EP1735116B1 - Procede de production de bandes en acier inoxydable austenititique d'aspect de surface mat - Google Patents

Procede de production de bandes en acier inoxydable austenititique d'aspect de surface mat Download PDF

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Publication number
EP1735116B1
EP1735116B1 EP05736552A EP05736552A EP1735116B1 EP 1735116 B1 EP1735116 B1 EP 1735116B1 EP 05736552 A EP05736552 A EP 05736552A EP 05736552 A EP05736552 A EP 05736552A EP 1735116 B1 EP1735116 B1 EP 1735116B1
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EP
European Patent Office
Prior art keywords
strip
process according
pickling
solution
pickling solution
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP05736552A
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German (de)
English (en)
French (fr)
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EP1735116A1 (fr
Inventor
Arnaud Dessis
Henri Giraud
Caroline Moison
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Aperam Stainless France SA
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Ugine et Alz France SA
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Priority to PL05736552T priority Critical patent/PL1735116T3/pl
Priority to SI200530274T priority patent/SI1735116T1/sl
Publication of EP1735116A1 publication Critical patent/EP1735116A1/fr
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    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/26Methods of annealing
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B3/00Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
    • B21B3/02Rolling special iron alloys, e.g. stainless steel
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D9/00Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
    • C21D9/52Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for wires; for strips ; for rods of unlimited length
    • C21D9/54Furnaces for treating strips or wire
    • C21D9/56Continuous furnaces for strip or wire
    • C21D9/561Continuous furnaces for strip or wire with a controlled atmosphere or vacuum
    • 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
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F17/00Multi-step processes for surface treatment of metallic material involving at least one process provided for in class C23 and at least one process covered by subclass C21D or C22F or class C25
    • 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08Iron or steel
    • C23G1/086Iron or steel solutions containing HF
    • 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00Apparatus for cleaning or pickling metallic material
    • C23G3/02Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • C23G3/021Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously by dipping
    • 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
    • C23GCLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00Apparatus for cleaning or pickling metallic material
    • C23G3/02Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • C23G3/027Associated apparatus, e.g. for pretreating or after-treating
    • C23G3/028Associated apparatus, e.g. for pretreating or after-treating for thermal or mechanical pretreatment
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B21MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
    • B21BROLLING OF METAL
    • B21B45/00Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills
    • B21B45/04Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing
    • B21B45/06Devices for surface or other treatment of work, specially combined with or arranged in, or specially adapted for use in connection with, metal-rolling mills for de-scaling, e.g. by brushing of strip material
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D2211/00Microstructure comprising significant phases
    • C21D2211/001Austenite

Definitions

  • the present invention relates to a method of continuous manufacture of an austenitic stainless steel strip having a matt surface appearance, annealed-pickled type.
  • the austenitic stainless steel strip is given either a glossy surface appearance or a matt surface appearance, depending on the application to which the band is intended.
  • gloss surface appearance means a surface having a gloss greater than 40 and an arithmetic mean roughness Ra of less than 0.08 ⁇ m, and by dull surface appearance, a surface having a lower gloss. at 30 and an arithmetic average roughness Ra greater than 0.12 ⁇ m.
  • the brightness corresponds to the measurement of the reflectivity of the surface and is measured at an angle of 60 °.
  • the austenitic stainless steel strips undergo a heat treatment in a bright annealing furnace in which a reducing atmosphere prevails.
  • the strips run in the oven consisting of an enclosure completely isolated from the outside atmosphere, comprising three zones, a first heating zone, a second temperature holding zone, and a third cooling zone, in which circulates a neutral or reducing gas.
  • This gas may be chosen for example from argon, hydrogen, nitrogen or a mixture of hydrogen and nitrogen, and has a dew point between -65 and -45 ° C.
  • the strips After being cold-rolled, the strips are heated in the first zone of the oven at a temperature of between 1050 and 1150 ° C.
  • an austenitic stainless steel strip having an annealed-stripped surface appearance ie a matt surface appearance
  • the procedure is as follows.
  • the previously cold-rolled strips undergo continuous annealing at a temperature of the order of 1100 ° C., for about 1 min, in an oven whose atmosphere is oxidizing.
  • the annealed strips then undergo air cooling and / or forced cooling by spraying water outside the oven.
  • they are stripped in several pickling tanks containing solutions capable of removing the oxide layer that has formed on the surface of the strip during annealing.
  • the inventors had the idea of stripping the bright annealed austenitic stainless steel strips so as to give them a matt surface appearance, of the annealed-pickled type. However, the inventors realized that in doing so, it was not possible to obtain a visually satisfactory surface appearance.
  • FIG. figure 1 annexed showing a schematic view of an installation that may be suitable for the implementation of the invention.
  • This installation comprises a bright annealing furnace 1, comprising a sealed enclosure 2 through which a strip 3 of austenitic stainless steel passes, means 4 for introducing a flushing gas into the sealed enclosure 2, and control means 5 of the dewpoint of the flushing gas.
  • a pickling installation 6 which comprises at least one pickling tank 7 resistant to acids, and containing a pickling solution.
  • the sealed enclosure 2 comprises, in the direction of travel of the band 3 represented by the arrow F, three successive zones, a first heating zone, a second temperature holding zone and a third cooling zone.
  • the first heating zone is equipped with powerful heating means (not shown) capable of rapidly heating the band 3 at a heating rate V1, up to a temperature T1.
  • Band 3 is maintained at this temperature T1 in the second zone, during a holding time M, then is cooled at a speed V2 to a temperature T2, in the third zone.
  • heat treatment of the strip 3 in the chamber 2 of the furnace 1, within which a gas circulates must be carried out. with a dew point greater than -15 ° C, to obtain a strip 3 covered with an oxide layer, then etch the strip 3 heat treated with an acid pickling solution.
  • the acid pickling solution is adapted to completely remove said oxide layer depending on its thickness and nature.
  • the acid pickling solution will have a pH of between 0 and 4.
  • gas having a dew point greater than -15 ° C a gas whose hygrometry rate is greater than 2000 ppm water.
  • the flushing gas is selected from neutral or reducing gases such as argon, hydrogen, nitrogen and mixtures thereof, and may further comprise less than 1% by volume of oxygen or less than 1% by weight. volume of air.
  • the strip 3 is subjected to a heat treatment consisting of a recrystallization annealing carried out at a speed V1 of greater than 10 ° C./s, a temperature T1 of between 1050 and 1150 ° C. and a holding time of between 1s and 120s, followed by forced cooling at a rate V2 greater than 10 ° C / s to a temperature T2 less than or equal to 200 ° C.
  • a heat treatment consisting of a recrystallization annealing carried out at a speed V1 of greater than 10 ° C./s, a temperature T1 of between 1050 and 1150 ° C. and a holding time of between 1s and 120s, followed by forced cooling at a rate V2 greater than 10 ° C / s to a temperature T2 less than or equal to 200 ° C.
  • the flushing gas circulating in enclosure 2 is sufficiently oxidizing so that a thin layer is formed. of oxide on the surface of the strip 3.
  • This thin oxide layer is capable of being etched by means of the acid pickling solution having a pH of between 0 and 4.
  • the amount of water present in the flushing gas is changed.
  • the dew point is greater than -10 ° C so as to form an oxide layer of sufficient thickness, but less than 30 ° C so as to limit the thickness of the oxide layer.
  • the thickness of the oxide layer it limits the amount of metal consumed by the oxidation but also the amount of acid solution necessary for proper etching of the surface of the strip 3, and thus avoids the reprocessing effluent is too important.
  • the dew point is between -5 and 10 ° C.
  • the recrystallization annealing of the strip 3 is carried out either with the aid of a resistance device or preferably of an induction device.
  • the induction heating of the band 3 is advantageous for the following reasons.
  • the processing time of the band 3 is very small compared to the treatment time with resistance heating.
  • the enclosure 2 of an induction heating treatment furnace is much less bulky than the chamber 2 of a resistance heating treatment furnace, and this makes it possible to modify the atmosphere prevailing in this enclosure 2 in much shorter times, in line with industrial requirements.
  • the forced cooling of the band 3 is performed by injecting gas whose temperature is between room temperature and 40 ° C. This is the gas contained in the chamber 2 of the oven 1 which is cooled by cooling means not shown, and which is then reinjected into the cooling zone of the chamber 2.
  • the strip 3 treated according to the invention is etched with an acid pickling solution adapted so that the elimination of the oxide formed on the band 3 is complete.
  • the acid pickling solution is adapted to the nature and the thickness of the oxide formed during the heat treatment.
  • the acid pickling solution has a pH of between 0 and 4.
  • the pickling solution is chosen from aqueous solutions comprising nitric acid, hydrofluoric acid and / or sulfuric acid.
  • Preferred pickling solutions are aqueous solutions comprising nitric acid, aqueous solutions comprising hydrofluoric acid and nitric acid, and aqueous solutions comprising hydrofluoric acid and Fe 3+ ferric ions.
  • the pickling solution may be an aqueous solution comprising 5 to 100 g / l of hydrofluoric acid, preferably 30 to 80 g / l, and 1 to 150 g / l of ferric ions, preferably 30 to 50 g / l .
  • the etching and more particularly the attack of the grain boundaries of the steel surface by the solution are insufficient, and the Matte surface appearance is not obtained.
  • the hydrofluoric acid concentration is greater than 100 g / l and the ferric ion concentration is greater than 150 g / l, the etching will be too large with the consequence of excessive removal of steel at the surface of the strip. 3, and a larger amount of used solution to be treated.
  • an aqueous solution comprising 10 to 80 g / l of hydrofluoric acid, preferably 30 to 50 g / l, and 60 to 140 g / l. 1 nitric acid, preferably 80 to 120 g / l.
  • the etching and more particularly the attack of the grain boundaries of the steel surface by the solution are insufficient, and the Matte surface appearance is not obtained.
  • the hydrofluoric acid concentration is greater than 80 g / l and the nitric acid concentration is greater than 140 g / l, the etching will be too large, with the consequence of excessive steel removal at the surface of the strip. 3, and a larger amount of used solution to be reprocessed.
  • the strip 3 To strip the strip 3, it is immersed in a pickling bath containing the pickling solution or is then sprayed with the pickling solution, so that the contact time of the pickling solution with the strip 3 is between 10 s and 2 min.
  • the contact time of the stripping solution with the strip 3 is less than 10 s, the grain boundary attack is insufficient and the matt appearance will not be obtained. But if the contact time of the stripping solution with the strip 3 is greater than 2 min, stripping is so important that it may dissolve too much the steel strip 3.
  • the temperature of the pickling solution is between 20 and 100 ° C, and preferably between 50 and 80 ° C. Indeed, a pickling solution temperature of less than 20 ° C requires processing times of the band 3 which do not comply with industrial requirements, that is to say about greater than 2 min. However, too high a temperature, ie greater than 100 ° C, promotes the evaporation of the solution and also poses safety problems.
  • the applied current density is greater than 5 A / dm 2 , and preferably less than 30 A / dm 2 . Indeed, when the current density is less than 5 A / dm 2 , pickling of the steel surface by the solution is insufficient, and the matte surface appearance is not obtained. However, when the current density is greater than 30 A / dm 2 , the etching is not done economically.
  • one of these strips has a surface appearance of conventional bright annealing type, and another of these strips having a surface appearance of the conventional stripped annealing type, that is to say a matte surface appearance , so as to have a surface reference.
  • the band under consideration is subjected to a heat treatment in the enclosure of a bright annealing furnace inside which circulates a mixture of 25% by volume of nitrogen and 75% by volume of hydrogen having a dew point of -50 ° C.
  • the strip is heated at a heating rate of 10 ° C / sec, brought to 1100 ° C, maintained at this temperature for about 6 seconds, and then cooled at a rate of 20 ° C / sec. at room temperature.
  • a strip In order to obtain a matt surface appearance by using the annealing-pickling method, a strip, previously cold-rolled, is heated to a heating rate of 10 ° C., to bring it to a temperature of 1100 ° C. in a oven that is not isolated from the outside atmosphere. The strip is held at this temperature for about 5 seconds, then cooled at a rate of 20 ° C / sec to ambient, quenched in air, and then water. Finally, it is scoured by plunging in several electrolytic pickling baths and then based on hydrofluoric acid.
  • All baths have a constant temperature of 65 ° C.
  • Table 2 Gloss when the dew point is -45 ° C Bath A Bath A ' Bath B Shine through Br L 53.5 53 58 Observations of the surface shiny appearance shiny appearance shiny appearance
  • samples were taken from austenitic stainless steel strips of AISI 340 heat treated according to the invention in a bright annealing furnace.
  • each of the samples of the series is stripped by plunging them either in the pickling bath A for 16 s, or in the pickling bath B for 90 s.
  • All baths have a constant temperature of 65 ° C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Thermal Sciences (AREA)
  • Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
  • Heat Treatment Of Strip Materials And Filament Materials (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
  • Catalysts (AREA)
EP05736552A 2004-03-25 2005-03-09 Procede de production de bandes en acier inoxydable austenititique d'aspect de surface mat Active EP1735116B1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PL05736552T PL1735116T3 (pl) 2004-03-25 2005-03-09 Sposób ciągłego wytwarzania taśmy ze stali nierdzewnej austenitycznej o matowym wyglądzie powierzchni
SI200530274T SI1735116T1 (sl) 2004-03-25 2005-03-09 Postopek za pripravo trakov iz avstenitnega nerjavečega jekla z mat površino

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0403106A FR2867991B1 (fr) 2004-03-25 2004-03-25 Bandes en acier inoxydable austenitique d'aspect de surface mat
PCT/FR2005/000556 WO2005102548A1 (fr) 2004-03-25 2005-03-09 Procede de production de bandes en acier inoxydable austenititique d’aspect de surface mat

Publications (2)

Publication Number Publication Date
EP1735116A1 EP1735116A1 (fr) 2006-12-27
EP1735116B1 true EP1735116B1 (fr) 2008-03-19

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EP05736552A Active EP1735116B1 (fr) 2004-03-25 2005-03-09 Procede de production de bandes en acier inoxydable austenititique d'aspect de surface mat

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US (1) US7914630B2 (ja)
EP (1) EP1735116B1 (ja)
JP (1) JP4607951B2 (ja)
KR (1) KR101042872B1 (ja)
CN (1) CN100409957C (ja)
AT (1) ATE389470T1 (ja)
BR (1) BRPI0509222A (ja)
DE (1) DE602005005462T2 (ja)
ES (1) ES2306136T3 (ja)
FR (1) FR2867991B1 (ja)
PL (1) PL1735116T3 (ja)
SI (1) SI1735116T1 (ja)
WO (1) WO2005102548A1 (ja)

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JP6081224B2 (ja) * 2013-02-27 2017-02-15 東洋鋼鈑株式会社 表面処理鋼板の製造方法
EP2878708A1 (en) * 2013-11-28 2015-06-03 Linde Aktiengesellschaft Method for the modification of the surface structure of a metal body
JP6137089B2 (ja) * 2014-09-02 2017-05-31 Jfeスチール株式会社 冷延鋼板の製造方法および冷延鋼板の製造設備
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CN107385166A (zh) * 2017-06-27 2017-11-24 湖南大学 一种改善奥氏体不锈钢冷轧板的强塑性及耐蚀性的方法
JP7535054B2 (ja) * 2019-03-08 2024-08-15 ストラウマン ホールディング アーゲー 歯科用ドリルの表面処理
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CN110170526B (zh) * 2019-04-26 2020-09-18 无锡华生精密材料股份有限公司 汽缸垫不锈钢带的生产方法
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CN116917546A (zh) * 2021-03-26 2023-10-20 杰富意钢铁株式会社 退火酸洗钢板的制造方法
CN113492153B (zh) * 2021-07-16 2023-01-31 山西太钢不锈钢股份有限公司 一种奥氏体不锈钢的轧制方法和电子元件用奥氏体不锈钢

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US7914630B2 (en) 2011-03-29
ES2306136T3 (es) 2008-11-01
JP4607951B2 (ja) 2011-01-05
US20070181230A1 (en) 2007-08-09
KR101042872B1 (ko) 2011-06-20
JP2007530282A (ja) 2007-11-01
BRPI0509222A (pt) 2007-09-04
ATE389470T1 (de) 2008-04-15
SI1735116T1 (sl) 2008-08-31
KR20070000498A (ko) 2007-01-02
FR2867991B1 (fr) 2007-05-04
DE602005005462D1 (de) 2008-04-30
PL1735116T3 (pl) 2008-08-29
DE602005005462T2 (de) 2009-04-09
CN100409957C (zh) 2008-08-13
EP1735116A1 (fr) 2006-12-27
CN1946493A (zh) 2007-04-11
FR2867991A1 (fr) 2005-09-30

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