EP2989236A2 - Elektrisch leitende flüssigkeiten auf der basis von metall-diphosphonat-komplexen - Google Patents
Elektrisch leitende flüssigkeiten auf der basis von metall-diphosphonat-komplexenInfo
- Publication number
- EP2989236A2 EP2989236A2 EP14821610.4A EP14821610A EP2989236A2 EP 2989236 A2 EP2989236 A2 EP 2989236A2 EP 14821610 A EP14821610 A EP 14821610A EP 2989236 A2 EP2989236 A2 EP 2989236A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- metal
- liquid
- diphosphonate
- mixtures
- electrolyte
- 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.)
- Granted
Links
Classifications
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0692—Regulating the thickness of the coating
-
- 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
-
- 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
- C25D3/30—Electroplating: Baths therefor from solutions of tin
-
- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25D3/54—Electroplating: Baths therefor from solutions of metals not provided for in groups C25D3/04 - C25D3/50
-
- 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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
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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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- 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
- C25D7/0628—In vertical cells
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/06—Wires; Strips; Foils
- C25D7/0614—Strips or foils
- C25D7/0664—Isolating rolls
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F7/00—Constructional parts, or assemblies thereof, of cells for electrolytic removal of material from objects; Servicing or operating
Definitions
- the present invention relates to electrically conductive liquids based on diphosphonate complexes and their use in processes for the electrolytic surface modification of a flat metal workpiece.
- the invention further relates to the flat metal workpieces produced by this method and the use of the metal workpieces as a substrate for the formation of solid adhesive bonds with a variety of materials and for the absorption of liquid and solid materials.
- a known method for the surface treatment of a metal workpiece such as a metal strip or a sheet, represents the electrolytic
- Coating a metal surface with a metal or a metal alloy is.
- the strip is passed through one or more electrolytic cells.
- the band is usually brought via so-called power rollers in a fixed-solid connection with the negative terminal of a rectifier.
- the band thus serves as a negative electrode, i. as a cathode.
- the positive electrode, i. the anode is usually formed as a pair of electrodes, wherein the band passes between the two electrodes.
- Residuals local resistance peaks occur, which can lead to penetration or local discoloration of the film, and (d) due to the pre-treatment used and the subsequent film run in the coating system, the activation of the
- the metal workpiece to be coated is uniformly provided on all sides with a substantially flat metal coating. Even with the use of metal workpieces with a relatively rough
- the surface is leveled.
- a smooth surface may be undesirable.
- Good adhesion between two materials is achieved when there is a chemical interaction and / or mechanical interlocking in topographical features of the adhesion partners. If this is not or not sufficiently the case, the adhesion deteriorates. So can a bad adhesion between one metal surface and the same or another
- Material such as a paint layer, a paint layer or an adhesive, lead to poor quality or even unusable products.
- an acidic electrolyte e.g. Sulfuric, phosphoric or chromic acid
- anodizing is limited to a few
- Aluminum, titanium and alloys limited. Above all, the anodizing of aluminum (anodizing process, electrolytic oxidation of aluminum) is of industrial importance.
- an aluminum oxide layer having a porous structure is formed on the surface of the aluminum material.
- MLP center conductor principle
- Coating step the same treatment liquid used.
- the open MLP (with separate baths) uses two different treatment liquids that are not in contact with each other.
- Proposed solutions for example by encapsulation of the electrode space of the removal zone with ion-specific membranes, as described for example in DE 199 51 324, in turn have disadvantages because (i) the carryover of the dissolved metal ions in the running direction of the continuous material is not prevented, (ii ) for the ion-specific membrane for a technically useful ion separation generally large differences in the properties or concentration of the ions to be separated must be present, (iii) in an ion exchange effect of these membranes redox processes between the ions are not suppressed and (iv) the continuity of
- Coating methods are used in addition to classic metal salt electrolytes
- Metal ions and simple anions such as aqueous metal sulfate solutions, including metal complexes of metal ions and ligands or complexing agents from the family of polyhydroxycarboxylic acids, the polyamino, -imino or -nitriloessigklaren, -methylenphosphonklaren and -3-propionic acids and mixtures thereof used.
- complexing agents serves to improve the deposition process and is essential for achieving sufficient solubility and stabilization of selected oxidation states of metal ions in certain pH ranges (typically 3.5 ⁇ pH ⁇ 11.5).
- Polyhydroxycarboxylic acids, polyamino, -imino- and - nitriloacetic acids, methylenephosphonic acids and -3-propionic acids, and mixtures thereof are not sufficiently stable in the electrolytic process, since they undergo destruction in the electrocolysis reaction or in a secondary reaction after the oxidation of the methylene, Decompose amino, imino or nitrile function.
- carboxylates are oxidized at the anode to carboxyl radicals, which stabilize with elimination of carbon dioxide in a highly reactive alkyl radical.
- Bonding fissions are in progress, and as a rule, this leads to the conversion of said ingredients into carbonate and poorly soluble decomposition products, which must be constantly removed from the process.
- Methylene phosphonates which are virtually derivatives of formaldehyde, behave similarly. This methylene group is also easily oxidized to formate or carbonate, breaking the N-methylene bond and the P-methylene bond. In the electrolyte then accumulate the very difficult to remove decomposition products, which are usually amines, hydroxylamines and phosphates.
- DE 3347593 describes electrolytes which comprise copper complexes of copper ions and a diphosphonate as complexing agent and a buffer for classical galvanic coatings.
- the diphosphonate-based electrolytes described therein are preferably prepared from copper (II) sulfate and used at elevated bath temperature for the deposition of a copper layer.
- Metal surface of a sheet metal workpiece without the existing disadvantages of the prior art. Part of this requirement is the creation of an electrolyte family, which shows virtually the same surface activity regardless of the metal to be removed and the metal to be deposited and which is able to optimally prepare the surface in the removal step due to the familial similarity to the subsequent deposition.
- the family of electrolytes should have a narrowly varying density and a pH varying to narrow limits, and be composed of identical components other than the ablated metal ions, not acidic and of high ionic strength.
- the separation of the removal and deposition zone in the MLP by a non-miscible, non-conductive, heavy, inert separation liquid is realistic, and the substrate can be removed with continuous wetting and cooling in the MLP and coated with substrate-foreign elements.
- metal surfaces can be modified by applying uniformly distributed aggregates of one or more different metals to provide, for example, sheet metal workpieces with improved adhesion of coatings applied to the metal workpieces.
- Another object of the present invention is to provide treatment liquids with which it is possible to work on flat metal workpieces
- an electrically conductive liquid comprising an aqueous solution of a
- Metal complex wherein the metal complex is a complex
- R 1 is H, C 1 -C 6 -n-alkyl or C 3 -C 8 -isoalkyl, C 5 -C 6 -cycloalkyl, unsubstituted or substituted benzyl and substituted or unsubstituted phenyl,
- R 2 R 1 , -OR 3 or -NHR 3 , and
- R 3 H, C 1 -C 4 -n-alkyl or C 3 -C 4 -silkalkyl, and wherein the liquid further optionally comprises an additive of the general formula (II):
- R 4 H, C 1-4 -alkyl or phenyl
- R 5 H, d-4-alkyl or phenyl
- R 6 is H, C 1-4 -alkyl or phenyl
- R 7 H, d-4-alkyl or phenyl
- R 8 H, d-4-alkyl or phenyl
- R 9 H, C 1-4 -alkyl or phenyl
- R 10 OH, COOH or COOR 11
- R 11 alkyl (in particular Ci- 4 alkyl), Li, Na, or K.
- the additive is preferably contained in an amount of 0.05 to 0.5% by weight, more preferably in an amount of 0.1 to 0.2% by weight.
- This electrically conductive liquid forms the treatment liquid (electrolyte) for a method according to the invention for the electrolytic surface modification of a flat metal work piece, in which at least one surface of the sheet metal
- Metallic workpiece is anodically polarized in a treatment liquid and thereby anodic dissolution process is induced, and then the at least one
- modified sheet metal workpieces which, according to another aspect of the invention, can serve as a substrate for the formation of strong adhesive bonds with other materials.
- the electroconductive liquid of the present invention which is referred to as
- Treatment liquid used in the method according to the invention for the electrolytic surface modification of a flat metal workpiece comprises an aqueous solution of a metal complex.
- the metal complex is the complex of a metal with ligands of formula (I) wherein the metal may be either a single or two or more different metals.
- the metal or metals of the metal complex are selected from the group consisting of Cu, Zn, Mn, In, Sn, Sb, Bi, Fe, Ni, Co, Ti, Zr, Nb, Y, Ce, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or mixtures thereof.
- the metal is selected from Cu, Zn, Mn, In, Sn, Sb, Bi, Co, Ti, Zr, Nb and mixtures thereof.
- the metal is particularly preferably selected from Mn, Cu, Zn, Cd, In, Sn, Sb, Bi and mixtures thereof, in particular Cu, Zn, Sn, Bi and mixtures thereof.
- the metal of the metal complex is Cu, Sn, Sb or a mixture thereof. If more than one metal is present, it is preferably a combination of Zn and Cu or Ni and Cu.
- the metal is selected from Cu, Zn, Mn, In, Sn, Sb, Bi, Fe, Ni, Co and mixtures thereof, and is doped with one or more dopant metals.
- Suitable doping metals in the present invention are Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Ti, Zr, Nb and mixtures thereof.
- Preferred combinations of metal and dopant metal are combinations of Sn and Gd; Sn and Zr; Zn and Y, Dy, Zr or mixtures thereof, or combinations of Fe, Ni, Co or mixtures thereof with Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or
- Suitable diphosphonate ligands are compounds of the general formula (I)
- R 1 H, C 1 -C 18 -n-alkyl or C 3 -C 18 -silkalkyl, C 5 -C 6 -cycloalkyl, unsubstituted or substituted benzyl and substituted or unsubstituted phenyl,
- R 2 R 1 , -OR 3 or -NHR 3 , and
- R 3 H, Ci-C 4 -n-alkyl or C 3 -C 4 -lsoalkyl.
- the bonded to the two phosphorus OH groups of the general formula (I) are independently protonated (OH) or deprotonated (0) before.
- X CR 1 R 2 .
- 2, 3 or 4 (all) of the bonded to the two phosphorus hydroxyl groups of the diphosphonate ligand of the general formula (I) are deprotonated.
- Such deprotonated diphosphonate ligands of the general formula (I) can be used in the pH range between about 6.5 and 11.0.
- the molar ratio of metal: diphosphonate is preferably 1: 2 to 1: 4.
- the diphosphonate ligand can also form different chelates with the central ions, where it can usually attach as bidentate or tridentate.
- the size of the chelating ranges from 4 to 5 to 6.
- Metal diphosphonate complexes are variously available in the complex depending on the metal or metals.
- oxides or carbonates of the desired metals are treated with the free diphosphonic acid.
- the neutralization is carried out, for example, with potassium hydroxide to set the optimum pH range, which is usually in the range of 8.5 to 10.
- This process is preferably suitable for preparing the diphosphonate complexes of copper, zinc, manganese, indium, tin, antimony, bismuth, yttrium, lanthanum and lanthanides praseodymium, neodymium, samarium, europium, gadolinium, terbium, Dysprosium, holmium, erbium, thulium, ytterbium and lutetium. Also diphosphonate complexes of cobalt are accessible in this way, although their stability is limited at pH values between 8.5 and 10. The cobalt diphosphonate complex is stable for up to 48 h in solution. However, to achieve longer shelf life, it must preferably be blended within 8 hours of recovery with the diphosphonate complex of a lanthanide (III) ion.
- III lanthanide
- Diphosphonate complexes of the trivalent ions of Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu used, for example, from the corresponding metal oxides, 1 - hydroxyethane-1, 1-diphosphonic acid (HEDP) and potassium hydroxide simple are to produce.
- Mixed metal diphosphonate complexes are accessible, for example, by co-treating suitable metal salts with free diphosphonic acid, by metallizing a Y and / or Ln diphosphonate or by blending metal diphosphonate complexes with Y and / or Ln diphosphonate complexes, the latter being often referred to as dilution complexes in this function.
- the individual diphosphonate-based solutions are usually miscible with each other in any ratio.
- electrolytic deposition of the unsaturated lanthanide diphosphonate with iron (II) ions is the optimal way to produce a ready-to-use for the production of the liquids containing iron diphosphonate
- the nickel diphosphonate electrolytes are best prepared by the co-dissolution of lanthanide (III) oxide and nickel (II) hydroxide or nickel (II) carbonate in HEDP followed by potassium hydroxide pH adjustment, the nickel content being compared to the sum of all complexing Ions must never be more than 20 mol%.
- Stable cobalt diphosphonates can also be prepared by co-dissolution of lanthanide (III) oxide and cobalt (II) carbonate in HEDP and subsequent pH adjustment with potassium hydroxide, the cobalt content may be up to 85 mol% of the sum of all complexing ions.
- Titanium and zirconium are also referred to as inert ions in the present invention because they can not be electrodeposited from water as metals. In the form of their oxides, they have considerable potential in corrosion protection and in Cr (VI) -free passivation of metal surfaces. Your preparation and
- corresponding diphosphonate complexes of these Ti (IV) or Zr (IV) ions are prepared via the solution of the acidic sulfates, since the HEDP is not acidic enough to dissolve the basic carbonates or even oxides of these elements.
- the stable complex solutions have a maximum of a metal (IV) diphosphonate ratio of 1: 3.
- the mixture of the acid sulphates and the HEDP solution precipitates the HEDP, which is reversed by the rapid, extremely exothermic adjustment by means of caustic potash. Immediately after the dissolution of the HEDP, the precipitation of well-crystallized potassium sulfate starts due to the high potassium excess in the solution.
- the residual concentration of sulfate in these diphosphonate complexes of Ti (VI) and Zr (IV) is less than 1 g / l.
- the solution obtained after separation of the precipitated sulphate is treated with a barium diphosphonate slurry with stirring (slurry: 1 part by mass 60% strength by weight solution of diphosphonic acid in water and 1.84 parts by mass of barium hydroxide octahydrate).
- slurry 1 part by mass 60% strength by weight solution of diphosphonic acid in water and 1.84 parts by mass of barium hydroxide octahydrate.
- Precipitate is filtered off after 2 h.
- the sulphate concentration after this additional treatment method is about 1 mg / l.
- the electrically conductive liquid according to the invention may comprise as an additional component an additive of the general formula (II): R 10 -CHR 8 -CHR 9 -Z- (CHR 4 -CHR 5 -Z) n -CHR 6 -CHR 7 -R 10 (II) wherein:
- n an integer from 1 to 1, in particular an integer from 1 to 3,
- R 4 H, C 1-4 -alkyl or phenyl
- R 5 H, d-alkyl or phenyl
- R 6 H, d-alkyl or phenyl
- R 7 H, d-alkyl or phenyl
- R 8 H, d-alkyl or phenyl
- R 9 H, d_ 4 alkyl or phenyl
- R 10 OH, COOH or COOR 11
- R 11 alkyl (in particular C 1 4 -alkyl), Li, Na, or K.
- CI_ 4 alkyl methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl or sec-butyl, preferably methyl, ethyl, n-propyl, or n-butyl.
- R 4 H, methyl, ethyl, n-propyl, or n-butyl,
- R 5 H, methyl, ethyl, n-propyl, or n-butyl
- R 6 H, methyl, ethyl, n-propyl, or n-butyl,
- R 7 H, methyl, ethyl, n-propyl, or n-butyl
- R 9 H, methyl, ethyl, n-propyl, or n-butyl,
- R 10 OH, COOH or COOR 11 .
- R 11 K, methyl, ethyl, or n-propyl.
- the additive of formula (II) is a compound of formula
- n an integer from 1 to 1 1
- a particularly preferred additive of the general formula (II) is 1,8-dihydroxy-3,6-dithiaoctane (DTO).
- DTO 1,8-dihydroxy-3,6-dithiaoctane
- the additives of the formula (II) are commercially available or can be obtained by known chemical synthesis methods or analogously to these.
- Treatment liquid one or more of the above-described electrically conductive liquids is used.
- This embodiment is so interesting because existing equipment can be used by the stain is rebuilt by installing the auxiliary cathodes in the Abtragszelle and get the classic deposition by replacing the power rollers against pulleys and maintaining the anodes as a deposition zone in the open center conductor principle remains.
- Metal workpiece from a metal or a metal alloy and the remaining portion of the sheet metal workpiece may be any material, if this is suitable for use in the inventive method.
- the sheet metal workpiece is preferably passed through the treatment liquid and past the at least one cathode and the at least one anode during the electrolysis. This is done in a manner that results in the described anodic polarization and cathodic polarization and the induced anodic dissolution process and cathodic deposition process.
- endless metal foils or strips they are usually passed through the treatment liquid using guide elements (eg deflection rollers).
- guide elements eg deflection rollers.
- electrolysis baths electrolysis cells
- many arrangements of the at least one cathode and the at least one anode are conceivable.
- the sheet metal workpiece is first anodically polarized by two cathodes disposed on the same side of the sheet metal workpiece and then cathodically polarized by two anodes both located on the same side of the sheet metal workpiece as the cathodes.
- the soluble anodes consist of the metal to be coated or the metal alloys to be coated.
- suitable soluble anodes are anodes of copper or tin.
- Suitable cathodes may be made of the same material as the material of the anodes.
- a cathode for example, a copper cathode can be used.
- copper electrodes are used both as an anode and as a cathode, in particular if copper is to be deposited on the surface of the flat metal workpiece.
- the treatment fluid may include an additive such as 1,8-dihydroxy-3,6-dithiaoctane (DTO).
- DTO 1,8-dihydroxy-3,6-dithiaoctane
- Treatment fluids substantially free of sulfate and halide ions are substantially free of sulfate and halide ions.
- essentially free in the context of this invention means a
- Metal aggregates affect without being decomposed during the process.
- the layers deposited from the lanthanide-zirconium treatment liquids with zinc, copper, nickel, cobalt, iron, tin and / or bismuth also show extreme resistance to corrosion on copper. This is particularly noticeable and interesting with iron and tin.
- the drying rate of the iron layers on copper plays virtually no role in the deposition of the diphosphonates.
- iron deposited from acidic treatment fluids already corrodes during rinsing after coating.
- Tin layer on steel or on copper only in the ppm range zirconium is detected, these layers tend under thermal stress near the melting point of the tin or significantly less yellowing or graying. This also applies to already melted tin layers from this deposit.
- Nickel aggregates on the nickel surface are adherent and provide a clear
- the doping metals are preferably deposited in a concentration in the range from 1 ppm to 20,000 ppm, based on the host metals.
- the relative amount of doping metal can be determined by varying the average current density of the deposition and variation of the
- Adjust the concentration ratio (preferably in the range of 1: 5 to 150: 1) between the dopant metal and the host metal in the treatment liquid.
- the inventive method is particularly suitable for the deposition of corrosion-stable iron and / or tin surfaces and of recrystallization-inhibited tin surfaces.
- the devices comprise at least one container for receiving a
- Electrode housing designed as a flow electrode, comprising an electrode housing with a metal grid through which the treatment liquid (hereinafter also referred to as
- the flow opening is usually arranged so that the exiting electrolyte flows past the metal grid.
- the flow past substantially parallel to the metal grid. In operation, this results in a substantially laminar flow in the space between the electrode and the flat metal workpiece, which is preferably a continuous metal strip or a continuous metal foil.
- the electrode housing also includes a lid to prevent falling out of the metal balls and a defined flow through the
- the lid may be releasably connected to the electrode housing with thumbscrews and may further include contacts for connection to a power source.
- the flow electrode is connected anodically or cathodically to a current source, wherein usually the metal grid is contacted anodically or cathodically.
- the electrolyte which has passed through the metal balls is preferably collected in an electrolyte channel and then supplied to the flow port.
- the Electrolyte channel and the flow opening are preferably in the bottom of the electrode housing.
- the flow opening is preferably designed as a flow lip, which preferably extends over the entire length of the metal grid in the bottom of the electrode housing. If a filter fleece arranged in front of the metal grid is used as anode bag, the flow opening is arranged such that the electrolyte emerges in front of the filter fleece and flows along it, substantially laminar.
- the electrode housing may for example consist of a plastic, such as polypropylene.
- the metal balls may consist of the metals mentioned above for the anode and cathode.
- at least one anode is in the form of the above
- the metal balls are preferably made of the metal or metals to be deposited on the sheet metal workpiece.
- the metal balls are preferably made of the metal or metals to be deposited on the sheet metal workpiece.
- Metal balls copper balls.
- the metal grid is preferably an expanded metal grid (expanded metal blend surface), in particular a titanium expanded metal.
- the cathodes 40 a and 40 b and the anodes 44 a and 44 b are connected to a current source 45.
- the first and third deflection rollers 34a, 34c are arranged above the container 31 outside the treatment liquid 36 and above the first and second working electrodes, while the second deflection roller is located at the bottom of the container 31 within the treatment liquid and below the working electrodes.
- the dissolution / deposition cell 30 has a separator 48 for reducing reactive currents.
- the region 38a of the flat metal workpiece 32 located between the two cathodes 40a, 40b is positively (anodically) polarized by the two cathodes 40a, 40b.
- the two cathodes 40a, 40b define a resolution region 42.
- impurities present on the surface of the sheet metal workpiece 32 and any foreign metals present and / or certain (eg uneven) metal structures are largely eliminated.
- a contaminant-free, homogeneous and defined surface of the sheet metal workpiece 32 is obtained, which is suitable for obtaining defined metal structures in the subsequent deposition step.
- the flat metal workpiece 32 After passing through the cathodes 40a, 40b, i. of the dissolution region 42, the flat metal workpiece 32 is passed through the second deflection roller 34b, which is likewise not connected to a power source, between the two anodes 44a, 44b, which are located in each case on one of the two sides of the flat metal workpiece 32 and form the second working electrode.
- the two anodes 44a, 44b Through the two anodes 44a, 44b, a region 38b of the flat metal workpiece 32 is negatively (cathodically) polarized.
- the two anodes define a deposition region 46.
- section of the deposition region 46 migrate the positively charged metal ions of the treatment liquid 36 to the negatively polarized surface of the sheet metal workpiece 32 and divorced in a defined manner on the surface of the sheet metal workpiece 32 from.
- the sheet metal workpiece 32 runs out of the treatment liquid 36 and over the third deflection roller 34c, which is not connected to a power source.
- the flat metal workpiece 32 electrolytically treated in this way with a treatment liquid according to the invention has sub-micron-sized metal aggregates defined on its surface and shows surprisingly good adhesion and adhesive properties.
- TM Release agent zone
- a copper diphosphonate DTO electrolyte (CuE) is located in the dissolution zone, the liquid level of which reaches up to an overflow opening (ÜL-Cu) in the dissolving zone of the container.
- a tin-gadolinium diphosphonate DTO electrolyte (SnGdE) the liquid level extends to an overflow opening (ÜL-Sn) in the deposition zone of the container.
- a auxiliary cathode HK
- auxiliary anode which contains copper balls (Cu) surrounded by a titanium expanded metal window (TiF).
- an auxiliary anode (HA) emerges, which is surrounded by a titanium expanded metal window (TiF)
- Tin granules contains.
- the inflow of the copper diphosphonate DTO electrolyte (ES-Cu) takes place in the dissolution zone via the auxiliary cathode, that of the tin-gadolinium diphosphonate DTO electrolyte (ES-Sn) in the deposition zone via the auxiliary anode, as in FIG shown.
- the scraper nozzles AD-Cu and AD-TM serve the complete
- the cleaning cycle (RKL-TM) is the extractive washing / care of the release agent of entrained electrolyte residues.
- the dissolving / separating zones furthermore each have two deflection rollers (UW), one being arranged above the electrolyte and one each in the separating agent zone.
- the flat copper workpiece runs in the strip or film running direction (BLR) over the first deflection roller into the copper diphosphonate DTO electrolyte-containing treatment liquid and past the auxiliary cathode in the dissolution zone, whereby the flat metal workpiece positive (Anodic) polarized and a removal of impurities and uneven metal structures present on the surface of the sheet copper workpiece takes place.
- BLR strip or film running direction
- the copper workpiece then enters the release agent zone and is transported from there by means of the deflection rollers therein under constant fluid contact in the deposition zone.
- the copper workpiece is negatively (cathodically) polarized when passing through the auxiliary anode and positively charged tin ions from the tin-gadolinium diphosphonate DTO treatment liquid are deposited in a defined manner on the negatively charged copper surface of the copper workpiece.
- gadolinium can be deposited in the ppm range together with the tin.
- Metal growths on the surface of the sheet metal workpiece produced by the electrolytic deposition of one or more metals.
- the metal aggregates are usually uniformly distributed on the surface and may have a different appearance. Typical are compact aggregates on a crystalline basis with different habit.
- the size of the metal aggregates is usually in
- FIG. 3 shows an SEM image of a copper foil treated in the closed MLP with the electrolytically obtained Cu-DTO diphosphonate electrolyte.
- the surface very small black pyramids, also referred to as vsbp, looks depending on the aggregate density brown to black off. Blackening is thought to be a physical process of extinguishing the light by surface interference.
- the depicted smallest aggregates have grown with their lattice plane base on the previously removed foil and show flat crystal surfaces. They consist (in terms of measurement accuracy) of copper only.
- the layer thickness is less than 0.5 ⁇ m.
- the extension in the plane of the film is in the range of 30 nm to 300 nm.
- the roughness of the metal surface increases slightly due to the deposition of the metal aggregates.
- the mean roughness values Ra and Rz determined in accordance with DIN EN ISO 4288: 1998, preferably in the range from 0.22 to 0, 32 ⁇ for Ra and in particular in the range of 0.24 to 0.28 ⁇ for Ra, and preferably in the range of 1, 4 to 2.1 ⁇ for Rz and in particular in the range of 1, 6 to 1, 9 ⁇ for Rz ,
- the mean roughness values Ra and Rz determined in accordance with DIN EN ISO 4288: 1998, preferably in the range from 0.22 to 0, 32 ⁇ for Ra and in particular in the range of 0.24 to 0.28 ⁇ for Ra, and preferably in the range of 1, 4 to 2.1 ⁇ for Rz and in particular in the range of 1, 6 to 1, 9 ⁇ for Rz .
- the mean roughness values Ra and Rz determined in accordance with DIN EN ISO 4288: 1998, preferably in the range from 0.22 to 0, 32 ⁇ for Ra and in particular in the range of 0.24 to 0.
- the present invention therefore also relates to the use of the according to the
- metal workpieces as a substrate for the formation of solid adhesives with other materials such as thermoplastics, resins, adhesives, paints and pastes.
- produced sheet metal workpieces can be used, u.a. Laminates of copper with PET for the shielding of cables and plug and device housings against electromagnetic interference, in particular in signal transmission. Furthermore, the use as an electrical conductor in the production of MID (Molded Interconnect Devices) circuits should be mentioned. These are circuits based on hot stamping of metallic foils on thermoplastic substrates. Another application is as a substrate for electrode material in battery technology. In particular, the
- flat metal workpieces according to the invention also in the production of stable, needed in printed circuit board technology for the production of copper laminates
- the resulting deep blue solution is filtered at room temperature over a filter with activated carbon ( ⁇ 50 ⁇ ), and after filtration is made up to 1000 ml with demineralized water.
- the obtained copper diphosphonate electrolyte A is a colorless liquid having a pH of 9.2 ⁇ 0.5 and a density of 1.31 g / cm 3 at 25 ° C.
- the molar ratio of Cu: P: K is 1: 4.0 ⁇ 0.2: 5.4 ⁇ 0.4 (determined by optical
- ICP-OES Inductively Coupled Plasma
- the resulting colorless solution may still have a slight fog which is lost by storage for 24 hours. If the fog remains, it is filtered through a filter ( ⁇ 50 ⁇ m) filled with activated charcoal, and after filtration, it is made up to 1000 ml with demineralized water.
- the obtained bismuth diphosphonate electrolyte B is a colorless liquid having a pH of 8.8 ⁇ 0.3 and a density of 1.355 g / cm 3 at 25 ° C.
- the molar ratio of Bi: K: P is 1: 7.6 ⁇ 0.4: 6.4 ⁇ 0.3 (determined by ICP-OES, 6%
- the reaction temperature is always maintained at ⁇ 85 ° C. After 15 minutes, the addition of the potassium hydroxide solution is complete. The resulting solution is then kept at 90 ° C for 1 h, whereby the evaporation loss is constantly balanced. It is then cooled to 25 ° C, the pH adjusted to 9.0 to 10 with potassium hydroxide. The rich pink solution is filtered through a filter ( ⁇ 50 ⁇ ) with activated carbon, and after filtration is made up to 1000 ml with demineralized water. The obtained cobalt diphosphonate electrolyte C is a pinkish liquid with a pH of 9.5 ⁇ 0.5 and a density of 1.32 g / cm 3 at 25 ° C. The molar ratio of Co: P: K is 1: 4.0 ⁇ 0.2: 4.9 ⁇ 0.3 (determined by ICP-OES, 6%
- Reaction temperature is always maintained at ⁇ 80 ° C.
- the addition of the potassium hydroxide solution is complete.
- the resulting solution is kept at 80 ° C for 6 h, whereby the evaporation loss is constantly compensated. It is then cooled to 25 ° C and stored for a further 48 h.
- the pH is adjusted to 9.0 to 10 with potassium hydroxide.
- the resulting colorless solution still has a colorless veil and an oily top film and is filtered through a filter with activated carbon ( ⁇ 50 ⁇ ). After filtration, make up to 1000 ml with demineralized water.
- the obtained tin diphosphonate electrolyte D is a colorless liquid having a pH of 9.4 ⁇ 0.3 and a density of 1.34 g / cm 3 at 25 ° C.
- the molar ratio of Sn: P: K is 1: 4.9 ⁇ 0.3: 8.5 ⁇ 0.5 at a variable Sn (II): Sn (IV) ratio (determined by ICP-OES, 6% Nitric acid).
- the resulting red solution must not have a haze. If a fog remains, it is filtered through a filter ( ⁇ 50 ⁇ m) filled with activated charcoal and, after filtration, the volume is made up to 1000 ml with demineralized water.
- the resulting erbium diphosphonate electrolyte E is a raspberry red liquid having a pH of 9.0 ⁇ 0.5 and a density of 1.43 g / cm 3 at 25 ° C.
- the molar Ratio of Er: P: K is 1: 4.0 ⁇ 0.2: 4.8 ⁇ 0.3 (determined by ICP-OES, 6% nitric acid).
- terbium diphosphonate electrolyte F was found to be a pale green liquid having a pH of 9.0 ⁇ 0.5, a density of 1.43 g / cm 3 and a molar ratio of Tb: P: K of 1: 4.0 ⁇ 0.2: 4.8 ⁇ 0.3.
- Reaction temperature is always maintained at ⁇ 90 ° C.
- the addition of the potassium hydroxide solution is complete.
- the resulting solution is kept for 2 h at 90 ° C, whereby the evaporation loss is constantly compensated. It is then cooled to 25 ° C and the pH adjusted to 8.5 to 9.5 with potassium hydroxide.
- the resulting colorless solution still has a slight fog, which can be lost by storage for 24 hours. If the fog remains, it is filtered through a filter ( ⁇ 50 ⁇ m) filled with activated charcoal. After filtration, make up to 1000 ml with demineralized water.
- the obtained gadolinium diphosphonate electrolyte G is a colorless liquid having a pH of 9.0 ⁇ 0.5 and a density of 1.32 g / cm 3 at 25 ° C.
- the molar Ratio of Gd: P: K is 1: 4.0 ⁇ 0.2: 4.8 ⁇ 0.3 (determined by ICP-OES, 6% nitric acid).
- reaction temperature is always maintained at ⁇ 90 ° C.
- addition of the potassium hydroxide solution is complete.
- the resulting solution is kept for 1 h at 90 ° C, wherein constantly the
- Evaporation loss is compensated. It is then cooled to 25 ° C and the pH adjusted to 9.0 to 9.8 with potassium hydroxide. At the end, make up to 1000 ml with demineralized water.
- the obtained neodymium diphosphonate electrolyte H is a red-violet liquid having a pH of 9.4 ⁇ 0.4 and a density of 1.34 g / cm 3 at 25 ° C.
- the molar ratio of Nd: P: K is 1: 6.0 ⁇ 0.4: 9.0 ⁇ 0.5 (determined by ICP-OES, 6% nitric acid).
- Gadolinium (III) oxide Gadolinium (III) oxide.
- the oxides initially dissolve, then forming a pale yellow mud and an almost colorless sediment that does not contain green matter may contain. After the end of the addition of the oxides, the beaker is in a
- the resulting nickel-gadolinium diphosphonate electrolyte I is a green-yellow liquid having a pH of 9.0 ⁇ 0.5 and a density of 1.32 g / cm 3 at 25 ° C.
- the molar ratio of [Gd + Ni]: P: K is 1: 4.1 ⁇ 0.3: 4.4 ⁇ 0.3 with a Ni: Gd ratio of 1: 3.9 (determined by ICP-OES , 6% nitric acid).
- 1000 ml of this electrolyte are prepared by blending 950 ml (1254 g) of the nickel-gadolinium diphosphonate electrolyte I of Synthesis Example 9 with 50 ml (70.5 g) of the terbium (III) diphosphonate electrolyte F of Synthesis Example 6.
- the resulting nickel-gadolinium-terbium diphosphonate solution is then heated to 60 ° C and with good stirring in stages with a total of 0.5 wt .-%, based on the total weight of the electrolyte, (5.5 g) 1, 8 Dihydroxy-3,6-dithiaoctane (DTO) to give the electrolyte J as a green-yellow liquid with a pH of 9.0 ⁇ 0.5, a density of 1.32 g / cm 3 at 25 ° C, a molar ratio [Gd + Tb + Ni]: P: K of 1: 4.0 ⁇ 0.3: 4.5 ⁇ 0.3 and a Ni: Gd: Tb ratio of 1: 3.9: 0, 2 (ICP-OES, 6% nitric acid).
- DTO Dihydroxy-3,6-dithiaoctane
- the resulting colorless solution is clear and is made up to 1000 ml with demineralized water.
- the colorless liquid has a pH of 8.8 ⁇ 0.3, a density of 1.27 ⁇ 0.02 g / cm 3 at 25 ° C, and a K: P molar ratio of 1.5: 1 ( ICP-OES, 6% nitric acid).
- immersed anode surface opposite to the cathode surface is 10: 1.
- the cathode is wrapped with a bag of PP fiber to keep away unwanted separating and partially peeling copper from the solution.
- the apparatus is fitted with a magnetic stir bar and positioned on a magnetic stirrer in a water bath. The apparatus is stirred at 600 rpm, becomes a rectifier
- Power supply is a power supply of the type Statron type 3254.1 with preselected
- the pH of the solution is then adjusted to about 9.5 with potassium hydroxide (45%) and the apparatus is made up to 860 ml with demineralized water.
- the resulting copper diphosphonate solution is a deep blue liquid with a pH of 9.5 ⁇ 0.3 and a density of 1.31 ⁇ 0.02 g / cm 3 at 25 ° C.
- the Cu concentration is 15.3 g / l
- the molar ratio of Cu: P: K is about 1: 1 1: 14.8 (determined by ICP-OES, 6% nitric acid)
- the above solution was then heated to 60 ° C and with good stirring in stages with a total of 0.05 wt .-%, based on the total weight of the electrolyte, (0.56 g) of 1, 8-dihydroxy-3,6-dithiaoctane (DTO) to obtain the copper diphosphonate DTO electrolyte K.
- DTO 1, 8-dihydroxy-3,6-dithiaoctane
- DTDA 4,7-Dithiadecanedioic acid
- DMDTK Dipotassium 2,9-dimethyl-4,7-dithiadecanedioate
- DMDTDA 2,9-Dimethyl-4,7-dithiadecanedioic acid
- a copper diphosphonate solution was prepared by Aufmetallmaschine. The solution was then heated to 60 ° C and treated with stirring with 1, 57 g of 2,9-dimethyl-4,7-diethiadecanedioic acid (DMDTDA) (0.12 wt .-% based on the total weight of the electrolyte of 1000 ml) to obtain the copper diphosphonate DMDTDA electrolyte K3.
- DMDTDA 2,9-dimethyl-4,7-diethiadecanedioic acid
- the DMDTDA dissolves completely within 20 seconds.
- the deep blue color of the solution remains unchanged.
- the pH of the electrolyte is readjusted to the range around 9 by the addition of potassium hydroxide solution (50%).
- the static electrolytic cell comprises a 1000 ml beaker filled with an electrolyte (900 ml).
- the beaker stands on a stirrer.
- the stirrer is used to heat the electrolyte, the temperature is constantly through a
- Thermocouple with stainless steel sheath is tested and within ⁇ 2 ° C constant is held. Stirring speed is maintained at 1000 rpm and agitation is transferred to the electrolyte solution through a 40xd6 round magnetic stir bar (PTFE).
- PTFE 40xd6 round magnetic stir bar
- a cover plate made of PP which is placed over the beaker and has an inert electrode made of Ti / lr0 2 on each side at a distance of 30 mm.
- These electrodes are flat sheets that dive parallel to each other and each perpendicular to the electrolyte solution.
- the single-sided, immersed surface is between 60 mm x 80 mm and 60 mm x 100 mm per electrode.
- the plastic plate was provided parallel to the inert electrodes with an opening of 20 mm x 80 mm, through which the flexible film holder can be inserted into the cell. This film holder was therefore designed to be flexible so that the film, once clamped, then the entire process including the pre and
- the film holder consists of two PP frames with a window of 80 mm x 60 mm, in which the film is clamped.
- the clamping screws are made of PA6 plastic. The lower clamping screws serve only to tension the film, the upper clamping screws additionally serve to produce a releasable press contact to a TiPt expanded metal grid.
- This contact point dips into the solution, so that the film is completely immersed in the electrolyte and the contact point is blinded by the frame of the film holder relative to the field of the cell.
- the expanded metal used for contacting protrudes at the top of the cell and is over a
- a tinned copper foil with pure tin deposit of about 2 ⁇ , a copper layer thickness of 35 ⁇ , a length of 8.5 cm (effective) and a width of 5.0 cm was initially subjected to a pretreatment comprising the following steps in the order given:
- the thus pretreated copper foil was then surface-modified in the described static electrolysis device using the electrolyte D of Synthetic Example 4 at 60 ° C.
- the current densities used were varied between 0.52 A dm 2 and 10.4 A / dm 2 .
- the anodic current efficiency is up to a current density of 1.2 A / dm 2 or a charge density of 23.7 C / dm 2 at 100%.
- the removal from the film remains constant at 7.5 ⁇ 0.6 mg / dm 2 , ie the anodic current efficiency drops continuously above the limit values.
- the deposition / deposition reaction was immediately following the ablation reaction
- the inert electrodes were before the first energization in the electrolyte with a
- Anodensack provided to keep in the Polassemble these electrodes from cathodic to anodically peeled tin particles from the electrolyte.
- the surface-modified film was subjected to a post-treatment comprising the following steps in the order given:
- the deposited tin layer shows highly branched aggregates and reaches at a charge density of 208 C / dm 2 a growth height of> 5 ⁇ on the film.
- the deposited tin aggregates are brittle and the color of the resulting surface changes from light gray to matt dark gray.
- the electrolyte was analyzed for the content of tin (II) (iodatometric), total tin and additionally for the entry of copper from the film core (Sn, Cu - ICP-OES, nitric acid):
- the concentration of tin in the electrolyte dropped from 64.7g / l to 59.3g / l.
- the tin (II) content dropped from originally 14.7 g / L (22.7%) to 1.6 g / L (2.7%).
- Example 2 Modification of a copper foil by deposition of Kupferqqqqq on the film surface according to the closed center conductor principle
- a closed-center foil conveyor system was used, which was designed for foils or strips up to a width of 330 mm.
- the plant essentially corresponds to the plant shown in FIG. 1 and has a chute and a reel with electronic tension control.
- the control options include amperage of each
- the rectifiers used are from the company plating electronic type pe86CW-6 424-960-4 with 4 outputs.
- the maximum pulse current is 960 A, the maximum continuous current is 424 A.
- the temporal course of the current can be defined as a pulse sequence via the associated software.
- the electrolytic cell of the film conveyor system used comprises a cathode and an anode for one-sided electrolytic deposition.
- the cathode and the anode are positioned parallel to the film run and arranged so that during the film run the same side or surface of the metal foil is opposite first to the cathode and then to the anode. Furthermore, the cathode and the anode are completely surrounded by electrolyte.
- a variety of different configurations may be used, for example, a dual cathode and a double anode for double-sided electrodeposition, or two sequentially arranged cathodes and anodes.
- Electrodes anode and cathode flow electrodes were used in this experiment, which comprise a polypropylene electrode housing and a high-current titanium contact frame with a titanium expanded metal blend surface backfilled with copper balls.
- the electrode is located in an anode bag made of PP fabric.
- the flow rate is possible up to 20 l / min.
- the electrolyte is introduced into the flow electrode via an electrolyte feed, flows past the metal balls in the direction of the housing bottom of the electrode housing and is received by an electrolyte channel in the bottom of the electrode housing.
- the electrolyte then exits the electrolyte channel via a flow opening in the form of a flow lip and flows upwards past the metal grid.
- the electrolyte after passing through the flow electrode, passes into the electrolytic bath and from there via an overflow into a reservoir, from which the electrolyte is then pumped again into the flow electrode.
- a three-part copper sheet convection electrode can also be used.
- the individual electrode segments can be controlled separately via a rectifier or switched Gleichpolig.
- the electrode is located in an anodic bag made of polypropylene fabric. The necessary flow is generated by means of a B2-rod pump from Lutz
- a hard-rolled copper foil having a thickness of 0.035 mm and a width of 300 mm was first subjected to a pretreatment comprising the following steps in the order given:
- the pretreated copper foil was then in the described
- Pulse sequence 10 ms at 132 A, 10 ms pause
- Electrolyte temperature 50 ⁇ 2 ° C
- the surface-modified copper foils were subjected to a post-treatment comprising the following steps in the order given:
- a hard-rolled copper foil having a thickness of 0.035 mm and a width of 300 mm was first subjected to a pretreatment comprising the following steps in the order given:
- the pretreated copper foil was then in the described
- Pulse sequence 10 ms at 132 A, 10 ms pause
- Electrolyte temperature 50 ⁇ 2 ° C
- the surface-modified copper foils were subjected to a post-treatment comprising the following steps in the order given:
- Treated film conveyor system and then subjected to the aftertreatment.
- Example 3 Modification of a Copper Foil by Separation of Zinnaqqreqaten on the Folienobe simulation on the open center conductor principle
- an apparatus as shown in Figure 2 For modifying a copper foil by depositing a tin layer in the open center conductor method, an apparatus as shown in Figure 2 is used as discussed above.
- a copper foil substrate is a 40-meter-long and 200 mm wide copper foil with a thickness of about 35 ⁇ .
- the separating liquid used is 2-methoxy-1-iodobenzene.
- a container for the continuous apparatus is a polypropylene container with a side wall thickness of 20 mm and a
- As a treatment liquid for the removal of 30 l of copper diphosphonate DTO electrolyte M (of Synthesis Example 13) having a copper content of 17.1 g / l, a density of 1, 32 g / cm 3 at 25 ° C and pH 9.2 at 60 ° C used.
- the auxiliary cathode for the removal is a frame electrode
- the PP frame is designed so that the inflow of the circulated treatment liquid through the electrode frame so This ensures that the copper balls, the potential-forming window and the space between the auxiliary electrode window and the film to be treated are washed around in a targeted manner.
- As the treating liquid for the deposition a total of 30 l of a blend of the tin diphosphonate electrolyte D (of Synthesis Example 4) and the gadolinium diphosphonate electrolyte G (of Synthesis Example 7) is used in a ratio of 80% Sn and 20% Gd.
- Electrode length in film direction is 1 10 mm.
- the current density used is applied in different pulses and is 6.82 A / dm 2 .
- the applied charge density is 1 12 C / dm 2 .
- the deposited layer weight of tin / Gd on the copper foil After the treatment of the copper foil, the deposited layer weight of tin / Gd on the copper foil, the proportion of Gd versus tin in the layer, the
- An adhesive tape (Tesafilm® Transparent 57404-00002) was deposited over the electrolytically treated, dry, cold and at least 15 minutes
- the peeled tape was then glued to a piece of white paper and the color change caused by metal aggregates released from the paper
- the peel strength was determined according to DIN EN 60249 on a Zwick BZ2 / TN1 S peeling tool with Xforce HP 500 N load cell and software testXpert 12.3.
- the samples were cut from a pressed composite panel and peeled or peeled the film at an angle of 180 °.
- the pressed composite panel was produced by pressing the film with a plastic substrate at a temperature of 160 ⁇ 10 ° C and a compression pressure of 120 ⁇ 5 bar over a period of 60 ⁇ 5 min.
- the results of the peel test are given in N / mm.
- Example 4 Adhesion on tin-diphosphonate electrolvt treated tinned copper foil
- Example 1 The non-brittle tin growth films (Examples Nos. 1 to 14, see Table 1) obtained in Example 1 were subjected to the above-described adhesion test. To the Comparison served classically produced, unpassivated and non-oiled films (Examples Nos. 1 to 14, see Table 1) obtained in Example 1 were subjected to the above-described adhesion test. To the Comparison served classically produced, unpassivated and non-oiled films (Examples. 1 to 14, see Table 1) obtained in Example 1 were subjected to the above-described adhesion test. To the Comparison served classically produced, unpassivated and non-oiled
- Tinplate surfaces in the original (dendritic) deposition state and in the de-melted state (overlay 8.2 g Sn / m 2 surface, 0.32 mm core band, unstructured (gable KWW GmbH Iserlohn)). All samples showed a significantly improved adhesive strength of the adhesive strip on the tin-coated metal surface compared to the tinplate surface, which manifested as graying of the film adhesive layer by torn-off tin aggregates. Samples 4-14 no longer permit easy peeling off of the adhesive strip; the adhesive layer remains adhered to the surface of the film, and in some cases, the film tears when peeled off. On the other hand, the tinplate surfaces used for comparison allow in every case a complete removal of the adhesive strip. The removal of the adhesive strip from the surface of the tinplate in the molten state is carried out to 80%, without leaving any visible traces on the surface.
- the surface modification of copper foils using copper diphosphonate electrolyte with the addition of additive, for example in the closed center conductor principle thus provides adherent surfaces, the u.a. have excellent adhesion to adhesive tape.
- Example 6 Adhesion to tin-diphosphonate electrolvt treated copper foil
- Example 4 The adhesion test described above and in Example 4 was repeated with the copper foil obtained in Example 3 in the open center conductor method Sn-modified method. The test showed excellent adhesion of the adhesive film on the Tin layer. The adhesive layer of the film remained on the tin layer, or the film strip was destroyed in the attempt to peel off the tin surface.
- Example 7 Peel Strengths of Pressed Composite Panels of Copper DTO Electrolyte Modified Copper Foils and Various Plastics
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Abstract
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PCT/EP2014/078556 WO2015091854A2 (de) | 2013-12-19 | 2014-12-18 | Elektrisch leitende flüssigkeiten auf der basis von metall-diphosphonat-komplexen |
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CN113054257A (zh) * | 2021-03-16 | 2021-06-29 | 广州天赐高新材料股份有限公司 | 磷酸酯类电解液添加剂、电解液及锂离子电池 |
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US2602816A (en) | 1947-06-18 | 1952-07-08 | Goodrich Co B F | Method for preparing sulfur-containing carboxylic acids |
BE791401A (fr) * | 1971-11-15 | 1973-05-14 | Monsanto Co | Compositions et procedes electrochimiques |
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CA1144304A (en) * | 1978-10-23 | 1983-04-12 | Glenn O. Mallory, Jr. | Electroless deposition of copper |
US4253920A (en) * | 1980-03-20 | 1981-03-03 | American Chemical & Refining Company, Incorporated | Composition and method for gold plating |
CA1228000A (en) * | 1981-04-16 | 1987-10-13 | David E. Crotty | Chromium appearance passivate solution and process |
FR2538815B1 (fr) | 1983-01-03 | 1990-02-02 | Omi Int Corp | Procede pour former, par electrolyse, un revetement de cuivre sur un substrat, a partir d'un bain exempt de cyanure, et anode pour la mise en oeuvre de ce procede |
DE19951325C2 (de) * | 1999-10-20 | 2003-06-26 | Atotech Deutschland Gmbh | Verfahren und Vorrichtung zum elektrolytischen Behandeln von elektrisch gegeneinander isolierten, elektrisch leitfähigen Strukturen auf Oberflächen von elektrisch isolierendem Folienmaterial sowie Anwendungen des Verfahrens |
DE19951324C2 (de) | 1999-10-20 | 2003-07-17 | Atotech Deutschland Gmbh | Verfahren und Vorrichtung zum elektrolytischen Behandeln von elektrisch leitfähigen Oberflächen von gegeneinander vereinzelten Platten- und Folienmaterialstücken sowie Anwendung des Verfahrens |
DE10046600C2 (de) * | 2000-09-20 | 2003-02-20 | Schloetter Fa Dr Ing Max | Elektrolyt und Verfahren zur Abscheidung von Zinn-Kupfer-Legierungsschichten und Verwendung des Elektrolyten |
DE10243139A1 (de) * | 2002-09-17 | 2004-03-25 | Omg Galvanotechnik Gmbh | Dunkle Schichten |
RU2276205C1 (ru) * | 2004-09-13 | 2006-05-10 | Федеральное государственное унитарное предприятие "Калужский научно-исследовательский институт телемеханических устройств" | Способ приготовления электролитов и растворов для получения покрытий металлами и сплавами |
JP4756886B2 (ja) * | 2005-03-22 | 2011-08-24 | 石原薬品株式会社 | 非シアン系のスズ−銀合金メッキ浴 |
JP4799887B2 (ja) * | 2005-03-24 | 2011-10-26 | 石原薬品株式会社 | 電気銅メッキ浴、並びに銅メッキ方法 |
EP1961840B1 (de) * | 2007-02-14 | 2009-12-30 | Umicore Galvanotechnik GmbH | Kupfer-Zinn-Elektrolyt und Verfahren zur Abscheidung von Bronzeschichten |
JP5368442B2 (ja) * | 2008-06-26 | 2013-12-18 | 日本高純度化学株式会社 | 還元型無電解スズめっき液及びそれを用いたスズ皮膜 |
CN101660183B (zh) * | 2008-08-27 | 2012-03-28 | 比亚迪股份有限公司 | 一种镁合金电镀方法 |
EP2588644B1 (de) * | 2010-06-30 | 2014-06-18 | Schauenburg Ruhrkunststoff GmbH | Tribologisch belastbare edelmetall/metallschichten |
-
2013
- 2013-12-19 DE DE102013021502.1A patent/DE102013021502A1/de not_active Ceased
-
2014
- 2014-12-18 WO PCT/EP2014/078556 patent/WO2015091854A2/de active Application Filing
- 2014-12-18 US US15/105,816 patent/US20160319451A1/en not_active Abandoned
- 2014-12-18 EP EP14821610.4A patent/EP2989236B1/de not_active Not-in-force
Also Published As
Publication number | Publication date |
---|---|
DE102013021502A1 (de) | 2015-06-25 |
WO2015091854A2 (de) | 2015-06-25 |
WO2015091854A3 (de) | 2015-09-11 |
US20160319451A1 (en) | 2016-11-03 |
EP2989236B1 (de) | 2018-06-27 |
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