WO2023004907A1 - Substrat à surface de ponçage et son procédé de préparation, et plaque étamée/plaque chromée - Google Patents

Substrat à surface de ponçage et son procédé de préparation, et plaque étamée/plaque chromée Download PDF

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Publication number
WO2023004907A1
WO2023004907A1 PCT/CN2021/114194 CN2021114194W WO2023004907A1 WO 2023004907 A1 WO2023004907 A1 WO 2023004907A1 CN 2021114194 W CN2021114194 W CN 2021114194W WO 2023004907 A1 WO2023004907 A1 WO 2023004907A1
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Prior art keywords
work roll
substrate
roll
roughness
concentration
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PCT/CN2021/114194
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English (en)
Chinese (zh)
Inventor
黄久贵
俞炜
郭宏
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江苏沙钢集团有限公司
江苏省沙钢钢铁研究院有限公司
张家港扬子江冷轧板有限公司
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Priority to KR1020237029818A priority Critical patent/KR20230170643A/ko
Publication of WO2023004907A1 publication Critical patent/WO2023004907A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/22—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling plates, strips, bands or sheets of indefinite length
    • B21B1/227—Surface roughening or texturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B24—GRINDING; POLISHING
    • B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
    • B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C25D3/08—Deposition of black chromium, e.g. hexavalent chromium, CrVI
    • 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
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C25D5/505—After-treatment of electroplated surfaces by heat-treatment of electroplated tin coatings, e.g. by melting
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D9/00—Electrolytic coating other than with metals
    • C25D9/04—Electrolytic coating other than with metals with inorganic materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B1/00—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations
    • B21B1/38—Metal-rolling methods or mills for making semi-finished products of solid or profiled cross-section; Sequence of operations in milling trains; Layout of rolling-mill plant, e.g. grouping of stands; Succession of passes or of sectional pass alternations for rolling sheets of limited length, e.g. folded sheets, superimposed sheets, pack rolling
    • B21B2001/386—Plates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B2265/00—Forming parameters
    • B21B2265/12—Rolling load or rolling pressure; roll force
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21B—ROLLING OF METAL
    • B21B2267/00—Roll parameters
    • B21B2267/10—Roughness of roll surface

Definitions

  • the invention relates to the technical field of metal material processing, in particular to a substrate with a sanded surface, a preparation method thereof, and a tin-plated plate/chrome-plated plate.
  • Tin-plated/chrome-plated sheets are widely used in beverage packaging. Usually, steel billets are hot-rolled into strips of about 2.0mm in steel plants, and then undergo processes such as acid rolling, annealing, smoothing, tin/chrome plating, and passivation. Finally, it is made into a tin plate/chrome plate, and then it is made into a can body through iron printing and can making processes, which is used to hold various beverages. Since the content contained is acidic, high-protein and other substances, it is required that the tin plate/chrome plate products have high corrosion resistance.
  • the surface morphology of the tin plate/chrome plate selected for necking cans (attachment 1) or easy open end (attachment 2) is R1 (fine stone surface), and the roughness Ra is controlled between 0.29 and 0.55 ⁇ m , the texture of the board surface is stone-like, with a general sense of drawing (visually similar to thin and shallow scratches), and it presents a lighter graininess under strong light.
  • the necked cans or easy-open ends made of such tin-plated/chrome-plated plates is easily corroded by the contents and cannot meet the requirements of corrosion resistance.
  • the technical problem to be solved by the present invention is to provide a tin-plated/chrome-plated sheet from which necked cans or easy-open lids have good corrosion resistance so that they will not be corroded by the contents.
  • the present invention provides the following technical solutions:
  • the first aspect of the present invention provides a method for preparing a substrate with a sanded surface, comprising the following steps:
  • a screed machine comprising a first frame and a second frame
  • the first frame includes a first work roll and a third work roll oppositely arranged
  • the second frame includes a second work roll and a fourth work roll oppositely arranged
  • the first work roll and the second work roll are located on the same side, the first work roll and the second work roll are used to contact the first surface of the substrate and form the sanding surface, wherein:
  • the first work roll is an electric spark textured roll
  • the second work roll is a ground smooth roll
  • the roughness of the surface of the first work roll is 1.6-2.2 ⁇ m
  • the roughness of the surface of the second work roll is The degree is 0.35 ⁇ 0.75 ⁇ m
  • the base plate to be cold-rolled is sent into the tempering machine, and the base plate is sequentially passed between the first work roll and the third work roll, between the second work roll and the fourth work roll, so that the The sanded surface is formed on the first surface of the substrate.
  • the rolling force of the first stand is 3500-4500 kN
  • the rolling force of the second stand is 3500-4000 kN.
  • the roll changing period of the first work roll and the second work roll is 120 ⁇ 20km, and the rolling tonnage is 150 ⁇ 30t.
  • both the third work roll and the fourth work roll are ground smooth rolls, and the surface roughness of the first work roll is 1.8 ⁇ 0.2 ⁇ m,
  • the roughness of the surface of the second work roll is 0.70 ⁇ 0.05 ⁇ m
  • the roughness of the surface of the third work roll is 0.70 ⁇ 0.05 ⁇ m
  • the roughness of the surface of the fourth work roll is 0.40 ⁇ 0.05 ⁇ m
  • the The rolling force of the first stand is 3500 ⁇ 100kN
  • the rolling force of the second stand is 3500 ⁇ 100kN.
  • the third work roll is an EDM textured roll
  • the fourth work roll is a ground smooth roll
  • the surface of the first work roll is The roughness of the surface of the second work roll is 2.0 ⁇ 0.2 ⁇ m
  • the roughness of the surface of the second work roll is 0.40 ⁇ 0.05 ⁇ m
  • the roughness of the surface of the third work roll is 1.2 ⁇ 0.2 ⁇ m
  • the roughness of the surface of the fourth work roll The rolling force of the first stand is 0.40 ⁇ 0.05 ⁇ m
  • the rolling force of the first stand is 4000 ⁇ 100kN
  • the rolling force of the second stand is 3500 ⁇ 100kN.
  • a fine stone surface is formed on the second surface.
  • the third work roll is an EDM textured roll
  • the fourth work roll is a ground smooth roll
  • the surface of the first work roll is The roughness of the surface of the second work roll is 2.0 ⁇ 0.2 ⁇ m
  • the roughness of the surface of the second work roll is 0.40 ⁇ 0.05 ⁇ m
  • the roughness of the surface of the third work roll is 1.5 ⁇ 0.2 ⁇ m
  • the roughness of the surface of the fourth work roll The thickness is 0.70 ⁇ 0.05 ⁇ m
  • the rolling force of the first stand is 4500 ⁇ 100kN
  • the rolling force of the second stand is 4000 ⁇ 100kN.
  • a rough stony finish is formed on the second surface.
  • the second aspect of the present invention provides a substrate with a sanded surface prepared by using the preparation method described in the first aspect, one side of the substrate is a sanded surface, the other side is a non-sanded surface, and the sanded surface Consisting of dot-like concave-convex bottoming lines and silky lines on part of the bottoming lines, the distribution of the bottoming lines and the silky lines makes the roughness of the sanding surface 0.50-0.80 ⁇ m .
  • the material of the base plate is MR type, L type or D type original plate steel.
  • non-sanding surface is a smooth surface, a fine stone texture surface, a coarse stone texture surface, a silver surface, a rough silver surface or a matte surface.
  • the third aspect of the present invention provides a tinned plate, which is obtained by electroplating metal tin on the surface of the substrate described in the second aspect and reflowing.
  • the concentration of divalent tin in the electroplating solution is 20-25g/L
  • the concentration of methanesulfonic acid is 30-50mL/L
  • the concentration of antioxidant is 35-60mL/L
  • the concentration of additives The concentration is 20-30mL/L; during the electroplating process, the temperature of the electroplating solution is controlled to be 38-45°C, and the current density is 22-28A/mm 2 .
  • the reflow setting temperature is 260-290°C
  • the reflow feedback temperature is 255-295°C
  • the reflow power ratio is 30%-50%.
  • one side of the substrate is a sanded surface, and the other side is a fine stone textured surface.
  • the fourth aspect of the present invention provides a chrome-plated plate, which is obtained by electroplating metal chromium and chromium oxide on the surface of the substrate as described in the second aspect.
  • the concentration of chromic anhydride in the electroplating solution is 140-160g/L, and the concentration of ammonium fluoride is 3-4g/L; during the electroplating process, the temperature of the electroplating solution is controlled to be 36-40°C, The current density is 50-80A/mm 2 , the concentration of chromic anhydride in the first recovery tank is ⁇ 50g/L, and the concentration of chromic anhydride in the second recovery tank is ⁇ 40g/L.
  • the concentration of chromic anhydride in the electroplating solution is 60-70g/L, the concentration of ammonium fluoride is 1-2g/L, and the concentration of sodium hydroxide is 8-10g/L; , controlling the temperature of the electroplating solution to be 31-35°C, the current density to be 9-22A/mm 2 , and the weight of the formed chromium oxide layer to be 8-15g/m 2 .
  • one side of the substrate is a sanded surface, and the other side is a fine stone textured surface.
  • the fifth aspect of the present invention provides a necked tank, the necked tank is prepared from the tin-plated or chrome-plated plate.
  • the sixth aspect of the present invention provides an easy-open end, the easy-open end is prepared from the tin-plated sheet.
  • the present invention creatively proposes a new treatment process for tin-plated/chrome-plated substrates, so that the substrate has two different surfaces inside and outside, and a new surface morphology is produced on the inner surface used to form the inner wall of the tank ——Sanded surface, the roughness of which is 0.50-0.80 ⁇ m, and the microscopic appearance includes dot-like concave-convex grounding lines and silky lines on some of the grounding lines. Substrates with such a sanded surface can be more evenly distributed on the surface of the substrate during tin or chrome plating.
  • the coating at the necked part and the pre-scribed film is not easily damaged, has good corrosion resistance, and will not be corroded by the contents.
  • the outer surface used to form the outer wall of the tank can retain the original surface morphology, so that the tin-plated/chrome-plated substrate produced by the present invention can retain the existing tank packages when forming various tank packages. visual characteristics, thereby avoiding the marketing cost caused by switching to new can packaging products, so that the substrate of the present invention has stronger universality.
  • the present invention improves the existing tin-plating and chrome-plating processes.
  • the new electroplating process improves the compactness of the tin-plated layer and the chrome-plated layer and the uniformity of the alloy layer coverage, reduces the depth of the pores, so that the coating can be The substrate is better protected, and the corrosion resistance of the substrate is further improved.
  • Fig. 1 is the structural representation of necking tank
  • Fig. 2 is a schematic structural view of the easy-open end
  • Figure 3 is the surface texture of the R1 surface under the microscope
  • Figure 4 is the surface texture of the Rs surface under the microscope
  • Fig. 5 is a schematic diagram of wire drawing lines on R1 surface (a) and Rs surface (b);
  • Fig. 6 is when adopting existing tinning process (a) and tinning process (b) of the present invention, the surface topography figure of tin layer on the substrate;
  • Fig. 7 is when adopting existing reflow process (a, b, c) and tin plating process (d, e, f) of the present invention, the surface topography figure of alloy layer on the substrate;
  • Fig. 8 is the surface topography figure of the metal chromium layer that adopts electroplating metal chromium process of the present invention to obtain;
  • Fig. 9 is an integrated surface topography diagram of a metal chromium layer and a chromium oxide layer obtained by the electroplating chromium oxide process of the present invention.
  • the surface morphology of the tin plate/chrome plate selected for the necking can (accompanying drawing 1) or the easy-open end (accompanying drawing 2) is R1 (fine stone surface), and the roughness Ra is controlled between 0.29 and 0.55 ⁇ m, the texture of the surface of the board is stone-like, with a general feeling of drawing (visually similar to thin and shallow scratches), and it presents a lighter grainy feeling under strong light.
  • the necked cans or easy-open lids made of such tin-plated/chrome-plated plates are easily corroded by the contents at the necked or pre-scribed areas during use, which cannot meet the corrosion resistance requirements.
  • the inventors found that the main reason why the constriction or the pre-scribing film is easily corroded by the content is the surface morphology of the tin/chrome-plated substrate. Since the content surface of the substrate in the prior art is the fine stone texture surface R1, its surface has a brushed appearance. The presence of wire drawing causes obvious height difference on the surface of the substrate. As shown in Figure 3, when observed under a microscope, the wire drawing part shows serious unevenness, which is generally distributed on the surface of the substrate like ravines.
  • the amount of tin plating on the protruding part of the substrate will be greater than that on the concave part, thus hindering the tin plating. uniform deposition.
  • the tin deposited on the substrate will melt and flow. When it flows to the recessed part, the recessed part will hinder the further flow of the tin melt, thereby hindering the leveling of the tin after melting, and finally affecting Alloy layer formation.
  • metal chromium is electroplated on the surface of the substrate, the pores on the surface of the coating are less, but in the form of deep pits, which is mainly due to the body-centered cubic structure of the electroplated metal chromium layer, which is formed by the preferred orientation of the crystal lattice as the current density changes; and
  • the current efficiency of chromium plating is generally 20% to 25%, and the side reaction is hydrogen evolution reaction, which increases the pores of the metal chromium layer along the longitudinal direction.
  • the longitudinal pores are further deepened, so that the deposition of metallic chromium at the bottom of the wire-drawing groove is further reduced during the electrochrome plating process.
  • the chromium oxide layer has a network and layered structure, and as the degree of gully increases, its protection to the metal chromium layer is further reduced, resulting in a decrease in the corrosion resistance of the chrome-plated plate.
  • the substrate surface morphology of tin plate/chrome plate has B (bright surface), R1 (fine stone surface), R2 (coarse stone surface), S1 (silver surface), S2 ( Coarse silver surface), M (matte surface), the appearance specifications and standards of each product are shown in Table 1.
  • Table 1 The appearance specifications and standards of existing tinplate/chrome plate products
  • a sanded surface As shown in Figure 4, when observed under a microscope, the surface of this Rs has a dot-shaped concave-convex texture and silky lines located on part of the texture, the texture and the silk The distribution of the shaped lines makes the roughness of the sanded surface 0.50-0.80 ⁇ m.
  • the surface of Rs When observed under normal light, the surface of Rs has a grainy feel, which is relatively fine, and there is a slight brushing feeling under strong light. The gloss of the board surface is slightly light silver, and the reflectivity is poor.
  • the wire drawing lines on the Rs surface of the present invention are shorter and shallower, thereby reducing the degree of wire drawing (scratching), and eliminating the deposition and reflow of electroplated tin due to substrate grooves caused by wire drawing.
  • the impact of tin leveling in the process so that the surface of the substrate is evenly covered with tin layer and alloy layer; and because tin has good ductility, it finally increases the corrosion resistance of the deformation zone in the process of can making and lid.
  • the invention provides a method for preparing a substrate with a sanded surface, which specifically includes the following steps:
  • the tempering machine includes a first frame and a second frame, the first frame includes a first work roll and a third work roll oppositely arranged, the second frame including a second work roll and a fourth work roll oppositely arranged, the first work roll and the second work roll are located on the same side, and the first work roll and the second work roll are used to contact the first surface of the substrate And form the sanded surface, wherein:
  • the first work roll is an electric spark textured roll
  • the second work roll is a ground smooth roll
  • the roughness of the surface of the first work roll is 1.6-2.2 ⁇ m
  • the roughness of the surface of the second work roll is The degree is 0.35 ⁇ 0.75 ⁇ m
  • the EDM texturing roll is a roll prepared by the EDM texturing (EDT) technology, which produces pit-shaped burrs on the surface of the roll based on the principle of EDM, and can be formed on the surface of the substrate by rolling the EDM texturing roll. granular morphology.
  • the ground smooth roll is formed on the surface of the roll based on the grinding process. Through the rolling of the ground smooth roll, a wire-like morphology can be formed on the surface of the substrate.
  • the topography and roughness of the surface of the first work roll and the second work roll under the action of the external rolling force, the topography and roughness of the roll surface are printed on the surface of the substrate, thereby The surface of the substrate forms the sanded surface topography.
  • the rolling force applied by the first stand to the first work roll is 3500-4500 kN
  • the rolling force applied by the second stand to the second work roll is 3500-4000 kN.
  • the first work roll and the second work roll need to be replaced after being used for a certain period of time, and whether they need to be replaced can be determined according to the roll change cycle or rolling tonnage.
  • the roll change cycle refers to the total length of the base material rolled by the work rolls
  • the rolling tonnage refers to the total weight of the base material rolled by the work rolls. For example, if the roll changing period is 120km, it means that the line will be stopped and changed after the work roll reaches 120km of substrate. Similarly, the rolling tonnage is 150 tons, which means that the line will be stopped and replaced after the work roll reaches 150 tons of substrate. roll.
  • the roll changing cycle of the first work roll and the second work roll is preferably 120 ⁇ 20km, and the rolling tonnage is preferably 150 ⁇ 30t.
  • the inventor abandoned the traditional double-sided R1 surface manufacturing process, and adopted a new type of differentiated surface morphology control.
  • the outer surface of the tank still adopts the original R1 surface, and the inner surface adopts the Rs surface of the present invention, thereby obtaining a differentiated shape.
  • differential shape control Rs content surface/R1 outer surface
  • the substrate with the Rs/R1 differential morphology can be used to prepare necked cans or easy-open lids after tin plating, and can be used to prepare necked cans after chrome plating.
  • the above-mentioned base plate can adopt the base plate material commonly used in the can making industry, preferably MR-type, L-type or D-type raw plate steel.
  • the substrate with the above Rs/R1 differential morphology can be prepared by controlling the types, surface roughness and rolling force of the third work roll and the fourth work roll.
  • the third work roll is controlled to be an EDM textured roll
  • the fourth work roll is a ground smooth roll
  • the surface roughness of the first work roll is 2.0 ⁇ 0.2 ⁇ m
  • the second work roll is The roughness of the roll surface is 0.40 ⁇ 0.05 ⁇ m
  • the roughness of the surface of the third work roll is 1.2 ⁇ 0.2 ⁇ m
  • the roughness of the surface of the fourth work roll is 0.40 ⁇ 0.05 ⁇ m
  • the The rolling force is 4000 ⁇ 100kN
  • the rolling force of the second stand is 3500 ⁇ 100kN.
  • substrates with differentiated morphologies on the second surface can be obtained, such as Rs/B substrates, Rs/R2 substrates, and the like.
  • the method for preparing the above-mentioned Rs/B substrate is: control the third work roll and the fourth work roll to be ground smooth rolls, the surface roughness of the first work roll is 1.8 ⁇ 0.2 ⁇ m, and the second work roll
  • the roughness of the roll surface is 0.70 ⁇ 0.05 ⁇ m
  • the roughness of the surface of the third work roll is 0.70 ⁇ 0.05 ⁇ m
  • the roughness of the surface of the fourth work roll is 0.40 ⁇ 0.05 ⁇ m
  • the The rolling force is 3500 ⁇ 100kN
  • the rolling force of the second stand is 3500 ⁇ 100kN
  • the bright surface (B) is formed on the second surface of the substrate after being cold-rolled by a temper mill.
  • the method for preparing the above-mentioned Rs/R2 substrate is: controlling the third work roll to be an EDM textured roll, the fourth work roll to be a ground smooth roll, and the surface roughness of the first work roll to be 2.0 ⁇ 0.2 ⁇ m, the roughness of the surface of the second work roll is 0.40 ⁇ 0.05 ⁇ m, the roughness of the surface of the third work roll is 1.5 ⁇ 0.2 ⁇ m, the roughness of the surface of the fourth work roll is 0.70 ⁇ 0.05 ⁇ m,
  • the rolling force of the first stand is 4500 ⁇ 100kN, and the rolling force of the second stand is 4000 ⁇ 100kN. After the substrate is cold-rolled by a temper mill, rough stones are formed on its second surface. Textured surface (R2).
  • Table 2 shows in detail the roll matching schemes for preparing the above-mentioned substrates with different morphologies.
  • the present invention further studies the tin plating and reflow process of the substrate.
  • the inventor improved the existing tinning process and provided a new tinning process, as shown in Table 4.
  • the concentration of divalent tin in the electroplating solution is 15-25g/L
  • the concentration of methanesulfonic acid is 30-50mL/L
  • the concentration of antioxidant is 35-60mL/L
  • the concentration of additives is 25 ⁇ 30mL/L.
  • the temperature of the electroplating solution is controlled to be 38-45° C.
  • the current density is 22-28 A/mm 2 .
  • the concentration of divalent tin in the electroplating solution is 20g/L to control the concentration of divalent tin in the electroplating solution
  • the concentration of methanesulfonic acid is 40mL/L
  • the concentration of antioxidant is 45mL/L
  • the concentration of additive is 25mL/L.
  • the temperature was 42°C and the current density was 25A/mm 2 .
  • the above-mentioned antioxidants can be selected from commonly used oxidants in the field, including but not limited to one or more of phenol, hydroquinone, resorcinol, and catechol.
  • the antioxidant used is QUAKERTIN TM TPMW AOX antioxidant of Quaker Chemical.
  • the above-mentioned additives may be additives commonly used in the art, including but not limited to one or more of surfactants and grain refiners.
  • the additive used is Quake Chemical's QUAKERTIN TM Additive additive.
  • the surface morphology of the tin layer on the substrate is shown in Figure 6(b). It can be seen from the figure that the grains of the tin layer are fine and compact, and the gap between grains is small, which can better protect the substrate and improve the corrosion resistance of the substrate.
  • the tin layer is melted and flowed through a reflow process to obtain an alloy layer, thereby improving the uniformity of the tin layer.
  • Table 5 shows the existing electrolytic tin plating reflow process parameters.
  • the alloy layer formed by the existing reflow process has relatively fine grains, so the corrosion resistance is also poor.
  • the present invention also improves the reflow process, as shown in Table 6.
  • the height of the reflow box used is 3.5-5.5m
  • the reflow setting temperature is 260-290°C
  • the reflow feedback temperature is 255-295°C
  • the reflow power ratio is 30%-50%.
  • the height of the reflow box used is 4.5m
  • the set reflow temperature is 270°C
  • the reflow feedback temperature is 275°C
  • the reflow power ratio is 40%.
  • the present invention also studies the chrome plating process of the substrate.
  • the metal chromium layer produces deep pit-shaped pores along the longitudinal direction. Therefore, improving the density of grains and reducing the depth of pores in the process of metal chromium deposition are important measures to improve the corrosion resistance of chromium-plated plates.
  • the present invention improves the process of electroplating metal chromium, as shown in Table 8.
  • electroplating metal chromium control the concentration of chromic anhydride in the electroplating solution to be 140-160g/L, the concentration of ammonium fluoride to be 3-4g/L, the concentration of chromic anhydride in the first recovery tank to be ⁇ 50g/L, and the second recovery
  • concentration of chromic anhydride in the tank is ⁇ 40g/L; during the electroplating process, the temperature of the electroplating solution is controlled to be 33-43°C, and the current density is 25-100A/mm 2 .
  • the concentration of chromic anhydride in the control electroplating solution is 150g/L
  • the concentration of ammonium fluoride is 3.5g/L
  • the concentration of chromic anhydride in the first recovery tank is 30g/L
  • the second recovery tank The concentration of internal chromic anhydride is 10g/L; during the electroplating process, the temperature of the electroplating solution is controlled at 38°C, and the current density is 65A/mm 2 .
  • the surface morphology of the obtained metal chromium layer is shown in FIG. 8 . It can be seen from the figure that a shallow and dense metal chromium layer with deep pits can be obtained through the above electroplating process. The metal chromium layer with this shape can better protect the substrate and improve its corrosion resistance.
  • the present invention improves the electroplating chromium oxide process, as shown in Table 10.
  • the concentration of chromic anhydride in the electroplating solution is 60-70g/L
  • the concentration of ammonium fluoride is 1-2g/L
  • the concentration of sodium hydroxide is 6-12g/L
  • the temperature of the liquid is 27-37°C
  • the current density is 9-22A/mm 2
  • the weight of the formed chromium oxide layer is 8-15g/m 2 .
  • the concentration of chromic anhydride in the electroplating solution is 65g/L, the concentration of ammonium fluoride is 1.5g/L, and the concentration of sodium hydroxide is 9g/L;
  • the temperature is 32°C, the current density is 19A/mm 2 , and the weight of the formed chromium oxide layer is ⁇ 10g/m 2 .
  • the integrated surface morphology of the obtained metal chromium layer and chromium oxide layer is shown in FIG. 9 . It can be seen from the figure that according to the chromium oxide electroplating process of the present invention, a dense reticular chromium oxide layer can be obtained, which is beneficial to improving the corrosion resistance of the chrome-plated plate.
  • the present invention provides a new surface topography Rs of tin-plated/chrome-plated substrates, the substrate with this surface topography has a more uniform coating distribution during the electroplating process, so that it can be used in the preparation of necking tanks/easy During the process of opening the cap, the coating at the neck and pre-scribing film is not easy to deform and crack, thus improving the corrosion resistance of the neck can/easy-open end.
  • the present invention also improves the tin plating and chrome plating process, improves the compactness of the plating layer, and thus can also improve the corrosion resistance of the necked can/easy-open end.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)

Abstract

L'invention concerne un procédé de préparation d'un substrat comportant une surface de ponçage. Le procédé de préparation consiste à : utiliser un laminoir à aplatir qui comprend une première crémaillère et une seconde crémaillère, la première crémaillère comprenant un premier cylindre de travail et un troisième cylindre de travail qui sont disposés l'un en face de l'autre, la seconde crémaillère comprenant un deuxième cylindre de travail et un quatrième cylindre de travail qui sont disposés l'un en face de l'autre, le premier cylindre de travail et le deuxième cylindre de travail se trouvant sur le même côté, le premier cylindre de travail étant un cylindre de texturation par étincelle électrique, le deuxième cylindre de travail étant un cylindre de meulage et de polissage, la rugosité d'une surface du premier cylindre de travail étant comprise entre 1,6 et 2,2 μm, et la rugosité d'une surface du deuxième cylindre de travail étant comprise entre 0,35 et 0,75 μm; et faire passer le substrat successivement entre le premier cylindre de travail et le troisième cylindre de travail, puis entre le deuxième cylindre de travail et le quatrième cylindre de travail, de manière à former une surface de ponçage sur une première surface du substrat. Après étamage ou chromage du substrat comportant la surface de ponçage, lorsque le substrat est transformé en un réservoir présentant un étranglement ou en un bouchon facile à ouvrir, des revêtements au niveau d'une position d'étranglement et un film de pré-traçage ne sont pas susceptibles d'être endommagés, de telle sorte que la résistance à la corrosion de celui-ci est bonne.
PCT/CN2021/114194 2021-07-28 2021-08-24 Substrat à surface de ponçage et son procédé de préparation, et plaque étamée/plaque chromée WO2023004907A1 (fr)

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NL2032597B1 (en) 2023-06-26

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