atoms than that in capyrlic acid; corresponding unsaturated fatty acids; hydroxy carboxylic acids; naphthenic acids; dicarboxylic acids; and natural products composed mainly of the above acids, such as animal oil fatty acids, hardened animal oil fatty acids, vegetable oil fatty acids, hardened vegetable oil fatty acids, petroleum acids etc.
  • amines to be added to the above higher carboxylic acids there are, for example, primary mono-amines such as lauryl amine and cyclohexyl amine; secondary monoamines such as di-iso-propyl amine and di-cyclohexyl amine; tertiary monoamines such as triethyl amine; polyamines such as di-amino-propane; and oxazines and imid azoles.
  • primary mono-amines such as lauryl amine and cyclohexyl amine
  • secondary monoamines such as di-iso-propyl amine and di-cyclohexyl amine
  • tertiary monoamines such as triethyl amine
  • polyamines such as di-amino-propane
  • oxazines and imid azoles there are, for example, primary mono-amines such as lauryl amine and cyclohexyl amine
  • secondary monoamines
  • the material may be heated or dissolved in an organic solvent to liquidize it and then applied on the sheet surface by roll coating, spray coating, brush coating, mop coating, dip coating, flow coating, etc.
  • the solid material may be directly spread on the steel surface and then refiowed by heating with an infra-red beam, hot air, etc.
  • the metallic coating Although the primary purpose of the metallic coating is that of a reaction medium for forming the metallicsoap-like substance, it also acts as a rust preventing coating. Further, it produces uniform coatings by its aflinity to the higher carboxylic acid based coating material.
  • Zinc or lead metallic coatings of various thickness were applied on steel sheet substrates and the higher carboxylic acid diluted in a solvent was applied thereon.
  • the results showed that in case of the non-alloyed zinc or lead coatings, a uniform coating of the higher carboxylic acid based coating material is obtained when the zinc or lead coating is not less than 250 mg./m.
  • zinc or lead alloy coatings were used, a uniform coating of the coating material was obtained when the total content of lead or zinc in the alloy was not less than 250 mg./m. An excellent forming character is obtained in these ranges.
  • the higher carboxylic acid based coating material reacts more easily with the metallic coating. It has been found that the lubricating effect by the higher carboxylic acid coating will be improved until the amount of the metallic coating or the the total metal content increases to 2500 mg./m. However, the surface lubricating effect does not decrease and remains almost constant even when the amount of the metallic coating exceeds 2500 mg./m. Therefore any amount of not less than 250 mg./m. of the metallic coatmay be used. As for the rust preventing effect by the metallic coating, a better result can, of course, be obtained by a thicker coating.
  • a very small amount of the higher carboxylic acid based coating material which is solid at room temperatures is effective. Remarkable effects can be obtained when the coating material is used in an amount greater than 10 mg./m. Although the lubricating effect increases as the amount of this coating material increases, the practical upper limit of the coating material is 5 g./m. in view of possible adherence and accumulation of the coating material on the sheet feeder or forming tools, and re-adherence of the accumulated coating material on the steel sheet, time required for removing the coating material at the last stage, and the necessity to minimize the contamination of the removing liquid.
  • the present invention includes not only a steel sheet both sides of which are surface treated but also a steel sheet wherein only one side is surface treated and further a steel sheet wherein only a part thereof is surface treated.
  • the latter sheets are at times suitable to certain types of forming operations.
  • the present steel sheets are produced in three steps; production of steel shet substrate (non-plated), coating of metal; and application of the higher carboxylic acid based coating material. However, it is not necessary to conduct the above three steps in the same shop. Each of the steps can be done in a separate shop. The last step of applying the higher carboxylic acid based coating material may be done on the blanking line or just before the forming operation.
  • the higher carboxylic acid based coating material can be easily removed by an alkaline degreaser or an organic solvent. Contamination by the coating material, particularly, of the alkaline degreaser, is negligible due to the nature of the coating material and the fact that the coating material is applied in a small amount. Also, the zinc and lead based metallic coatings may be, if necessary, removed by an acid solution, such as sulphuric acid, acetic acid, hydrochloric acid, or by a strong alkaline solution.
  • an acid solution such as sulphuric acid, acetic acid, hydrochloric acid, or by a strong alkaline solution.
  • the metallic coating can be utilized as a protective and decorative layer for the final product or as a paint coating base or a base for a chemical treatment (such as chromate treatment and phosphate treatment).
  • the zinc base metallic coating dissolves acting as a sacrificing anode to the steel sheet substrate during the acid pickling.
  • the finally exposed, naked surface of the steel sheet has very high activity just as in case of cathodic acid pickling and provides an excellent base for permanent plating.
  • a thinner zinc base coating (zinc content in the coating is 250- 2500 mg./m. is advantageous in view of economy and its easier removal.
  • Such a metallic coating is also useful as a pre-coating for promoting a phosphate treatment applied on the steel sheet as paint base etc. and for uniformly forming such a phosphate coating.
  • EXAMPLE 2 1 g./m. of zinc coating was applied on a cold rolled rimmed steel sheet of 0.8 mm. thickness, and then palmitic acid dissolved in toluene was coated on the surface and dried. The amount of the palmitic acid coating was increased stepwise and press formability of the steel sheet was tested. The results are shown in Table 3.
  • EXAMPLE 3 10 g./m. of zinc electroplating was applied on cold rolled, rimmed steel sheets of 0.8 mm. thickness, and then the following treatments were applied. Results of various tests are shown in Table 4. Testpieces A-K are present inventive steel sheets and L-P are comparison steel sheets.
  • Treatments Testpieces (inventive steel sheets):
  • A-Lauric acid as toluen solution was applied and dried (non-volatile matter: 200 mm./m.
  • B-Palmitic acid as toluen solution was applied and dried (non-volatile matter: 200 mg./m.
  • DBehenic acid as toluen solution was applied and dried (non-volatile matter: 200 mg./m.
  • E-Sebacic acid as toluen solution was applied and dried (non-volatile matter: 200 mg./m.
  • G-Palm oil fatty acid as toluen solution was applied and dried (non-volatile matter: 200 mg./m.
  • HHardened castor oil fatty acid as toluen solution was applied and dried (non-volatile matter: 200 mg./m.
  • IHardened fish oil fatty acid as toluen solution was ap plied and dried (non-volatile matter: 200 mg./m.
  • J-Palmitic acid was melted by heating and applied (nonvolatile matter: 200 mg./rn.
  • KSolid palmitic acid was directly spread on the steel surface and melted by an infra-red lump (non-volatile matter: 200 mg./m.
  • NSame treatment as A was applied on non-plated, cold rolled, rimmed steel sheet of 0.8 mm. thickness.
  • OSame treatment was C was applied on non-plated, cold rolled, rimmed steel sheet of 0.8 mm. thickness.
  • EXAMPLE 4 Various zinc base metallic coatings were applied on cold rolled, rimmed steel sheets (A-J) of 0.8 mm. thickness, and a toluene solution of palmitic acid was coated on the one side of the steel sheets and dried to give 2 g./m. of non-volatile matter coating. Forming qualities of these steel sheets and the comparison steel sheets B and K were tested. The results are shown in Table 5.
  • BCommercial press oil was applied on similar steel sheet as B (Comparison) CCoated with hot dip zinc-tin alloy (Sn: 25%) plating of 100 g./m.
  • K--Commcrcial press oil was applied on a non-plated steel sheet.
  • EXAMPLE 5 A number of test pieces similar to steel sheets A and B of Example 4 were made, and conical cup tests were done with the treated surfaces of the testpiece faced on the die side. As comparison, non-treated steel sheets A and B corresponding to steels A and B, were subjected to conical cup tests. Sheets A and B were lubricated with spindle oil on their die sides. The results are shown in FIG. 2, in which the average conical cup values of every five testpieces from the beginning of the test are plotted against the testing order.
  • testpieces A and B were continuously subjected to Erichsen tests with the treated surface faced on the punch side, and as comparison, nontreated testpieces A' and B corresponding to the testpieces A and B were also tested with Vaseline lubricated on the punch side surface of the testpieces. Results are shown in FIG. 3, in which the ordinate shows an average value for every five testpieces.
  • the chromate treatment does not hinger the lubricity of the present steel sheet.
  • the maximum punch load in case of the present steel sheets was 520% lower that of the steel sheets which were applied with other oil lubricant.
  • EXAMPLE 8 Lead electroplated (plating thickness: 1 g./m. steel sheets of 0.8 mm. thickness were coated with various amounts of palmitic acid as toluene solution on the side and subjected to formability tests, the results of which are shown in Table 7.
  • Amount of palmitic acid (mg/m9):
  • Steel sheets A to I were subjected to various tests, the results of which are shown in Table 8.
  • Steel sheets A to E are lead-tin alloy (Sn: 15 wt. percent) hot dip plated (plating thickness, 100 g./m. and are treated as under on one side, and there sheets fall within the scope of the present invention.
  • Steel sheets F to J are set forth as comparison and include plated steel sheets with various treatments and non-plated steel sheets with various treatments.
  • EXAMPLE 10 the die side. Results are shown in FIG. 4, in which the ordinate shows an average value for every five testpieces in series from the beginning of the test.
  • testpieces B were continuously subjected to Erichsen tests with the treated surface faced on the punch side.
  • similar lead-tin alloy plated steel sheets B which were not surface treated were also tested with vaseline applied on the steel surface on the punch side. Results are shown in FIG. 5, in which the ordinate shows an average value for every five testpieces.
  • Surface treated steel sheet suitable for forming works which comprises metallic coating applied on a steel sheet surface, said metallic coating being composed of material selected from the group consisting of zinc, lead, zinc base alloy and lead base alloy, and a layer of higher carboxylic acid based material applied on the metallic coating, said higher carboxylic acid based material being solid at room temperatures.
  • the metallic coating is not less than 250 mg./m. in respect of zinc or lead content, and the layer of higher carboxylic acid based material is not more than 5 g./-m.
US704496A 1966-09-30 1967-10-02 Surface treated steel sheet suitable for forming Expired - Lifetime US3506413A (en)

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JP6457466 1966-09-30
JP7051166 1966-10-26
JP5299767 1967-08-18

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US4600662A (en) * 1985-03-18 1986-07-15 Illinois Tool Works Inc. Ferrous article layered with ion vapor deposited non-oxidized aluminum
US5324594A (en) * 1991-10-30 1994-06-28 Kawasaki Steel Corporation Galvannealed steel sheets exhibiting excellent press die sliding property
US20070266753A1 (en) * 2006-05-18 2007-11-22 Gutter Protection Systems, Inc. Gutter Cover Manufacturing Apparatus

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US5491035A (en) * 1992-03-27 1996-02-13 The Louis Berkman Company Coated metal strip
US5489490A (en) * 1993-04-05 1996-02-06 The Louis Berkman Company Coated metal strip
US5429882A (en) * 1993-04-05 1995-07-04 The Louis Berkman Company Building material coating
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US1597189A (en) * 1921-01-11 1926-08-24 Westinghouse Lamp Co Method of cold-drawing refractory materials
US1963298A (en) * 1929-07-23 1934-06-19 American Steel & Wire Co Wire drawing method
US2365959A (en) * 1931-11-17 1944-12-26 American Steel & Wire Co Stainless steel wire
US2990943A (en) * 1956-10-09 1961-07-04 Armour & Co Metal working process
US3258319A (en) * 1962-11-23 1966-06-28 Du Pont Lubricant coated formable metal article
US3220233A (en) * 1963-03-06 1965-11-30 Universal Oil Prod Co Working of metals with salts of amine carboxylic acids and amine alkyl phosphate

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4486512A (en) * 1982-02-10 1984-12-04 Mitsui Mining & Smelting Co., Ltd. Radioactive waste sealing container
US4600662A (en) * 1985-03-18 1986-07-15 Illinois Tool Works Inc. Ferrous article layered with ion vapor deposited non-oxidized aluminum
US5324594A (en) * 1991-10-30 1994-06-28 Kawasaki Steel Corporation Galvannealed steel sheets exhibiting excellent press die sliding property
US20070266753A1 (en) * 2006-05-18 2007-11-22 Gutter Protection Systems, Inc. Gutter Cover Manufacturing Apparatus

Also Published As

Publication number Publication date
DE1627741B2 (de) 1973-11-22
DE1627741A1 (de) 1971-11-04
FR1584717A (xx) 1970-01-02
GB1194751A (en) 1970-06-10
DE1627741C3 (de) 1974-06-20
NL6713287A (xx) 1968-04-01

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