WO2013104530A2 - Method for passivating tinplate - Google Patents
Method for passivating tinplate Download PDFInfo
- Publication number
- WO2013104530A2 WO2013104530A2 PCT/EP2012/077108 EP2012077108W WO2013104530A2 WO 2013104530 A2 WO2013104530 A2 WO 2013104530A2 EP 2012077108 W EP2012077108 W EP 2012077108W WO 2013104530 A2 WO2013104530 A2 WO 2013104530A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- steel strip
- aftertreatment agent
- tinned
- layer
- agent
- Prior art date
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- 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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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12611—Oxide-containing component
Definitions
- the invention relates to a method for passivating the surface of tin-plated steel strips, which are moved at a belt speed through a coating plant, by anodic oxidation and post-treatment of the tinned steel strip with a chromium-free aftertreatment agent.
- the invention further relates to the use of complex-linked transition metal agents or organic additives normally used to disperse or improve wetting, as a chromium-free aftertreatment agent in the manufacture of tinned steel strips.
- the invention further relates to a tin-plated steel strip or sheet with a carrier layer of a fine or Feinstblech made of steel and a deposited thereon tin layer and a surface layer of a chromium-free aftertreatment agent.
- Tinplate is a versatile, economically and ecologically advantageous material that is mainly used in the packaging industry. Tinplate is cold-rolled steel sheet with a thickness of up to 0.5 millimeters, which is coated with a thin layer of tin to protect the steel sheet from corrosion. The tin layer is, for example, applied electrolytically to the metal sheet.
- the coated steel sheet is chemically or electrochemically passivated and then greased to make the tin-plated steel resistant to oxidation and to lower the coefficient of friction, so that the tinned steel during subsequent processing, eg. in the production of tinplate packaging for food, can be processed better.
- the passivation is usually carried out using Cr 6+ -containing solutions.
- DE4205819A discloses an anhydrous composition for producing anticorrosive coatings on metallic surfaces based on silane compounds and compounds of tetravalent titanium or zirconium.
- EP1002143A discloses a process for the alkaline passivation of galvanized and alloy galvanized steel surfaces as well as of aluminum and its alloys in strip lines. This passivation with an aqueous solution results in a corrosion protection layer, which can serve as the basis for subsequent painting.
- EP1270764A discloses a surface-treated tinplate comprising an alloy layer on a surface of a steel sheet, a tin layer coated on the alloy layer so that the alloy layer is exposed on an area of 3.0% or more, and thereon a film comprising P and Si with a coating weight of 0.5 to 100 mg / m 2 or 250 mg / m 2 applied to the exposed alloy layer and the tin layer.
- Chromium-free aftertreatment agents for tinplate are described in US 2009/0155621 Al and the publications cited therein. Disadvantages of the prior art
- the passivation here must prevent excessive growth of the tin oxide layer during storage of the coated steel sheet or the food containers produced therefrom until painting and beyond until consumption of the preserve.
- the passivation should prevent discoloration of the coated metal surface. Such discolorations occur, for example, in the sterilization of cans with sulfur-containing contents, because the sulfur reacts with the tin of the coated sheet steel surface, if it is not sufficiently passivated.
- the matt discoloration (marbling) or gold coloration of the surface of the packaging may give the consumer the impression that the product is spoiled.
- the reaction with sulfur can also lead to paint adhesion problems, which can be avoided by passivation of the coated steel sheet.
- the passivation must also ensure the resistance of the painted metal container after filling with food against acids contained in the food, such.
- Such acid anions in the product can cause delamination of the inner coating of the container in case of insufficient passivation.
- the cold-rolled fine or ultra-fine sheet is first melted by heating to temperatures above the tin melting point after tinning and then quenched in a water bath. Passivation is then carried out by treating the tinned steel sheet with a chromate solution and finally rinsing with demineralized water and drying it thermally. This is followed by electrostatic lubrication with dioctyl sebacate (DOS) or acetyltributyl citrate (ATBC).
- DOS dioctyl sebacate
- ATBC acetyltributyl citrate
- the Cr 3+ precipitates as Cr 3+ hydroxide.
- the passivation layer no longer contains Cr 6+ ions after rinsing and drying the tinplate surface.
- the object of the invention is to provide a process for the chromium-free passivation of the surface of steel strips coated with a tin coating, which are moved at a belt speed through a coating system, which enables an efficient passivation of the steel belt surface even at high belt speeds ,
- an improved paint adhesion and resistance to acids in foods, especially against sulfur-containing amino acids can be achieved.
- an anodic oxidation of the tin surface is provided.
- the invention is based on the recognition that the passivation of the tinned surface of the steel strip by aftertreatment with a chromium-free aftertreatment agent alone is not sufficient to protect the surface over the entire surface and permanently against corrosion and discoloration (marbling).
- chromium-free aftertreatment agents do not protect the tin-plated steel strip surface from reaction with sulfur.
- the resistance of the tinned steel strip surface against corrosion and reaction with sulfur increases considerably can be, if prior to the post-treatment with a chromium-free aftertreatment agent initially carried out an inerting of the tinned steel strip surface by an anodic oxidation.
- the anodic oxidation produces an oxide layer with a layer thickness in the nm range on the tinned steel strip surface.
- the oxide layer is essentially a layer of tetravalent tin oxide (SnO 2 ) which is substantially more inert than divalent tin oxide (SnO). If, according to the invention, a thin surface layer of a chromium-free aftertreatment agent is applied to this oxide layer, the surface of the tinned steel strip is fully and effectively protected against corrosion and against reaction with sulfur.
- Step 1 The method according to the invention will be described in more detail below with reference to an exemplary embodiment: Step 1
- an electrochemical tinning of a cold-rolled steel strip takes place in a strip-tinning plant.
- the steel strip is thereby moved through an electrolytic bath at a belt speed, which is usually in the range from 200 m / min to 750 m / min, and electrolytically coated with tin.
- the steel strip is conductively or inductively (or conductively and inductively) heated to temperatures above the tin melting point (232 ° C) to melt the tin coating.
- the moving steel strip is quenched in a water bath. With this fresh surface, the tinned steel strip reaches the second step of the process, namely the anodic oxidation of the tin surface.
- Step 2 In the second step of the process according to the invention, anodic oxidation takes place in soda solution, ie in sodium carbonate solution.
- the tinned steel strip is thereby moved further at the belt speed and connected as an anode in the soda-electrolyte bath polarized.
- the electrolyte used is an aqueous soda solution.
- the concentration of sodium carbonate in the soda solution is preferably 1 wt .-% to 10 wt .-%, preferably 2 wt .-% to 8 wt .-%, preferably 3 wt .-% to 7 wt .-%, especially 4 Wt .-% to 6 wt .-%, in particular about 5 wt .-%.
- the device for electrolytic anodic oxidation expediently comprises an electrolytic immersion bath with a vertical tank.
- a deflection roller is arranged within the vertical tank, via which the tinned steel strip is deflected.
- the vertical tank is filled with the electrolyte.
- a potential is applied between the tin-plated steel strip and the counter-electrode (for example, a steel cathode) in the vertical tank.
- the charge amount Q.sub.2 is expediently between 0.2 C and 2 C, preferably between 0.2 C and 0.6 C, at a current density of 1-3 A / dm 2 .
- the anodization time corresponds to the residence time of the tinned steel strip in the electrochemical oxidation bath (electrolyte bath). This is predetermined by the length of the electrolyte bath or its fill level as well as the anode length and the belt speed and is advantageously in the range of 0.1 s to 1 s, in particular between 0.1 s and 0.7 s, preferably in the typical belt speeds Range from 0.15s to 0.5s, and ideally 0.2s.
- the anodization time depending on the belt speed, can be set to the values suitable according to the invention via the fill level.
- the distance between the steel strip and the counter electrode in the electrolyte bath is set by the system. It is, for example, in the range of 3 to 15 cm, preferably in the range of 5 to 10 cm and in particular by 10 cm.
- the temperature of the electrochemical oxidation bath is preferably in the range of 30 to 60 ° C, more preferably in the range of 35 to 50 ° C, and especially around 45 ° C.
- the current density is set in the range of 1.0 to 3 A / dm 2 , preferably 1.3 to 2.8 A / dm 2 , more preferably 2 to 2.6 A / dm 2 , more preferably 2.4 A / dm 2 ,
- the total amount of charge moves in the range between 0.2 C and 0.6 C and is preferably, for example, 0.48 C.
- the corresponding charge densities (with respect to the area of the treated tape) are in the range of 0.2 C / dm 2 to 0.6 C / dm 2 .
- thorough rinsing of the tinned and oxidized steel strip with distilled or completely desalted water followed by drying e.g. can be done with hot air.
- other drying measures are suitable, such as drying with water-absorbing solvents and then drying with a cold or hot air blower, which also the use of hot air is preferred for drying with air-convection drying equipment such as IR radiation body, inductive heating or resistance heating, or the drying only with a cold or hot air blower, preferably a hot air blower.
- the tinned and oxidized steel strip surface is coated with a post-treatment agent.
- a solution of the aftertreatment agent preferably a solution with water or an organic solvent, or a ready-to-use preparation of the aftertreatment agent is sprayed onto the steel belt moving at the belt speed.
- the solution of the aftertreatment agent is then squeezed off by means of squeezing rollers and dried. After squeezing and drying, only a thin film of the aftertreatment agent still remains on the surface of the coated metal strip, wherein the support of this thin film is usually between 2 and 30 mg / m 2 .
- the aftertreatment agent is, for example, sprayed on pipes, which are arranged at a distance from the coated metal strip surface and transversely to the strip running direction, and Have holes or nozzles through which passes the aftertreatment agent on the coated steel strip surface. At least one tube with such bores is preferably arranged on each side of the steel strip in order to spray or spray both sides of the metal strip with the aftertreatment agent.
- the distance of the tubes to the tinned and anodized steel strip is adjusted and the position of the bores or nozzles with respect to the direction of movement of the steel strip is selected so that the exiting liquid treatment agent perpendicular to the steel strip surface or at least within an angular range of + - 45 °, preferably impinge on the surface of the steel strip within an angular range of + - 15 ° around the normal (vertical).
- the squeezed from the Ouetschrollen solution collects in a storage tank, from where the excess post-treatment solution is fed via a pump, if necessary, a treatment and reuse.
- the agents defined below can be used. Representative of these is the application of a Ti / Zr-containing post-treatment agent is described.
- Ti / Zr containing the post-treatment agent available from Henkel KGaA under the trade mark ® 1456 Granodine substance is, for example, used. This is prepared as a solution with a dry coverage in the range of 0.5 to 2 mg Ti / m 2 , more preferably 0.8 to 1.5 mg Ti / m 2 , in particular by 1 mg Ti / m 2 , on the tinned and oxidized steel strip surface applied.
- Step 5 The fifth step is again a drying step, wherein the drying temperature (belt temperature) is in the range of 30 to 95 ° C and preferably between 35 and 60 ° C.
- the drying time is adapted to the belt speed.
- the drying devices mentioned in step 3 can be used.
- a tin-plated steel sheet is achieved with a layer structure, which is composed as follows: At the bottom is as a support a cold-rolled steel sheet, in particular a fine or Feinstblech with a thickness of 0.5 mm to 3 mm (sheet) or less than 0.5 mm (fine sheet). On the steel plate follows as the next layer, for example. Electrodeposited tin layer.
- the tin coating is usually 0.1 to 11.2 g / m 2 , but in individual cases may be less than 0.1 g / m 2 or more than 11.2 g / m 2 . Any alloy layers of support material and tin are neglected here as separate intermediate layers.
- On the tin layer then follows the oxide layer produced by the anodic oxidation with a thickness of a few nm, which consists essentially of tetravalent tin oxide. The thickness of the tin oxide layer is estimated to be in the range of 2 to 10 nm.
- the surface layer is followed by the aftertreatment agent layer which has been deposited on the thin oxide layer by the post-treatment and subsequent drying.
- the application of the post-treatment agent in the dry state (dry coating) is expediently between 2 and 30 mg / m 2 .
- the sheet metal produced and treated according to the invention is either cut up in the form of metal sheets or rolled up as a roll (coil).
- the end user for example, the manufacturer of tin cans, the sheet is then usually provided with a coat of paint, for example. With a tin can or an epoxy paint.
- a tin can or an epoxy paint By deep-drawing the painted sheet is then processed into moldings, for example to tin cans.
- the layer structure resulting from the treatment according to the invention contributes, in comparison to known tinplate materials, to an improved paint adhesion and a reduced flaking off of the paint, for example due to the presence of mercapto-group-containing amino acids.
- the substances which are suitable for use in the process according to the invention for the after-treatment of the surface of anodized tinplate must have properties such that they can adhere to the tin surface and at the same time permit wetting of the lacquer layer to be applied during the subsequent coating of the tin surface.
- the bond between the functional group on the anodized tin surface and the functional groups of the lacquer surface with their adhesion promoter molecules must be so strong after drying of the lacquer film that they are in the cysteine test (sterilization of the painted tinplate at 121 ° C.
- the substances used for the aftertreatment should be chromium-free and be used without addition of organic solvents, or be soluble in distilled water, since the use of solubilizers cause too high concentrations of solvents in the exhaust air and would make costly cleaning equipment for the removal of solvents required .
- Substances which are particularly suitable as aftertreatment agents have, for example, proved to be substances which are preferably used in practice as additives for the better dispersion of pigments in paints or for improving the wetting and / or the adhesion of paints to metal surfaces.
- Such agents are selected from copolymers of acrylates, polymethylsiloxanes with polyether side chains, acidic polyethers, and polymers having heterocyclic groups. But even those substances which are used as corrosion inhibitors for sheets, for example in the automotive industry, for example, Bonder or Parkertechnischsstoff, can be used advantageously.
- Such materials are selected from acidic, aqueous, liquid compositions containing complex metal fluoride anions with di- to tetravalent cations and polymeric materials
- Particularly suitable after-treatment agents for the process according to the invention, besides copolymers of acrylates are the following substances:
- a modified with fluorine carbonate polyacrylate neutralized with dimethylethanolamine, wherein an aqueous solution with 59 to 61 wt .-% of active ingredients at 20 ° C, a density of 1.04 to 1.06 g / cm 3 according to DIN 51757, a refractive index of 1.420 to 1,440 according to DIN 53491 and an acid value of 50-70 mg KOH / g according to DIN 53402, [EFKA 3570],
- a modified polyacrylate which at a content of 38-42 wt .-% active substance in water has a density of 1.02 to 1.06 g / cm 3 according to DIN 51757 and an amine value of 22 to 28 mg KOH / g according to DIN 16945 [EFKA 4560], a polymer containing:
- Ri, R 2 , R 3 and R 4 may be the same or different and H or
- R 5 , R 6 and R 7 may be the same or different and represent H or alkyl, and R 8 is alkyl or substituted alkyl, and the alkyl group R 8 may be interrupted by - 0 - groups, iii) 5-50 mol% of one or more monomers containing a heterocyclic group having at least one basic ring nitrogen atom or to which such heterocyclic group is located after polymerization,
- the substance d) is preferably an acidic, aqueous, liquid composition which, in addition to water, contains the following components:
- fluorometalate anions each consisting of: (i) at least four fluorine atoms and (ii) at least one atom of a metallic element selected from the group consisting of titanium, zirconium, hafnium, silicon, aluminum and boron, is selected; and optionally (iii) ionizable hydrogen atoms, and / or optionally (iv) one or more oxygen atoms;
- (B) an amount of one or more di- to tetravalent, especially divalent and / or tetravalent cation (s) of cobalt, magnesium, manganese, zinc, nickel, tin, copper, zirconium, iron and / or strontium, so that Ratio of the total number of the cation (s) to the number of anions in the component (A) is at least 1: 5 but not greater than 3: 1;
- the substance d) is an acidic aqueous liquid composition substantially free of hexavalent chromium and / or ferricyanide for treating metal surfaces not more than 1.0% and preferably not more than 0.0002 % of both the hexavalent chromium and the ferricyanide and which otherwise contain besides water the following components:
- component (D) at least 0.10% and preferably at least 0.20% of a water-soluble (or more water-dispersible) and / or water-dispersible (water-dispersible) organic polymer (s) and / or polymer-forming resin (s) where the amount of said component is such that the ratio of the solids content of the organic polymer (s) and polymer-forming resin (s) in the composition to the solids content of component (A) ranges from 1: 2 to 3: 1 lies.
- component d) comprises dihydrogen hexafluorotitanate (2-) and organic polymers.
- Particularly preferred is the component Granodine 1456.
- the polymer (D) may be a polymer compound comprising a copolymer material, wherein at least a part of the copolymer has the structure
- Such a polymer may e.g. be prepared as follows:
- a slurry of 263.3 g of N-methylglucamine in 400 ml of deionized water is added and the mixture is heated to 60-65 ° C with stirring. Then 100.2 ml 37% Formaldehyde added over one to one and a half hours. The mixture is then heated to 90 ° C and held for 6 hours. After cooling, the mixture is diluted with deionized water to 9.6 wt% solids.
- the pH of the final solution is 9.1 and the solution comprises an N-methylglucamine derivative.
- Such a polymer may e.g. be prepared as follows:
- Propasol P a propoxylated propanol solvent obtained from Union Carbide Corp., Danbury, Connecticut
- an amine oxide which does not require an additional step of neutralization is formed by adding 0.75 moles of 30% H 2 O 2 (85 g) to the reaction mixture. The reaction mixture is allowed to stir overnight and then diluted with 960 ml of deionized water. The result of this optional step is a water-soluble amine oxide resin which does not require neutralization for water stability.
- Suitable treatment agent with the complexed transition metals for example, products in the Granodine ®, which represent an aqueous solution containing the complexed transition metals (Ti, Mn, Zr) and optionally a silane.
- titanium-containing and / or zirconium aftertreatment agents have shown such products in the Granodine ® (manufacturer: Henkel) or Gardobond ® (manufacturer: Chemetall), in particular the products “Granodine ® 1456" and "Gardobond ® X 4707".
- These titanium-containing and zirconium-containing products are expediently metered as aftertreatment agent for the process according to the invention such that after squeezing and drying a titanium coating (dry coating) of 0.5 mg / m 2 to 2 mg / m 2 and in particular of about 1.0 mg / m 2 is present on the surface of the treated tinplate.
- aqueous solutions of these aftertreatment agents typically 1.5 to 10% aqueous solutions of these aftertreatment agents are used, wherein the titanium content in the aqueous solution is preferably between 0.2 and 1.2 g / l and more preferably between 0.2 and 0.5 g / l is.
- Components (a) to (c) were developed by EFKA Chemicals and EFKA Additives, respectively, and are currently supplied by BASF SE.
- acrylate-containing agents having N-heterocyclic groups have been found to be particularly suitable, e.g. EFKA 4560. These correspond to the components (c) defined above.
- the solids content was then adjusted to 40% by weight with butyl acetate.
- These substances are sprayed undiluted or as an aqueous solution onto the tinned steel strip according to the above-described method of the invention and optionally subsequently squeezed off and dried.
- dry runs in the range of 2 to 15 mg / m 2 and preferably between 2 and 10 mg / m 2 are suitable.
- the (further) tin oxide growth on the coated metal strip surface can be greatly reduced during its storage until it is painted.
- the paint adhesion is improved.
- the tinplate surfaces treated according to the invention have proven to be very easy to paint.
Abstract
Description
Claims
Priority Applications (9)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2012365534A AU2012365534B2 (en) | 2012-01-12 | 2012-12-31 | Method for passivating tinplate |
ES12813895.5T ES2573340T3 (en) | 2012-01-12 | 2012-12-31 | Procedure for tin passivation |
JP2014551567A JP5977365B2 (en) | 2012-01-12 | 2012-12-31 | Tinplate surface passivation method |
CA2858004A CA2858004C (en) | 2012-01-12 | 2012-12-31 | Method for passivating tinplate |
EP12813895.5A EP2802688B1 (en) | 2012-01-12 | 2012-12-31 | Method for passivating tinplate |
BR112014017080-0A BR112014017080B1 (en) | 2012-01-12 | 2012-12-31 | tinned steel strip or sheet and process for passivating the surface of tinned steel strip or tinned steel sheet |
RU2014132049/02A RU2593248C2 (en) | 2012-01-12 | 2012-12-31 | Method of passivating white tin |
CN201280066604.5A CN104040037B (en) | 2012-01-12 | 2012-12-31 | Method for being passivated galvanized iron sheet |
US14/371,624 US20150010773A1 (en) | 2012-01-12 | 2012-12-31 | Method for passivating tinplate |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102012000414.1 | 2012-01-12 | ||
DE102012000414.1A DE102012000414B4 (en) | 2012-01-12 | 2012-01-12 | Process for passivating tinplate and tinned steel strip or sheet |
Publications (2)
Publication Number | Publication Date |
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WO2013104530A2 true WO2013104530A2 (en) | 2013-07-18 |
WO2013104530A3 WO2013104530A3 (en) | 2014-05-30 |
Family
ID=47557133
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP2012/077108 WO2013104530A2 (en) | 2012-01-12 | 2012-12-31 | Method for passivating tinplate |
Country Status (12)
Country | Link |
---|---|
US (1) | US20150010773A1 (en) |
EP (1) | EP2802688B1 (en) |
JP (1) | JP5977365B2 (en) |
CN (1) | CN104040037B (en) |
AU (1) | AU2012365534B2 (en) |
BR (1) | BR112014017080B1 (en) |
CA (1) | CA2858004C (en) |
DE (1) | DE102012000414B4 (en) |
ES (1) | ES2573340T3 (en) |
PL (1) | PL2802688T3 (en) |
RU (1) | RU2593248C2 (en) |
WO (1) | WO2013104530A2 (en) |
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EP2845929A1 (en) * | 2013-09-09 | 2015-03-11 | ThyssenKrupp Rasselstein GmbH | Tinplate with a polymer coating and method for producing the same |
EP2867390B1 (en) * | 2012-07-02 | 2017-09-06 | Tata Steel IJmuiden BV | Method for producing tinplate and product produced therewith |
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AT514961B1 (en) * | 2013-12-23 | 2015-05-15 | Miba Gleitlager Gmbh | Multilayer plain bearings |
JP6610794B2 (en) * | 2017-08-25 | 2019-11-27 | Jfeスチール株式会社 | Steel plate for container and manufacturing method thereof |
DE102019101997A1 (en) | 2019-01-28 | 2020-07-30 | Koenig & Bauer Ag | Process and printing machine in each case for printing a metallic printing material |
CN110029381B (en) * | 2019-04-25 | 2020-12-15 | 首钢集团有限公司 | Production method of tin plate with high tin plating amount |
MX2022011286A (en) | 2020-03-13 | 2022-10-07 | Tata Steel Ijmuiden Bv | Method for passivating a tinplate strip and apparatus for producing said passivated tinplate strip. |
IT202000014572A1 (en) | 2020-06-18 | 2021-12-18 | Tenova Spa | PASSIVATION PROCEDURE FOR A TIN-PLATED STEEL BAND |
EP4305400A1 (en) * | 2021-03-11 | 2024-01-17 | AMS Trace Metals, Inc. | Tin electrolysis to protect piping and minimize corrosion |
EP4276219A1 (en) * | 2022-05-09 | 2023-11-15 | Atotech Deutschland GmbH & Co. KG | Process for wet-chemical formation of a stable tin oxide layer for printed circuit boards (pcbs) |
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- 2012-12-31 EP EP12813895.5A patent/EP2802688B1/en active Active
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- 2012-12-31 ES ES12813895.5T patent/ES2573340T3/en active Active
- 2012-12-31 RU RU2014132049/02A patent/RU2593248C2/en not_active IP Right Cessation
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Also Published As
Publication number | Publication date |
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BR112014017080A8 (en) | 2017-07-04 |
AU2012365534B2 (en) | 2015-08-13 |
CA2858004C (en) | 2017-05-16 |
CN104040037B (en) | 2017-08-04 |
EP2802688B1 (en) | 2016-03-23 |
DE102012000414B4 (en) | 2014-03-20 |
EP2802688A2 (en) | 2014-11-19 |
RU2593248C2 (en) | 2016-08-10 |
BR112014017080B1 (en) | 2021-01-12 |
JP5977365B2 (en) | 2016-08-24 |
AU2012365534A1 (en) | 2014-07-10 |
RU2014132049A (en) | 2016-02-27 |
JP2015503679A (en) | 2015-02-02 |
BR112014017080A2 (en) | 2017-06-13 |
CN104040037A (en) | 2014-09-10 |
PL2802688T3 (en) | 2016-09-30 |
ES2573340T3 (en) | 2016-06-07 |
WO2013104530A3 (en) | 2014-05-30 |
DE102012000414A1 (en) | 2013-07-18 |
CA2858004A1 (en) | 2013-07-18 |
US20150010773A1 (en) | 2015-01-08 |
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