EP0868951B1 - A method of producing metal cans and metal cans produced thereby - Google Patents

A method of producing metal cans and metal cans produced thereby Download PDF

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Publication number
EP0868951B1
EP0868951B1 EP98302604A EP98302604A EP0868951B1 EP 0868951 B1 EP0868951 B1 EP 0868951B1 EP 98302604 A EP98302604 A EP 98302604A EP 98302604 A EP98302604 A EP 98302604A EP 0868951 B1 EP0868951 B1 EP 0868951B1
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EP
European Patent Office
Prior art keywords
max
metal
low carbon
thickness
carbon steel
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP98302604A
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German (de)
English (en)
French (fr)
Other versions
EP0868951A2 (en
EP0868951A3 (en
Inventor
John Selwyn Williams
Brian John Bastable
Joseph Bulso
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Corus UK Ltd
Redicon Corp
Original Assignee
Corus UK Ltd
Redicon Corp
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Publication date
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Publication of EP0868951A2 publication Critical patent/EP0868951A2/en
Publication of EP0868951A3 publication Critical patent/EP0868951A3/en
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Publication of EP0868951B1 publication Critical patent/EP0868951B1/en
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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21DWORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D51/00Making hollow objects
    • B21D51/16Making hollow objects characterised by the use of the objects
    • B21D51/26Making hollow objects characterised by the use of the objects cans or tins; Closing same in a permanent manner
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21DWORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20Deep-drawing
    • B21D22/22Deep-drawing with devices for holding the edge of the blanks
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21DWORKING OR PROCESSING OF SHEET METAL OR METAL TUBES, RODS OR PROFILES WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21D22/00Shaping without cutting, by stamping, spinning, or deep-drawing
    • B21D22/20Deep-drawing
    • B21D22/30Deep-drawing to finish articles formed by deep-drawing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/12Cans, casks, barrels, or drums
    • B65D1/14Cans, casks, barrels, or drums characterised by shape
    • B65D1/16Cans, casks, barrels, or drums characterised by shape of curved cross-section, e.g. cylindrical
    • B65D1/165Cylindrical cans
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65DCONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D1/00Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
    • B65D1/22Boxes or like containers with side walls of substantial depth for enclosing contents
    • B65D1/26Thin-walled containers, e.g. formed by deep-drawing operations
    • B65D1/28Thin-walled containers, e.g. formed by deep-drawing operations formed of laminated material

Definitions

  • This invention relates to a method of producing metal cans and to metal cans produced by this method.
  • Metal cans such as beverage cans are conventionally produced from two pieces by a process in which the base and wall of the can is formed from a single blank of starting material.
  • One such process is known as the drawn and wall ironed (DWI) process.
  • DWI drawn and wall ironed
  • the starting material is tinplate or aluminium and the blank is cut and drawn into a cup which is then formed into a can shell by precise thinning of the wall. This thinning is accomplished by forcing the cup through a series of annular rings using a punch, the gap between each ring and the punch gradually decreasing thereby "ironing" the metal.
  • the can is then cleaned and coated internally and externally with organic lacquers to provide protection against corrosion and decoration to the external can surfaces.
  • the DWI process suffers from two major drawbacks.
  • WO-A-8302577 discloses a typical DWI process.
  • DRD draw-redraw
  • ECCS electro-chromium coated steel
  • the present invention sets out to alleviate many of the problems associated with conventional can production processes, some of these being discussed above.
  • the invention addresses the difficulties associated with can shaping, especially can doming.
  • the dome of a can has to withstand high internal pressures to meet industrial standards at steels of low thickness (typically 0.15-0.16mm).
  • DWI cans are internally coated with a spray coat of 'lacquer' which must cover all the exposed metal. This is difficult to achieve on surfaces close to the vertical and on sharp radii.
  • a DWI can dome may be 'reformed' after spraying to alter geometry. Therefore, it is an object of the present invention to achieve the desired geometries without the need for reforming.
  • This object can be achieved by a process according to claim 1 and a metal can according to claim 10.
  • a process for producing metal cans from a feedstock comprising a low carbon steel strip or sheet coated on each of its surfaces with a coherent laminated coating of a thermoplastic polymer material, the process including one or more redrawing stages in which the side walls are reduced in thickness by a stretching operation, and forming in the can base an inwardly projecting dome bordered by upstanding walls which subtend an angle of between 0 and 5° to the vertical.
  • the feedstock preferably comprises a low carbon steel strip or sheet of less than 0.25mm thickness and coated on each of its surfaces with coherent laminated films of a thermoplastic polymer, the laminate coating having sufficient formability to withstand without loss of integrity reductions in thickness of up to 40%.
  • the polymer laminates may comprise films of polyethylene terephthalate and polypropylene. Other film materials may however be used.
  • the films may be bonded to the surfaces of the feedstock using heat and pressure.
  • the films may be coextruded whereby a bonding film of approximately 2 ⁇ m first makes contact with the feedstock followed by a polymer film coating which, after coating, is heated and cooled to produce an amorphous structure in the polyethylene terephthalate and a minimal crystalline structure in the polypropylene.
  • the process comprises an initial cupping operation followed by first and second stretch redraw operations. Additional redraw stages may be introduced.
  • the base of the can may be shaped to include an inwardly projecting dome during or immediately following the second stretch (or final) redraw operation. Stretching is preferably achieved by restricting - but not preventing - movement of the cupped feedstock between opposed faces of a pressure sleeve and die.
  • One surface of the die on which the cupped feedstock seats may be recessed and a curved annular projection may extend inwardly from an upper face of the die to define a stretch point for the cupped feedstock.
  • the process provides a metal can whose wall thickness is of the order of 5 to 40% less than the thickness of its base.
  • the invention provides a process for producing a metal can from a feedstock comprising a low carbon steel strip or sheet coated on each of its surfaces with a coherent laminated coating of a thermoplastic polymer material, the process including one or more redrawing stages in which the side walls are reduced in thickness by a stretching operation.
  • the feedstock for cans to be produced in accordance with this invention is double reduced high-strength high ductility low carbon steel having a proof strength in the range 480 to 690 N/mm 2 .
  • the maximum carbon level for the steel is typically 0.05% by weight.
  • a typical specification for this steel is by weight %, C 0.01 - 0.04; S 0.02 max; P 0.015 max; Mn 0.15-0.30; Ni 0.04 max; Cu 0.06 max; Sn 0.02 max; As 0.01 max; Mo 0.01 max; Cr 0.06 max; Al 0.02-0.09 and N 2 0.003 max.
  • the steel is reduced by hot or cold rolling to a gauge typically of between 0.12mm and 0.25mm and is processed by known appropriate heating cycles and continuous annealing.
  • the steel has a minimum earing quality and a strength typically in the range 500 to 600N/mm 2 .
  • the steel is a high strength ductile steel known as TENFORM DR (RTM).
  • Strip produced from the feedstock may then be subjected to an electrolytic coating process.
  • the steel strip is cleaned and pickled before being passed through a plating bath in which it is coated with a thin layer of chromium metal (typically of 0.01 ⁇ m thickness) followed by a thin layer of chromium oxide (again typically of 0.01 ⁇ m thickness).
  • a plating bath in which it is coated with a thin layer of chromium metal (typically of 0.01 ⁇ m thickness) followed by a thin layer of chromium oxide (again typically of 0.01 ⁇ m thickness).
  • tinplate, blackplate or other suitable substrate could be employed.
  • the strip is then laminated with a polymer material, typically that known under the name "Ferrolite” (RTM).
  • a film of PET (polyethylene terephthalate) and/or PP (polypropylene) and/or nylon either separately or simultaneously is bonded to the surface of the metallic coated steel strip or sheet using heat and pressure.
  • the films are co-extruded so that a bonding layer of ⁇ 2 ⁇ m first makes contact with the steel and forms a strong bond.
  • the polymer films are melted and held above the recrystallisation temperatures for a few seconds before being rapidly quenched to below their softening temperatures. This produces an amorphous structure in the PET and a minimal crystalline structure in the PP.
  • the thickness of the external polymer coating is of the order of 25 ⁇ m thickness and the internal thickness is between 15 and 30 ⁇ m.
  • the strip is fed to a cupper either in a pre waxed condition or is passed through a waxer on entry to the cupping system.
  • the wax may be edible and petroleum based with film weights in the range of 5-20 mg/ft 2 .
  • the laminate may be heated in the range 70°-120°C. Alternatively the heating process may be carried out after the cupping or first redrawing stage. Pre-heating relieves stresses and ageing effects in the laminate so that subsequent forming is carried out more easily.
  • Discs are stamped from the strip or sheet. The cup is stretch drawn in one operation using a disc with a diameter typically in the range 150mm to 200mm. This diameter is dependent (with gauge) upon the required can size and type of application.
  • the draw ratio (i.e. ratio of the diameter of the disc to that of the cup) is typically in the range 1.0-2.0:1.
  • the geometry of the tooling is designed in combination with the correct blank holding load to give a reduction in wall thickness at the cupping stage of up to 10%. This is accomplished with a die radius range typically between 0.5mm and 1.5mm and a parallel land length of up to 5mm.
  • the blank holding load is achieved by use of a boosted air pressure of up to 200 psi fed into a series (typically three) of internal multiplying pistons.
  • the punch/die gap is important and is controlled by the feedstock gauge and coating and gaps of 1.20 - 1.50 times the starting total laminate thickness are typically used.
  • the punch nose radius is carefully controlled to achieve the required stretch whilst minimising subsequent can wall marking which could lead to laminate rupture. Punch nose radii in the range 2.5mm to 7mm are generally required.
  • the cupper cup is passed into the stretch redraw press which contains tooling for both first and second redraw operations.
  • the diameter of the cup is reduced in the first redraw operation with a draw ratio in the range 1.0-1.7:1, and with a wall thickness reduction of up to 25% of the ingoing cup wall thickness.
  • the wall thickness reduction is achieved by a stretching technique.
  • the wall thickness reduction is balanced with the draw ratio and is achieved by use of pressure sleeve and die geometries in combination with controlled blank holding loads.
  • the tooling geometries typically fall in the following ranges:
  • the blankholding load is achieved by use of air pressure of up to 100 psi fed into a stack of two or more internal multiplying pistons.
  • the radius of the nest diameter with the die at the base of the nest is in the range 0.10 - 2.00mm.
  • the punch has a taper which is typically between 40mm and 60mm from the punch nose with an increase in punch diameter of 0.25mm to 0.50mm to aid stripping.
  • the gap between the largest punch diameter and die (per side) is generally controlled to between 1.20 and 1.50 times the starting laminate thickness.
  • the punch radius is important to achieve the required stretch whilst minimising subsequent can wall marking which could lead to laminate rupture.
  • Punch nose radii in the range 1mm to 3mm are typically used.
  • Gap control or arrested draw is employed at the first redraw stage to
  • gaps of 0.10 to 0.15mm between the pressure sleeve and die face are generally used depending upon the laminate feedstock used.
  • a small reverse draw in the cup base may also be used in this operation depending upon the dome required in the final can.
  • Domes for carbonated beverages may be 206 (2 6/16 inches), 204 or 202 diameter.
  • the purpose of the reverse draw is to eliminate the tendency to form chime wrinkles in the finished can and to make the cup base more rigid and thus keep the can circular and eliminate the tendency for oval cans.
  • the first redraw cup is passed back into the stretch redraw press in a station containing the second redraw tooling.
  • the cup diameter is reduced in this operation to the final can diameter.
  • This may be 211 for normal beverage cans or 209 for shaped beverage cans.
  • the draw ratio used is generally in the range 1.0-1.7:1 with a wall thickness reduction of up to 25% of the ingoing cup wall thickness.
  • the wall thickness reduction is again achieved by a stretching technique using a combination of pressure sleeve and die geometries with controlled blankholding loads.
  • the correct choice of diameter reduction ratio to achieve the finished can is also important in enabling the stretching process to be successful.
  • the tooling geometries used are typically in the following ranges:
  • the blankholding load is achieved by use of air pressure up to 100 psi fed into a stack of two or more internal multiplying pistons.
  • the radius of the nest diameter with the die at the base of the nest is typically in the range 0.10 - 2.0mm.
  • the punch has a taper located between 15mm and 30mm from the top of the second redraw cup in the range 0.10mm - 0.25mm increase in diameter to aid stripping of the can from the punch.
  • the gap between the punch and the die (per side) at the widest point is controlled to between 1.0 and 1.20 times the starting laminate thickness.
  • Gap control or arrested draw is employed again as the second redraw stage to eliminate cup high spot clip offs or the generation of laminate "whiskers".
  • gaps of 0.10mm to 0.15mm are used between the pressure sleeve and die face dependent upon the laminate feedstock used.
  • the overall can wall thinning employed is 5 - 40% dependent upon the end use of the can.
  • a dome is formed in the can at this stage by use of a doming station with a forming ring acting as a blank holder.
  • the blankholding load on the form ring is achieved by use of a boosted air pressure up to 500 psi fed into a series (typically three) of internal stacked pistons.
  • the positions of the forming ring relative to the dome die is important in that the ring must clamp the laminate to the dome chime of the punch before the dome die starts to draw the dome.
  • domes of 202, 204 and 206 are used for carbonated beverage cans.
  • the dome profile must be capable of withstanding a dome reversal pressure of 90 - 100 psi depending upon can contents (pasteurised or non pasteurised).
  • the dome, the can walls and neck must be capable of withstanding an axial load of 1.0KN. This is achieved by the combination of the high strength formable DR steel and the geometry of the design. It is also facilitated by the polymer laminate coatings which can withstand the forming operations and still offer protection at sharp radii and angles.
  • Normally DWI cans are internally coated with a spray coat of 'lacquer' which must cover all exposed metal, but this is difficult to achieve on surfaces close to the vertical and on sharp radii.
  • a DWI can dome may be 'reformed' after spraying to alter geometry but in this can the geometry described below is achieved without reforming.
  • the depth of the dome which is preferably > 11 mm
  • the spherical radius of the dome which preferably lies between 48 and 54mm
  • the radius at the the point where the inner upstanding wall meets the spherical dome is preferably less than 0.6mm and most importantly, the angle made between the upstanding walls (which border the inwardly projecting dome) should lie between 0 and 5° to the vertical.
  • the can is trimmed and passed through an oven.
  • This oven is typically held at 200-230°C and the pass time is typically between 1 and 3 minutes. This facilitates the removal of petroleum wax lubricant to such a level so that it does not interfere with the laydown of printing inks used to decorate the can. It also raises the surface energy of the PET coating to at least 38 dynes/cm which increases the wettability of the PET surface to printing inks.
  • the temperature cycle in the oven is chosen to minimise recrystallisation of the PET by rapid temperature rise and cooling times.
  • Can fillers are continually seeking methods of product differentiation in various forms. To date, this has mainly been achieved by the use of various decorations and decorating techniques. Another method of product differentiation being sought is by the use of shaped cans.
  • the key to the solution of can shaping is the formability inherent in the can wall presented to the shaping machine.
  • There are various methods of achieving the desired shape but all rely on a measure of formability, given by a combination of can wall thickness and ductility.
  • Three-piece cans have can walls with mechanical properties and thickness essentially the same as the ingoing plate. Two-piece cans have walls that are thinner than the starting material and hence due to strain hardening effects, stronger and less ductile than the starting material.
  • Cans in accordance with the invention however, have been shaped successfully and with diametrical expansions recorded of 10% with much higher levels expected. This is possible with the increased formability of the can wall resulting from the special steel and production route used which is designed to increase ductility with little reduction in strength. This property, coupled with the strain hardening property of the steel also results in the formation of a shaped can with relatively high axial crush strength. Shaping is typically achieved using expandable mandrels which locate within the can interior, but other methods (such as hydro-forming) are possible.
  • a further advantage of the present invention is that if either an aluminium or steel DWI can is shaped, coating is particularly difficult with the problems of internal lacquer damage and the difficulty of internally spraying a shaped can.
  • Cans in accordance with the invention are particularly suited since the coating is abrasion resistance and withstands current shaping operations, whilst maintaining good corrosion protection.
  • FIG 1 shows five stages of a cupping operation of the method of the present invention.
  • the five stages are labelled A to E.
  • Stage 1 A shows a feedstock strip 1 of laminated steel strip held between a draw pad 2 and a blank and draw die 3.
  • a disc 4 of the required diameter is cut from the strip, by downward movement of a cutter 5 (see Figure 1B).
  • a punch 6 ( Figures 1 C and 1 D) is then moved downwardly with the disc edges trapped between the opposed surfaces of the draw pad 2 and draw die 3.
  • a cup 7 is thereby formed which is removed from the die by air pressure (see Figure 1E).
  • the feedstock strip is of the order of 0.16mm gauge. This compares with a gauge of around 0.28mm for conventional aluminium feedstock.
  • the cup 7 is then placed on a die 8 for first redraw purposes.
  • This stage is illustrated in Figure 2A.
  • the die is formed with a shaped lip 9 and has a curved annular projection 10 protruding inwardly from its upper surface.
  • the lip 9 and projection 10 can be seen more clearly from Figure 4.
  • a pressure sleeve 11 and punch 12 move downwardly and within the side wall of the cup 7.
  • the outer rim of the cup base seats between the opposed surfaces of the pressure sleeve 11 and the die 8.
  • the gap between these members is sufficient only to restrict movement of the cup 7, not to impose a force sufficient to deform or iron the cup.
  • the punch is moved downwardly, so the cup wall is stretched to increase cup height.
  • cup 7 is again shown positioned on the die 8. See Figure 3A.
  • the pressure sleeve 11 is moved downwardly as shown in Figure 3B to position the sleeve within the cup 7. Again, the spacing between the sleeve 11 and the die 8 is to restrict movement of the cup, not to preclude such movement.
  • a punch 14 including a recessed base 15 is moved downwardly into engagement with the cup base to once again stretch the cup side wall and effect elongation thereof.
  • the stretching operation being as described above in relation to Figure 2. This stretching operation is shown in Figures 3C and 3D.
  • the fully stretched and formed cup is the ejected using air pressure as shown in Figure 3F.
  • the fully stretched and formed cup has a midwall thickness of around 0.12mm and a top wall thickness of around 0.15mm. These dimensions compare with 0.104mm and 0.165mm respectively for conventional aluminium cans.
  • the shape imposed in the can base by the forming ring and dome die is shown in Figure 5.
  • This dome has to withstand internal pressures of at least 95 psi to meet current industrial standards at steel thicknesses below 0.20mm (typically 0.15/0.16mm). This is achieved by the combination of the high strength formable DR steel and the geometry of the design. It is also facilitated by the polymer laminate coatings which can withstand the forming operations and still offer protection at sharp radii and angles. Normally DWI cans are internally coated with a spray coat of 'lacquer' which must cover all exposed metal, but this is difficult to achieve on surfaces close to the vertical and on sharp radii.
  • a DWI can dome may be 'reformed' after spraying to alter geometry but in this can the geometry described below is achieved without reforming.
  • the important features are the depth of the dome, DD, which should be > 11 mm, the spherical radius of the dome, SR, which should lie between 48 and 54mm, the radius at position 20 which should be less than 0.6mm and the angle ⁇ which should lie between 0 and 5°.
  • the can is to be shaped, this can be achieved by insertion of an expandable mandrel which, one expanded, imposes any required shape to the can. This is possible only because of the particular pre-coated laminated strip feedstock employed which has sufficient inherent formability to withstand the stretching and forming operation discussed without any loss of coating integrity.
  • Other can shaping processes including hydroforming can be employed.
  • the invention provides can shaping by mechanical expansion (typically up to 10%) with no intermediate treatment, upgauging or lacquer repair system required.
  • mechanical expansion typically up to 10%
  • the expansion potential for lightweight cans is maximised and the higher strength and work hardening achieved results in improved axial crush performance.
  • solvent emissions are virtually eliminated and all coatings are PVC free. Waste products from the can making process are also significantly reduced.

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Ceramic Engineering (AREA)
  • Containers Having Bodies Formed In One Piece (AREA)
  • Shaping Metal By Deep-Drawing, Or The Like (AREA)
  • Laminated Bodies (AREA)
  • Glass Compositions (AREA)
  • Thermally Insulated Containers For Foods (AREA)
  • Rigid Containers With Two Or More Constituent Elements (AREA)
EP98302604A 1997-04-04 1998-04-02 A method of producing metal cans and metal cans produced thereby Expired - Lifetime EP0868951B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9706873A GB2323803B (en) 1997-04-04 1997-04-04 A method of producing metal cans
GB9706873 1997-04-04

Publications (3)

Publication Number Publication Date
EP0868951A2 EP0868951A2 (en) 1998-10-07
EP0868951A3 EP0868951A3 (en) 1999-03-24
EP0868951B1 true EP0868951B1 (en) 2004-09-01

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EP (1) EP0868951B1 (es)
AT (1) ATE275013T1 (es)
DE (1) DE69825930T2 (es)
ES (1) ES2227772T3 (es)
GB (2) GB2323803B (es)

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DE102012102230A1 (de) 2012-03-16 2013-09-19 Thyssenkrupp Rasselstein Gmbh Verfahren zum Veredeln einer metallischen Beschichtung auf einem Stahlblech

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CN102275067B (zh) * 2011-08-02 2013-04-24 西安西工大超晶科技发展有限责任公司 一种航天器燃料用半球形金属贮箱的加工制备方法
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DE102018114002A1 (de) 2018-06-12 2019-12-12 Gebrüder Leonhardt GmbH & Co. KG Blema Kircheis Verfahren und Vorrichtung zur Herstellung eines Behälters

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DE102012102230A1 (de) 2012-03-16 2013-09-19 Thyssenkrupp Rasselstein Gmbh Verfahren zum Veredeln einer metallischen Beschichtung auf einem Stahlblech

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DE69825930T2 (de) 2005-09-29
GB2323803B (en) 2001-09-19
EP0868951A2 (en) 1998-10-07
GB2323803A (en) 1998-10-07
DE69825930D1 (de) 2004-10-07
ATE275013T1 (de) 2004-09-15
GB2355679A (en) 2001-05-02
GB2355679B (en) 2001-09-19
GB9706873D0 (en) 1997-05-21
ES2227772T3 (es) 2005-04-01
EP0868951A3 (en) 1999-03-24
GB0029668D0 (en) 2001-01-17

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