CN104919091A - Chromium-chromium oxide coatings applied to steel substrates for packaging applications and a method for producing said coatings - Google Patents

Chromium-chromium oxide coatings applied to steel substrates for packaging applications and a method for producing said coatings Download PDF

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Publication number
CN104919091A
CN104919091A CN201380068666.4A CN201380068666A CN104919091A CN 104919091 A CN104919091 A CN 104919091A CN 201380068666 A CN201380068666 A CN 201380068666A CN 104919091 A CN104919091 A CN 104919091A
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coating
chromium
resin
thermoplastic
blackplate
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J·H·O·J·温伯格
M·斯蒂格
J·P·彭宁
I·珀特吉斯则瓦特
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Tata Steel Ijmuiden BV
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Tata Steel Ijmuiden BV
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
    • 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
    • C25D11/38—Chromatising
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • 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
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12556—Organic component
    • Y10T428/12569—Synthetic resin

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Details Of Rigid Or Semi-Rigid Containers (AREA)

Abstract

The invention relates to a coated steel substrate for packaging applications, said substrate containing 1. a recrystallisation annealed single or double reduced packaging steel blackplate, or 2. a cold-rolled and recovery annealed blackplate, wherein one or both sides of the substrate is coated with a chromium metal-chromium oxide coating layer produced in a single process step by using a trivalent chromium electroplating process, and to a process for obtaining said coated steel substrate.

Description

Be applied to for the chromium-chromated oxide coating of the steel substrate of packaging application and the method for the preparation of described coating
The present invention relates to chromium-chromated oxide (Cr-CrOx) coating and the method related to for the preparation of described coating that are applied to for the steel substrate of packaging application.
Zinc-plated rolled products (tin mill product) comprises tin plate, electrolysis chromium plated steel (ECCS, also referred to as tin-free steel or TFS) and blackplate (uncoated steel).Packaging steel provides with tin plate or with ECCS usually, can be applied with organic coating thereon.When tin plate, this organic coating is generally paint, and (such as exists when ECCS when) use polymeric coating such as PET or PP more and more.
The feature of tin plate is erosion resistance and the weldability of its excellence.(usually between 1.0 and 11.2g/m in the coating wt of certain limit 2between) supply tin plate, this coating wt is applied by electrolytic deposition usually.At present, the fluid aftertreatment most of tin plate of applying method containing sexavalent chrome Cr (VI) that dipping or electrolysis are assisted is used.The object of this aftertreatment is that passivation tin surfaces is to stop or reducing the growth (because too thick oxide skin can finally cause about the problem of organic coating as the sticking power of paint) of tin-oxide.Importantly Passivation Treatment not only should stop or eliminate tin-oxide growth but also should be able to keep or improve organic coating adhesion level.The passivation outside surface of tin plate is very thin (being less than 1 micron thickness) and is made up of the mixture of tin and chromated oxide.
ECCS is made up of the blackplate product being coated with metallic chromium layer, and this metallic chromium layer is coated with film of chromium oxide, and metallic chromium layer and film of chromium oxide are all applied by electrolytic deposition.ECCS gives prominence in the sticking power of organic coating and the maintenance of coating integrity at the temperature exceeding the fusing point of tin (232 DEG C).In these cases, tin plated materials can not be used.This packaging steel being coated with polymkeric substance for preparation is important, because steel substrate can be heated to the temperature more than 232 DEG C during thermoplastic coating applying process, the actual maximum temperature values used depends on the type of applied thermoplastic coating.In order to make the initial heat seal/bonding (thermal pretreatment) of thermoplastic material and base material become possibility, needing this heating period and be often that postheat treatment is to change the character of polymkeric substance after it.It is believed that chromium oxide layer causes the excellent adhesive attraction character of thermoplastic coating such as polypropylene (PP) or polyterephthalate (PET) and ECCS.Also can supply ECCS in the coating wt of certain limit for Cr and CrOx coating, usually be respectively 20-110 and 2-20mg/m 2.Both sides ECCS for steel band can provide equal coating specification, or every side provides different coating wts, and the latter is called poor thickness coating band.The preparation of ECCS relates to the solution used based on the chromium (being also called sexavalent chrome or Cr (VI)) being in its hexavalent state at present.
Nowadays think that sexavalent chrome is objectionable impurities, it is potential harmful and form dangerous with regard to worker safety for environment.Therefore, there is the motivation of the substituting metallic coating of exploitation, this substituting metallic coating can substitute conventional tin plate and ECCS and not need to rely on chromic use during manufacture.
An object of the present invention is to provide the surrogate using sexavalent chrome for passivation tin plate.
An object of the present invention is to provide the surrogate of conventional tin plate to improve product property in such as corrosive nature and resistant to sulfur are tarnish resistance.
Another object of the present invention is to provide the substituting base material of tin plate and ECCS, and this substituting base material provides the dry sticking power of the excellence to organic coating, and is combined with not rely on and uses chromic corrosion prevention during manufacture.
One or more by what provide packaging steel substrate to reach in these objects, this packaging steel substrate comprises:
1. recrystallization annealing once or the packaging steel substrate (i.e. blackplate) of reroll, or
2. the cold rolling and blackplate of recovery annealing,
Chromium metal-chromated oxide (Cr-CrOx) coat by using trivalent chromium plating method to prepare in single plating steps is wherein adopted to apply the one or both sides of this base material.
Preferably provide this packaging steel substrate with ribbon form.
For the preparation of EECS, the chromium solution and coating method of usual three types uses in the whole world.These three kinds of methods are " the vertical method of a step " (V-1), " the vertical method of two steps " (V-2) and " the horizontal high current density method of a step " (HCD), and based on Cr (VI) ionogen.According to european norm EN 10202:2001 by the specification standardization of ECCS.The vertical method of two steps uses not vitriolated Cr (VI) ionogen to be used for applying chromium oxide layer in the second step.Sulfuric acid is need and the chromium metallization step be therefore generally used in these methods for the good efficiencies applying chromium metal." step is vertical " and " step horizontal high current density (HCD) method " has vitriol usually in the oxide layer, because produce chromium metal and chromated oxide (Boelen in identical ionogen simultaneously, thesis TU Delft 2009,8-9 page, ISBN978-90-805661-5-6).In all cases, ECCS is made up of the chromium oxide layer on chromium metal.
In the method according to the invention, deposited the coat comprising chromium metal and chromated oxide, instead of first deposition chromium metal level, provide chromium oxide layer as conversion coating on top subsequently.Cr-CrOx layer should be made up of the mixture of Cr oxide compound and Cr metal and Cr oxide compound should not exist with layer independent in outmost surface, but is blended in whole layer Cr-CrOx.If such as will deposit and comprise chromium metal with, so certainly can there are these single plating steps more than one by succeedingly in the thicker coat of chromium oxide layer.The single plating steps of phrase therefore nobe limited to and mean onlyuse in these single plating steps.
Usually provide packaging steel substrate with the ribbon form of low-carbon (LC) (LC), pole low-carbon (LC) (ELC) or Ultra-low carbon (ULC), these ribbon forms have respectively as expressed in weight percent between 0.05 and 0.15 (LC), between 0.02 and 0.05 (ELC) or the carbon content lower than 0.02 (ULC).Add alloy element such as manganese, aluminium, nitrogen, sometimes also have element such as boron, to improve mechanical properties (also see such as EN 10 202,10 205 and 10 239).In one embodiment of the invention, this base material forms by without the low, extremely low of brilliant gap or ultra low-carbon steel (such as titanium stabilizedization, niobium stabilization or titanium-niobium stabilization without brilliant gap steel).
Discovery provides the excellent adhesive attraction to organic coating by chromium metal-chromated oxide (Cr-CrOx) coating prepared based on chromic electrochemical plating.In this, compared with the conventional ECCS prepared by sexavalent chrome electrodip process, chromium metal-chromated oxide (Cr-CrOx) coating standby by Electrodeposition of Trivalent Chromium legal system has closely similar sticking power character.By increasing the thickness of Cr-CrOx coat, the porosity of coating reduces and its erosion resistance improved properties.
Cr-CrOx coating can be applied to the electrolysis of conventional non-passivation and optional soft heat tin plateon (ETP, electrolytic tinning steel plate).Cr-CrOx layer ensure that the growth suppressing tin-oxide, and namely it has deactivation function.Adopt the Cr-CrOx thickness increased, unexpectedly find that wet adhesion performance i.e. organic coating sticking power is after sterilization better than the tin plate of conventional sexavalent chrome passivation.In addition, the resistivity to so-called sulphur corrosion (namely by the decolouring contacting caused tin plate with sulfur-bearing weighting material (fill-good)) is suppressed completely by applying enough thick Cr-CrOx coating.Therefore material according to the invention is very suitable for the tin plate of alternative sexavalent chrome passivation, the technical feature restriction of the tin plate that is optionally above standard.From method angle, the fact applying Cr-CrOx coat in single method step means and combines two method stepss, and this is useful in method economy and in environmental influence.
Or also Cr-CrOx coating can be applied directly to blackplatepackaging steel substrate does not apply tin coating in advance, is namely applied directly to naked steel on the surface.According to Merriam Webster, blackplate is defined as the steel plate not also being made into steel plate galvanized by coating orthe steel plate used when being provided protection there is no need by tin uncoatedly.Find for thermo-setting paint and thermoplastic coating, the dry adhesion level of this material to organic coating can reach usually relevant to using ECCS dry adhesion level.Material according to the invention can be used for the ECCS of the application directly substituted for needing moderate erosion resistance.
Large advantage in environmental influence and health and safety two is the fact: adopt the use that invention prevents hexavalent chromium chemistry product, can retain the product performance character usually owing to ECCS and tin plate simultaneously.
In one embodiment, the Cr-CrOx coat be applied on the tin plate of non-passivation comprises at least 20mg Cr/m 2, to produce tin-oxide passivation effect.This thickness is enough for many purposes.
In one embodiment, the Cr-CrOx coat be applied on the tin plate of non-passivation comprises at least 40mg Cr/m 2, preferred at least 60Cr/m 2, to produce tin-oxide passivation effect and prevent or eliminate sulphur corrosion.In order to prevent or eliminate sulphur corrosion, find 20mg Cr/m 2layer too thin.With about 40mg Cr/m 2thickness start, sulphur corrosion greatly reduces, and at least about 60mg Cr/m 2layer thickness under practically eliminate sulphur corrosion.
Find that suitable maximum ga(u)ge is 140mg Cr/m 2.Preferably, the Cr-CrOx coat be applied on the tin plate of non-passivation comprises at least 20 to 140mg Cr/m 2, more preferably at least 40 and/or 90mg Cr/m at the most 2, and most preferably at least 60 and/or 80mg Cr/m at the most 2.
These embodiments are intended to the tin plate of alternative sexavalent chrome passivation.Except from manufacture, the major advantage eliminated except sexavalent chrome is the potentiality producing the product with the tarnish resistance erosion resistance with improving of excellent resistant to sulfur.
Find that the color of material changes along with the Cr-CrOx layer thickness increased, along with the coat-thickness increased, product becomes comparatively dark (namely lower L-value).Because the optical property of packing steel is very important for the attractive aesthetic appearance producing metal vessel such as aerosol canister, this can be considered the shortcoming of the invention for application-specific.Such as, but a kind of mode avoiding these problems can be use different coatings, the side of material uses low Cr-CrOx coating wt, and applies thicker Cr-CrOx coating wt on another side.Surface containing thicker Cr-CrOx coating wt should be used for the inner side of container, to utilize the benefit of the erosion resistance character of improvement.In this case, the surface with lower Cr-CrOx coating wt is on the outside of container, and for the outside of container, erosion resistance requires usually not too harsh, thus guarantees the optical property of optimization.
In one embodiment, Cr-CrOx coat on blackplate is applied to at least 20mg Cr/m 2, to produce the material of the function (such as to the excellent adhesive attraction of organic coating and be combined with moderate erosion resistance) reaching ECCS.Preferably, Cr-CrOx coat on blackplate at least 40 and more preferably at least 60mg Cr/m is applied to 2.Find that suitable maximum ga(u)ge is 140mg Cr/m 2.Preferably, the Cr-CrOx coat be applied on blackplate comprises at least 20 to 140mg Cr/m 2, more preferably at least 40mg Cr/m 2, and most preferably at least 60mg Cr/m 2.In one embodiment, suitable maximum value is 110mg Cr/m 2.
The blackplate being coated with Cr-CrOx is intended to alternative ECCS.Except from manufacture, the major advantage eliminated except sexavalent chrome is the potentiality of the product of the application of the erosion resistance character of the excellence produced for not needing tin plate.From method angle, the fact applying Cr-CrOx coat in single method step means and combines two method stepss, and this is useful in method economy and in environmental influence.
Also Cr-CrOx coating can be applied to cold rolling and on the blackplate of recovery annealing or be applied to the cold rolling and electrolysis of recovery annealing and on the tin plate of optional soft heat.These base materials have the base material of recovery annealing, instead of the ETP of recrystallize rolling or blackplate, or the blackplate of reroll.Do not find that the difference of the microstructure of base material affects Cr-CrOx coating from material.
Find that material according to the invention can be combined with thermoplastic coating, but also can be used for wherein traditionally ECCS be combined with paint and (namely such as bake and bank up with earth listen tank for baking and banking up with earth apparatus, or there is the product that moderate erosion resistance requires) application, or the requirement be used as wherein in erosion resistance is the substitute of the conventional tin plate of moderate application.
In one embodiment, coated substrate is also provided with organic coating, and this organic coating is made up of thermoset organic coating or thermoplastic single ply polymeric coating or thermoplastic multilayer polymeric coating.Cr-CrOx layer provides the excellent adhesive attraction to organic coating, and it is similar to the sticking power by using conventional ECCS to realize.
In a preferred embodiment, thermoplastic polymer coating is comprise the polymer coating system of one or more layers, it comprises use thermoplastic resin such as polyester or polyolefine, but also can comprise acrylic resin, polymeric amide, polyvinyl chloride, fluorocarbon resin, polycarbonate, styrene type resin, ABS resin, penton, ionomer, urethane resin and functionalized polymer.For the sake of clarity:
The polymkeric substance that polyester is made up of dicarboxylic acid and glycol.The example of suitable dicarboxylic acid comprises terephthalic acid, m-phthalic acid, naphthalene dicarboxylic acids and cyclohexane dicarboxylic acid.The example of suitable glycol comprises ethylene glycol, propylene glycol, butyleneglycol, hexylene glycol, cyclohexanediol, cyclohexanedimethanol, neopentyl glycol etc.The dicarboxylic acid more than two types or glycol can be used together.
Polyolefine comprises polymkeric substance or the multipolymer of such as ethene, propylene, 1-butylene, 1-amylene, 1-hexene or 1-octene.
Acrylic resin comprises polymkeric substance or the multipolymer of such as vinylformic acid, methacrylic acid, acrylate, methacrylic ester or acrylamide.
Polyamide resin comprises such as so-called nylon 6, nylon66 fiber, nylon 46, NYLON610 and nylon 11.
Polyvinyl chloride comprises homopolymer and multipolymer, such as, with the multipolymer of ethene or vinyl-acetic ester.
Fluorocarbon resin comprises such as tetrafluoro polyethylene, trifluoro monochloro polyethylene, hexafluoroethylene-acrylic resin, fluorinated ethylene propylene and polyvinylidene difluoride (PVDF).
Such as by the functionalized polymer of maleic anhydride graft, comprise such as modified poly ethylene, modified polypropene, ethene improved-acrylate copolymer and ethene improved-vinyl-acetic ester.
The mixture of two or more resins can be used.In addition, this resin can mix with antioxidant, thermo-stabilizer, UV absorption agent, softening agent, pigment, nucleator, static inhibitor, releasing agent, release agent etc.The use showing such thermoplastic polymer coating system jar make and jar use in provide the performance of excellence, such as storage life.
According to second aspect, the present invention is realized in the method for the coated steel base material for the preparation of packaging application, the method comprises the galvanic deposit of chromium metal-chromated oxide coating on base material: the electrolytic deposition of the described chromium metal-chromated oxide coating on the substrate occurred in single plating steps by coating solution, this coating solution comprise trivalent chromium compound, optional sequestrant, optional conduction strengthen salt, optional depolarizer, optional tensio-active agent and wherein add acid or alkali to regulate pH.
In one embodiment, by using ionogen to realize the galvanic deposit of Cr-CrOx coating, in this ionogen, this sequestrant comprises formic acid negatively charged ion, and this conduction strengthens salt and comprises alkali metal cation and this depolarizer comprises salt containing bromide.
In one embodiment, the cationic substance that this sequestrant, conduction strengthen in salt and depolarizer is potassium.Its existence in the electrolyte significantly enhances the electroconductibility (more than other alkali metal cation any) of solution to use the benefit of potassium to be, thus maximally causes the reduction for the bath voltage driven required for electrodeposition process.
In one embodiment of the invention, the ionogen for Cr-CrOx deposition consists of: 120g/l basic chromium sulfate, 250g/l Repone K, 15g/l Potassium Bromide and 51.2g/l potassium formiate.By adding sulfuric acid by pH regulator to the value between 2.3 and 2.8 measured at 25 DEG C.
According to the present invention, preferably between 40 and 70 DEG C, under the bath temperature of preferably at least 45 DEG C and/or at least 60 DEG C, depositing Chromium coating by based on chromic ionogen.
Find unexpectedly, can by this ionogen electrodeposited chromium metal-chromated oxide coat in single method step.Reach a conclusion from prior art: strict needs occurs to ionogen interpolation buffer reagent such as boric acid to enable the galvanic deposit of chromium metal.In addition, reported due to this buffering effect (but galvanic deposit for chromium metal needs buffer reagent gets rid of the formation of chromated oxide, and vice versa), can not by identical electrolyte deposition chromium metal and chromated oxide.But, if find to apply sufficiently high cathode current density, so do not need such buffer reagent to add and carry out deposition chromium metal.
Measure XPS depth curve and measure peak be Fe2p, Cr2p, O1s, Sn3d, C1s.Observe Cr layer to be made up of the mixture of Cr oxide compound and Cr metal, and Cr oxide compound does not exist with layer independent in outmost surface, but be blended in whole layer.This is also represented by the O peak be present in whole Cr layer.In all cases, Cr-CrOx layer has glossiness metal appearance.
It is believed that, the galvanic deposit that chromium metal occurs be must be over to certain threshold values of current density, due to the precipitation of hydrogen and the equilibration of various (chelating) poly-chromium hydroxide complex compound (poly chromium hydroxide complex), this threshold values is closely connected with the pH reaching certain value at strip surface place.Find after crossing this threshold values of current density chromium metal-chromated oxide coat galvanic deposit along with increase current density almost linearly increase, as what observe according to the conventional electrodeposition of Faraday's law metal.The actual value of valve current density seems to be closely connected with the mass transfer situation at strip surface place: observing this threshold values increases along with the rate of mass transfer increased.This phenomenon makes an explanation by the change of the pH value at strip surface place: under the rate of mass transfer increased, oxonium ion to strip surface supply increases, and the increase of cathode current density is become must to maintain the specific pH level (apparently higher than overall pH) at strip surface place under steady-state process situation.From the validity of testing the result that obtains and support this supposition, overall electrolytical pH changes between 2.5 and the value of 2.8 in these experiments: the threshold values of current density reduces along with the pH value increased.
About by the electrodip process based on chromic electrolytical Cr-CrOx coating, importantly prevent/minimize anode place trivalent chromium to the oxidation of its hexavalent state and suitable anode or anode material must be selected.The hydrogen diffusion anodes applying in EP12193623 by using (copending) of as described below and common trial, can prevent the formation of Cr (IV).
In embodiment of the present invention, by use one, multiple or only hydrogen diffusion electrode (herein by hydrogen (H 2(g)) oxidation) prevent the formation of Cr (IV).H in the aqueous solution +(proton) and one or more water molecules, such as, as oxonium ion (H 3o +).H 2g () is to H +(aq) oxidation prevents the generation of unwanted oxidizing reaction, such as the formation of Cr (IV), when being used in there by water (H 2o) oxygen (O is oxidized to 2(g)) anode time it occurs under comparatively high anode overpotential.
Reaction H 2(g) → 2H +(aq)+2e -occur under the anode potential of 0.00V (SHE).Reaction 2H 20 → 4H +(aq)+0 2(g)+4e -occur under the anode potential of 1.23V (SHE).When being used in there and Water oxidize being become the anode of oxygen, can be impossible reaction when being used in the anode of there by oxidation of hydrogen be then possible.
One of unwanted oxidizing reaction is like this oxidation of Cr (III) to Cr (VI), and by being used in there by H 2g () is oxidized to H +hydrogen diffusion anodes (GDA) get rid of this oxidizing reaction completely.
In an embodiment of the method, sentence the current efficiency of at least 99%, preferably 100% by H at gas diffusion anode 2g () is oxidized to H +(aq).Current efficiency is higher, and the possibility of unwanted side reaction is less.It is therefore preferable that current efficiency is at least 99%, and preferably 100%.Consider based on thermodynamics and kinetics, can think the risk using hydrogen diffusion anodes to completely eliminate Cr (III) to be oxidized, because anode operation electromotive force is more much lower than there is the electromotive force that Cr (III) is oxidized.
On thermodynamics, at the standard conditions (namely under the pressure of the temperature of 25 DEG C and 1atm), the electrode potential of >0V has been enough to H 2g () is oxidized to H +(aq), and for by H 2o is oxidized to O 2g (), needs the electrode potential of >1.23V.As electrode potential >1.35V, only Cr (III) can be oxidized to Cr (VI).
Relative to standard hydrogen electrode potential electrode electromotive force.Standard hydrogen electrode (being abbreviated as SHE) is redox electrode, and it forms the basis of the thermodynamic temperature scale of oxidation-reduction potential.Its absolute electrode potential is estimated as 4.44 ± 0.02V at 25 DEG C, but in order to form the basis for comparing with other electrode reactions all, the Standard Electrode Potentials (E of statement hydrogen 0) be zero at all temperatures.At the same temperature the electromotive force of other electrode any and the electromotive force of standard hydrogen electrode are compared.
Activity by inserting suitable temperature, pressure and electroactive substance calculates general balance (zero current) electromotive force by Nernst equation.Anode operation (non-zero current) electromotive force for producing specific anodic current is determined by activation overpotential (namely for the potential difference required for drive electrode reaction) and Concentration overpotential (for compensating the potential difference of the concentration gradient of the electroactive substance at electrode place).
Due to for by H 2g () is oxidized to H +(aq) the low anode overpotential required for, the value (see Fig. 4, wherein electric current being mapped to the anode potential relative to SHE) that anode operation electromotive force will rest on usually far below Cr (III) can occur being oxidized.First, this causes the comparatively lower power intake of electrodeposition process.Secondly, under the anode potential lower than about 1.35V, the oxidation of Cr (III) to Cr (VI) is impossible (representing with the arrow drawing fork).
In one embodiment, depolarizer is not added to ionogen.When using hydrogen diffusion anodes, so no longer need to add depolarizer to ionogen.
Hydrogen diffusion anodes is used to have the advantage of increase: under the risk formed not having chlorine, to use the ionogen of chloride to become possibility.This chlorine is potential harmful and be therefore unwanted for environment and staff.This means that, in Cr (III) electrolytical situation, ionogen can partially or completely based on muriate.Use and be that electrolytical electroconductibility is more much higher than the ionogen only based on vitriol based on muriatic electrolytical advantage, this causes the lower bath voltage for running required for galvanic deposit, and this causes lower energy expenditure.
The oxidizing reaction of hydrogen on active eelctro-catalyst surface of dissolving is process very fast.Because the solubleness of hydrogen in liquid electrolyte is low often, this oxidizing reaction easily can become and control by mass transfer limitation.Devise porous electrode especially to overcome mass transfer limitation.Hydrogen diffusion anodes is porous anode, its three phase boundary of solid eelctro-catalyst (such as platinum) comprising hydrogen, fluid electrolyte and be applied to conductive porous matrix (such as porous carbon or porous metal foam).Use the major advantage of such porous electrode to be the very large internal surface area which provided for being included in the reaction in small volume, and be combined with the diffusion path length of the very big reduction from gas-liquid interface to reactive site.Significantly enhanced the rate of mass transfer of hydrogen by this design, under given total electrode current density, reduce real local current densities simultaneously, cause lower electrode potential.
The gas diffusion anode assembly that will use in the electro-deposition method proposed generally includes and uses following functions parts (see Fig. 5): gas supply chamber 1, collector 2 and gas diffusion anode, this gas diffusion anode is made up of (see Fig. 5) in conjunction with hydrophilic responding layer 4 hydrophobic porous gas diffusion transport layer 3.The latter forms by with the microporosity network of liquid electrolyte (part) submergence.Optionally, this responding layer is provided with proton exchange membrane such as on outside 5 film is to prevent the diffusion of the chemical substance (such as negatively charged ion or large neutral molecule) existed in the most of liquid electrolyte in gas diffusion anode, because these compounds can poison electrocatalyst sites potentially, cause the deterioration of electro catalytic activity.
The major function of gas supply chamber is hydrophobic back side hydrogen being fed to equably hydrogen diffusion anodes.This gas supply chamber needs two connections: one be supply hydrogen and one be can purge a small amount of hydrogen to prevent in the hydrogen of supply potentially with the accumulation of vapor phase contaminants that trace exists.This gas supply chamber comprises channel-style structure usually to guarantee to distribute hydrogen equably in hydrophobic back side.
Electrojet body 2 (usually) is attached to the back side 3 of hydrogen diffusion anodes to make it possible to the electric current produced in anode is transported to rectifier (not shown in Figure 5).This current collector plate must be designed by this way: make hydrogen can contact the back side of hydrogen diffusion anodes, therefore can be transported to the reaction side in gas diffusion anode.Usually this has conducting plates, the sieve in a large amount of holes by use or is realized by the expanded metals sheet that such as titanium is obtained.
Also the functional group of supply gas passage and electrojet body can be synthesized single part, be pressed to the hydrophobic back side of gas diffusion anode subsequently.
Once hydrogen diffuses through the hydrophobic back side of hydrogen diffusion anodes, it just contacts with ionogen, in the hydrophilic segment that this ionogen is present in anode and responding layer (see Fig. 5, right side).To be dissolved in ionogen at gas-liquid interface (between 3 and 4) place hydrogen and to be transported to the electro catalytic activity site of hydrogen diffusion anodes by diffusion.Usual use platinum as eelctro-catalyst, but also can use other material as platinum-ruthenium or platinum-molybdenum alloy.Hydroxide electrocatalysis site will be dissolved: the conducting base (being generally carbon base body) that the electronics produced passes gas diffusion anode is transported to collector 2, simultaneously oxonium ion (H +) be diffused in ionogen through proton exchange membrane.
In one embodiment, coated substrate is provided with organic coating on one or both sides further, and this organic coating is by by the thermoset organic coating of japanning step or by film lamination step or directly the thermoplastic single ply of pressing steps or thermoplastic multilayer polymkeric substance form.
In one embodiment, thermoplastic polymer coating is comprise the polymer coating system of one or more layers, it comprises use thermoplastic resin such as polyester or polyolefine, but also can use acrylic resin, polymeric amide, polyvinyl chloride, fluorocarbon resin, polycarbonate, styrene type resin, ABS resin, penton, ionomer, urethane resin and functionalized polymer; And/or its multipolymer; And/or its blend.
Preferably, by base material being immersed at the temperature of 35 and 65 DEG C containing Na between 1 to 50g/l 2cO 3sodium carbonate solution in Cr-CrOx galvanic deposit before, this base material clean, and wherein applying between 0.5A/dm 2and 2A/dm 2between cathode current density continue between 0.5 second and 5 seconds period.
Preferably, this sodium carbonate solution comprises the Na of at least 2 and/or 5g/l at the most 2cO 3.
Explain the present invention further by following nonrestrictive embodiment and accompanying drawing now.
Embodiment 1: first to having 2.8g Sn/m on both sides 2tin plate (common the grade of steel not and state) sheet material of soft heat of non-passivation of routine of tin coating weight carry out electrolysis pretreatment to make tin oxide layer minimizing thickness.This is by being impregnated into the sodium carbonate solution (Na of 3.1g/l by sheet material 2cO 3, the temperature of 50 DEG C) and neutralization applying 0.8A/dm 2cathode current density continue within 2 seconds, come.After with deionized water rinsing, be impregnated into by sample in the trivalent chromium ionogen remained at 50 DEG C, this ionogen is made up of 120g/l basic chromium sulfate, 250g/l Repone K, 15g/l Potassium Bromide and 51.2g/l potassium formiate.By adding sulfuric acid by the pH regulator of this solution to measure at 25 DEG C 2.3.10A/dm is applied as to electrode by using platinized and titanized anode 2cathode current density continue about 1 second will containing 21-25mg Cr/m 2the Cr-CrOx of (being measured by XRF) is coated with and is deposited upon on the surface.The sample of preparation like this shows glossiness metal appearance.
The passivation of thin Cr-CrOx coating on research tin plate, the standing storage that sample is stood under the static humidity level of 80%RH at 40 DEG C is tested.Subsequently in 2 week and the amount measuring the tin-oxide developed on the surface at tin plate between the shelf lives in the exposure in 4 week afterwards, and by its with store test before (representing with " 0 week ") amount of tin-oxide of being present on sample compare.Use as at S.C.Britton, " Tin vs corrosion ", No. 510th, ITRI Publication (1975), the coulomb assay method described in the 4th chapter is to complete the determination of tin-oxide layer thickness.By controlled little cathodic current in Hydrogen bromide (HBr) solution (by oxygen-free with nitrogen washing) of 0.1%, tin oxide layer is reduced.Be potential measurement after the reduction process of oxide compound and for reducing the electric charge that passes through completely (with coulomb/m 2or C/m 2represent) serve as measuring of tin-oxide layer thickness.Present the result of the sample according to embodiment 1 in Table 1, comprise the performance of reference material, this reference material is the identical tin plate material using sexavalent chrome passivation, i.e. so-called 311 passivation tin plates.
Table 1-tin-oxide layer thickness is (with C/m 2meter)
Result display shows perfect stability with the tin plate obtaining the non-passivation of light Cr-CrOx coating according to process of the present invention and completely suitable with traditional 311 passivation tin plates in performance in tin-oxide growth.
Embodiment 2: first to having 2.8g Sn/m on both sides 2tin plate (common the grade of steel not and state) sheet material of soft heat of non-passivation of routine of tin coating weight carry out electrolysis pretreatment to make tin oxide layer minimizing thickness.This is by being impregnated into the sodium carbonate solution (Na of 3.1g/l by sheet material 2cO 3, the temperature of 50 DEG C) and neutralization applying 0.8A/dm 2cathode current density continue within 2 seconds, come.After with deionized water rinsing, be impregnated into by sample in the trivalent chromium ionogen remained at 50 DEG C, this ionogen is made up of 120g/l basic chromium sulfate, 250g/l Repone K, 15g/l Potassium Bromide and 51.2g/l potassium formiate.By adding sulfuric acid by the pH regulator of this solution to measure at 25 DEG C 2.3.15A/dm is applied as to electrode by using platinized and titanized anode 2cathode current density continue about 1 second will containing 65-75mg Cr/m 2the Cr-CrOx of (being measured by XRF) is coated with and is deposited upon on the surface.The all samples of preparation like this shows glossiness metal appearance.Show typical SEM image in fig 1 and 2, it is presented at the deposition of chromium metal-chromated oxide crystal grain very thin on tin surfaces.
With the after-applied commercially available epoxy-anhydride paint system (Vitalure supplied by AkzoNobel tM120) by sheet material japanning.Then, rush by Erichsen the sheet material local deformaton that cup makes japanning.
In order to analyze the performance of the tin plate being coated with chromium-chromated oxide, complete several sterilizing test to evaluate the wet adhesion performance on material that is smooth and that be out of shape.5 kinds of different sterile mediums are altogether employed at these test periods, as shown in table 2.
The condition of table 2-sterilizing test
After sterilization, have evaluated the decolouring of the level (by crosscut and tape test (ISO2409:1992 (E))) of the paint sticking power of panel, bubble formation (size of bubble and number) and vision.Present total result in table 3, comprise the performance of reference material, this reference material is the identical tin plate material using sexavalent chrome passivation, i.e. so-called 311 passivation tin plates.Performance grading based on from 0 to 5 grade, 0 is excellent properties, and 5 is the performance of non-constant.In multiple observation, result is averaged, causes mixed decimal value mark.
Table 3-paints the result of sticking power test
Contriver finds that tin plate variant performance constructed in accordance is constant and is parity with or superiority over the standard tin plate (i.e. reference substance) using sexavalent chrome passivation.Surprisingly material according to the invention is not found to the fact of sulphur corrosion, this is be difficult to realize and for adopting the alternative passivation of not chromyl tin plate to be notoriously difficult to realize for adopting conventional passivation tin plate.
Embodiment 3: process in the machining production line run with the linear velocity of 20m/ minute not containing the blackplate coiled material (common grade of steel not and state) of any metallic coating.Processing sequence is by the alkalescence of steel is by the following method clean: the solution making band run through the NaOH of commercial detergent (Percy P3) containing 30ml/l and 40g/l continues about 10 seconds, at this solution remains on 60 DEG C.In the clean period of band, apply 1.3A/dm 2anodic current density.After with deionized water rinsing, this steel band is made to continue about 10 seconds, with activating surface by acid solution.This acid solution is by the 50g/l H remained at 25 DEG C 2sO 4composition.After with deionized water rinsing, steel band is passed into containing remain at 50 DEG C based in chromic electrolytical electrolytic plating pool.This ionogen is made up of 120g/l basic chromium sulfate, 250g/l Repone K, 15g/l Potassium Bromide and 51.2g/l potassium formiate.By adding sulfuric acid by the pH regulator of this solution to measure at 25 DEG C 2.3.This electrolytic plating pool comprises one group of anode be made up of platinized titanium.Between the processing period of band, only in 1 second, apply about 17A/dm 2cathode current density with by 60-70mg Cr/m 2chromium-chromated oxide coating the galvanic deposit of (being measured by XRF) to blackplate on the surface.The all samples of preparation like this shows glossiness metal appearance.Show typical SEM image in fig 1 and 2, the deposition of chromium metal-chromated oxide crystal grain that its display is very thin on the steel surface.
Make the material of so preparation by coating line to be applied the PET film of commercially available 20 micron thickness by heat seal.After rete pressure, by coated strip post-heating to higher than the temperature of PET fusing point, and quenching-in water at room temperature subsequently, as according to be used for metal pet layer pressure usual working method.For the manufacture of reference material, the ECCS coiled material using business to prepare carries out identical operation.
The material of lamination is used to carry out preparation standard food DRD tank (211 × 400).In all cases, the dry sticking power of PET film and tank is excellent.This confirms by measuring the T peeling force of PET film on tank skin, and for the PET film being applied to material according to the invention and business ECCS, this T peeling force shows similar value (~ 7N/15mm).
Subsequently with different Filled Dielectrics DRD tanks, closed and be exposed to sterilising treatment.Some tanks processing of cut obtained on tank skin will be included in, to simulate and to observe the impact of the even coating damage deposited.The type general introduction of the sterilizing test presented in table 4.
Table 4-sterilizing test
After sterilising treatment, DRD tank is cooled to room temperature, emptying, rinse and dry one day.Bottom and tank skin is visually passed judgment on the existence of hot spot and bubble.Sterilization ability as the result display material according to the invention presented in table 5 is generally speaking not so good as ECCS reference substance slightly.This material seems to be easier to corrosion/coating delamination after coating damage.But these sterilizings test is quite harsh, and therefore material according to the invention can be used for the regioselective application relating to sterilizing in practice.
Performance grading based on from 0 to 5 grade, 0 is excellent properties, and 5 is the performance of non-constant.
The result of table 5-sterilizing test
Sterilization type ECCS (reference) BP+Cr-CrOx
Salt solution 1(1) * 1(4) *
Acetic acid 1 3
Halfcystine 0 0
In bracket *symbol relates to the DRD tank on tank skin with cut.
Embodiment 4: with process not containing the blackplate coiled material (common grade of steel not and state) of any metallic coating in the identical machining production line described in preceding embodiment, to apply Cr-CrOx coating.
With after-applied commercially available epoxy-phenol paint system (Vitalure supplied by AkzoNobel tM345) the sheet material japanning will cut from this coiled material.Then, rush by Erichsen the sheet material local deformaton that cup makes japanning.
In order to analyze the performance of the blackplate being coated with chromium-chromated oxide, complete several sterilizing test to evaluate the wet adhesion performance on material that is smooth and that be out of shape.5 kinds of different sterile mediums are altogether employed at these test periods, as shown in table 6.
The condition of table 6-sterilizing test
After sterilizing test, decolour about the paint level (by crosscut and tape test (ISO2409:1992 (E))) of sticking power, bubble formation (size of bubble and number) and vision and have evaluated panel.Present total result in table 7, comprise the performance of reference material, commercially available ECCS is used for this reference material.Performance grading based on from 0 to 5 grade, 0 is excellent properties, and 5 is the performance of non-constant.
The result of table 7-sterilizing test
Contriver finds, the constructed in accordance blackplate material performance being coated with Cr-CrOx is similar to conventional ECCS consistently.
Brief description of the drawings:
Fig. 1 and 2 shows typical SEM image, which show very thin chromium metal-chromated oxide grained deposits on the surface.Fig. 1 relates to tin plate base material and Fig. 2 relates to blackplate base material.
Fig. 3 shows the general introduction of various packaging application.X-axis is packaging grade of steel is other, and shows in Y-axis for using according to the typical thickness range these application of packaging steel substrate of the present invention.
Fig. 4 show by electric current to relative to SHE anode potential mapping and Fig. 5 shows the schematic diagram of gas diffusion anode.

Claims (9)

1., for the coated steel base material of packaging application, it comprises:
1. recrystallization annealing once or reroll packaging steel blackplate, or
2. the cold rolling and blackplate of recovery annealing,
Chromium metal-chromated oxide the coat by using trivalent chromium plating method to prepare in single method step is wherein adopted to apply the one or both sides of this base material.
2. the coated substrate for packaging application according to claim 1, wherein chromium metal-chromium oxide layer comprises preferably between 20mg/m 2and 140mg/m 2between, more preferably between 40mg/m 2and 90mg/m 2between and most preferably between 60mg/m 2and 80mg/m 2between total chrome content.
3. the coated substrate for packaging application any one of aforementioned claim, wherein coated substrate is provided with organic coating further, this organic coating is by thermoset organic coating, or thermoplastic single ply coating or thermoplastic multilayer polymeric coating composition, preferably, wherein thermoplastic polymer coating is comprise the polymer coating system of one or more layers, this one or more layer comprises thermoplastic resin such as polyester or polyolefine, acrylic resin, polymeric amide, polyvinyl chloride, fluorocarbon resin, polycarbonate, styrene type resin, ABS resin, penton, ionomer, urethane resin and functionalized polymer, and/or its multipolymer, with or its blend.
4., by carrying out the method for the preparation of the coated steel base material of packaging application at the deposited on substrates chromium metal-chromated oxide coating for packaging application, this base material being used for packaging application comprises
1. recrystallization annealing once or reroll packaging steel blackplate, or
2. the cold rolling and blackplate of recovery annealing,
The method comprise by coating solution in single method step by described chromium metal-chromated oxide electrolytic deposition on the substrate, this coating solution comprise trivalent chromium compound, sequestrant, optional conduction strengthen salt, optional depolarizer, optional tensio-active agent mixture and wherein add acid or alkali to regulate pH.
5. method according to claim 4, wherein this sequestrant comprises formic acid negatively charged ion, and this conduction strengthens salt and comprises alkali metal cation and this depolarizer comprises salt containing bromide.
6., according to the method for claim 4 or 5, the cationic substance that wherein this sequestrant, conduction strengthen in salt and depolarizer is potassium.
7. the method any one of claim 4 to 6, wherein coated substrate is provided with organic coating on one or both sides further, this organic coating is by the thermoset organic coating by japanning step, or pass through thermoplastic single ply or the thermoplastic multilayer polymkeric substance composition of film lamination step or direct pressing steps, preferably, wherein thermoplastic polymer coating is comprise the polymer coating system of one or more layers, this one or more layer comprises thermoplastic resin such as polyester or polyolefine, acrylic resin, polymeric amide, polyvinyl chloride, fluorocarbon resin, polycarbonate, styrene type resin, ABS resin, penton, ionomer, urethane resin and functionalized polymer, and/or its multipolymer, with or its blend.
8. the method any one of claim 4 to 7, wherein selects during plating steps, to reduce or eliminate the anode of Cr (III) ion to the oxidation of Cr (VI) ion, such as gas diffusion anode.
9. the method any one of claim 4 to 8, wherein preferred by between 40 DEG C and 70 DEG C, at the temperature of preferably at least 45 DEG C and/or at least 60 DEG C based on chromic electrolyte deposition Chromium coating.
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