[go: up one dir, main page]

EP0960221B1 - Procede de decapage de produits constitues d'un alliage de metaux contenant du fer et de produits realises en titane ou en alliages de titane - Google Patents

Procede de decapage de produits constitues d'un alliage de metaux contenant du fer et de produits realises en titane ou en alliages de titane Download PDF

Info

Publication number
EP0960221B1
EP0960221B1 EP97949093A EP97949093A EP0960221B1 EP 0960221 B1 EP0960221 B1 EP 0960221B1 EP 97949093 A EP97949093 A EP 97949093A EP 97949093 A EP97949093 A EP 97949093A EP 0960221 B1 EP0960221 B1 EP 0960221B1
Authority
EP
European Patent Office
Prior art keywords
pickling
titanium
alloys
products made
solution
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.)
Expired - Lifetime
Application number
EP97949093A
Other languages
German (de)
English (en)
Other versions
EP0960221A1 (fr
Inventor
Franco Mancia
Sandro Fortunati
Ezio Novaro
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.)
Acciai Speciali Terni SpA
Original Assignee
Acciai Speciali Terni 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 Acciai Speciali Terni SpA filed Critical Acciai Speciali Terni SpA
Publication of EP0960221A1 publication Critical patent/EP0960221A1/fr
Application granted granted Critical
Publication of EP0960221B1 publication Critical patent/EP0960221B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C25F1/06—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
    • 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
    • C23G1/086—Iron or steel solutions containing HF
    • 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
    • C23G1/10—Other heavy metals
    • C23G1/106—Other heavy metals refractory metals
    • 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
    • C23G1/36—Regeneration of waste pickling liquors
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C25F1/08—Refractory metals

Definitions

  • the present invention relates to a method for pickling products made of stainless steel, which avoids the use of nitric acid as an oxidising agent.
  • the present invention can also be applied for pickling of titanium and alloys thereof.
  • pickling is the process used to remove the layer of oxidation that forms as a result of heat treating of steel.
  • nitric acid HNO 3
  • hydrofluoric acid HF
  • a method exists that foresees a reduction in the amount of nitrogen oxides NO x that are developed by the bath.
  • Said method is generally based on the use of hydrogen peroxide, which not only makes it possible, if necessary, to reduce the total amount of nitric acid in the bath and required for the process, but also to oxidise the nitrogen oxides to the highest state of oxidation.
  • Another method is known, the purpose of which is to eliminate the presence of nitric acid altogether, using sulphuric acid, ferric sulphate and hydrogen peroxide alongside the hydrofluoric acid, the presence of which remains practically unchanged in the processes examined here.
  • the aim of the present invention is therefore to solve the above mentioned problems, providing a method for pickling products made of stainless steel, and products made of titanium and alloys thereof, in the absence of nitric acid as an oxidising agent, wherein the product to be pickled is submerged in the pickling solution which forms the anolyte of an electrolytic cell in which the anolyte is made up of an aqueous solution of sulphuric acid, of hydrofluoric acid and optionally of phosphoric acid and hydrochloric acid, and with the catholyte made up of an aqueous solution of sulphuric acid, the oxidising agent in the pickling solution being the ferric ion, or the ions titanium(III) and titanium(IV), formed in the anode by oxidation of the ferrous ion, or of the ion titanium(II), resulting from dissolution of the surface layers of the product to be pickled, and the anodic reaction being potentiostatically controlled.
  • the catholyte of the cell is preferably made up of an aqueous solution of sulphuric acid and is send out of the cathodic compartment into the pickling solution, to reintegrate the H 2 SO 4 that is consumed during the pickling reaction.
  • the pickling bath forms the anolyte of the cell, and is maintained at a temperature preferably comprised between 45 and 85°C, and it is made up of an aqueous solution of sulphuric acid, of hydrofluoric acid and optionally of hydrochloric and phosphoric acid, with the following composition expressed as a percentage by weight:
  • products containing iron for which the method according to the present invention is applicable are selected from the group comprising:
  • products containing titanium for which the method according to the present invention is applicable are selected from the group comprising:
  • the method object of the present invention is based on the replacement of nitric acid and on the theory that this acid performs two basic operations:
  • the overall action of the nitric acid can thus be obtained using various reagents capable of guaranteeing these two specific actions, even separately.
  • the reagents selected to control the total acidity are therefore mineral acids and oxidising agents.
  • the method according to the present invention does not resort to direct addition of reagents into the bath, but uses electro-chemical treatment of the solution which generates the desired oxidising agent directly in the pickling bath.
  • the method object of the present invention is based on the used of a pickling bath that does not contain nitric acid, but contains in its place a mineral acid (for example sulphuric acid) and as an oxidant contains only the ferric ion Fe 3+ (or, in the case of titanium, the ions Ti 3+ and Ti 4+ ).
  • the ferric ion is not added in the form of a reagent, but is obtained directly in the pickling solution by anodic oxidation in an electrolytic cell of the ions Fe 2+ that are generated during the pickling process itself (dissolution of the steel).
  • anodic oxidation of the Ti 2+ ions to Ti 3+ and Ti 4+ ions is carried out in the cell.
  • FIG. 1 A diagram of a preferred embodiment of the method according to the invention is illustrated in figure 1.
  • an electro-chemical cell of the membrane type is used, worked by controlling the anodic potential or using a galvanostatic control.
  • the cell anolyte (in which the reaction generating Fe 3+ ions takes place) is made of the same solution as the pickling bath, whereas the catholyte used is a solution of sulphuric acid that is destined to be sent to the pickling bath.
  • the mineral acids used as anolyte are mixtures of hydrofluoric, sulphuric, hydrochloric and phosphoric acid.
  • the method provides a self-balancing system, that is to say one that is capable of controlling the process kinetics and the final quality of the product.
  • the pickling kinetics are in fact directly controllable according to the speed of production of Fe 3+ ions in the cell.
  • Control of the concentration of Fe 3+ ions in the pickling bath also allows close control of the most critical process parameter (that is to say the redox potential value of the system), also giving obvious advantages for the final quality of the product.
  • the pickling bath can conveniently use the following reagents:
  • the method object of the invention foresees electro-chemical treatment of the solution, by which it is possible to obtain direct formation of the oxidising agent and control of the correct concentration levels directly within the bath.
  • the same pickling solution is used, and is continuously circulated (but discontinuous treatment can also be foreseen) from the bath by pumping;
  • This reaction produces the Fe 3+ that serves to maintain the concentration of the oxidising agent Fe 3+ in the pickling bath constant.
  • the pickling mechanism in the presence of Fe 3+ as an oxidant takes place using the following reactions: (1) Fe ⁇ Fe 2+ + 2e (primary oxidation semi-reaction to dissolve the metallic iron); (2) Fe 3+ + e ⁇ Fe 2+ (reduction semi-reaction).
  • reaction (4) is the inverse reaction to (2).
  • the ion Fe 3+ reduces to Fe 2+ during (2) in the bath and oxidises again in the cell from Fe 2+ in (4).
  • the oxidising capacity of the system is thus guaranteed by passage of the anodic current in the cell in reaction (4), in which the ion Fe 3+ is a go-between and, according to the present method, no other reagents are added as oxidants.
  • reaction (7) and (4) would, in fact, decrease the efficiency of the cell, attenuating the undesired water hydrolysis reaction by developing oxygen.
  • the chosen potential E is thus in the range of between 771 and 1229 mV SHE.
  • chrome with valence 6 often toxic
  • the cell is provided with a suitable membrane. It is possible to use membranes of different effectiveness, working temperature and duration.
  • the electro-chemical cell in reference when tested in the system has provided the following performance levels, which are given below in the form of an example:
  • the anodic cell potential in this case is selected within the range of between -368 mV SHE (oxidation of Ti 2+ to Ti 4+ ) and 1229 mV SHE (development of oxygen).
  • the method according to a second embodiment of the invention foresees, for pickling of titanium and alloys thereof, the use of the same baths and acid solutions containing Fe 3+ that are used for pickling of stainless steel. This method is very convenient, because the majority of titanium coil manufacturers process these coils on the same lines used for stainless steel.
  • the ion Fe 3+ (and the ion Fe 2+ from which it is formed) does not participate in the overall reaction balance, so there is no consumption of the quantity of iron ions contained in the bath, whereas the oxidising capacity, in terms of electron transfer, is ensured by the passage of current to the cell anode.
  • the example of a pickling process refers to a coil of hot laminated and peened AISI 304 steel.
  • the initial pickling solution is made up of:
  • the pickling process commences (tape sent into the pickling bath) at the line speed foreseen.
  • the line speed, the thickness and the width of the treated tape obviously define the production level per hour, expressed in t/h of pickled tape (e.g. at a speed of 18 metres/minute, tape thickness 3.2 mm and width 1500 mm the production of pickled tape will be approximately 40 t/h).
  • the tape is 3.2 mm thick (typical average thickness of hot-laminated products).
  • the pickling bath can be made up of the anodic part of the cell, without the need to create external circulation of the anolyte between the bath and the cell.
  • the catholyte it is not necessarily essential to resort to solutions using sulphuric acid, as different electrolytes can be chosen (e.g. HCl, mixtures of HCl/H 2 SO 4 or others), including the pickling solution itself which is eliminated as waste. Input of the catholyte into the bath may also not be necessary, in particular when electrolytes other than those used in the pickling bath are chosen. All the above variations are alternatives to the one described and illustrated as the preferred embodiment, and are understood to fall within the scope of the present invention.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Electrochemistry (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
  • Refinement Of Pig-Iron, Manufacture Of Cast Iron, And Steel Manufacture Other Than In Revolving Furnaces (AREA)
  • Electrolytic Production Of Metals (AREA)

Claims (11)

  1. Procédé pour le décapage de produits réalisés à partir d'acier inoxydable ou de produits réalisés en titane ou en alliages de titane, en l'absence d'acide nitrique en tant qu'agent oxydant, dans lequel le produit à décaper est immergé dans la solution de décapage qui forme l'anolyte d'une cellule électrolytique, dans laquelle l'anolyte consiste en une solution aqueuse d'acide sulfurique, d'acide fluorhydrique et facultativement d'acide phosphorique et d'acide chlorhydrique, et avec le catholyte consistant en une solution aqueuse d'acide sulfurique, l'agent oxydant dans la solution de décapage étant l'ion ferrique, ou les ions titane (III) et titane (IV), formés dans la cathode par oxydation de l'ion ferreux, ou de l'ion titane (II), résultant de la dissolution des couches de surface du produit à décaper, et la réaction anodique étant contrôlée potentiostatiquement.
  2. Procédé pour le décapage de produits réalisés à partir d'acier inoxydable selon la revendication 1, dans lequel le potentiel électrochimique de travail de l'anode de cellule se situe entre 771 et 1299 mV SHE (Electrode d'hydrogène étalon).
  3. Procédé pour le décapage de produits réalisés en titane et en alliages de titane selon la revendication 1, dans lequel le potentiel électrochimique de travail de l'anode de cellule se situe entre -368 et 1229 mV SHE (Electrode d'hydrogène étalon).
  4. Procédé pour le décapage de produits réalisés en acier inoxydable, et de produits réalisés en titane et alliages de titane selon l'une quelconque des revendications précédentes, dans lequel les opérations de décapage sont exécutées d'une manière continue ou discontinue au moyen de la circulation continue ou discontinue de l'anolyte.
  5. procédé pour le décapage de produits réalisés en acier inoxydable, et de produits réalisés en titane et en alliages de titane selon la revendication précédente, dans lequel le bain de décapage contenant l'anolyte forme le compartiment anodique dans la cellule électrochimique.
  6. Procédé pour le décapage de produits réalisés en acier inoxydable, et de produits réalisés en titane et en alliages de titane selon l'une quelconque des revendications précédentes, dans lequel le catholyte de la cellule électrolytique consiste en une solution d'acide sulfurique et est envoyée, après avoir quitté le compartiment cathodique, dans la solution de décapage en tant qu'anolyte.
  7. Procédé selon la revendication précédente, dans lequel la solution de catholyte consiste en tout électrolyte pouvant être envoyé ou non dans l'anolyte.
  8. Procédé selon l'une quelconque des revendications précédentes, dans lequel le catholyte consiste en une solution de décapage et elle est consécutivement déchargée de la zone cathodique comme matière de déchet.
  9. Procédé pour le décapage de produits réalisés à partir d'acier inoxydable, et de produits réalisés en titane et en alliages de titane selon l'une quelconque des revendications précédentes, dans lequel le bain de décapage a une température entre 40 et 90 °C et consiste en une solution aqueuse contenant les composants suivants :
    HCL libre entre 0 et 50 g/l
    H3PO4 entre 0 et 200 g/l
    H2SO4 de 50 à 250 g/l
    HF libre de 5 à 50 g/l
    Fetot dans la solution > 50 g/l
    et en variante, pour des produits en titane et alliages de titane, Titot en solution > 50 g/l.
  10. Procédé pour le décapage de produits réalisés à partir d'acier inoxydable selon l'une quelconque des revendications 1,2 et 4-9, dans lequel lesdits produits réalisés en acier inoxydable sont choisis à partir du groupe comprenant :
    l'acier inoxydable, laminé ou en tout cas travaillé à chaud et/ou à froid; et
    des super alliages à base de Ni.
  11. Procédé pour le décapage de produits réalisés à partir du titane et en alliages de titane selon l'une quelconque des revendications 1,3 et 4-10, dans lequel lesdits produits contenant le titane et les alliages de titane sont choisis à partir du groupe comprenant :
    du Titane PC (pureté commerciale) de différentes qualités;
    des alliages de titane.
EP97949093A 1996-12-09 1997-12-05 Procede de decapage de produits constitues d'un alliage de metaux contenant du fer et de produits realises en titane ou en alliages de titane Expired - Lifetime EP0960221B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
ITRM960849 1996-12-09
IT96RM000849A IT1288407B1 (it) 1996-12-09 1996-12-09 Metodo per il decapaggio di prodotti in lega metallica contenente ferro e di titanio e sue leghe
PCT/IT1997/000300 WO1998026111A1 (fr) 1996-12-09 1997-12-05 Procede de decapage de produits constitues d'un alliage de metaux contenant du fer et de produits realises en titane ou en alliages de titane

Publications (2)

Publication Number Publication Date
EP0960221A1 EP0960221A1 (fr) 1999-12-01
EP0960221B1 true EP0960221B1 (fr) 2002-03-13

Family

ID=11404582

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97949093A Expired - Lifetime EP0960221B1 (fr) 1996-12-09 1997-12-05 Procede de decapage de produits constitues d'un alliage de metaux contenant du fer et de produits realises en titane ou en alliages de titane

Country Status (9)

Country Link
EP (1) EP0960221B1 (fr)
AT (1) ATE214436T1 (fr)
AU (1) AU7847898A (fr)
DE (1) DE69711090T2 (fr)
ES (1) ES2178023T3 (fr)
IT (1) IT1288407B1 (fr)
TW (1) TW451001B (fr)
WO (1) WO1998026111A1 (fr)
ZA (1) ZA9710983B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7611588B2 (en) 2004-11-30 2009-11-03 Ecolab Inc. Methods and compositions for removing metal oxides
CN103572303A (zh) * 2013-10-24 2014-02-12 奇瑞重工股份有限公司 一种钢材化学前处理方法及所用酸洗液

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1297076B1 (it) * 1997-11-24 1999-08-03 Acciai Speciali Terni Spa Metodo per il decapaggio di prodotti in acciaio
IT1302202B1 (it) 1998-09-11 2000-07-31 Henkel Kgaa Processo di decapaggio elettrolitico con soluzioni esenti da acidonitrico.
DE19850524C2 (de) * 1998-11-03 2002-04-04 Eilenburger Elektrolyse & Umwelttechnik Gmbh Nitratfreies Recycling-Beizverfahren für Edelstähle
AT406486B (de) * 1998-12-22 2000-05-25 Andritz Patentverwaltung Verfahren zum beizen von edelstahl
IT1312556B1 (it) * 1999-05-03 2002-04-22 Henkel Kgaa Processo di decapaggio di acciaio inossidabile in assenza di acidonitrico ed in presenza di ioni cloruro
ATE478975T1 (de) 2002-10-15 2010-09-15 Henkel Ag & Co Kgaa Lösung und verfahren zum beizen von rostfreiem stahl
EP1980650A1 (fr) * 2007-04-05 2008-10-15 Kerma S.A. Composition de décapage exempte de nitrates et de peroxydes, et procédé mettant en oeuvre une telle composition
CN111057935B (zh) * 2019-12-25 2021-04-02 浦项(张家港)不锈钢股份有限公司 一种耐热不锈钢的制备方法
CN113788520A (zh) * 2021-10-08 2021-12-14 北京首钢吉泰安新材料有限公司 一种铁铬铝酸洗的工艺及废水处理方法和废水处理装置

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS50133125A (fr) * 1974-04-10 1975-10-22
DE3937438C2 (de) * 1989-02-23 1998-01-29 Wilfried Simmer Verfahren zum Beizen von Stahl
FR2650303B1 (fr) * 1989-07-26 1993-12-10 Ugine Aciers Chatillon Gueugnon Procede de decapage en bain acide de produits metalliques contenant du titane ou au moins un element chimique de la famille du titane
JPH04362183A (ja) * 1991-06-07 1992-12-15 Nippon Paint Co Ltd アルミニウム表面洗浄浴の再生方法
IT1282979B1 (it) * 1996-05-09 1998-04-03 Novamax Itb S R L Procedimento per il decapaggio dell'acciaio nel quale la ossidazione dello ione ferroso formatosi viene effettuata per via elettrochimica

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7611588B2 (en) 2004-11-30 2009-11-03 Ecolab Inc. Methods and compositions for removing metal oxides
CN103572303A (zh) * 2013-10-24 2014-02-12 奇瑞重工股份有限公司 一种钢材化学前处理方法及所用酸洗液

Also Published As

Publication number Publication date
ATE214436T1 (de) 2002-03-15
TW451001B (en) 2001-08-21
DE69711090D1 (de) 2002-04-18
ITRM960849A0 (it) 1996-12-09
ITRM960849A1 (it) 1998-06-09
WO1998026111A1 (fr) 1998-06-18
IT1288407B1 (it) 1998-09-22
ZA9710983B (en) 1998-06-15
ES2178023T3 (es) 2002-12-16
AU7847898A (en) 1998-07-03
DE69711090T2 (de) 2003-07-24
EP0960221A1 (fr) 1999-12-01

Similar Documents

Publication Publication Date Title
US2337062A (en) Pickling solution and method
EP0960221B1 (fr) Procede de decapage de produits constitues d'un alliage de metaux contenant du fer et de produits realises en titane ou en alliages de titane
EP1115917B1 (fr) Procede de decapage electrolytique a l'aide de solutions exemptes d'acide nitrique
EP0505606B1 (fr) Procédé de décapage et de passivation de l'acier inoxydable sans utilisation de l'acide nitrique
CN1318652C (zh) 使用交流电源电解池的用于金属产品的连续电解酸洗方法
EP0972862A2 (fr) Procédé de fabrication d'un film à base de phosphate et sur des fils d'acier et dispositif
CN105431574B (zh) 酸洗高铬铁素体不锈钢的方法
US5690748A (en) Process for the acid pickling of stainless steel products
JP6031606B2 (ja) オーステナイト系ステンレス冷延鋼板を製造するための高速酸洗プロセス
US6221234B1 (en) Method for pickling products of a metal alloy in absence of nitric acid and for recovering exhausted pickling solutions and apparatus therefore
US6500328B1 (en) Method for pickling steel products
JPH04362183A (ja) アルミニウム表面洗浄浴の再生方法
EP1358367B1 (fr) Decapage et decalaminage par voie electrolytique continue de l'acier au carbone et de l'acier inoxydable
JPH05306497A (ja) リン酸塩化成処理方法
JP2000080497A (ja) 鋼線材にりん酸塩皮膜を迅速に形成する方法および装置
JP3256009B2 (ja) ぶりき材表面処理液及び表面処理方法
KR101353856B1 (ko) 오스테나이트계 스테인리스 냉연강판을 제조하기 위한 저온 고속 산세 프로세스
JPH03226599A (ja) ステンレス鋼板の脱スケール法
WO2002086199A2 (fr) Procede electrolytique continu realise dans une solution acide pour decalaminer des aciers inoxydables, en presence d'effets indirects d'un flux de courant
JPH0711080B2 (ja) 鋼質金属の高速電解溶解法
JPH0711079B2 (ja) 鋼質金属の高速陰極電解溶解法
JPH0466699A (ja) 焼鈍ステンレス鋼帯用脱スケール液の劣化防止方法

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

17P Request for examination filed

Effective date: 19990706

AK Designated contracting states

Kind code of ref document: A1

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

17Q First examination report despatched

Effective date: 20000405

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ACCIAI SPECIALI TERNI S.P.A.

RTI1 Title (correction)

Free format text: METHOD FOR PICKLING PRODUCTS OF A METAL ALLOY CONTAINING IRON AND OF TITANIUM AND ALLOYS THEREOF

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

RTI1 Title (correction)

Free format text: METHOD FOR PICKLING PRODUCTS OF A METAL ALLOY CONTAINING IRON AND OF TITANIUM AND ALLOYS THEREOF

GRAG Despatch of communication of intention to grant

Free format text: ORIGINAL CODE: EPIDOS AGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

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 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: 20020313

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: 20020313

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: 20020313

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: 20020313

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: 20020313

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: 20020313

REF Corresponds to:

Ref document number: 214436

Country of ref document: AT

Date of ref document: 20020315

Kind code of ref document: T

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

REF Corresponds to:

Ref document number: 69711090

Country of ref document: DE

Date of ref document: 20020418

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

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: 20020613

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 FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20020614

NLV1 Nl: lapsed or annulled due to failure to fulfill the requirements of art. 29p and 29m of the patents act
RAP2 Party data changed (patent owner data changed or rights of a patent transferred)

Owner name: THYSSENKRUPP ACCIAI SPECIALI TERNI S.P.A.

ET Fr: translation filed
REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

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: 20021205

Ref country code: IE

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

Effective date: 20021205

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20021211

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20021216

Year of fee payment: 6

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2178023

Country of ref document: ES

Kind code of ref document: T3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20021217

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20021218

Year of fee payment: 6

Ref country code: BE

Payment date: 20021218

Year of fee payment: 6

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20021220

Year of fee payment: 6

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

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20030130

Year of fee payment: 6

26N No opposition filed

Effective date: 20021216

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: 20030701

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: GB

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

Effective date: 20031205

Ref country code: FI

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

Effective date: 20031205

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 NON-PAYMENT OF DUE FEES

Effective date: 20031206

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 NON-PAYMENT OF DUE FEES

Effective date: 20031209

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

Ref country code: BE

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

Effective date: 20031231

REG Reference to a national code

Ref country code: FR

Ref legal event code: CD

BERE Be: lapsed

Owner name: *THYSSENKRUPP ACCIAI SPECIALI TERNI S.P.A.

Effective date: 20031231

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 NON-PAYMENT OF DUE FEES

Effective date: 20040701

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20031205

EUG Se: european patent has lapsed
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

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

Effective date: 20040831

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20031209