EP0451437B1 - Galvanisiertes Stahlblech mit hohen Pressumformungseigenschaften und Verfahren zu seiner Herstellung - Google Patents

Galvanisiertes Stahlblech mit hohen Pressumformungseigenschaften und Verfahren zu seiner Herstellung Download PDF

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Publication number
EP0451437B1
EP0451437B1 EP91100089A EP91100089A EP0451437B1 EP 0451437 B1 EP0451437 B1 EP 0451437B1 EP 91100089 A EP91100089 A EP 91100089A EP 91100089 A EP91100089 A EP 91100089A EP 0451437 B1 EP0451437 B1 EP 0451437B1
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European Patent Office
Prior art keywords
steel sheet
galvanized steel
galvanized
inorganic compound
press formability
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EP91100089A
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English (en)
French (fr)
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EP0451437A3 (en
EP0451437A2 (de
Inventor
Yoichi C/O Technical Research Division Tobiyama
Chiaki C/O Technical Research Division Kato
Nobuyuki C/O Technical Research Division Morito
Hajime C/O Reseach Laboratories Kimura
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JFE Steel Corp
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Kawasaki Steel Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/78—Pretreatment of the material to be coated
    • 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
    • C10M103/00—Lubricating compositions characterised by the base-material being an inorganic material
    • C10M103/06—Metal compounds
    • 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
    • C10M173/02—Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • 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
    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
    • C10M2201/02—Water
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    • C10M2201/00—Inorganic compounds or elements as ingredients in lubricant compositions
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    • C10M2201/0613—Carbides; Hydrides; Nitrides used as base material
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    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2201/084—Inorganic acids or salts thereof containing sulfur, selenium or tellurium
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    • C10M2201/085—Phosphorus oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
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    • C10M2201/086—Chromium oxides, acids or salts
    • C10M2201/0863—Chromium oxides, acids or salts used as base material
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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    • C10M2201/087—Boron oxides, acids or salts
    • C—CHEMISTRY; METALLURGY
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    • C10M2201/103—Clays; Mica; Zeolites
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Definitions

  • the present invention relates to a galvanized steel sheet with a high press formability characteristic adapted for use as an automotive non-corrosion steel sheet and a method for manufacturing the same.
  • FR-A-262 9 103 discloses a steel sheet which is provided on at least one side thereof with a thin film of a saponification agent which forms soap through reaction with oil.
  • the oil is usually used in a press working station.
  • the saponification agent are alkali metal salts and alkali earth metal salts.
  • alloy electroplated steel sheets such as hot dip galvanized steel sheets, galvannealed steel sheets, electrogalvanized steel sheets, steel sheets electrogalvanized with Zn-Ni, etc., have been developed and placed into use.
  • the inventors hereof examined the press formability of those galvanized steel sheets. Thereupon, it was revealed that the galvanized steel sheets, in contrast with the conventionally used cold-rolled steel sheets, are subjected to so great a frictional resistance against a mold during press forming operation that their press formability is relatively low.
  • the steel sheet is prevented from being smoothly introduced into those portions which are subjected to hard sliding motion, such as a bead portion of a press mold for fixing the steel sheet at the time of press forming.
  • the steel sheet may be broken. Since the proper cushion pressure range (range of cushion pressure within which the steel sheet cannot be wrinkled or broken) of the galvanized steel sheets for the press forming is much narrower than that of the cold-rolled steel sheets, the galvanized sheets are poorer in productivity. Therefore, an improvement of the frictional characteristics of the galvanized steel sheets is urgently needed.
  • the frictional characteristics experienced during a press forming operation are greatly influenced by the properties of the plating surface which is directly in contact with the mold. Accordingly, the frictional characteristics are tentatively improved by coating the plating surface with some material other than a zinc plating, e.g. an organic high molecular film, so that the plating surface is kept from direct contact with the mold and is lubricated.
  • some material other than a zinc plating e.g. an organic high molecular film
  • a method for improving the formability of a steel sheet by improving the frictional characteristics of the sheet surface is disclosed in Published Examined Japanese Patent Application No. 61-26600, for example. According to this method, a specific organic high molecular film is formed on the steel sheet surface. Further, a lubricated-surface steel sheet is proposed which is coated with a film composed mainly of metallic soap or higher fatty acid wax, for example.
  • galvanized steel sheets When galvanized steel sheets are used for automotive purposes, they are usually phosphated before being coated after the press forming operation. In doing this, however, the organic film partially remains on the steel sheet without being thoroughly removed by alkali degreasing as a pretreatment for the phosphating process. Therefore, a normal crystal of a phosphate on galvanized layer cannot be produced by the phosphating process. As a result, the adhesion of the coating film is lowered, so that the corrosion resistance of the coated steel sheet is deteriorated.
  • the object of the present invention is to provide a galvanized steel sheet having better frictional characteristics and considerably improved in press formability without lowering the phosphatability thereof.
  • a galvanized steel sheet with high press formability which has an inorganic compound on a metallic galvanized layer thereof, wherein said inorganic compound is a hydrous borate of alkaline metal, wherein 10 to 1000 mg/m2 of a film of said hydrous borate is applied on the plating surface of said galvanized steel sheet, the friction coefficient of said galvanized sheet being 0.15 or less and the amount of insoluble slimes of said inorganic compound left after water washing or alkali degreasing being less than 1 mg/m2.
  • a method for manufacturing a galvanized steel sheet with high press formability comprising steps of bringing the plating surface of the galvanized steel sheet into contact with a water solution containing 0.1 wt% or more of a borate of alkaline metal, and drying the steel sheet by heating within a temperature range of 60 to 400°C.
  • the inventors hereof examined the relationship between the coefficient of friction and press formability of a galvanized steel sheet. Thereupon, it was observed that the friction coefficient of a galvanized steel sheet, subjected to galvanizing such as electrogalvanizing, galvannealing, etc., is 0.15 or more, compared with about 0.10 for that of a conventional cold-rolled steel sheet with high press formability.
  • the friction coefficient is a value which is obtained by oiled-state measurement in a draw-bead extraction test.
  • the galvanized steel sheet has such a high friction coefficient because zinc and zinc alloy have so low a melting point and so great an affinity for other metals, especially for cast iron and the like frequently used for press molds, that they can easily stick to a mold. Since the frictional characteristics during press forming are influenced by the properties of the plating surface which is brought directly into contact with the mold, it was supposed that the frictional characteristics can be improved by coating the plating surface with some other material than a zinc plating so that the un-coated plating surface is kept from direct contact with the mold and is lubricated.
  • the inventors continued the examination to find that the aforementioned problem on the press forming can be solved by providing a specific inorganic compound on the plating surface so that the resulting friction coefficient is 80% or less of the friction coefficient obtained without any specific substance on the plating surface, preferably 0.15 or less.
  • a galvanized steel sheet according to the invention has an inorganic compound on its metallic galvanized layer.
  • Such galvanized steel sheets include galvannealed steel sheets, hot dip galvanized steel sheets, electrogalvanized steel sheets, steel sheets electrogalvanized with alloyed zinc, such as Zn-Ni, Zn-Fe, etc., and steel sheets flashed with Fe-P, Fe-Zn, etc., for example.
  • the inorganic compound should be one whose friction coefficient can be lowered when it exists on the metallic galvanized layer of the galvanized steel sheet, and the greater part of which can be removed by dissolution in water or by alkali degreasing. Any inorganic compounds may be used for the purpose provided they fulfill these requirements.
  • Inorganic compounds suitably used according to the present invention include borates, carbonates, phosphates, sulfates, nitrates, chlorides, hydroxides, and oxides of alkaline metals such as Na and K, alkaline earth metals such as Ca and Mg, and metals or metalloids such as Fe, Ni, Co, Al, Ti, Si, etc., for example.
  • the galvanized steel sheet according to the present invention can be easily manufactured by bringing the steel sheet into contact with a water solution of the inorganic compound and then drying the resulting sheet, as mentioned later.
  • the inorganic compound is expected to be water-soluble.
  • the inorganic compound should preferably be low-priced, in view of costs, and be highly soluble in water or basic aqueous solutions, since it is to be dissolved and removed by water washing or alkali degreasing.
  • salts of alkaline metals are particularly suited for the purpose.
  • hydrous borates of alkaline metals are very effective for the improvement of the frictional characteristics, and they typically include borax (sodium tetraborate: Na2B4O7 ⁇ 10H2O) which can be industrially mass-produced and is low-priced.
  • hydrous borates of alkaline metals greatly surpasses an anhydrous one in solubility in water for washing or alkali for alkali degreasing.
  • film is thoroughly dissolved by the alkali degreasing preceding the phosphating, and never remains on the steel sheet at all. This is the reason why hydrous borates of alkaline metals are preferably used.
  • the inorganic compound on the zinc-based plating is not limited in form.
  • a filmy or particulate compound is used for the purpose.
  • the coating weight of the inorganic compound on the surface of the galvanized steel sheet has to be adjusted so that the friction coefficient of the galvanized steel sheet with the inorganic compound on plated layer is 80% or less of that of a galvanized steel sheet with no inorganic compound thereon, preferably 0.15 or less at the absolute value of coefficient of friction.
  • the amount of insoluble slimes of the inorganic compound should be less than 1 mg/m2 at the end of the degreasing process before the phosphating process, lest the production of a satisfactory phosphate crystal be hindered during the phosphating process.
  • the coating weight of a hydrous borate of alkaline metal is restricted to a range of 10 to 1,000 mg/m2 for the following reasons. If the coating weight is less than 10 mg/m2, a satisfactory improvement of the frictional characteristics cannot be achieved. If the coating weight exceeds 1,000 mg/m2, on the other hand, the effect of the improvement of the frictional characteristics is saturated, and besides, the film partially remains on the plated layer without being thoroughly removed in the degreasing process before the phosphating process, thus exerting a bad influence on the subsequent phosphating process.
  • the coating weight ranges from 100 to 1,000 mg/m2.
  • Fig. 1 shows the relationships between the coating weight of borax (sodium tetraborate: Na2B4O7 ⁇ 5H2O) on a galvannealed steel sheet, the coefficient of friction obtained in a frictional characteristic test, and the water-resistant secondary adhesion. These individual tests are conducted in the manner described later in connection with various examples. As shown in Fig. 1, the frictional characteristics can be greatly improved without affecting satisfactory phosphatability in the case where the coating weight of borax ranges from 10 to 1,000 mg/m2.
  • a galvanized steel sheet having the aforesaid film of the hydrous borate of alkaline metal thereon may be manufactured in the following manner.
  • the galvanized steel sheet is brought into contact with a water solution containing 0.1 wt% or more of the borate of alkaline metal by dipping, spraying, or coating by means of a roll coater or the like, and is then dried by heating within a temperature range of 60 to 400°C.
  • the borate content of the alkaline metal is adjusted to 0.1 wt% or more for the following reason.
  • the present method in which the galvanized steel sheet is dried by heating after being brought into contact with the aqueous solution, entails some operational disadvantages, such as lowering of line speed.
  • the lower limit of the heating temperature range for the drying is adjusted to 60°C because if the heating temperature is lower than 60°C, a solid film effective for the improvement of the frictional characteristics as aforesaid cannot be formed on the plating.
  • the upper limit is set at 400°C because if the sheet is heated to a temperature exceeding 400°C, the hydrous crystal of the borate of alkaline metal turns into an anhydrous crystal, so that borate film turns into one, which is difficult to dissolve.
  • Fig. 2 shows a process for manufacturing the galvanized steel sheet.
  • numeral 1 denotes the steel sheet; 2, a hot zinc pot; 3, coating weight control means; 4, a galvannealing furnace; and 5, a cooling zone.
  • a aqueous solution containing the aforesaid borate of alkaline metal is sprayed so that the steel sheet is brought into contact with a mist of the solution.
  • the solution containing the borate of alkaline metal may be sprayed at any positions kept at a temperature within the temperature range for the steel sheet.
  • the spraying can be effected at positions A, B and C of Fig. 2, which will be described later in connection with the examples.
  • a aqueous solution containing 5 wt% of potassium tetraborate (K2B4O7 ⁇ 4H2O) was sprayed on the steel sheet at a position (position A of Fig. 2) reached immediately after the steel sheet is wiped over the melt plating pot.
  • the sheet temperature immediately before the spraying was 380°C.
  • a aqueous solution containing 0.7 wt% of sodium metaborate (NaBO2 ⁇ 4H2O) was sprayed on the steel sheet at a position (position B of Fig. 2) reached immediately after the steel sheet gets out of the alloying furnace.
  • the sheet temperature immediately before the spraying was 250°C.
  • An electrogalvanized steel sheet with the coating weight of 60/60 g/m2 (equivalent to the green material of Example 1).
  • a hot dip galvanized steel sheet with the coating weight of 90/90 g/m2 (equivalent to the green material of Example 4).
  • a galvannealed steel sheet with the coating weight of 45/45 g/m2 and alloy content of 9/9% (equivalent to the green material of Example 5).
  • Rust preventing oil containing 10 wt% of molybdenum sulfide (MoS2) was applied to a steel sheet electroplated with Zn-Ni alloy having the coating weight of 30/30 g/m2 and Ni content of 11/11%.
  • Phosphatability Phosphating was effected using a treatment solution, PALBOND L3020 (produced by Nihon Parkerizing Co., Ltd.), and phosphate crystals were observed by means of a 1,500-power scanning electron microscope (SEM). The phosphatability was evaluated in accordance with the following criteria based on the crystalline grain size.
  • a galvanized steel sheet whose press formability is considerably improved without lowering the phosphatability thereof.
  • the galvanized steel sheet according to the present invention has the inorganic compound thereon which serves to improve the frictional characteristics of the steel sheet and can be substantially thoroughly removed by the alkali degreasing or water washing preceding the phosphating process, so that it can reconcile the press formability and phosphatability.
  • Use of the galvanized steel sheet of the invention greatly improves the productivity for the press forming.
  • the steel sheet can be easily manufactured at low cost by bringing the galvanized steel sheet into contact with the aqueous solution containing 0.1 wt% or more of the borate of alkaline metal and then drying the sheet by heating within the temperature range of 60 to 400°C, or by only spraying the aqueous solution on the steel sheet after the galvanizing or galvannealing process in the case of the hot dip galvanized steel sheet.
  • the steel sheet of the present invention is easy to manufacture.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Coating With Molten Metal (AREA)

Claims (3)

  1. Verzinktes Stahlblech mit hoher Pressformbarkeit, welches eine anorganische Verbindung auf einer metallischen Zinkschicht darauf aufweist, wobei die anorganische Verbindung ein wäßriges Alkalimetallborat ist, wobei 10 bis 1000 mg/m² eines Filmes aus dem wäßrigen Borat auf die Plattieroberfläche des verzinkten Stahlblechs aufgebracht wird, der Reibungskoeffizient des verzinkten Blechs 0,15 oder weniger beträgt und die Menge an unlöslichen Schlämmen der anorganischen Verbindung, die nach dem Waschen mit Wasser oder dem alkalischen Entfetten zurückbleibt, weniger als 1 mg/m² beträgt.
  2. Verfahren zur Herstellung eines verzinkten Stahlblechs mit großer Pressformbarkeit gemäß Anspruch 1, umfassend die Schritte des Inkontaktbringens der Plattieroberfläche des verzinkten Stahlblechs mit einer Wasserlösung, enthaltend 0,1 Gew.-% oder mehr eines Alkalimetallborats, und Trocknen des Stahlblechs durch Erwärmen innerhalb eines Temperaturbereichs von 60 bis 400 °C.
  3. Verfahren zur Herstellung eines verzinkten Stahlblechs mit großer Pressformbarkeit gemäß Anspruch 2, wobei, wenn die Temperatur des Stahlblechs innerhalb des Bereichs von 60 bis 400°C nach dem Schmelzverzinken oder nach dem darauf folgendem Feuerverzinken mit nachträglicher Wärmebehandlung des Überzugs liegt, die 0,1 Gew.-% oder mehr eines Alkaliborats enthaltende Wasserlösung auf die Plattieroberfläche in einem Herstellungsverfahren, bei dem das Stahlblech einem Schmelztauchverzinken unterworfen wird, aufgesprüht wird.
EP91100089A 1990-04-09 1991-01-02 Galvanisiertes Stahlblech mit hohen Pressumformungseigenschaften und Verfahren zu seiner Herstellung Expired - Lifetime EP0451437B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP9334890 1990-04-09
JP93348/90 1990-04-09
JP334296/90 1990-11-30
JP33429690 1990-11-30

Publications (3)

Publication Number Publication Date
EP0451437A2 EP0451437A2 (de) 1991-10-16
EP0451437A3 EP0451437A3 (en) 1992-01-22
EP0451437B1 true EP0451437B1 (de) 1995-04-05

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CA (1) CA2033862C (de)
DE (1) DE69108594T2 (de)

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1347427A (fr) * 1962-02-02 1963-12-27 Paroxite London Ltd Perfectionnements apportés aux produits d'enrobage utilisés pour le formage à froid des métaux
US3364081A (en) * 1965-01-15 1968-01-16 Lubrizol Corp Aqueous phosphating solutions
FR2339446A1 (fr) * 1976-01-28 1977-08-26 Servimetal Procede de filage a tres grande vitesse de metaux et alliages legers
CH629845A5 (en) * 1977-10-26 1982-05-14 Bbc Brown Boveri & Cie High-temperature lubricant
FR2629103B1 (fr) * 1988-03-23 1993-01-08 Lorraine Laminage Tole metallique pour emboutissage; procede et dispositif de traitement de surface pour sa fabrication

Also Published As

Publication number Publication date
EP0451437A3 (en) 1992-01-22
EP0451437A2 (de) 1991-10-16
CA2033862C (en) 1999-05-11
CA2033862A1 (en) 1991-10-10
DE69108594T2 (de) 1995-08-17
DE69108594D1 (de) 1995-05-11

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