METHOD FOR PRODUCING A PLATE MATERIAL ELECTROCHEMICAL METHOD

Description

[0001] The present invention relates to a method for manufacturing a plate material which is used in the electrochemical process of metal, such as electrorefining or electrowinning.

[0002] The surface roughness of a cathode plate material is an important parameter for the adhesion of electrochemically plated metals in the hydrometallurgical industry. Experiences from the industry have shown that the surface needs to be rough enough to ensure adhesion and avoid prestripping of the plated metal, but on the other hand not too rough to prevent the adhesion force to be too high making the removal of the plated metal very difficult or damaging the plates in the stripping process. In the copper industry stainless steels have been used as cathode plates both for electrorefining and for electrowinning. The preferred stainless steel grade for a cathode plates has been the grade EN 1.4404 (316L / UNS S31603) with a cold rolled surface 2B. This stainless steel grade contains typically 10 - 13 weight % nickel, which is an expensive component. Therefore, the copper industry is not only looking for more cost efficient alternatives such as duplex stainless steels as cathode plates, but also more economical processes to manufacture a cathode plate.

[0003] An electrochemical process step is one of the final steps in processing of for instance metallic copper. In electrorefining copper anodes and cathodes are positioned in an electrolytic solution that contains copper sulphate and sulphuric acid. An electric current is passed through the solution causing copper from the positively charged anode to be deposited on the negatively charged cathode. Electrowinning of copper is performed by a similar process, but the copper is removed from the solution, instead of the anode, and deposited on the cathode. When an appropriate amount of copper has been deposited on the cathode, the cathode is removed from the solution and stripped in order to remove the copper deposit from the surface of the cathode plate.

[0004] The US patent 7,807,029 relates to a permanent stainless steel cathode plate, the cathode being composed of a low-nickel duplex steel or a lower grade "304" steel, wherein at least one of the cathode surfaces has a surface roughness to produce the adhesion necessary to allow operational adherence. The adhesion is insufficiently strong to prevent the mechanical separation of the copper deposit from the surface. However, the desired adhesion in the US patent 7,807,029 is only based on the predetermined adhesion characteristics, which determines for the respective surface a surface roughness R a within the range of 0,6 - 2,5 micrometre. Any specific determination for adhesion on the surface is not presented as well as the method for manufacturing a cathode plate.

[0005] The WO publication 2012 / 175803 describes a permanent cathode and a method for treating the surface of a permanent cathode. In the method the grain boundaries of the permanent cathode plate surface are treated chemically or electrochemically to achieve the desired surface properties for the adhesion of deposited metal on the surface and the stripping of metal from the surface.

[0006] Both the cited US patent 7,807,029 and the cited WO publication 2012 / 175803 focus the surface treatment to an individual and separate cathode plate to be used as an electrode in electrowinning of electrorefining. These references do not describe anything how the individual and separate cathode plate has been produced.

[0007] The JP publication JPH05306485A describes the electrodeposition property of a stainless-steel baseboard for copper electrolysis by specifying the surface roughness. The surface of a stainless-steel sheet to be used as the baseboard for producing a starting sheet for copper electrolysis is ground to control the centerline average roughness (Ra) to 0.5-1.53mum. Consequently, the electrodeposition property and releasability of the deposit are ameliorated, and the durability of the baseboard is improved.

[0008] The US 4414071 A describes an electrode for use as a cathode in a chloralkali cell or a water electrolysis cell comprises an electrically-conductive matrix having a very low metal loading surface electrocatalytic noble metal-containing deposit which may be prepared by a displacement deposition technique.

[0009] The WO 2008099057 A1 describes a method of manufacturing a cathode plate that is used in the electrolytic cleaning and recovery of metals, the cathode plate being at least partly manufactured of stainless steel and the surface of the cathode plate being treated in at least one stage, whereby the cathode plate is formed by cutting it from a solid plate-like material, whereby, essentially before cutting the cathode plate to shape, at least part of the surface constituting the cathode plate is subjected to a mechanical treatment to improve the adhesion properties of the surface. The invention also relates to the cathode plate.

[0010] The JP2009132973 A describes a method for producing a martensitic stainless steel sheet excellent in punching-out workability with which the martensitic stainless steel sheet much used as a raw material for disk-brake, the steel excellent in punching workability can be produced, and at the step of coldrolling on the way of producing, the desired hardness can be adjusted.

[0011] EP 2770076 A1 describes an invention relates to an inexpensive Sn-containing duplex stainless steel. In addition, the present invention relates to an inexpensive duplex stainless steel which contains a combination of Cu and Sn and which is excellent in corrosion resistance. In detail, the present invention relates to a duplex stainless steel, a duplex stainless steel slab (a cast steel of a duplex stainless steel), and a duplex stainless steel material which are able to be used in a seawater desalination unit, tanks for a transport ship, various types of containers, or the like.

[0012] CN 103526130 A discloses a processing method for direct cold rolling of two-phase stainless steel as-cast state billet steel after solid solution treatment, and belongs to the field of steel rolling and heat treatment. The processing method for a two-phase stainless steel cold-rolled sheet comprises the following steps: smelting and performing continuous casting or molded casting to form a casting blank of which the thickness is 4-20mm, performing solid solution treatment at 1050-1150 DEG C, preserving the temperature for 4-6min / mm, performing water quenching to room temperature, then performing acid cleaning, and annealing at 1050-1150 DEG C for 3min / mm after a plurality of times of the cold rolling are performed. The cold-rolled sheet obtained by using the processing method is uniform in structure, tiny in grain and excellent in corrosion resistance, and the strength and the extensibility of the cold-rolled sheet are close to those of a cold-rolled sheet by adopting a conventional hot rolling and cold rolling process; compared with the conventional hot rolling and cold rolling process, a phenomenon of cracking easiness of hot rolling is avoided, and the material yield is increased. After the as-cast state solid solution treatment, the cold working performance of the cold-rolled sheet is good, the overall reduction of cold rolling reaches 85% without cracking, a hot rolling procedure is omitted, the cost is reduced, and the production efficiency is improved.

[0013] The object of the present invention is to prevent some drawbacks of the prior art and to achieve an improved method for manufacturing a plate material to be used in the electrochemical process of metal, such as electrorefining or electrowinning. The invention is directed to a method for manufacturing a plate material suitable for use as a cathode for electrochemical processing, wherein the method is as defined in the appended claims.

[0014] According to the present invention a plate material is used as a part of a cathode on which surface a metal is deposited in the electrochemical process of metal, such as electrorefining or electrowinning. The plate material is manufactured in a coil processing line, such as a cold rolling process line, so that the desired surface roughness for adhesion between the metal deposit and the plate material is achieved. The surface roughness of the plate to be used as a part of a cathode is made by at least one mechanical and / or chemical treatment in the coil processing line. The treatments for the desired surface roughness can be for instance one or more of the following treatments pattern rolling, wet-grinding, dry-grinding, shot blasting, pickling, brushing, skin passing or any combination of these treatments.

[0015] The plate material to be treated in the coil processing line is advantageously a strip made of stainless steel. After the final treatment in the coil processing line the plate material, a product received from the coil processing line, having the desired surface roughness is kept as a shape of plate, but can be advantageously treated to have a form of a coil. As a shape of a plate the material can be cut into the desired dimensions to be utilized as a part of a cathode on which surface a metal is deposited in an electrochemical process. In the case the plate material is as a form of a coil, the plate material is essentially easy to transfer to a site where the electrochemical process of metal is carried out. The coiled plate material is then cut for a shape advantageous for the operation of the electrochemical process of metal.

[0016] The coil processing line in accordance with the invention advantageously contains the process steps such as annealing, chemical surface treatment, mechanical surface treatment, cold rolling. The chemical surface treatment can be for instance pickling. The mechanical treatment can be for instance grinding, wet-grinding or dry-grinding, brushing and shot blasting. The cold rolling can be carried out for instance by pattern rolling. Any combinations of these process steps can be utilized in order to have a plate material with the desired surface roughness. According to one preferred embodiment of the invention the coil processing line for the plate material consists of the treatments pre-annealing and pickling, cold rolling, grinding, final annealing and pickling.

[0017] The plate material treated with the invention is utilized as a part of a cathode in an electrochemical process of metal, where the metal to be deposited on the plate material is for instance copper, nickel or silver. The electrochemical process can be for instance electrorefining or electrowinning.

[0018] In order to achieve a desired surface roughness for a plate to be used in the electrochemical process of metal, the adhesion in the electrochemical process of metal is determined by measuring a shearing force required to detach the deposited metal between the surface of a plate and metal deposited on the surface of the plate. The shearing force is measured using a tool for use in a tensile testing machine. A specimen made of a plate material such as stainless steel is placed in the tool so that the specimen is movable, but tight enough so that a metal deposit on the surface of the specimen remains on the tool wall where the metal piece is fixed. The tool with the specimen is then placed in a tensile testing machine so that the specimen is pressed down, while the metal deposit is kept at a fixed position. The shearing force required to separate the metal deposit from the specimen is measured when the specimen is lowered.

[0019] The invention is described in more details referring to the following drawing, where Fig. 1 shows one preferred embodiment of the invention, with copper as the metal to be deposited on the plate material, illustrating the correlation between the shearing force and the surface roughness R a , Fig. 2 shows one preferred embodiment of the invention, with copper as the metal to be deposited on the plate material, illustrating the correlation between the shearing force and the surface roughness R a in industrial scale.

[0020] The effects of a surface roughness and the chemical composition of the plate material to the shearing force between copper to be deposited and the plate to be used in the electrochemical process of copper are determined on one hand using different plate materials and on another hand different surface roughness values on the plate surface. In order to compare whether a plate material itself makes a difference to the shearing force, plate specimens are ground to a similar surface roughness value. For the determination of the effects to shearing force caused by the surface roughness, different surface roughnesses are achieved for the specimens made of the same plate material. Further, the effect of the alignment of grooves achieved advantageously by grinding on the surface of the plate specimen is determined by achieving on the surface both grinding grooves which are parallel to the length of the specimen and grinding grooves which are essentially perpendicular to the length of the specimen.

[0021] The copper deposit on the surface of the plate specimen is achieved in an electrochemical cell where an electrolyte consisting of hydrated copper sulphate, sodium chloride, thiourea and sulphur acid is simulating the industrial-scale electrolyte in the copper electrorefining. In the electrochemical cell a saturated calomel reference electrode (SCE) is used to register the potential during the operation, and a platinum mesh is served as a counter electrode. During the electrochemical process air is bubbled into the electrolyte to promote stirring. The electrochemical process will be stopped, when a desired amount of copper is deposited on the surface of the plate specimen.

[0022] The main element contents of the chemical compositions for the tested plate materials in weight % are in the following table 1: Table 1C % Mn % Cr % Ni % Mo % N % Cu % A0,020-17,210,12,1--B0,0305,021,51,50,300,220,30C0,020-22,05,73,10,17-

[0023] The alloy A represents an austenitic stainless steel of EN 1.4404 (316L / UNS S31603) which typically is used for a cathode plate and which contains in weight % less than 0,03 % carbon (C), less than 2 % manganese (Mn), 16,5 - 18,5 % chromium (Cr), 10 - 13 % nickel, 2 - 2,5 % molybdenum (Mo) and less than 0,10 % nitrogen (N).

[0024] The alloy B represents a duplex austenitic ferritic stainless steel of EN 1.4162 (LDX 2101 / UNS32101) which typically contains in weight % less than 0,04 % carbon (C), 4 - 6 % manganese (Mn), 21 - 22 % chromium (Cr), 1,35 - 1,70 % nickel, 0,1 - 0,8 % molybdenum (Mo), 0,2 - 0,25 % nitrogen (N) and 0,1 - 0,8 copper (Cu).

[0025] The alloy C represents a duplex austenitic ferritic stainless steel of EN 1.4462 (2205 / UNS32205) which typically contains in weight % less than 0,03 % carbon (C), less than 2 % manganese (Mn), 21 - 23 % chromium (Cr), 4,5 - 6,5 % nickel, 2,5 - 3,5 % molybdenum (Mo) and 0,10 - 0,22 % nitrogen (N).

[0026] For the determination of the correlation between the surface roughness and the shearing force in the alloys A - C, different surface roughness values are achieved by using different abrasive belts and using abrasive belts that have been more or less worn. Further, different surface roughnesses are achieved by dry grinding or wet grinding of the surface. Also shot blast and pickled surfaces are tested as well as a material which is skin passed in a coil processing line.

[0027] In accordance with the invention the surface roughness measurements for the surface roughness values R a (roughness average) are performed with a surface roughness meter where the cut-off is set to 0,8 mm and the needle traversal speed to 0,5 mm / s for those specimens with the R a value less than 2,26 micrometre. For the specimens having the R a value higher than 2,26 micrometre the cut-off is set to 2,5 mm and the needle traversal speed to 1 mm / s.

[0028] Each plate specimen was set in the electrochemical cell in order to achieve a copper deposit on the surface of each plate specimen. Before starting the shearing process it was noticed that the interface between the deposited copper and the specimen shows that copper has a very good penetration into very small topographic features of the specimen surface.

[0029] For the measurement of the adhesion by shearing force between the deposited copper and the plate surfaces the specimens with the deposited copper are set in a tool so that the specimen can be moved, but the deposited copper remains at the fixed position. The tool is then set in the tensile testing machine, and the cathode plate specimen is moved for the measurement the required force to separate the copper deposit from the plate specimen.

[0030] The plate specimens with their surface roughness as well as the measured shearing forces are listed in the following table 2 and in the Fig. 1 for the surface roughness R a . Also the values of the reference material are listed in table 2. In the table 2 the term "worn belt" means an abrasive belt which was utilized for the grinding treatment at least once before the actual treatment, while the term "new belt" means an abrasive belt which was not used for the treatment in accordance with the invention before the actual treatment. Table 2Test specimenAlloySurface roughness R a (µm)Shearing force (N)Reference surface (dry-ground)A0,36574,8Reference surface (dry-ground)B1,87487,5Reference surface (dry-ground)B1,2480,6Shot blast and pickledB2,89655,8Wet ground test 1 worn beltB0,96262,8Wet ground test 1 new beltB2,24551,5Wet ground test 2 new beltB1,55407,5Wet ground test 3 worn belt endB5,15633,3Wet ground test 3 new belt endB2,26323,9Wet ground test 3 worn belt startB4,56560,0Wet ground test 3 new belt startB2,18301,0

[0031] In the table 2 the results are based on three tests where the surface roughness is achieved by wet-grinding and one test where the surface roughness is achieved by the combination of shot-blasting and pickling. It is noticed that the adhesion measured by shearing force increases when the surface roughness values are increasing. An essentially linear trend can be seen for the wet ground surfaces. The shearing force measured between the plate and copper deposited on the surface of the plate is adjusted by the surface roughness of the plate, and as shown in Fig. 1 the shearing force is directly proportional to the surface roughness of the plate when the surface roughness of the plate is achieved by grinding. The highest shearing force value was measured for the specimen, which was treated as a combination of shot-blasting and pickling, first by shot blasting and then by pickling. Further, it was also noticed from the interface between the copper deposit and the stainless steel surface that the copper deposit has good penetration into very small topographic features of the stainless steel surface. Therefore, the surface roughness R a 0,7 - 5,5 micrometre, preferably 0,7 - 2,5 micrometre, is sufficient for the desired adhesion between copper deposit and the stainless steel surface. Thus the shearing force is 250 - 800 N, preferably 250 - 650 N.

[0032] The connection between the surface roughness and the shearing force was also tested in the industrial scale, and the results are given in the table 3 and respectively in the Fig. 2 for the alloy B. Table 3SpecimenSurface roughness R a (µm)Shearing force (N)10,9230221,0139731,150940,9940951,2552161,3550971,3165681,3350791,18505101,18506111,12516121,09474131521141,18492150,89370161,27624

[0033] The test results in the table 3 and in the Fig. 2 show that the surface roughness and the shearing force have a linear dependency to each other. Further, the results for the adhesion measured by shearing forces are essentially at the same ranges as the values for the shearing forces in the laboratory scale.

Claims

1. Method for manufacturing a plate material suitable for use as a cathode for electrochemical processing of a metal, wherein the metal is deposited on a surface of the cathode during the electrochemical processing , said method comprising the steps of • providing a processing line comprising a cold rolling unit and at least one surface treatment unit that is separate from the cold rolling unit; and • using the processing line to cold roll the plate material and modify a surface roughness of the surface of the plate material, wherein the surface of the plate material that has been modified is the surface of the cathode on which the metal is deposited during the electrochemical processing, the surface of the plate material that has been modified has roughness average Ra of 0,7 - 5,5 micrometre, and the surface of the plate material that has been modified provides a shearing force required to detach the deposited metal from the surface of the plate material that has been modified of 250 - 800 N, and wherein the plate material after modification is provided in the form of a coil.

2. Method according to the claim 1, characterized in that the surface roughness of the plate material is achieved mechanically.

3. Method according to the claim 1 or 2, characterized in that the surface roughness of the plate material is achieved by wet-grinding.

4. Method according to the claim 1 or 2, characterized in that the surface roughness of the plate material is achieved by dry-grinding.

5. Method according to the claim 1 or 2, characterized in that the surface roughness of the plate material is achieved by shot blasting.

6. Method according to the claim 1 or 2, characterized in that the surface roughness of the plate material is achieved by brushing.

7. Method according to the claim 1 or 2, characterized in that the surface roughness of the plate material is achieved by pattern rolling.

8. Method according to the claim 1, characterized in that the surface roughness of the plate material is achieved chemically.

9. Method according to the claim 1, characterized in that the surface roughness of the plate material is achieved mechanically and chemically.

10. Method according to the claim 9, characterized in that the surface roughness of the plate material is achieved by shot blasting and pickling.

11. Method according to any of the claims 1 - 10, characterized in that the surface roughness of the plate material is achieved by a combination of the treatments.

12. Method according to any of the preceding claims 1 - 11, characterized in that the surface roughness of the plate material by roughness average Ra is 0,7 - 2,5 micrometre.

13. Method according to any of the preceding claims 1 - 11, characterized in that the shearing force of the plate material is 250 - 650 N.

14. Method according to any of the preceding claims 1 - 13, characterized in that the plate material is for electrochemical process of copper.

15. Method according to the claim 14, characterized in that the plate material is for electrorefining of copper.

16. Method according to the claim 14, characterized in that that the plate material is for electrowinning of copper.

17. Method according to any of the preceding claims 1 - 13, characterized in that the plate material is for electrochemical process of silver.

18. Method according to the claim 17, characterized in that the plate material is for electrorefining of silver.

19. Method according to the claim 17, characterized in that that the plate material is for electrowinning of silver.

20. Method according to any of the preceding claims 1 - 13, characterized in that the plate material is for electrochemical process of nickel.

21. Method according to the claim 20, characterized in that the plate material is for electrorefining of nickel.

22. Method according to the claim 20, characterized in that that the plate material is for electrowinning of nickel.

23. Method according to any of the preceding claims, characterized in that the plate material as a product from a coil processing line is made of an austenitic stainless steel which contains in weight % less than 0,03 % carbon (C), less than 2 % manganese (Mn), 16,5 - 18,5 % chromium (Cr), 10 - 13 % nickel, 2 - 2,5 % molybdenum (Mo) and less than 0,10 % nitrogen (N).

24. Method according to any of the preceding claims 1 -22, characterized in that the plate material as a product from a coil processing line is made of a duplex austenitic ferritic stainless steel which contains in weight % less than 0,04 % carbon (C), 4 - 6 % manganese (Mn), 21 - 22 % chromium (Cr), 1,35 - 1,70 % nickel, 0,1 - 0,8 % molybdenum (Mo), 0,2 - 0,25 % nitrogen (N) and 0,1 - 0,8 copper (Cu).

25. Method according to any of the preceding claims 1 - 22, characterized in that the plate material as a product from a coil processing line is made of a duplex austenitic ferritic stainless steel which contains in weight % less than 0,03 % carbon (C), less than 2 % manganese (Mn), 21 - 23 % chromium (Cr), 4,5 - 6,5 % nickel, 2,5 - 3,5 % molybdenum (Mo) and 0,10 - 0,22 % nitrogen (N).

26. Method according to any of the claims 1 - 25, characterized in that the plate material is produced in the form of a coil.

27. Method according to any of the claims 1 - 25, characterized in that the plate material is produced in the form of a plate.