CA2558572A1 - Method for lowering the coefficient of friction of the surface of metal bands with a coating and device for applying a metallic coating onto a steel band - Google Patents

Method for lowering the coefficient of friction of the surface of metal bands with a coating and device for applying a metallic coating onto a steel band Download PDF

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Publication number
CA2558572A1
CA2558572A1 CA002558572A CA2558572A CA2558572A1 CA 2558572 A1 CA2558572 A1 CA 2558572A1 CA 002558572 A CA002558572 A CA 002558572A CA 2558572 A CA2558572 A CA 2558572A CA 2558572 A1 CA2558572 A1 CA 2558572A1
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Prior art keywords
band
tenside
tube
solution
coated
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Granted
Application number
CA002558572A
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French (fr)
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CA2558572C (en
Inventor
Theodor Florian
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ThyssenKrupp Rasselstein GmbH
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Rasselstein GmbH
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00Electroplating characterised by the article coated
    • C25D7/06Wires; Strips; Foils
    • C25D7/0614Strips or foils
    • C25D7/0628In vertical cells
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48After-treatment of electroplated surfaces
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M173/00Lubricating compositions containing more than 10% water
    • C10M173/02Lubricating compositions containing more than 10% water not containing mineral or fatty oils
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36Elongated material
    • C23C2/40Plates; Strips
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/82After-treatment
    • C23C22/83Chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/04Ethers; Acetals; Ortho-esters; Ortho-carbonates
    • C10M2207/046Hydroxy ethers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/28Esters
    • C10M2207/283Esters of polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2209/00Organic macromolecular compounds containing oxygen as ingredients in lubricant compositions
    • C10M2209/10Macromolecular compoundss obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C10M2209/103Polyethers, i.e. containing di- or higher polyoxyalkylene groups
    • C10M2209/104Polyethers, i.e. containing di- or higher polyoxyalkylene groups of alkylene oxides containing two carbon atoms only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10MLUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/04Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions containing sulfur-to-oxygen bonds, i.e. sulfones, sulfoxides
    • C10M2219/044Sulfonic acids, Derivatives thereof, e.g. neutral salts

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Coating With Molten Metal (AREA)

Abstract

The invention provides a method for lowering the coefficient of friction of the surface of metal bands with a coating, especially of tin-plated or chromium-plated steel bands (S), which are passed through a coating installation at a band speed (v). To be able to lower the coefficient of friction of the surface of the coating even at high band speeds through the coating installation, according to the invention, an aqueous solution of a tenside is sprayed onto the coated metal band passed at the band speed (v) after the coating process. The invention further provides a device for applying a metallic coating onto a steel band, especially in a band tin-plating installation or band chromium-plating installation.

Description

METHOD FOR LOWERING THE COEFFICTENT OF FRICTION OF THE SURFACE
OF METAL BANDS WITH A COATING AND DEVICE FOR APPLYING A
METALLIC COATING ONTO A STEEL BAND
FIELD OF THE INVENTION
The invention relates to a method .for lowering the coefficient of friction of the surface of metal bands with a coating, especially of tin-plated or chromium-plated steel bands, which arc moved with a band speed through a coating installation, as well as to a device for applying a metallic coating onto a steel band, especially a bond tin-plating installation or band chromium-plating installation.
BACKGROUND OF TH.E INVENTION
In the production of tinplate, especially in electrolytically operating band tin-plating installations, and in the production of black plate with electrolytic chromium (ECCS), the metal-coated and chemically or electrochemically passivated steel plate (tinplate with tin metal and chromium metal + chromium III hydroxide or ECCS = electrolytic chromium coated steel with chromium metal + chromium III hydroxide) is greased after the coating process in order to lower the coefficient of friction of the coated steel plate, in order to make it able to be better processed during subsequent processing. For this purpose, for example, in the production of tinplate in band tin-plating installations, the tin-plated and passivatcd steel sheet metal band is greased electrostati.cally after a drying process with dioctyl sebacate (DOS), acetyl tributyl citrate (ATBC) or butyl stearate (BSO), typically with a deposition of 2-6 mg/mz.
Methods for lubricating the surface of coated metals, e.g., tinplate, axe described in US 2,579,778 and US 3,826,675, with an aqueous lubricant emulsion with a pH
value between 2 and 6 produced from a weakly ionizablc organic acid being used in US
2,579,778, and citric acid ester being used in US 3,826,675.
In band tin-plating installations in which the steel sheet-metal band passes through with a band speed of less than 150 m/min, DOS can be deposited as an emulsion in a mixture of, e.g., 0.8 g/L DOS with 0.08 g/L lauryl ethoxylate in an immersion process after passivation and after 3U rinsing the tin-plated. steel sheet-metal band in an immersion tank. The DOS emulsion that adheres to the sheet-metal band. surface due to the passage of the tin-plated steel sheet-metal band through the immersion tank is then pinched off and dried with a band drier. However, in fast-cunning band tin-plating installations, in which the steel shed-metal band passes tlm-ough the installation at band speeds of 300 to G00 m/min, the aforementioned DOS
emulsion has proven to be disadvantageous because of problems occurring with the distribution of the height of the DOS deposition over the band width, when the pinching rollers, with which the emulsion captured in the immersion taut was pinched, had been in use for a long time and exhibited wear, especially erosion at their edges.
Therefore, an objective of the invention is to provide a method for lowering the coefficient of friction of the surface of metal bands with a coating, especially of a tin-plated or chromium-plated steel sheet-metal band, in which the mc;tal band passes through a coating installation at a high speed and is coated there with the rr~etal coating, with the method being able to be performed with the highest possible tluoughput and. especially at a high band speed.
SUMMARY OF THE INVENTION
The objectives of the invention are obtained by a method for lowering the coefficient of friction of the surface of metal bands with a coating, cspc;cially of tin-plated or chromium-plated steel bands, which are moved with a band speed through a coating installation characterized in that after the coating process, an aqueous solution of a te;nside is sprayed onto the coated metal band moved at the band speed. The objectives of the invention are also achieved wiih a device for applying a metallic coating onto a steel band, especially a band tin-plating installation or band chromium-plating installation, with a deposition device for electrolytic deposition of a thin metal layer on the steel band passing through the dcposit:ion device at a band speed, a passivation device for passivation of the deposited metal layer, a rinsicig bath for rinsing the coated and passivated steel band, and a processing device for reducing the coefficient of friction of the surface of the coated steel band, through which the steel band coated with the metal layer passes at the band speed, characterized in that the greasing device comprises at least one tube arranged at a distance from the coated steel band, with the tube having a plurality of boreholes in the tube jacket, through which an aqueous solution of a tenside is sprayed onto the coated steel band passed through the greasing device According to the method of the invention, an aqu~°ous solution of a tenside is sprayed onto the moving metal band, especially a steel band, after the coating process, for example, after the electrolytic tin-plating in a band tin-plating installation or the electrolytic chromium-plating in the production of ECCS. Here, the tenside solution is ~~prayed onto the meial band surface in amounts that are so small that only a thin tenside layer composed of a few molecular layers is adsorbed onto the metal band surface. Here, the sprayed tenside solution is then preferably pinched by means of pinching rollers and then dried. After the pinching of the tcnside solution and the drying, a tenside film with a coating of, e.g., ca. 0.1-10 mg/mz remains on the surface of the metal. band.
The tcnside preferably involves a non-ionogenic vlenside, which is sprayed onto the surface of the coated metal band in an aqueous solution with a concentration of 0.01-20 g~L.
However, other tensides, especially anionic-active or cationic-active and also amphoteric tensides, can also be used.
For spraying the aqueous tenside solution onto the metal band surface, an arrangement with a tube with a plurality ofboreholes in the tube jacket has proven to be advantageous. Here, the tube with the boreholes is arranged at a distance fron-i the metal hand surface and charged with the aqueous tenside solution. This solution emerges through the boreholes and is led in the form of spraying streams onto the moving metal band. Preferably, on each side of the metal band, at least one such tube with boreholes is arranged, through which the tenside solution is sprayed onto the metal band surface opposite the borehol.es. The tubes arranged on both sides of the metal band preferably are at a distance of 5-15 em from the metal band surface. The fluid streams emerging from the boreholes of the tube intersect the surface of the coated metal band preferably at a right angle or especially at an angle in the range from -15° to +15° with respect to the normal, and are pinched by one or more pinching rollers arranged behind the intersection point in the advancing direction of the band.
In one preferred embodiment of the method according to the invention, the spraying of the tenside solution is performed within a vertical tank, which has an open outlet. In the vertical tank, the excess tensile solution, especially the solution pinched off by the pinching rollers, is collected and can flow via the outlet into a storage tank underneath the vertical tank and from there can be supplied for reuse.
With the method according to the invention, the coefficients of sliding friction of tinplate and ECCS are reduced to values required by the specific application.

BRIEF DESCRIPTION OF THE DRAWINGS
Below, the invention is explained in more detail with reference to an embodiment, with reference being made to the enclosed drawings. These show:
Figure 1, schematic view of the quenching and post-treatment of a band tin-plating installation for manufacturing tinplate; and Figure 2, perspective view of a processing device of the band tul-plating installation from Figure 1.
DETAILED DESCRIPTION OF THE DRAWINGS
The section of a band tin-plating installation shown schematically in Figure 1 for manufacturing tinplate includes a deposition device not illustrated here. The steel band S moved by a tin-plating bath is provided electrolytically with a tin coating. The steel band S is degreased electrolytically before the tin-plating process, rinsed with deionized water, and then coated with deionized water in a pickling and rinsing process. The steel band S cleaned in this way and connected as a cathode is then led into a tin-plating bath, which contains the electrolytes and the tin anodes. Under continuous monitoring and regulation of the tin-plating conditions for high current density, a fixed, dense, and uniform tin deposit is formed on the steel band. Then during electrolysis after a rinsing process, the tin surlace is fluxed, i.e., wetted, pinched, dried, and briefly melted inductively or through resistance heating i~.i a melting tower in a 20-70°C warm solution of I g/L HCl or 3 g/L zinc chloride/ammonium chloride solution, in order to achieve visual unprovement of the surface quality of the tinplate.
Then the tin-plated steel band S is led through a quenching tank 1 via a deflection roller U. In the quenching tank 1, there is deionized water (VE water) with a temperature of 70-95°C.
Then the steel band S is led through the passivation device 2 via deflection rollers U at the band speed v, which typically equals beriveen 200 and G00 m/rnin. The passivation device 2 comprises one to two passivation tanks 2a and optionally 2b, in which is located a passivation fluid, for example, a 10-25 g/L sodium dichromate solution with 50-70°C bath temperature. The passivation can be performed electrolytically or without current. For the electrolytic passivation, the tin-plated steel band S is polarized as a cathode in the passivation device via a cuwent roller SR and in this way is electrolyically passivated. For the ;most part, steel plates arc used as anodes in the passivation bath.

Then the tin-plated and passivatcd steel band S is led into a rinsing bath 3 via deflection rollers U. The rinsing bath 3 comprises, in the example in Figure 1, two counter flow rinsing tanks 3a and 3b, in which spraying tubes 3c, 3e are arranged in each tank in the top region. The deionized rinsing water is sprayed through the spraying tubes 3c onto the steel band and then pinched (3f) and finally passes into the vertical rinsing tank. From there, it is sprayed onto the band surface through the upper spraying tubes 3d in the run-off of the first rinsing tank 3a between a double pinching roller pair 3d and passes from there into the rinsing tank 3a and farther via an overflow from the rinsing tank 3a into a wastewater treatment plant. For counter flow rinsing with the use of spraying tubes, deionized water is necessary as the rinsing water al typical band speeds of 200-G00 m/min, 3-5 m3/h.
It is also possible to use the rinsing tank 3a and 3b without spraying tubes as opposite current sinks, with the deionized rinsing water being ftlled into the rinsing tank 3b and being led from there into the rinsing tank 3a via an overflow. Howc;ver, the amount of rinsing water necessary for this rinsing arrangement is greater than for the (additional) use of spraying tubes described above.
After the rinsing, the steel band S is led through a processing device 4 at band speed v via deflection rollers U for reducing the coefficient of friction of the surface of the coated steel band S. In the processuig device 4, the coefficient of sliding friction of the tin-plated, passivatcd, and rinsed steel band S is reduced to the values reduired for Inter use and processing. The processing device 4 comprises a vertical tank 5, which has in the base a permanently open outlet G. In the upper region of the vertical tank 5, tubes 11 with a plurality of boreholes in the tube jacket are arranged on both sides of the passing steel band S.
This arrangement is shown in detail in Figure 2. Iw Figure 2, the vertical tank 5 is shown with the outlet G. In the vicinity of the base, there is a deflection roller U, by means of which the coated steel baud S is deflected. In the upper region or above the vertical tank 5, tubes 11 are arranged on both sides of the passing steel band S. The tubes 11 run parallel to each other and are perpendicular or at least approximately perpendicular to l,he advancing direction v of the band (which here is directed from the bottom upwards in Figure 2). In the tubes 1 l, there are several boreholes 13 arranged in the longitudinal direction of the tube with a spacing relative to each other. These borcholes 13 lie opposite the passing steel band S. The tubes l 1 are charged via a pump 14 with an aqueous solution of a tenside. For each tube 11, a flowmeter 15 is arranged between the pump 14 and the tube inlet.
Behind the tubes 11 in the advancing direction v of the band (thus, above the tubes 1 1 in Figure 2), there are two pinching roller pairs 12a, l 2b. The spacing of the first pinching roller pair 12a to the tubes 13 in the advancing direction of the band equals approximately 20-100 cm.
The spacing between the tubes 11 and the tin-plated steel band S equals between 1 and 50 cm and lies preferably at 5 to 15 cm. Each tube l 1 has at least one borehole or opening, but preferably, as shown in Figure 2, there is a plurality of borcholcs in the tube jacket arranged at a distance relative to each other in the longitudinal direction of the tube. Preferably, each lobe has two to five boreholes with a diameter of 1 to 4 mm, preferably between 2 and 3 mm.
However, tubes with only one borehole or also with more boreholes, for example, up to f fry boreholes, can also be used.
The tubes 11 are charged with an aqueous solution of a tenside. The aqueous tenside solution emerges through the boreholes into the tubes 11 and strikes the moving, tin-plated steel 1 S band S in fluid streams. According to the distance of the tubes 11 from the steel band S and the position of the boreholcs relative to the movement dircctiion of the steel band S, the fluid streams strike the steel band surface either at a right angle or at a falling or rising angle. Preferably, the distance betweea~ the tubes 11 and the steel band S is set aid the position of the boreholes relative to the movement direction of the steel band is selected so that the fluid streams intersect at a right angle onto the steel band surface or at least within an angular range of=X45°, preferably within an angular range of t15°, with respect to the norrr~al (perpendicular) band surface.
With the pinching roller pairs 12a, 12b arranged approximately 50 to 100 cm behind the tubes 11 in the advancing direction, the tenside solution ;.prayed onto the steel bmd surface is pinched off, so that a tenside layer with only a few molecular layers, possibly only a one-molecule tenside layer, remains on the tin-plated steal band surface.
The excess tenside solution and especially the solution pinched by the pinching rollers 12 from the tin-plated steel band S collects in the vertical tank 5 and flows via the outlet 6 into a storage tank 4 under the vertical tank 5, from where the tenside solution can be supplied for reuse via a pump 8, in that the tcnside solution collected in the storage tank 4 is transferred to a tcnside application tank 9 and f sally pumped back into the tubes 11.

After passing through the processing device 4, the; tin-plated steel band S
finally passes into a drying device 10, which is formed by, for example, a hot-air drier, via deflection rollers U.
With the previously described processing device 4, tin-plated steel bands were treated with various tenside solutions in different concentrations and tested in terms of their coefficients of sliding friction.
For greasing the tinplate surface, a plurality of surface-active substances are suitable, especially cationic, anionic, non-ionogeuc, and arnphote:ric tensides.
Preferably, tensides are used that have meet legal requirements for food use according to FDA ~
178.9310, FDA
178.3400, and the EG guidelines 2002/72/EG and 1935i/2004/EG. For non-approved tensides, an expensive toxicological test and approval is necessary if the steel sheets processed according to the invention are to be used for creating food packages. In addition to the legal approval for food use, also required are good wettability and adhesion of the paint used for coating with the tinplate surface post-treated with tenside, i.e., the tenside used must be tailored to the paints used.
Due to the described application via spray tubes 11, the formation of foam by the tensides that are used does not cause interference in the post-processing of the coated steel band.
Comparison tests with the tenside lauryl ethoxylatc with 3 EO were performed in a band tin-plating installation that showed the suitability of the described method for large-scale application. This tenside is legally approved for food use according to FDA
~178.9310.
It was sprayed in an aqueous solution in concentrations of 1-8 g/L after the passivation and rinsing in the described band tin-plating installation made from two tubes 11 on each band side onto the tin-plated steel band S, with the two tubes 11 each having five boreholes with a 2.5 mm diameter at a distance of 25 cm from each other in the direction horizontal to the band surface. The two tubes 11 were arranged ca. 80 cm in front of a pinching roll pair 12a in the advancing direction of the band at a distance of 10 cm from the steel band surface. The fluid streams extended approximately horizontally from the boreholes in the tubes 11 onto the galvanized steel surface. The fluid streams striking the band surface were visible in the light of a lamp and one could see that the fluid pinched off by the pinching rollers 12 was distributed uniformly over the width of the pinching rollers 12, detached in the form of droplets, and finally fell into the vertical tank 5. The tin-plated steel band samples treated in this way were then analyzed with a Leco C-analyser at a maximum oven temperature of 400°C.
Here, in the scope of the analysis variation, tenside deposits with equal height over the width of the steel band were measured, which corresponded to 3 t 1.5 mg/mz lauryl ethoxylate.
In further tests, by varying the band speeds v, the tenside used, and its concentration and various surface roughness values of the tinplate band surfaces treated in this way, tcnside film deposits of 3 ~ 1.5 mg/m2 were detected. From this it results that the tenside-containing solution was pinched up to a no longer detectable fluid film of less than 0.5 mL/m2 of the tinplate surface.
In contrast, for tenside-free rinsing water, the fluid film o~n the tinplate surface is pinched off only up to a residue of 5-10 mL./m2 on the band surface.
The tenside coating remaining on tl~e tin-plated steel band surface after use of the method according to the invention is composed of the tenside deposit adsorbed onto the band surface, and the coating, which is produced from the thickness of the pinched fluid film and its tenside concentration. In comparison to tinplate rinsed conventionally (that is, with tenside-free rinsing water), the tinplate treated according to the method of the; invention has significantly lower energy needs for drying in the drying device connected after the processing device. The energy expense for drying the tinplate band can be reduced even more if the passivation fluid is heated in the passivation tanks 2a, 2b and/or the rinsing water is heated in the rinsing tanks 3a, 3b (for example, to temperatures of SO-70°C, the rinsing water also to temperatures up to 80°C).
The adsorption time of the tensidc solution sprayf:d onto the band surface according to the method of the invention is sufficiently short to guarantee a uniform adsorption of the tenside film onto the tinplate surface before the pinching rollers 12 pinch the excess tenside solution.
Due to the short adsorption time, it is presumably not necessary to spray the fluid onto the tinplate surface as uniformly as possible via fine spray nozzles. Instead, it is sufficient-as provided according to the invention-to spray the tenside solution relatively coarsely onto the wet tinplate surface. The advantage of spraying the tenside solution in the form of thin fluid streams distributed over the width of the steel band is that the risf; of forn~ing foam in the tank, in which the excess, especially the pinched tenside solution, collects is significantly lower than that when using spray tubes with nozzles, which would spray the tenside solution in a fine mist onto the tinplate surface. The larger borehole diameters of the spray tubes tend to accumulate less foreign matter than do the smaller diameters of the spray nozzles required for the same application.
The tinplate bands examined in the comparison tests were examined with a three-ball tribometer in terms of their coefficient of sliding friction before and after the treatment according to the invention. Here, the following coefficients of sliding friction were determined for eleet.rochcmically passivated tinplate with 2,8 g/m2 tin deposit and stone-finish surface:
without slip additive: ~ = 0.40 with 2 mg/mz lauryl ethoxylate: ~. = 0.24 with 4 mg/m2 dioctyl sebacate (DOS): ~ = 0.20 The tenside deposit does not reduce the sliding friction of the tin surface as much as does the DOS deposit. However, the sliding friction is good so~ that scratches and scrapes are not created on the tinplate surface when the tinplate rings break apart and the tables in the next post-processing stage can be cleared of packages without a problem.
However, in contrast to conventional electrostatic greasing of the tinplate surfaces with esters such as DOS, in the tinplate bands treated according to the invention, no tin dust caused by production has been observed. In contrast, especially for tinplate greased with DOS, a dust layer due to production is often observed, which is problematic, because it can be removed only through suitable, complicated, and careful measures duruig the installation.
The reason for the freedom from dust in the method according to the invention can be traced possibly to the rinsing effect of the tenside solution in the application after the passivation and rinsing, as well as to the better adhesion of the tinplate to the surfaces of the non-cLriven deflection rollers in the second loop tower of the band tin-plating installation. Due to the low slippage of the tinplate with the deflection rollers in the loop tower, in contrast to greasing; with conventional substances such as DOS, obviously no tin particles are rubbed off.
Another advantage over greasing tinplate conventionally, for example, with DOS, ATBC
(acetyl tributyl citrate) or BSO (butyl stearatc oil), is the ability for perfect (pore-free) painting of the tinplate surfaces treated according to the invention afi:er typical storage times (for example, more than l 2 months}. This advantage can be explained presumably in that the adsorbed tenside molecules do not coagulate into droplets, as is often the case for DOS
greasing with >4 mg/mz in the edge region of the tinplate tables. Paint, which cannot completely dissolve these droplets in the wet film on the tinplate surface, theta tends toward formation of pores in the paint layer.
The method according to the invention can also be applied in band tin-plating installations with horizontal rinsing cascades. In these horizontal rinsing cascades, rinsing water is sprayed through spray registers with nozzles onto both band surfaces for each rinsing stage up to 40 m~/h. The rinsing water is then pinched off and ilovvs back into a storage tank under the corresponding rinsing stage, from where it is pumped back into the horizontal rinsing stage. In these horizontal rinsing cascades, the method according to the invention can be used when the spray registers before the last pinching roller pair is replaced by the aforementioned tubes with boreholes, with which the aqueous tenside solution according to the invention is sprayed onto one or both band surfaces. For two-sided spraying of the 'tin-plated steel band, the tcnside solution is sprayed first through a W be arranged above the top side of the band. Second, the aqueous tenside solution is sprayed onto the bottom side of the band, by spraying the tenside solution through a tube with boreholes on the pinching roller adjacent to the bottom side of the band. In this way, the aqueous tenside solution is transported through the gap between the steel band and the pinching roller adjacent to the bottom side o~f the band, where the fluid mixes with the water film on the bottom side of the band and the band surface is "greased" in this way with the tcnside film. Here, the pinched off tenside solution also flows back into a storage tank-as in the described embodiment of the band tin-plating installation with a vertical tank - and can then be reused.
The method according to the invention applied in the processing device 4 of the described band tin-platuig installation can be used very generally for reducing the coefficient of friction of metal bands with a metallic coatilig, c.g., also special chromium-plated steel bands (ECCS).
Examples:
In the laboratory, black plate sheets with a stone finish surface with 17 x 20 cm area were - degreased electrolytically in an alkaline solution - rinsed with deionized water - pickled in 10U g/L sulfuric acid solution - rinsed again with deionized water and - elcctrolytically tin-plated in a tin methane sulfortatc bath with commercially available bath additives (replenisher and stanguard by Rohm & Haas) with 2 A/dn n current density (tin deposit 2.8 g/m2).
The tin-plated sample was - rinsed with deionized water and - electrolytically passivatcd in a 25 g/L. sodium dichromate solution (T =
Ci0°C; i =
1.5 Adm-2, t = 1 sec). The total chromium deposit of the passivation layer equaled 5 mg/mz. The sample was again thoroughly - rinsed with deionized water - fxed in a paint centrifuge {Erichsen) arid spun for 5 seconds ai 1000 rpm the tin surfaces were covered with aqueous solutions of 1 g/L of the following tcnsides, and the tenside solution was spun for 5 seconds at 1000 rpm:
(designated below as post-processing product X (with X = A, B, C, D) A: lauryl cthoxylate with 3 EO
l0 B: C12-14 carboxylic acid ethoxylate with 9 EO
C: C10-12 alkane sulfonic acid, Na salt, D: polyethylene oxide (average molecular weight 6000 Dalton) The samples were removed from the paint centrifuge and dried with hot air.
On the samples with the various tenside coatings, the following tests were performed:
- tin deposit - total chronuum deposit in the passivation layer tenside deposit (C contents of the tenside with the Leco carbon measurement device RD 412) - sliding friction - painting with S g/m2 epoxidc resin paint PPG 3907-301 /A
- sterilization in the following solutions:
- 3% ethanoic acid 30 min at 100°C
- 1% hydroxypropionic acid + 2% NaCI 30 min a1: 12l °C
- 0.5 g/L cysteine 90 111111 at 121 °C
- I.0 g/L cysteine 90 min at I 2I °C
The painting adhesion was tested after the sterilization test through a cross-cut adhesion test and tesa test according to EN ISO 2409.
The tinplate samples greased with the various non-ionogenic tensides also had low organic deposits with SS mg/mz like tinplate samples greased etectrostatically with dioctyl sebacate in a band tin-plating installation (desired deposit in the tinplate production at industrial scale: 4 t 2 mg/m2 DOS).

The tin oxide deposits and the chromium deposits. of the tinplate samples passivated in sodium chromate solution were within the desired range of commercial tinplate production.
With ~C = 0.13-0.24, the sliding friction of the tinplate samples greased with tcnside or DOS lay significantly under the sliding friction of ungrea~.sed tinplate with ~ = 0.4. The tinplate samples with sliding friction in the range of ~, = 0.13-U.24 have the same good sliding ability in further processing through painting and shaping in production.
The paint adhesion of the tinplate sample painted with S g/mZ paint PPG 3907-301 /A and stcrilizcd in various solutions wasjust as good for the greasing with tenside as for the greasing with DOS.
(Note: commas should be read as decimal points.]
RunningProduct for tin coatingpassivationtin-oxidetcnsidc Sliding No. treatment (glmz) (mg/mz/Cr)coating coating friction after coating (C/mz) (mglmZ coet~icient C) 1 A 2,8 5,0 15 2,3 U,24 i 2 B 2,9 4,8 20 2,7 0,24 -I

C 2,8 5,8 15 3,8 0,18 D 2,7 4,5 18 3,5 0,13 i I S Reference sample, tinplate, electrostatically greased with DOS (mg/mz) 5 Dioctylsebacat (DOS) 2,8 5,4 18 3,5 0,22 No..Product for treatment- Sterilization resistance after varnishing with after coating 5 gim'' varnish PPG
3907-3U1/A;
result of the cross-cut adhesion test*

3% ethanoic 0,5 g!1 ~ 1,0 g!1 1% Cystein Cystein lactic acid acid+ 2/<.
NaCI

30 90 tnin/121C90 min/121C
min/121C

30 i>/100C
mi 2 B G'f GT 0 GT 0 G'1' 0 3 C GTO GTO G'1'0 GTO
4 D GT G'f 0 ~ GT 0 (iT 0 Reference sample, tinplate, electrostatically greased with DOS
Dioctylsebacat (DOS) GT 0 GT 0 CT 0 GT 0 * cross-cut adhesion test according to D1N EN 2409.

Claims (26)

1. A method for lowering the coefficient of friction of a surface of metal bands with a coating, especially of tin-plated or chromium-plated steel bands, which are moved with a band speed through a coating installation, characterized in that after the coating process, an aqueous solution of a tenside is sprayed onto the coated metal band moved at the band speed.
2. The method according io claim 1, characterized in that the aqueous tenside solution is then pinched off by means of pinching rollers.
3. The method according to claim 2, characterized in that the coated metal band is dried after the tenside solution is pinched off.
4. The method according to claim 3, characterized in that after the tenside solution is pinched off and the surface of the coated metal band is dried, a tenside film is present with a deposit of 0.1-10 mg/m2, especially between 2 and 5 mg/m2.
5. The method according to claim 1, characterized in that the tenside includes an anionic, cationic, non-ionic, or amphoteric tenside.
6. The method according to claim 1, characterized in that the tenside includes a non-ionic block polymer, preferably with a concentration of 0.01 to 20 g/L.
7. The method according to claim 6, characterized in that the aqueous solution includes an aqueous solution of a non-ionic or anionic tenside.
8. The method according to claim 1, characterized in that the aqueous tenside solution is sprayed by means of at least one tube, which is arranged at a distance from the coated metal band surface and which has at least one borehole, through which the tenside solution is led to the coated surface of the metal band.
9. The method according to claim 8, characterised in that the tube or in that tube has between 1 and 50 boreholes each with a diameter of 0.1 to 5 mm, with the borehole diameter having to be selected so that the fluid streams strike the band surface.
10. The method according to claim 8, characterized in that at least one tube with boreholes, through which the tenside solution is sprayed onto the surface of the coated metal band opposite the boreholes in the tube, is arranged on each side of the metal band.
11. The method according to claim 8, characterized in that the tube or each tube is arranged horizontally and at a distance of 1 to 50 cm from the surface of the coated metal band.
12. The method according to claim 11, characterised in that the tube or in that each tube is arranged at a distance of 5 to 15 cm from the surface of the coated metal band.
13. The method according to claim 1, characterized in that the aqueous tenside solution is sprayed in the form of fluid streams onto the metal band surface(s), with the fluid streams striking the surface of the coated metal band at an angular range of between +45° and -45° with respect to the normal.
14. The method according to claim 13, characterized in that the fluid streams strike the surface of the coated metal band at an angular range of between +15°
and -15° with respect to the normal and preferably at a right angle.
15. The method according to claim 1, characterized in that the aqueous tenside solution within a vertical tank with a run-off for the excess tenside solution collecting in this tank is sprayed onto the coated metal band.
16. The method according to claim 13, characterized in that the fluid streams strike at least one surface of the metal band in the area or in the vicinity of the area at which a pinching roller contacts the metal band surface.
17. The method according to claim 1, characterized in that the coating of the metal band is passivated before the spraying of the aqueous tenside solution, especially in that the coated metal band is led through a passivation bath.
18. The method according to claim 17, characterized in that the coated metal band is rinsed with rinsing water by passing it through at least one rinsing tank after the passivation.
19. The method according to claim 18, characterized in that the passivation bath and/or the rinsing water is heated, especially to temperatures between 50°C
and 80°C.
20. The method according to claim 1, characterized in that the band speed is higher than 100 m/min.
21. The method according to claim 20, characterized in that the band speed is higher than 300 m/min and preferably between 400 and 600 m/min.
22. A device for applying a metallic coating onto a steel band, especially a band tin-plating installation or band chromium-plating installation, the device comprising:
a deposition device for electrolytic deposition of a thin metal layer on the steel band passing through the deposition device at a band speed;
a passivation device for passivation of the deposited metal layer;
a rinsing bath for rinsing the coated and passivated steel band; and a processing device for reducing the coefficient of friction of the surface of the coated steel band, through which the steel band coated with the metal layer passes at the band speed, characterized in that the processing device comprises at least one tube arranged at a distance from the coated steel band, with the tube having a plurality of boreholes in the tube jacket, through which an aqueous solution of a tenside is sprayed onto the coated steel band passed through the processing device.
23. The device according to claim 22, characterized in that a tube for two-sided spraying of an aqueous tenside solution onto the steel band is arranged on each side of the steel band passing through the processing device.
24. The device according to claim 22, characterized in that the processing device comprises a vertical tank with a run-off, in which the excess tenside solution collects and flows via the run-off into a storage tank arranged underneath the vertical tank.
25. The device according to claim 22, characterized in that at least one pinching roller pair for pinching the sprayed tenside solution is arranged behind the tube or behind each tube in the advancing direction of the steel band.
26. The device according to claim 22, characterized in that the boreholes are arranged along the tube at a uniform distance from each other on a line, which extends transverse, especially perpendicular, to the advancing direction of the moving steel band.
CA2558572A 2005-09-21 2006-09-01 Method for lowering the coefficient of friction of the surface of metal bands with a coating and device for applying a metallic coating onto a steel band Expired - Fee Related CA2558572C (en)

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DE102005045033A DE102005045033B3 (en) 2005-09-21 2005-09-21 Method for reducing coefficient of friction of tin- or chromium plated steel strip comprises spraying coated strip with surfactant solution while it is moving at same speed as that used during electroplating
DE102005045033.4 2005-09-21

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EP1767673A2 (en) 2007-03-28
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ATE478981T1 (en) 2010-09-15
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