CA2916430A1 - Method for producing galvanized fine or ultrafine sheet metal with high corrosion resistance - Google Patents
Method for producing galvanized fine or ultrafine sheet metal with high corrosion resistance Download PDFInfo
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- CA2916430A1 CA2916430A1 CA2916430A CA2916430A CA2916430A1 CA 2916430 A1 CA2916430 A1 CA 2916430A1 CA 2916430 A CA2916430 A CA 2916430A CA 2916430 A CA2916430 A CA 2916430A CA 2916430 A1 CA2916430 A1 CA 2916430A1
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0478—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing involving a particular surface treatment
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
- B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
- B21B2001/228—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length skin pass rolling or temper rolling
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- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0226—Hot rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0221—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
- C21D8/0236—Cold rolling
-
- C—CHEMISTRY; METALLURGY
- C21—METALLURGY OF IRON
- C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/04—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing
- C21D8/0421—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips to produce plates or strips for deep-drawing characterised by the working steps
- C21D8/0442—Flattening; Dressing; Flexing
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Mechanical Engineering (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Laminated Bodies (AREA)
- Coating With Molten Metal (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to a method for producing galvanized fine or ultrafine sheet metal with high corrosion resistance made of a hot-rolled steel strip, involving the following steps: - galvanically coating the steel strip (1) with zinc, - temper rolling the zinc-coated surface of the steel strip (1), - applying a polymer coating or an organic lacquer to the zinc-coated surface of the steel strip (1) on one or both sides. The invention further relates to a device for performing the method, comprising a transport device (7) for continuously transporting an endless steel strip (1), a cold rolling device (6) for cold-rolling the transported steel strip (1) to a thickness of less than 1mm, a coating device (11) for galvanically coating the steel strip (1) with zinc, a rolling device (5) with temper rollers (5a) for tempering the galvanized surface of the steel strip (1), a heating device (4) for heating the steel strip (1), and a plastic coating device (8) for applying a polymer coating or an organic lacquer onto the zinc-coated surface of the steel strip (1) on one or both sides.
Description
Method for producing galvanized fine or ultrafine sheet metal with high corrosion resistance The invention concerns a method for producing galvanized fine or ultrafine sheet metal with high corrosion resistance from a hot-rolled strip steel with the steps indicated in patent claim 1. The invention moreover concerns a device to carry out this method.
Cans for keeping and preserving foods (preserve cans) are manufactured from a steel sheet provided with a metallic corrosion protection layer, for example, from tinplate, from ECCS
(electrolytic chromium coated steel) or galvanized steel sheet. On the inside the cans are usually provided with a plastic coating. For the coating of tinplate or galvanized steel sheet with such a plastic coating, the surface of the steel sheet provided with such a plastic coating is painted with an organic enamel or coated with a polymer coating. The enamels and polymers used for this are plastics based on polyester, epoxy resins, or organosols. Epoxy resins have proven to be harmful to the health and the environment, since they have (at least small amounts of) substances harmful to the health such has bisphenol-A (BPA) and these, especially upon contact with acid-containing foods, can be given off to the contents of the can. The enamels generally used require the use of solvents in their processing, which can likewise be dangerous to the health and the environment.
Therefore, it has already been proposed in the prior art to provide steel sheets coated with a corrosion protection layer, such as tinplate, ECCS or galvanized sheet metal, with a plastic coating of a thermoplastic material on one or both sides by laminating a polymer film onto them. Thus, for example, a corrosion-resistant steel sheet is known from WO
97/03823-A, which has a metallic corrosion protection layer and is coated on one or both sides with a transparent polymer film of polyethylene terephthalate (PET) or polypropylene (PP) by laminating a polymer film onto the metallic corrosion protection layer.
Between the metallic corrosion protection layer of the steel sheet and the laminated polymer film there is placed a bonding agent, especially an adhesive layer. In order to make the stainless steel sheet, one uses a steel sheet with a thickness between 0.05 mm and 0.5 mm, which is galvanically coated with a metallic corrosion protection layer and passivated, and heats this to temperatures of around 160 C. On the heated steel sheet, a polymer film of polyethylene terephthalate (PET) or polypropylene (PP) is laminated by means of rotating rolls. The thickness of the laminated polymer film is between 5 and 100 tm.
The polymer film preferably has an adhesive layer on one side, having a lower melting point than the polymer material of the polymer film. The polymer film is laminated with the adhesive layer at the bottom onto the surface of the metallic corrosion protection layer of the steel sheet, the steel sheet being heated prior to the laminating of the polymer film to temperatures of around 160 C.
In the known method of laminating a polymer film onto the metallic corrosion protection layer of a steel sheet, a special polymer film with an adhesive layer is used in order to laminate this onto the surface of the corrosion protection layer of the steel sheet. Such polymer films with an adhesive layer are very costly to produce. Moreover, the handling of such polymer films with an adhesive layer is more time-consuming and the process parameters, especially the temperatures, must be held within given limit values during the lamination, which are dictated by the melting temperatures of the polymer film and the adhesive layer. Especially in the case of galvanized steel sheets, however, it has been found that one cannot easily do without an adhesive layer if one needs to ensure a sufficiently good adhesion of the polymer film to the galvanized surface of the steel sheet.
The problem which the invention proposes to solve is to indicate a method and a device for producing a galvanized fine or ultrafine sheet metal with the highest possible corrosion resistance, by which a protective layer can be applied without the use of solvents or plastics containing bisphenol-A to the zinc-coated surface of the steel strip without using a bonding agent or a conversion coating, yet still with good adhesion.
This problem is solved by the method with the features of claim 1 and by the device with the features of claim 17. Preferred embodiments of the method are indicated in the dependent claims.
In the method according to the invention, a hot-rolled fine or ultrafine sheet of steel is at first cold-rolled to a thickness of less than 1 mm and then annealed and recrystallized in order to again restore the deformability of the cold-rolled steel. After the recrystallization annealing, it may be expedient to perform a dressing or temper-rolling of the steel strip.
After this, the steel
Cans for keeping and preserving foods (preserve cans) are manufactured from a steel sheet provided with a metallic corrosion protection layer, for example, from tinplate, from ECCS
(electrolytic chromium coated steel) or galvanized steel sheet. On the inside the cans are usually provided with a plastic coating. For the coating of tinplate or galvanized steel sheet with such a plastic coating, the surface of the steel sheet provided with such a plastic coating is painted with an organic enamel or coated with a polymer coating. The enamels and polymers used for this are plastics based on polyester, epoxy resins, or organosols. Epoxy resins have proven to be harmful to the health and the environment, since they have (at least small amounts of) substances harmful to the health such has bisphenol-A (BPA) and these, especially upon contact with acid-containing foods, can be given off to the contents of the can. The enamels generally used require the use of solvents in their processing, which can likewise be dangerous to the health and the environment.
Therefore, it has already been proposed in the prior art to provide steel sheets coated with a corrosion protection layer, such as tinplate, ECCS or galvanized sheet metal, with a plastic coating of a thermoplastic material on one or both sides by laminating a polymer film onto them. Thus, for example, a corrosion-resistant steel sheet is known from WO
97/03823-A, which has a metallic corrosion protection layer and is coated on one or both sides with a transparent polymer film of polyethylene terephthalate (PET) or polypropylene (PP) by laminating a polymer film onto the metallic corrosion protection layer.
Between the metallic corrosion protection layer of the steel sheet and the laminated polymer film there is placed a bonding agent, especially an adhesive layer. In order to make the stainless steel sheet, one uses a steel sheet with a thickness between 0.05 mm and 0.5 mm, which is galvanically coated with a metallic corrosion protection layer and passivated, and heats this to temperatures of around 160 C. On the heated steel sheet, a polymer film of polyethylene terephthalate (PET) or polypropylene (PP) is laminated by means of rotating rolls. The thickness of the laminated polymer film is between 5 and 100 tm.
The polymer film preferably has an adhesive layer on one side, having a lower melting point than the polymer material of the polymer film. The polymer film is laminated with the adhesive layer at the bottom onto the surface of the metallic corrosion protection layer of the steel sheet, the steel sheet being heated prior to the laminating of the polymer film to temperatures of around 160 C.
In the known method of laminating a polymer film onto the metallic corrosion protection layer of a steel sheet, a special polymer film with an adhesive layer is used in order to laminate this onto the surface of the corrosion protection layer of the steel sheet. Such polymer films with an adhesive layer are very costly to produce. Moreover, the handling of such polymer films with an adhesive layer is more time-consuming and the process parameters, especially the temperatures, must be held within given limit values during the lamination, which are dictated by the melting temperatures of the polymer film and the adhesive layer. Especially in the case of galvanized steel sheets, however, it has been found that one cannot easily do without an adhesive layer if one needs to ensure a sufficiently good adhesion of the polymer film to the galvanized surface of the steel sheet.
The problem which the invention proposes to solve is to indicate a method and a device for producing a galvanized fine or ultrafine sheet metal with the highest possible corrosion resistance, by which a protective layer can be applied without the use of solvents or plastics containing bisphenol-A to the zinc-coated surface of the steel strip without using a bonding agent or a conversion coating, yet still with good adhesion.
This problem is solved by the method with the features of claim 1 and by the device with the features of claim 17. Preferred embodiments of the method are indicated in the dependent claims.
In the method according to the invention, a hot-rolled fine or ultrafine sheet of steel is at first cold-rolled to a thickness of less than 1 mm and then annealed and recrystallized in order to again restore the deformability of the cold-rolled steel. After the recrystallization annealing, it may be expedient to perform a dressing or temper-rolling of the steel strip.
After this, the steel
2 strip is galvanically coated with zinc, the application of the zinc coating being preferably less than 15 g/m2. After the galvanic coating of the steel strip with zinc, according to the invention there follows a temper rolling or glossy rolling of the zinc-coated surface of the steel strip.
Surprisingly, it has been found that thanks to the temper rolling tiny zinc buds on the zinc surface can be evened out and disruptive zinc oxides removed or distributed uniformly over the strip surface. Moreover, the temper rolling produces a shiny surface of the zinc coating, which is of great importance especially for the intended use of the metal sheet produced according to the invention for the making of packaging containers in the food industry, since a good shine of the surface of the packaging material is desirable there.
Furthermore, the temper rolling produces a finely structured surface of the zinc layer with a uniform texture, having a good wettability for enamels and an excellent adhesion for polymer coatings, especially those of PET or PP. During the temper rolling of the zinc-coated steel strip, a slight thickness reduction occurs with a skin pass level of 0.5-2%. After the temper rolling, a polymer coating or an organic enamel is applied to the zinc-coated surface of the steel strip on one or both sides. This can occur, for example, by laminating a polymer film, such as a PET or PP film, onto the zinc-coated surface of the steel strip. During the laminating of the polymer film, the zinc-coated steel strip is advisedly heated to temperatures above the melting temperature of the polymer material and the polymer film is laminated onto the zinc-coated surface of the steel strip by means of lamination rolls. Thanks to the good adhesiveness of the temper-rolled zinc surface, one can do without the use of a bonding agent and especially and additional adhesive layer between the zinc surface and the polymer film. One can do without a previous passivation or conversion coating of the zinc surface. This considerably simplifies and speeds up the process. The metal sheet produced according to the invention is free of solvents and chromium and free of bisphenol-A (BPA), since the polymer materials PET and PP
which are preferably used contain no BPA and can be processed without the use of solvents and the metallic corrosion protection layer of the steel strip is itself free of chromium and does not need to be passivated with chromium-containing after-treatment agents.
In one advisable sample embodiment of the method of the invention, the temper rolling occurs in a rerolling step, in which the thickness of the steel strip is reduced to rerolling levels of 4-45%. The rerolling step also increases the strength of the steel strip to values of Rm=300 to 1000 MPa and especially in the range of Rm=400-650 MPa. The steel strip so treated furthermore has a good breaking elongation of 1-40% and especially 5-25%.
Surprisingly, it has been found that thanks to the temper rolling tiny zinc buds on the zinc surface can be evened out and disruptive zinc oxides removed or distributed uniformly over the strip surface. Moreover, the temper rolling produces a shiny surface of the zinc coating, which is of great importance especially for the intended use of the metal sheet produced according to the invention for the making of packaging containers in the food industry, since a good shine of the surface of the packaging material is desirable there.
Furthermore, the temper rolling produces a finely structured surface of the zinc layer with a uniform texture, having a good wettability for enamels and an excellent adhesion for polymer coatings, especially those of PET or PP. During the temper rolling of the zinc-coated steel strip, a slight thickness reduction occurs with a skin pass level of 0.5-2%. After the temper rolling, a polymer coating or an organic enamel is applied to the zinc-coated surface of the steel strip on one or both sides. This can occur, for example, by laminating a polymer film, such as a PET or PP film, onto the zinc-coated surface of the steel strip. During the laminating of the polymer film, the zinc-coated steel strip is advisedly heated to temperatures above the melting temperature of the polymer material and the polymer film is laminated onto the zinc-coated surface of the steel strip by means of lamination rolls. Thanks to the good adhesiveness of the temper-rolled zinc surface, one can do without the use of a bonding agent and especially and additional adhesive layer between the zinc surface and the polymer film. One can do without a previous passivation or conversion coating of the zinc surface. This considerably simplifies and speeds up the process. The metal sheet produced according to the invention is free of solvents and chromium and free of bisphenol-A (BPA), since the polymer materials PET and PP
which are preferably used contain no BPA and can be processed without the use of solvents and the metallic corrosion protection layer of the steel strip is itself free of chromium and does not need to be passivated with chromium-containing after-treatment agents.
In one advisable sample embodiment of the method of the invention, the temper rolling occurs in a rerolling step, in which the thickness of the steel strip is reduced to rerolling levels of 4-45%. The rerolling step also increases the strength of the steel strip to values of Rm=300 to 1000 MPa and especially in the range of Rm=400-650 MPa. The steel strip so treated furthermore has a good breaking elongation of 1-40% and especially 5-25%.
3 The method according to the invention can be carried out in strip galvanization plants, the steel strip being moved at a speed of more than 200 m/min and preferably more than 500 m/min through the coating layout. The temper rolling and the lamination of the polymer coating also occurs at these strip speeds.
The fine or ultrafine sheet metal produced according to the invention is excellently suited to the making of packages, especially for foods, or parts of such packages, such as tabs, valve disks, can lids or can rings. The sheet metal produced according to the invention is characterized by a high shine of the refined surface, a very good adherence of the polymer coating or the organic enamel on the zinc-coated surface of the steel strip and by a very high corrosion resistance. The fine structure of the zinc coating created by the temper rolling of the zinc-coated surface minimizes the oxidation tendency of the zinc surface, so that a passivation or a conversion coating is not necessary for the warehousing of the zinc-coated steel strip prior to its coating with the polymer coating or prior to its enameling with an organic enamel.
It has been shown that the zinc-coated steel strips after the galvanization can be warehoused for periods of up to 6 months without any passivation or conversion treatment before they are provided with the polymer coating or the organic enamel. After the polymer coating or enameling of the zinc-coated surface, the metal sheets produced according to the invention are characterized by a very high corrosion resistance, because the pores in the polymer coating or the organic enamel cannot result in a corrosion of the steel sheet through the corrosion-stable zinc layer. The cut edges of the sheet not protected by the laminated polymer coating also have an electrochemical protection against corrosion thanks to the remote protection effect of the zinc, which is less noble than the steel.
These and other benefits and features of the invention will emerge from the following sample embodiment, described more closely with reference to the enclosed drawing, where the mentioned drawing of Fig. 1 shows a schematic representation of a device to carry out the method according to the invention for producing galvanized fine or ultrafine sheet metal.
The starting material for the method according to the invention is a hot-rolled and non-alloyed or low-alloyed steel strip with low carbon content of, e.g., 20 to 900 ppm.
The alloyage components of the steel advisedly meet the specifications of the international standard ASTM
A 623-11 (Standard Specification for Tin Mill Products), which ensures a use of the sheet metal produced according to the invention for the manufacture of food packagings. Basically,
The fine or ultrafine sheet metal produced according to the invention is excellently suited to the making of packages, especially for foods, or parts of such packages, such as tabs, valve disks, can lids or can rings. The sheet metal produced according to the invention is characterized by a high shine of the refined surface, a very good adherence of the polymer coating or the organic enamel on the zinc-coated surface of the steel strip and by a very high corrosion resistance. The fine structure of the zinc coating created by the temper rolling of the zinc-coated surface minimizes the oxidation tendency of the zinc surface, so that a passivation or a conversion coating is not necessary for the warehousing of the zinc-coated steel strip prior to its coating with the polymer coating or prior to its enameling with an organic enamel.
It has been shown that the zinc-coated steel strips after the galvanization can be warehoused for periods of up to 6 months without any passivation or conversion treatment before they are provided with the polymer coating or the organic enamel. After the polymer coating or enameling of the zinc-coated surface, the metal sheets produced according to the invention are characterized by a very high corrosion resistance, because the pores in the polymer coating or the organic enamel cannot result in a corrosion of the steel sheet through the corrosion-stable zinc layer. The cut edges of the sheet not protected by the laminated polymer coating also have an electrochemical protection against corrosion thanks to the remote protection effect of the zinc, which is less noble than the steel.
These and other benefits and features of the invention will emerge from the following sample embodiment, described more closely with reference to the enclosed drawing, where the mentioned drawing of Fig. 1 shows a schematic representation of a device to carry out the method according to the invention for producing galvanized fine or ultrafine sheet metal.
The starting material for the method according to the invention is a hot-rolled and non-alloyed or low-alloyed steel strip with low carbon content of, e.g., 20 to 900 ppm.
The alloyage components of the steel advisedly meet the specifications of the international standard ASTM
A 623-11 (Standard Specification for Tin Mill Products), which ensures a use of the sheet metal produced according to the invention for the manufacture of food packagings. Basically,
4 all grades of steel which have a composition suitable for the production of fine or ultrafine sheet metal can be used for the method according to the invention. The hot-rolled steel strip is at first pickled in a pickling layout (not shown), then rinsed and dried, and finally cold-rolled in a cold rolling device 6.
In the cold rolling step, the steel strip 1 is moved as an endless strip by a transport device 7 with a transport speed of preferably more than 200 m/min and up to 750 m/min through the cold rolling device 6 and rolled there to a thickness of less than 1.0 mm (fine sheet) and preferably to thicknesses of 0.1 to 0.5 mm (ultrafine sheet). The cold rolling device 6 is advisedly a cold rolling tandem mill with stands each having four rolls one above another, one large support roll on the outside and two smaller working rolls on the inside, between which the steel strip runs at the transport speed. The rolling gap is lubricated with a lubricant such as oil and the steel strip as well as the rolls are cooled with water.
After the cold rolling, the steel strip 1 ¨ as shown schematically in Fig. 1 ¨
is at first taken through a continuous annealing furnace 3, in which the steel strip is heated to temperatures of 550 C to 700 C, in order to anneal the steel strip to recrystallize. Thanks to the recrystallizing annealing, the deformability of the cold-rolled steel strip is again restored.
After the recrystallization annealing, the steel strip can be tempered in a rerolling mill 9 or rerolled if necessary to achieve a lesser thickness.
Next, the steel strip 1 is taken at the transport speed through a strip coating layout 2. The strip coating layout 2 shown schematically in Fig. 1 is a strip galvanization layout for electrolytic galvanization of sheet steel. This comprises a pretreatment device 10, in which the cold-rolled fine or ultrafine sheet is degreased, pickled and rinsed, as well as a coating device 11, in which it is then galvanically coated with zinc. For this, the steel strip 1 moving with the strip speed through the strip coating layout 2 is led through a zinc-containing electrolyte and hooked up there as the cathode and moved between two rows of zinc anodes. In this way, the zinc is dissolved from the anodes and deposited as a zinc coating onto the steel strip. The zinc can be deposited in any desired thickness and, if necessary, on both sides of the steel strip.
The thickness of the deposited zinc layer is generally between 1.0 g/m2 and 15 g/m2.
However, it is also possible to coat the steel strip with thinner or thicker zinc layers.
In the cold rolling step, the steel strip 1 is moved as an endless strip by a transport device 7 with a transport speed of preferably more than 200 m/min and up to 750 m/min through the cold rolling device 6 and rolled there to a thickness of less than 1.0 mm (fine sheet) and preferably to thicknesses of 0.1 to 0.5 mm (ultrafine sheet). The cold rolling device 6 is advisedly a cold rolling tandem mill with stands each having four rolls one above another, one large support roll on the outside and two smaller working rolls on the inside, between which the steel strip runs at the transport speed. The rolling gap is lubricated with a lubricant such as oil and the steel strip as well as the rolls are cooled with water.
After the cold rolling, the steel strip 1 ¨ as shown schematically in Fig. 1 ¨
is at first taken through a continuous annealing furnace 3, in which the steel strip is heated to temperatures of 550 C to 700 C, in order to anneal the steel strip to recrystallize. Thanks to the recrystallizing annealing, the deformability of the cold-rolled steel strip is again restored.
After the recrystallization annealing, the steel strip can be tempered in a rerolling mill 9 or rerolled if necessary to achieve a lesser thickness.
Next, the steel strip 1 is taken at the transport speed through a strip coating layout 2. The strip coating layout 2 shown schematically in Fig. 1 is a strip galvanization layout for electrolytic galvanization of sheet steel. This comprises a pretreatment device 10, in which the cold-rolled fine or ultrafine sheet is degreased, pickled and rinsed, as well as a coating device 11, in which it is then galvanically coated with zinc. For this, the steel strip 1 moving with the strip speed through the strip coating layout 2 is led through a zinc-containing electrolyte and hooked up there as the cathode and moved between two rows of zinc anodes. In this way, the zinc is dissolved from the anodes and deposited as a zinc coating onto the steel strip. The zinc can be deposited in any desired thickness and, if necessary, on both sides of the steel strip.
The thickness of the deposited zinc layer is generally between 1.0 g/m2 and 15 g/m2.
However, it is also possible to coat the steel strip with thinner or thicker zinc layers.
5 The strip coating layout 2 is followed in the strip movement direction by a melting device 12, in which the zinc coating deposited on the steel strip is heated to temperatures above the melting temperature of the zinc (419.5 C) in order to start melting the deposited coating. The partial melting produces a shiny surface of the zinc coating and increases the corrosion stability of the galvanized steel strip. The melting device 12 is followed by a cooling device 13, in which the melted zinc coating is quenched at a high cooldown rate.
The cooled and zinc-coated steel strip 1 is then tempered in a rolling device 5. The rolling device 5 has for this at least one pair of temper rolls 5a, which form a gap through which the zinc-coated steel strip passes with the transport speed. The temper rolls 5a exert a rolling force on the steel strip 1, advisedly in the range of 500 tons. Thanks to the pressure of the temper rolls 5a on the steel strip, a dressing (temper rolling) of the zinc-coated surface of the steel strip 1 occurs. In this tempering step, skin pass levels of 0.1 to 2.0 %
are achieved.
The temper rolls 5a are smooth, especially fine ground or polished rolls with hard surface, which are advisedly cooled and optionally moistened with water or steam or other wet dressing agents. The surface of the temper rolls 5a can be provided with a fine structure by sand blasting, for example, which is suitable to giving the substrate a desired roughness or texturizing. The degree of smoothness or the roughness of the dressed surface is influenced by the surface texture of the temper rolls 5a. Temper rolls with a roll roughness of less than 0.07 p.m have proven to be suitable to dressing the zinc surface to a preferred mean peak to valley height of Ra = 0.01 to 0.1 jam.
The purpose of the tempering is to compact and even out the surface of the zinc coating.
Surprisingly, it has been found that the tempering step can positively influence the deposited zinc layer both in terms of its brilliance and with respect to the corrosion resistance and the tendency to oxidation. In particular, zinc "buds" which occur on the surface are evened out by the temper rolling. Furthermore, it has been found surprisingly that any zinc oxide occurring is removed to a sufficient extent from the galvanized surface. In this way, a high gloss surface is obtained, which is especially desirable in the packaging industry. The structuring of the zinc surface after the temper rolling is very fine and does not affect the shine, yet offers a good adherence base for the later deposited organic layers, such as enamels or polymer coatings. Furthermore, the leveled-out and structurized surface slows down the formation of zinc oxides. This enables a warehousing of the galvanized steel strip after the galvanization
The cooled and zinc-coated steel strip 1 is then tempered in a rolling device 5. The rolling device 5 has for this at least one pair of temper rolls 5a, which form a gap through which the zinc-coated steel strip passes with the transport speed. The temper rolls 5a exert a rolling force on the steel strip 1, advisedly in the range of 500 tons. Thanks to the pressure of the temper rolls 5a on the steel strip, a dressing (temper rolling) of the zinc-coated surface of the steel strip 1 occurs. In this tempering step, skin pass levels of 0.1 to 2.0 %
are achieved.
The temper rolls 5a are smooth, especially fine ground or polished rolls with hard surface, which are advisedly cooled and optionally moistened with water or steam or other wet dressing agents. The surface of the temper rolls 5a can be provided with a fine structure by sand blasting, for example, which is suitable to giving the substrate a desired roughness or texturizing. The degree of smoothness or the roughness of the dressed surface is influenced by the surface texture of the temper rolls 5a. Temper rolls with a roll roughness of less than 0.07 p.m have proven to be suitable to dressing the zinc surface to a preferred mean peak to valley height of Ra = 0.01 to 0.1 jam.
The purpose of the tempering is to compact and even out the surface of the zinc coating.
Surprisingly, it has been found that the tempering step can positively influence the deposited zinc layer both in terms of its brilliance and with respect to the corrosion resistance and the tendency to oxidation. In particular, zinc "buds" which occur on the surface are evened out by the temper rolling. Furthermore, it has been found surprisingly that any zinc oxide occurring is removed to a sufficient extent from the galvanized surface. In this way, a high gloss surface is obtained, which is especially desirable in the packaging industry. The structuring of the zinc surface after the temper rolling is very fine and does not affect the shine, yet offers a good adherence base for the later deposited organic layers, such as enamels or polymer coatings. Furthermore, the leveled-out and structurized surface slows down the formation of zinc oxides. This enables a warehousing of the galvanized steel strip after the galvanization
6 until it is further processed by enameling or plastic coating, without the need for a passivation or conversion treatment of the galvanized surface of the steel strip. It has been found that the galvanized steel strips can be warehoused with no problem for a period of up to six months, with no oxide layer forming on the zinc surface, which would be a hindrance during the subsequent enameling or depositing of a polymer layer.
Prior to the temper rolling, the galvanized steel strip 1 can optionally be rolled by further pairs of rolls of the rolling device 5 in order to further reduce the thickness of the cold-rolled steel strip 1 if necessary. This optional rolling step is a cold rolling, which is carried out prior to the temper rolling and during which rerolling levels of up to 50 %, preferably 4 -45%, are achieved. Thanks to the rolling, the strength of the steel strip 1 is increased to values as much as 1000 MPa and in particular Rm = 300 to 650 MPa.
The temper-rolled steel strip 1 is then moved with the strip speed into a plastic coating device 8. Here, a polymer coating is applied to one or both sides of the galvanized steel strip. For this, the steel strip is at first heated in a heating device 4, which can be designed as an induction heating or also an infrared or microwave heating system, to temperatures lying above the melting temperature of the polymer material of the polymer coating.
Preferably, the polymer material is PET (with a melting temperature between around 235 and 260 C, depending on the degree of crystallization and the degree of polymerization) or PP (with a melting temperature of around 160 C) or also PE (with a melting temperature of around 130 -145 C). This can also be a film of a polymer laminate consisting of polyethylene terephthalate and polypropylene. The heated steel strip is supplied with a film 16 made from the polymer material (PET or PP film) in the plastic coating device 8 on one or both sides and this is pressed by means of lamination rolls 8a against the surface of the zinc coating. Thanks to the temperature of the heated steel strip, at least the portion of the polymer film 16 lying against the surface of the zinc coating starts to melt and thereby adheres to the surface of the zinc coating, which has been fine structured by the temper rolling.
After the laminating of the polymer film, the polymer coating is advisedly melted (entirely) and then quenched in a cooling device 15 (such as a water bath) to a temperature below the glass transition point. In this way, an amorphous structure is formed in the polyethylene terephthalate or a minimal crystalline structure in the polypropylene.
Especially advisedly, the melting of the polymer coating is done as described in patent DE 10130005 B4, or ¨ as shown
Prior to the temper rolling, the galvanized steel strip 1 can optionally be rolled by further pairs of rolls of the rolling device 5 in order to further reduce the thickness of the cold-rolled steel strip 1 if necessary. This optional rolling step is a cold rolling, which is carried out prior to the temper rolling and during which rerolling levels of up to 50 %, preferably 4 -45%, are achieved. Thanks to the rolling, the strength of the steel strip 1 is increased to values as much as 1000 MPa and in particular Rm = 300 to 650 MPa.
The temper-rolled steel strip 1 is then moved with the strip speed into a plastic coating device 8. Here, a polymer coating is applied to one or both sides of the galvanized steel strip. For this, the steel strip is at first heated in a heating device 4, which can be designed as an induction heating or also an infrared or microwave heating system, to temperatures lying above the melting temperature of the polymer material of the polymer coating.
Preferably, the polymer material is PET (with a melting temperature between around 235 and 260 C, depending on the degree of crystallization and the degree of polymerization) or PP (with a melting temperature of around 160 C) or also PE (with a melting temperature of around 130 -145 C). This can also be a film of a polymer laminate consisting of polyethylene terephthalate and polypropylene. The heated steel strip is supplied with a film 16 made from the polymer material (PET or PP film) in the plastic coating device 8 on one or both sides and this is pressed by means of lamination rolls 8a against the surface of the zinc coating. Thanks to the temperature of the heated steel strip, at least the portion of the polymer film 16 lying against the surface of the zinc coating starts to melt and thereby adheres to the surface of the zinc coating, which has been fine structured by the temper rolling.
After the laminating of the polymer film, the polymer coating is advisedly melted (entirely) and then quenched in a cooling device 15 (such as a water bath) to a temperature below the glass transition point. In this way, an amorphous structure is formed in the polyethylene terephthalate or a minimal crystalline structure in the polypropylene.
Especially advisedly, the melting of the polymer coating is done as described in patent DE 10130005 B4, or ¨ as shown
7 here in Fig. 1 ¨ by a repeat heating of the steel strip to temperatures above the melting point of the particular polymer material in a melting device 14. The quenching in the cooling device 15 can be done, e.g., by an air cooling or by dipping the steel strip into a tank with cooling liquid. After this, the coated steel strip 1 is wound onto a reel from the transport device 7.
The steel strip produced according to the invention is characterized by a good corrosion resistance, which is achieved by the metallic corrosion protection layer of zinc and the polymer coating. The combination of these corrosion protection layers is especially advantageous because even when pores are present in the polymer coating the underlying zinc layer still assures an adequate (electrochemical) corrosion protection. Even the cut edges not covered by the polymer coating are protected against corrosion by the remote protection effect of the zinc coating. The steel strip produced according to the invention is further characterized by a very good adherence of the polymer coating to the zinc layer, which is achieved even without bonding agent or additional adhesive layers thanks to the temper rolling of the surface of the zinc coating. Thanks to the surface properties of the zinc coating after the temper rolling, an otherwise customary passivation or a conversion coating after the galvanization of the steel strip is not necessary.
The steel strip produced according to the invention is suitable for making packaging containers, especially for foods, such as two-part cans (deep-drawn and stretched, DWI cans).
It is also possible to make parts of such packaging containers from the steel strip produced according to the invention, such as tabs, valve disks, can lids or can rings.
In addition, the method according to the invention can also be used for the making of steel sheets for use in other industries, such as the production of sheet metal for the construction industry.
The invention is not confined to the sample embodiment described. Thus, in particular, the rerolling steps in the rerolling mill 9 or with the additional pairs of rolls of the rolling device 5 can be omitted. Moreover, the partial melting of the zinc coating can also be omitted, especially when such slight roughness has been achieved during the temper rolling of the zinc surface that a high gloss surface is already formed. Furthermore, it is possible in the context of the invention to wind the steel strip 1 after the individual steps of the method into a roll (coil) and subject it in this form to the next step of the method. This is not shown in the schematic representation of the device according to the invention in Fig. 1.
The steel strip produced according to the invention is characterized by a good corrosion resistance, which is achieved by the metallic corrosion protection layer of zinc and the polymer coating. The combination of these corrosion protection layers is especially advantageous because even when pores are present in the polymer coating the underlying zinc layer still assures an adequate (electrochemical) corrosion protection. Even the cut edges not covered by the polymer coating are protected against corrosion by the remote protection effect of the zinc coating. The steel strip produced according to the invention is further characterized by a very good adherence of the polymer coating to the zinc layer, which is achieved even without bonding agent or additional adhesive layers thanks to the temper rolling of the surface of the zinc coating. Thanks to the surface properties of the zinc coating after the temper rolling, an otherwise customary passivation or a conversion coating after the galvanization of the steel strip is not necessary.
The steel strip produced according to the invention is suitable for making packaging containers, especially for foods, such as two-part cans (deep-drawn and stretched, DWI cans).
It is also possible to make parts of such packaging containers from the steel strip produced according to the invention, such as tabs, valve disks, can lids or can rings.
In addition, the method according to the invention can also be used for the making of steel sheets for use in other industries, such as the production of sheet metal for the construction industry.
The invention is not confined to the sample embodiment described. Thus, in particular, the rerolling steps in the rerolling mill 9 or with the additional pairs of rolls of the rolling device 5 can be omitted. Moreover, the partial melting of the zinc coating can also be omitted, especially when such slight roughness has been achieved during the temper rolling of the zinc surface that a high gloss surface is already formed. Furthermore, it is possible in the context of the invention to wind the steel strip 1 after the individual steps of the method into a roll (coil) and subject it in this form to the next step of the method. This is not shown in the schematic representation of the device according to the invention in Fig. 1.
8 The polymer coating can also be applied by coating methods other than lamination to the zinc coating. Thus, after the temper rolling for example a molten polymer material can be applied to the zinc coating, as described in the patent DE 197 30 893-C 1 .
Alternatively to the described application of a polymer coating by lamination of a polymer film or the direct extrusion of a liquid polymer material, an additional corrosion barrier can be applied to the steel strip by enameling the zinc-coated and temper-rolled surface on one or both sides with an organic enamel. Suitable enamels have proven to be, for example, phenol resin enamels such as epoxy phenol enamel (gold enamel), polyester enamels and acrylic resin enamels, such as white enamel based on polyacrylates or polyesters, as well as PVC and epoxy anhydride enamels. Preferably, BPA-free and solvent-free (water-based) enamels will be used.
Alternatively to the described application of a polymer coating by lamination of a polymer film or the direct extrusion of a liquid polymer material, an additional corrosion barrier can be applied to the steel strip by enameling the zinc-coated and temper-rolled surface on one or both sides with an organic enamel. Suitable enamels have proven to be, for example, phenol resin enamels such as epoxy phenol enamel (gold enamel), polyester enamels and acrylic resin enamels, such as white enamel based on polyacrylates or polyesters, as well as PVC and epoxy anhydride enamels. Preferably, BPA-free and solvent-free (water-based) enamels will be used.
9
Claims (17)
1. Method for producing galvanized fine or ultrafine sheet metal with high corrosion resistance from a sheet metal with high corrosion resistance from a hot-rolled steel strip with the following steps:
- galvanic coating of the steel strip (1) with zinc, - temper rolling of the zinc-coated surface of the steel strip (1), - depositing of a polymer coating or an organic enamel on one or both sides of the zinc-coated surface of the steel strip (1).
- galvanic coating of the steel strip (1) with zinc, - temper rolling of the zinc-coated surface of the steel strip (1), - depositing of a polymer coating or an organic enamel on one or both sides of the zinc-coated surface of the steel strip (1).
2. Method according to claim 1, wherein the hot-rolled steel strip prior to the coating with zinc is cold-rolled from its original thickness to a thickness of less than 1 mm and especially to a thickness of 0.1 to 0.5 mm.
3. Method according to claim 1 or 2, wherein the steel strip (1) is made from a low-carbon and non-alloyed or low-alloyed steel, the carbon content being less than 0.1 wt.
% and preferably between 20 and 900 ppm.
% and preferably between 20 and 900 ppm.
4. Method according to one of the preceding claims, characterized in that a skin pass level of 0.5 to 2.0% is achieved during the temper rolling.
5. Method according to one of the preceding claims, wherein the depositing of the zinc coating is less than 15 g/m2.
6. Method according to one of the preceding claims, wherein an additional cold rolling step is carried out prior to the temper rolling, preferably achieving a rolling level of 4 - 45 %.
7. Method according to claim 6, characterized in that the galvanized steel strip after the rerolling step has a strength of R m = 300 to 1000 MPa and especially R m =
400 to 650 MPa.
400 to 650 MPa.
8. Method according to one of the preceding claims, characterized in that the galvanized steel strip has a breaking elongation of 1 to 40 % and especially 5 to 25 %.
9. Method according to one of the preceding claims, wherein after the cold rolling the steel strip (1) is annealed for recrystallization, for which it is preferably heated inductively to temperatures between 550 C and 800 C.
10. Method according to one of the preceding claims, characterized in that the steel strip (1) is moved with a speed of at least 200 m/min.
11. Method according to one of the preceding claims, characterized in that the polymer coating is laminated onto the steel strip (1), while the steel strip (1) is held at temperatures above the melting temperature (T m) of the polymer material during the lamination of the polymer coating.
12. Method according to one of the preceding claims, characterized in that the polymer material of the polymer coating is polyethylene terephthalate (PET) or polypropylene (PP) or polyethylene (PE).
13. Method according to one of the preceding claims, characterized in that the polymer coating is deposited onto the steel strip (1) immediately after the temper rolling without preceding passivation, adhesive or conversion coating of the steel strip surface.
14. Method according to one of the preceding claims, characterized in that the zinc-coated surface of the steel strip (1) after the temper rolling has a mean peak to valley distance of R a = 0.01 to 0.1 µm.
15. Method according to one of the preceding claims, characterized in that the method and the produced sheet metal are free of solvents, free of chromium, and/or free of bisphenol-A (BPA).
16. Use of a galvanized fine or ultrafine metal sheet, obtainable according to one of the preceding claims, for the making of packages, especially for foods, or parts of such packages, especially tabs, valve disks, can lids or can rings.
17. Device for carrying out the method according to one of claims 1 to 15, comprising ¨ a transport device (7) for the continuous transport of an endless steel strip (1) in a transport direction with a transport speed which is preferably greater than 200 m/min, ¨ a cold rolling device (6) for the cold rolling of the steel strip (1) moved with the transport speed through the cold rolling device to a thickness of less than 1 mm, ¨ a coating device (11) for the galvanic coating of the steel strip (1) moving at the transport speed through the coating device with zinc, ¨ a rolling device (5) with temper rolls (5a) for tempering the galvanized surface of the steel strip (1) moving at the transport speed through the rolling device, ¨ a heating device (4) for heating the steel strip (1) moving at the transport speed through the heating device, ¨ a plastic coating device (8) for depositing a polymer coating or an organic enamel on one or both sides of the zinc-coated surface of the steel strip (1).
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE102013100730.9 | 2013-01-25 | ||
| DE102013100730.9A DE102013100730B3 (en) | 2013-01-25 | 2013-01-25 | Method and apparatus for producing galvanized fine or fine sheet with high corrosion resistance and use of galvanized fine or Feinstblechs |
| PCT/EP2013/069956 WO2014114370A1 (en) | 2013-01-25 | 2013-09-25 | Method for producing galvanized fine or ultrafine sheet metal with high corrosion resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2916430A1 true CA2916430A1 (en) | 2014-07-31 |
| CA2916430C CA2916430C (en) | 2019-04-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2916430A Active CA2916430C (en) | 2013-01-25 | 2013-09-25 | Method for producing galvanized fine or ultrafine sheet metal with high corrosion resistance |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP2948302B1 (en) |
| CA (1) | CA2916430C (en) |
| DE (1) | DE102013100730B3 (en) |
| ES (1) | ES2675587T3 (en) |
| PL (1) | PL2948302T3 (en) |
| PT (1) | PT2948302T (en) |
| RS (1) | RS57558B1 (en) |
| TR (1) | TR201809605T4 (en) |
| WO (1) | WO2014114370A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020182538A1 (en) * | 2019-03-14 | 2020-09-17 | Tata Steel Ijmuiden B.V. | Laminated steel product |
| US11117164B2 (en) * | 2016-08-10 | 2021-09-14 | Swimc Llc | Edge build and edge blister performance of coil coatings |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102014017492A1 (en) * | 2014-11-27 | 2016-06-02 | Thyssenkrupp Ag | Semi-finished product, method for producing a semifinished product and its use |
| DE102019118578A1 (en) * | 2019-07-09 | 2021-01-14 | Thyssenkrupp Steel Europe Ag | Method of manufacturing a sheet metal product and a sheet metal product |
| CN110318013B (en) * | 2019-07-19 | 2021-07-09 | 首钢京唐钢铁联合有限责任公司 | Production method of hot-dip galvanized strip steel |
| CN110396686B (en) * | 2019-07-25 | 2022-05-20 | 首钢集团有限公司 | Method for improving corrosion resistance of passive film coated steel |
| DE102020200326A1 (en) * | 2020-01-13 | 2021-07-15 | Thyssenkrupp Steel Europe Ag | Process for the production of a surface-refined and surface-conditioned steel sheet |
| CN113106368A (en) * | 2020-12-31 | 2021-07-13 | 鞍钢冷轧钢板（莆田）有限公司 | Production method of hot-dip galvanized sheet |
| DE102021200229A1 (en) | 2021-01-13 | 2022-07-14 | Thyssenkrupp Steel Europe Ag | Process for producing an electrolytically coated steel sheet |
| DE102021121303A1 (en) | 2021-08-17 | 2023-02-23 | Thyssenkrupp Steel Europe Ag | Process for producing a laser-textured skin-pass roll, process for skin-passing a steel sheet and correspondingly skin-passed steel sheet |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2303330B (en) * | 1995-07-21 | 1999-09-08 | British Steel Plc | Improvements in and relating to laminated tin mill products and methods of producing the same |
| DE19730893C1 (en) * | 1997-05-02 | 1998-07-23 | Rasselstein Hoesch Gmbh | Coating metal band with plastic on one or both sides by direct extrusion |
| DE10130005B4 (en) * | 2001-06-25 | 2004-12-23 | Rasselstein Gmbh | Process for coating the surface of a metal strip with a plastic film and use of a laminate produced by the process |
| JP4256721B2 (en) * | 2003-05-21 | 2009-04-22 | 新日本製鐵株式会社 | Method for producing silver metallic design-plated steel sheet |
| WO2012030726A1 (en) * | 2010-08-30 | 2012-03-08 | Ak Steel Properties, Inc. | Galvanized carbon steel with stainless steel-like finish |
-
2013
- 2013-01-25 DE DE102013100730.9A patent/DE102013100730B3/en not_active Expired - Fee Related
- 2013-09-25 RS RS20180885A patent/RS57558B1/en unknown
- 2013-09-25 CA CA2916430A patent/CA2916430C/en active Active
- 2013-09-25 ES ES13771437.4T patent/ES2675587T3/en active Active
- 2013-09-25 EP EP13771437.4A patent/EP2948302B1/en not_active Not-in-force
- 2013-09-25 TR TR2018/09605T patent/TR201809605T4/en unknown
- 2013-09-25 WO PCT/EP2013/069956 patent/WO2014114370A1/en active Application Filing
- 2013-09-25 PL PL13771437T patent/PL2948302T3/en unknown
- 2013-09-25 PT PT137714374T patent/PT2948302T/en unknown
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11117164B2 (en) * | 2016-08-10 | 2021-09-14 | Swimc Llc | Edge build and edge blister performance of coil coatings |
| WO2020182538A1 (en) * | 2019-03-14 | 2020-09-17 | Tata Steel Ijmuiden B.V. | Laminated steel product |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2014114370A1 (en) | 2014-07-31 |
| TR201809605T4 (en) | 2018-07-23 |
| PT2948302T (en) | 2018-07-09 |
| PL2948302T3 (en) | 2018-10-31 |
| EP2948302B1 (en) | 2018-05-16 |
| ES2675587T3 (en) | 2018-07-11 |
| RS57558B1 (en) | 2018-10-31 |
| EP2948302A1 (en) | 2015-12-02 |
| DE102013100730B3 (en) | 2014-06-05 |
| CA2916430C (en) | 2019-04-23 |
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