EP1008676A2 - Procédé accéléré de décapage de bandes en acier et Stahlbandes et dispositif pour exécuter le procédé - Google Patents

Procédé accéléré de décapage de bandes en acier et Stahlbandes et dispositif pour exécuter le procédé Download PDF

Info

Publication number
EP1008676A2
EP1008676A2 EP99830766A EP99830766A EP1008676A2 EP 1008676 A2 EP1008676 A2 EP 1008676A2 EP 99830766 A EP99830766 A EP 99830766A EP 99830766 A EP99830766 A EP 99830766A EP 1008676 A2 EP1008676 A2 EP 1008676A2
Authority
EP
European Patent Office
Prior art keywords
pickling
bath
tank
cell
pickling bath
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP99830766A
Other languages
German (de)
English (en)
Other versions
EP1008676A3 (fr
EP1008676B1 (fr
Inventor
Alessandro c/o C. Sviluppo Mat. S.p.A. Dulcetti
Armando c/o C. Sviluppo Mat. S.p.A. Giannetti
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rina Consulting Centro Sviluppo Materiali SpA
Original Assignee
Centro Sviluppo Materiali SpA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Centro Sviluppo Materiali SpA filed Critical Centro Sviluppo Materiali SpA
Publication of EP1008676A2 publication Critical patent/EP1008676A2/fr
Publication of EP1008676A3 publication Critical patent/EP1008676A3/fr
Application granted granted Critical
Publication of EP1008676B1 publication Critical patent/EP1008676B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G3/00—Apparatus for cleaning or pickling metallic material
    • C23G3/02—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously
    • C23G3/024—Apparatus for cleaning or pickling metallic material for cleaning wires, strips, filaments continuously by a combination of dipping and spraying

Definitions

  • the present invention relates to the continuous pickling in a non-oxidizing acid bath of hot-rolled strips of magnetic and stainless ferritic steels.
  • the state of the art substantially provides three possible interventions for obtaining pickled surfaces that are completely clean of oxides.
  • the first intervention comprises the use of non-oxidizing pickling baths with very lengthy immersion times.
  • the second possible intervention comprises the addition of hydrofluoric acid to the pickling bath.
  • the third type of intervention comprises the use of oxidizing baths with the entailed cost-effectiveness and environmental impact drawbacks.
  • none of those extremely aggressive methods can preserve the non-oxidized matrix of the underlying steel.
  • the adoption of the first type of intervention (anyhow including lengthy treatment times that entail negative repercussions on productivity) is hindered by the occurrence of inconveniences due to operational problems, whereas the adoption of the second and of the third type of intervention are hindered by cost-effectiveness and environmental protection reasons.
  • the present invention permits to satisfy this object, further showing other advantages that will be apparent hereinafter.
  • the present invention is related to a process for the continuous pickling, in a non-oxidizing acid bath, of hot-rolled steel strips, characterised in that the strip to be pickled is subject to the pickling action of the bath additioned with a pickling catalyst, under turbulent conditions.
  • the pickling catalyst is at least one organic compound including at least one thiolic group. Satisfactory results were obtained with an organic compound comprising at least one thiolic group selected from a list comprising thioglycolic acid, its ammonium chloride, and combinations thereof.
  • the concentration of the organic compound comprising a thiolic group inside the pickling bath is comprised in the range 0.005-0.01 moles/litre.
  • a further object of the present invention is a device apt to carry out the aforedescribed process.
  • This device is characterised in that it comprises the following components in combination:
  • the means for drawing the pickling bath from the tank and delivering it to the nozzles can be a pumping circuit.
  • the means for recirculating the pickling bath from the cell to the tank can be a slit-shaped overflow inside the cell from which the bath cascades into the tank.
  • the cell body can be monolithic and integral with the storage tank, or it can be made of two overlapped portions, the lower thereof being integral with the tank, whereas the upper thereof is integral with the cover of the tank, thus being movable.
  • the most important technical effect yielded by the invention is that of accelerating the mass transfer at the interface with the surface to be pickled, and in performing a mechanic action to ease the detachment of oxide residues therefrom.
  • the present invention can be applied to the conventional pickling baths inclusive of non-oxidizing acids, thereby increasing the pickling capacity thereof.
  • the invention can also be applied with reasonable costs to the extant immersion pickling lines in order to improve/accelerate the performances thereof.
  • the accelerating effect is most evident for oriented and nonoriented, hot-rolled, annealed or non annealed magnetic steels, and the annealed ferritic stainless steels (AISI 400).
  • the deriving combined effect permits to obtain for the magnetic steels, the quantity of dissolved material being equal, clean surfaces with 30 to 60% shortened immersion times, even in presence of internally oxidized zones that usually are not easily pickled.
  • the final performance being equal, the temperature and/or the acidity of the pickling bath can be decreased.
  • the yielded surfaces are clean of oxides, and smoother than the ones yielded by the non-additioned pickling systems.
  • Figure 1 is a schematic side view of an embodiment of the turbulence tank according to the present invention.
  • Figure 2 is a schematic front view of the embodiment of the turbulence tank according to the invention depicted in figure 1.
  • Figure 4 shows the weight loss values function of the pickling time, and the linear interpolation for an AISI 430 stainless steel, pickled in a pickling solution including sulphuric acid at 80°C, with and without the application of the present invention.
  • the closed storage tank containing the catalyst-additioned pickling bath is indicated with 1
  • the three cells in a sequence, having the top portion thereof integral to the movable cover 7 of the tank are indicated with 2, positioned above the free surface of the bath, inside which the strip to be pickled, guided by supporting rolls 4, travels horizontally.
  • the reference number 5 indicates submersed nozzles, located above and below the strip, positioned and shaped so as to feed under pressure the pickling bath to the cell, thereby creating a directional flow of the pickling solution itself that generates the required turbulent conditions.
  • the reference number 6 indicates the pumping circuit that draws the solution from the storage tank and delivers it to the nozzle batteries.
  • the pickling solution exits by the overflow from each cell through the slit 7 and cascades into the tank 1.
  • the concentration of the accelerating additive (thioglycolic acid) in the pickling solution is 0.005 moles/l.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
EP99830766A 1998-12-10 1999-12-09 Procédé accéléré de décapage de bandes en acier et dispositif pour exécuter le procédé Expired - Lifetime EP1008676B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITRM980761 1998-12-10
IT1998RM000761A IT1302912B1 (it) 1998-12-10 1998-12-10 Procedimento accelerato per il decapaggio di nastri d'acciaio edispositivo per realizzarlo.

Publications (3)

Publication Number Publication Date
EP1008676A2 true EP1008676A2 (fr) 2000-06-14
EP1008676A3 EP1008676A3 (fr) 2000-11-08
EP1008676B1 EP1008676B1 (fr) 2004-05-26

Family

ID=11406249

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99830766A Expired - Lifetime EP1008676B1 (fr) 1998-12-10 1999-12-09 Procédé accéléré de décapage de bandes en acier et dispositif pour exécuter le procédé

Country Status (4)

Country Link
EP (1) EP1008676B1 (fr)
AT (1) ATE267893T1 (fr)
DE (1) DE69917569D1 (fr)
IT (1) IT1302912B1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003099573A1 (fr) * 2002-05-29 2003-12-04 Yoon-Soo Cho Procede et appareil de transfert automatique d'un motif sur la surface d'un volant
WO2003104500A1 (fr) * 2002-06-06 2003-12-18 Le Four Industriel Belge Dispositif de refroidissement et/ou de rinçage de fils et/ou rubans en acier
WO2004055240A1 (fr) * 2002-12-18 2004-07-01 Le Four Industriel Belge Procede et dispositif de decapage de fils et/ou rubans metalliques
US8128754B2 (en) 2008-11-14 2012-03-06 Ak Steel Properties, Inc. Ferric pickling of silicon steel
CN102764720A (zh) * 2012-06-27 2012-11-07 中冶南方工程技术有限公司 一种热轧不锈钢炉前氯化盐溶液喷涂装置
EP3967789A1 (fr) * 2020-09-11 2022-03-16 Centre de Recherches Métallurgiques ASBL - Centrum voor Research in de Metallurgie VZW Procédé de décapage ultrarapide et installation associée

Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1780594A (en) * 1929-10-09 1930-11-04 Grasselli Chemical Co Acid treatment of metal articles
GB2031036B (en) * 1978-10-10 1982-11-03 Midland Ross Corp Liquid trestment of metal strip
JPS605888A (ja) * 1983-06-23 1985-01-12 Mitsubishi Heavy Ind Ltd 酸化鉄スケ−ルの化学的洗浄法
DE3629894A1 (de) * 1986-08-29 1988-03-03 Mannesmann Ag Anlage zur oberflaechenbehandlung von kontinuierlich durchlaufenden baendern, insbesondere beizanlage
JPH01168883A (ja) * 1987-12-24 1989-07-04 Sumitomo Chem Co Ltd 酸化鉄スケールの溶解除去剤
JP3064080B2 (ja) * 1991-01-16 2000-07-12 三菱重工業株式会社 噴流酸洗装置
JP2588646B2 (ja) * 1991-05-14 1997-03-05 新日本製鐵株式会社 鋼質金属の高速酸洗方法
DE4240572A1 (de) * 1992-12-03 1994-06-09 Schloemann Siemag Ag Beizanlage und Verfahren zum Betreiben der Beizanlage
US5879465A (en) * 1996-12-20 1999-03-09 Mckevitt; Patrick Method and apparatus for descaling hot rolled stainless steel strip

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2003099573A1 (fr) * 2002-05-29 2003-12-04 Yoon-Soo Cho Procede et appareil de transfert automatique d'un motif sur la surface d'un volant
WO2003104500A1 (fr) * 2002-06-06 2003-12-18 Le Four Industriel Belge Dispositif de refroidissement et/ou de rinçage de fils et/ou rubans en acier
BE1014869A3 (fr) * 2002-06-06 2004-05-04 Four Industriel Belge Dispositif de refroidissement et/ou de rincage de fils et/ou
US7404923B2 (en) 2002-06-06 2008-07-29 Le Four Industriel Belge Device for cooling and/or rinsing steel wires and/or tapes
WO2004055240A1 (fr) * 2002-12-18 2004-07-01 Le Four Industriel Belge Procede et dispositif de decapage de fils et/ou rubans metalliques
BE1015255A3 (fr) * 2002-12-18 2004-12-07 Four Industriel Belge Procede et dispositif de decapage de fils et/ou rubans metalliques.
US8128754B2 (en) 2008-11-14 2012-03-06 Ak Steel Properties, Inc. Ferric pickling of silicon steel
CN102764720A (zh) * 2012-06-27 2012-11-07 中冶南方工程技术有限公司 一种热轧不锈钢炉前氯化盐溶液喷涂装置
EP3967789A1 (fr) * 2020-09-11 2022-03-16 Centre de Recherches Métallurgiques ASBL - Centrum voor Research in de Metallurgie VZW Procédé de décapage ultrarapide et installation associée
WO2022053515A1 (fr) 2020-09-11 2022-03-17 Centre De Recherche Metallurgiques Asbl -Centrum Voor Research In De Metallurgie Vzw Procédé de décapage ultrarapide et installation associée

Also Published As

Publication number Publication date
ITRM980761A1 (it) 2000-06-10
DE69917569D1 (de) 2004-07-01
IT1302912B1 (it) 2000-10-10
EP1008676A3 (fr) 2000-11-08
ITRM980761A0 (it) 1998-12-10
ATE267893T1 (de) 2004-06-15
EP1008676B1 (fr) 2004-05-26

Similar Documents

Publication Publication Date Title
Li et al. Mechanism of single and multiple step pickling of 304 stainless steel in acid electrolytes
EP0582121B1 (fr) Procédé de décapage et de passivation d'acier inoxydable sans utilisation d'acide nitrique
EP0776993B1 (fr) Procédé de décapage d'acier
EP1008676B1 (fr) Procédé accéléré de décapage de bandes en acier et dispositif pour exécuter le procédé
KR20140053322A (ko) 도금 습윤성 및 도금 밀착성이 우수한 용융 아연 도금층을 구비한 강판과 그 제조 방법
FI81126C (fi) Foerfarande foer betning av produkter av rostfritt staol.
US20170268114A1 (en) Method and system of treating a stainless steel strip, especially for a pickling treatment
EP1381714A1 (fr) Technique de decapage au peroxyde d'hydrogene pour aciers inoxydables
GB2035379A (en) Continuous pickling of steel sheet
CN104024476B (zh) 化成处理性和涂装后耐腐蚀性优异的冷轧钢板的制造方法
US6149744A (en) Method of making austenitic stainless steel sheet
CN105431574B (zh) 酸洗高铬铁素体不锈钢的方法
US20140342182A1 (en) Galvannealed steel sheet having high corrosion resistance after painting
JPS6056418B2 (ja) 溶融亜鉛メツキ鋼板の製造法
JPS63216986A (ja) 低Ｃｒ鋼の高速酸洗方法
CN106835159B (zh) 一种中高铬不锈钢冷轧卷的连续酸洗方法及酸洗液
JPH0121240B2 (fr)
JPH01165783A (ja) ステンレス鋼帯用酸洗浴の更新方法
KR960004787B1 (ko) 마르텐사이트계 스테인레스강대의 스케일 제거방법
JP3078456B2 (ja) 高張力溶融亜鉛めっき鋼板の製造方法
JPS602392B2 (ja) ＮＯｘ発生を抑制したステンレス鋼の酸洗方法
JPWO2006106999A1 (ja) 溶融めっき熱延鋼板の製造方法
JPH11279781A (ja) 表面に模様のないオーステナイト系ステンレス鋼板の製造方法
JPS63192882A (ja) 連続酸洗方法
Karner et al. Modern pickling and acid regeneration technology

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A2

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

PUAL Search report despatched

Free format text: ORIGINAL CODE: 0009013

AK Designated contracting states

Kind code of ref document: A3

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

AX Request for extension of the european patent

Free format text: AL;LT;LV;MK;RO;SI

17P Request for examination filed

Effective date: 20010504

AKX Designation fees paid

Free format text: AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

17Q First examination report despatched

Effective date: 20030401

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LI LU MC NL PT SE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040526

Ref country code: LI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040526

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRE;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.SCRIBED TIME-LIMIT

Effective date: 20040526

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040526

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040526

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040526

Ref country code: CH

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040526

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040526

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040526

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 69917569

Country of ref document: DE

Date of ref document: 20040701

Kind code of ref document: P

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040826

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040826

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040826

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040827

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20040906

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041209

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041209

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041209

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041231

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20050301

EN Fr: translation not filed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20041209

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20041026