EP0505606A1 - Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Verwendung von Salpetersäure - Google Patents

Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Verwendung von Salpetersäure Download PDF

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Publication number
EP0505606A1
EP0505606A1 EP91113628A EP91113628A EP0505606A1 EP 0505606 A1 EP0505606 A1 EP 0505606A1 EP 91113628 A EP91113628 A EP 91113628A EP 91113628 A EP91113628 A EP 91113628A EP 0505606 A1 EP0505606 A1 EP 0505606A1
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EP
European Patent Office
Prior art keywords
bath
pickling
h2so4
stainless steel
acid
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
EP91113628A
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English (en)
French (fr)
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EP0505606B1 (de
EP0505606B2 (de
Inventor
Marco Bianchi
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Henkel AG and Co KGaA
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ITB Srl
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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
    • 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
    • C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
    • 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

Definitions

  • a pickling system which does not involve the use of nitric acid is therefore of considerable industrial interest and various proposals have been advanced in this respect throughout the world, especially during the last ten years.
  • the process is based on the use of a pickling bath containing ferric ions, H2SO4, HF, H2O2 and conventional additives such as wetting agents, emulsifiers, brighteners and anticorrosives, into which a strong air flow is continuously blown.
  • the operating temperature is generally between 30 and 70°C and preferably between 45 and 55°C.
  • the basic characteristics of the process are as follows: Inorganic mineral acid content of the bath: on preparing the pickling bath a solution is prepared containing at least 150 g/l and preferably about 170 g/l of H2SO4, and at least 40 g/l and preferably about 50 g/l of HF.
  • These acids have various functions, of which the most important are to maintain the process pH at less than 1 and preferably between 0 and 0.5, to solubilize the oxides originating from the heat treatment, and, in the case of the hydrofluoric acid, to complex the Fe3+ and Cr3+ ions to the maximum extent.
  • Fe3+ ion content of the bath on preparing the bath, an Fe3+ ion quantity of not less than 15 g/l is introduced into the pickling solution in the form of ferric sulphate.
  • the function of this ion is to replace nitric acid as oxidizing agent in the reaction 2Fe3+ + Fe ---> 3Fe2+, favoured by the bath pH conditions.
  • the correct conditions for maximizing the ferric rather than ferrous form for the iron dissolved in the bath must be continuously created.
  • the quantity of hydrogen peroxide consumed must be as small as possible. For this reason it is important to use hydrogen peroxide containing a known stabilizer effective in preventing or at least substantially retarding peroxide decomposition under the operation conditions (temperature up to 70°C, very acid bath pH, iron up to 100 g/l, presence of Ni and Cr ions).
  • a particularly suitable stabilizer is that marketed by Interox (Laporte-Solvay) under the name Interox S 333 or Interox S 333C.
  • the use of suitably stabilized H2O2 in combination with the use of air blown into the bath as complementary oxidation medium has resulted in a process in which the use of H2O2 is economically convenient, this never having been possible with known processes.
  • the pickling bath is prepared with an H2O2 concentration of between 1 and 20 g/l, and preferably 2-5 g/l.
  • the continuous H2O2 feed is regulated on the basis of the type of steel to be pickled, the surface characteristics of the material (or semi-finished product), and the quantity and quality of scale resulting from rolling or annealing. Generally an H2O2 quantity of between 0.3 and 1 g/l of bath per hour of operation is fed.
  • a continuous air flow into the bath is maintained at a rate of at least 3 m3/m3 of bath per hour of operation.
  • This air flow if fed in at a suitable speed, contributes to good bath agitation, this being an important condition for effective pickling as it continuously disturbs the laminar layer in proximity to the surface to be treated, hence ensuring that this surface is always in direct contact with a fresh pickling solution.
  • the blown air also oxidises the ferrous ions in combination with the hydrogen peroxide, so resulting in a considerable reduction in the consumption of this latter.
  • Control of Redox potential it is well known that the behaviour of stainless steel in acid mixtures is characterised by polarization curves which present activity, passivity and transpassivity phases for different potentials, so that the bath must be kept under those conditions in which the material does not corrode, ie the process must be operated at a potential falling within the passivity range, which can be predetermined based on the type of steel.
  • additives for this type of process are used, chosen from non-ionic surfactants acting as wetting agents, emulsifiers, brighteners and acid attack inhibitors. These additives, by mutual synergic action, improve and favour the pickling action. They are used in a total quantity of about 1 g/l of bath.
  • the process according to the invention reduces to a minimum or even prevents sludge formation with consequent further cost saving.
  • This advantage is due inter alia to an appropriate HF concentration during the process and to proper control of the concentration of ferrous ions, which are immediately and adequately oxidized to ferric ions.
  • facility for automatic control the process can be constantly controlled by automatic equipment which on the basis of analytical measurements (free and total acid, free fluoride ion content, bivalent ferrous ion content, Redox potential) meter the quantities of pickling products and stabilized hydrogen peroxide to be fed to achieve correct operating parameters.
  • analytical measurements free and total acid, free fluoride ion content, bivalent ferrous ion content, Redox potential
  • Process versatility the process of the invention is easily adaptable to all industrial stainless steel treatment plants, requiring only modest modification. It is also suitable for treating articles and semifinished products of any type, including wire, rod, strip, plate and tubes, the treatment parameters (temperature, time, concentrations) being able to undergo variation without in any way prejudicing results.
  • the process is suitable for steel of any type: martensitic, ferritic, anstenitic.
  • 70 t of steel rod of average diameter 6 mm equivalent to about 5000 m2 of the following materials: AISI 303, AISI 304 L, AISI 304 K, AISI 304 K2, AISI 316 L, AISI 316 R, AISI 316 Ti and AISI 430, were treated in an industrial tank with a useful bath capacity of 5 m3.
  • the initial pickling bath had the following composition: 172 g/l of H2SO4 48 g/l of HF 15 g/l of Fe3+ 5 g/l of H2O2 2 g/l of H2O2 stabilizer 1 g/l of miscellaneous additives.
  • the hydrogen peroxide stabilizer was Interox S 333 of Laporte Interox.
  • the additives consisted of non-ionic surfactants and acid attack inhibitors of known type for pickling baths.
  • the initially measured Redox potential was about 700 mV.
  • H2SO4 was added at intervals to a total of 340 kg, as were HF to a total of 460 kg and additives of the aforesaid type to a total of 25 kg.
  • the bath temperature was maintained between 50 and 60°C and the air flow at 30 m3/h.
  • the treatment time varied between 40 and 75 minutes according to the type of steel treated, with pickling kinetics similar to if not in various cases better than those of the traditional process based on nitric acid and hydrofluoric acid, which was simultaneously compared in a parallel tank.
  • the Redox potential measured periodically, remained between 350 and 450 mV, hence ensuring optimum surface finish of the material treated.
  • the total iron content was about 100 g/l with an Fe3+ content of 60 g/l and an Fe2+ content of 40 g/l.
  • Tests were carried out on AISI 303, AISI 304 and AISI 316 strip and plate in an industrial plant using the process of the invention and the traditional process for comparison.
  • the useful bath capacity of the 2nd and 3rd tank was each 10,000 litres.
  • the ratio of the material quantity used to the test tank capacity was equal to that of normal industrial cycles.
  • the temperature was fixed at 50°C and the treatment time varied from 30 to 60 minutes depending on the type of material.
  • the new stainless steel pickling and passivation process characterised by a bath of specific composition, control of the bath during the entire operation, in particular of its Redox potential, and continuous air blowing, represents an optimum solution in terms of the technical result of the treatment, process economy (in particular due to the low H2O2 consumption), and the pollution problem posed by traditional nitric acid processes.
EP91113628A 1991-03-29 1991-08-14 Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Verwendung von Salpetersäure Expired - Lifetime EP0505606B2 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
ITMI910879A IT1245594B (it) 1991-03-29 1991-03-29 Processo di decapaggio e di passivazione di acciaio inossidabile senza acido nitrico
ITMI910879 1991-03-29

Publications (3)

Publication Number Publication Date
EP0505606A1 true EP0505606A1 (de) 1992-09-30
EP0505606B1 EP0505606B1 (de) 1995-11-02
EP0505606B2 EP0505606B2 (de) 2003-02-26

Family

ID=11359360

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91113628A Expired - Lifetime EP0505606B2 (de) 1991-03-29 1991-08-14 Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Verwendung von Salpetersäure

Country Status (9)

Country Link
EP (1) EP0505606B2 (de)
JP (1) JP2655770B2 (de)
AT (1) ATE129753T1 (de)
DE (2) DE505606T1 (de)
DK (1) DK0505606T3 (de)
ES (1) ES2082063T5 (de)
FI (1) FI101234B (de)
GR (1) GR3018681T3 (de)
IT (1) IT1245594B (de)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0582121A1 (de) * 1992-08-06 1994-02-09 Itb S.R.L. Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Verwendung von Salpetersäure
DE4237021C1 (de) * 1992-11-02 1994-02-10 Poligrat Gmbh Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels
EP0592892A1 (de) * 1992-10-12 1994-04-20 Itb S.R.L. Verfahren zum kontinuierlichen Beizen und Passivieren von Titanbleche ohne Verwendung von Salpetersäure
DE4417284A1 (de) * 1993-05-24 1994-12-01 Mannesmann Ag Verfahren zum Beizen von Werkstücken aus hochlegierten Werkstoffen
EP0769575A1 (de) * 1995-10-18 1997-04-23 NOVAMAX ITB s.r.l. Beiz- und Passivierungsverfahren für rostfreien Stahl ohne Salpetersäure
EP0776256A1 (de) * 1994-09-26 1997-06-04 Calgon Vestal, Inc. Säurebehandlung von rostfreiem stahl
FR2745301A1 (fr) * 1996-02-27 1997-08-29 Usinor Sacilor Procede de decapage d'une piece en acier et notamment d'une bande de tole en acier inoxydable
FR2772050A1 (fr) * 1997-12-10 1999-06-11 Imphy Sa Procede de decapage d'acier et notamment d'acier inoxydable
WO1999031296A1 (de) * 1997-12-12 1999-06-24 Henkel Kommanditgesellschaft Auf Aktien Verfahren zum beizen und passivieren von edelstahl
EP0974682A1 (de) * 1998-07-18 2000-01-26 Henkel Kommanditgesellschaft auf Aktien Verfahren zur chemischen Behandlung von Metalloberflächen und dazu geeignete Anlage
US6565735B1 (en) 1998-09-11 2003-05-20 Henkel Kommanditgesellschaft Auf Aktien Process for electrolytic pickling using nitric acid-free solutions
WO2003044244A1 (de) * 2001-11-22 2003-05-30 Sms Demag Aktiengesellschaft Verfahren und vorrichtung zum behandeln der oberflächen eines metallstrangs, insbesondere zum beizen eines stahlbandes
WO2004035861A1 (en) * 2002-10-15 2004-04-29 Henkel Kommanditgesellschaft Auf Aktien Pickling or brightening/passivating solution and process for steel and stainless steel
EP1793016A1 (de) * 2005-12-01 2007-06-06 Elpochem AG Polier- und Entgratungsmittel für Werkstücke aus Kohlenstoffstahl und Verfahren zum chemischen Polieren und Entgraten
GB2499000A (en) * 2012-02-02 2013-08-07 Henkel Ag & Co Kgaa Aqueous acidic pickling solution with hydroxylamine accelerators
CN108220937A (zh) * 2018-01-18 2018-06-29 浙江苏泊尔股份有限公司 一种不锈钢工件抗高温变色的处理方法
US10392710B2 (en) 2012-12-11 2019-08-27 Henkel Ag & Co. Kgaa Brightening and passivation of stainless steel surfaces
CN113906162A (zh) * 2020-01-09 2022-01-07 普锐特冶金技术日本有限公司 钢板的酸洗方法及酸洗装置

Families Citing this family (7)

* Cited by examiner, † Cited by third party
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IT1303814B1 (it) * 1998-12-02 2001-02-23 Henkel Kgaa Apparecchiatura e metodo per controllare processi di decapaggio peracciaio.
DE10160318A1 (de) 2001-12-07 2003-06-18 Henkel Kgaa Verfahren zum Beizen von martensitischem oder ferritischem Edelstahl
KR100936348B1 (ko) * 2007-12-21 2010-01-12 주식회사 포스코 저 크롬계 스테인레스강의 고내식성 표면처리용액 조성물 및 이를 이용한 스테인레스강의 부동태 처리방법
CN102337548B (zh) * 2011-09-14 2012-12-05 西部钛业有限责任公司 一种钛、锆材的无酸雾酸洗方法
DE102012024542A1 (de) * 2012-12-14 2014-06-18 Poligrat Gmbh Thixotropes Beizmittel
JP6526406B2 (ja) * 2014-12-10 2019-06-05 株式会社Ihi ステンレス鋼部品の不動態化処理方法及びステンレス鋼部品用の不動態化処理液
JP6592624B2 (ja) * 2019-01-15 2019-10-16 株式会社Ihi ステンレス鋼部品の不動態化処理方法及びステンレス鋼部品用の不動態化処理液

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GB2000196A (en) * 1977-06-24 1979-01-04 Tokai Electro Chemical Co Controlling stainless steel pickling solution by hydrogen peroxide and sulphuric acid addition
EP0188975A1 (de) * 1985-01-22 1986-07-30 S.A. Ugine Verfahren zum säuren Beizen von Stahlen, insbesondere von rostfreien Stahlen

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JPS5442850A (en) * 1977-09-10 1979-04-05 Kubota Ltd Method of treating raw sewage
JPS5551514A (en) * 1978-10-12 1980-04-15 Osaka Cement Steel fiber mixing method and its device
JPS568109A (en) * 1979-07-03 1981-01-27 Toshikazu Iwasaki Reflecting telescope
FR2587369B1 (fr) * 1985-09-19 1993-01-29 Ugine Gueugnon Sa Procede de decapage acide de produits en acier inoxydable

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2000196A (en) * 1977-06-24 1979-01-04 Tokai Electro Chemical Co Controlling stainless steel pickling solution by hydrogen peroxide and sulphuric acid addition
EP0188975A1 (de) * 1985-01-22 1986-07-30 S.A. Ugine Verfahren zum säuren Beizen von Stahlen, insbesondere von rostfreien Stahlen

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* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 11, no. 80 (C-409)(2527) 11 March 1987 & JP-A-61 235 581 (C UYEMURA AND CO LTD) 20 October 1986 *
PATENT ABSTRACTS OF JAPAN vol. 6, no. 106 (C-108)(984) 16 June 1982 & JP-A-57 035 686 (KAWASAKI SEITETSU K.K.) 26 February 1982 *

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0582121A1 (de) * 1992-08-06 1994-02-09 Itb S.R.L. Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Verwendung von Salpetersäure
EP0592892A1 (de) * 1992-10-12 1994-04-20 Itb S.R.L. Verfahren zum kontinuierlichen Beizen und Passivieren von Titanbleche ohne Verwendung von Salpetersäure
DE4237021C1 (de) * 1992-11-02 1994-02-10 Poligrat Gmbh Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels
EP0596273A1 (de) * 1992-11-02 1994-05-11 POLIGRAT Holding GmbH Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels
DE4417284A1 (de) * 1993-05-24 1994-12-01 Mannesmann Ag Verfahren zum Beizen von Werkstücken aus hochlegierten Werkstoffen
DE4417284C2 (de) * 1993-05-24 1999-03-25 Alfred Schmitz Verfahren zum Beizen von Werkstücken aus hochlegierten Werkstoffen
EP0776256A1 (de) * 1994-09-26 1997-06-04 Calgon Vestal, Inc. Säurebehandlung von rostfreiem stahl
EP0776256A4 (de) * 1994-09-26 1998-05-20 Squibb & Sons Inc Säurebehandlung von rostfreiem stahl
US5843240A (en) * 1995-10-18 1998-12-01 Novamax Itb S.R.L. Process for stainless steel pickling and passivation without using nitric acid
EP0769575A1 (de) * 1995-10-18 1997-04-23 NOVAMAX ITB s.r.l. Beiz- und Passivierungsverfahren für rostfreien Stahl ohne Salpetersäure
FR2745301A1 (fr) * 1996-02-27 1997-08-29 Usinor Sacilor Procede de decapage d'une piece en acier et notamment d'une bande de tole en acier inoxydable
EP0792949A1 (de) * 1996-02-27 1997-09-03 USINOR SACILOR Société Anonyme Verfahren zum Beizen von Stahlwerkstücken, insbesondere Blechband aus rostfreiem Stahl
US5851304A (en) * 1996-02-27 1998-12-22 Usinor Sacilor Process for pickling a piece of steel and in particular a sheet strip of stainless steel
US5992196A (en) * 1996-02-27 1999-11-30 Usinor Process for pickling a piece of steel and in particular a sheet strip of stainless steel
EP0922787A1 (de) * 1997-12-10 1999-06-16 Imphy S.A. Verfahren zum Beizen von rostfreiem Stahl
FR2772050A1 (fr) * 1997-12-10 1999-06-11 Imphy Sa Procede de decapage d'acier et notamment d'acier inoxydable
WO1999031296A1 (de) * 1997-12-12 1999-06-24 Henkel Kommanditgesellschaft Auf Aktien Verfahren zum beizen und passivieren von edelstahl
EP0974682A1 (de) * 1998-07-18 2000-01-26 Henkel Kommanditgesellschaft auf Aktien Verfahren zur chemischen Behandlung von Metalloberflächen und dazu geeignete Anlage
US6171409B1 (en) 1998-07-18 2001-01-09 Henkel Kommanditgesellschaft Auf Aktien Process for the chemical treatment of metal surfaces and installation suitable therefor
US6565735B1 (en) 1998-09-11 2003-05-20 Henkel Kommanditgesellschaft Auf Aktien Process for electrolytic pickling using nitric acid-free solutions
WO2003044244A1 (de) * 2001-11-22 2003-05-30 Sms Demag Aktiengesellschaft Verfahren und vorrichtung zum behandeln der oberflächen eines metallstrangs, insbesondere zum beizen eines stahlbandes
US8192556B2 (en) 2002-10-15 2012-06-05 Henkel Kgaa Pickling or brightening/passivating solution and process for steel and stainless steel
WO2004035861A1 (en) * 2002-10-15 2004-04-29 Henkel Kommanditgesellschaft Auf Aktien Pickling or brightening/passivating solution and process for steel and stainless steel
EP1793016A1 (de) * 2005-12-01 2007-06-06 Elpochem AG Polier- und Entgratungsmittel für Werkstücke aus Kohlenstoffstahl und Verfahren zum chemischen Polieren und Entgraten
GB2499000A (en) * 2012-02-02 2013-08-07 Henkel Ag & Co Kgaa Aqueous acidic pickling solution with hydroxylamine accelerators
WO2013113811A1 (en) 2012-02-02 2013-08-08 Henkel Ag & Co. Kgaa Use of nitrogen compounds in the pickling of stainless steel
US10392710B2 (en) 2012-12-11 2019-08-27 Henkel Ag & Co. Kgaa Brightening and passivation of stainless steel surfaces
CN108220937A (zh) * 2018-01-18 2018-06-29 浙江苏泊尔股份有限公司 一种不锈钢工件抗高温变色的处理方法
CN113906162A (zh) * 2020-01-09 2022-01-07 普锐特冶金技术日本有限公司 钢板的酸洗方法及酸洗装置
EP3951014A4 (de) * 2020-01-09 2022-08-31 Primetals Technologies Japan, Ltd. Verfahren und vorrichtung zum beizen von stahlplatten
CN113906162B (zh) * 2020-01-09 2023-06-23 普锐特冶金技术日本有限公司 钢板的酸洗方法及酸洗装置

Also Published As

Publication number Publication date
ATE129753T1 (de) 1995-11-15
DK0505606T3 (da) 1995-12-04
IT1245594B (it) 1994-09-29
DE505606T1 (de) 1994-02-03
FI101234B (fi) 1998-05-15
EP0505606B1 (de) 1995-11-02
DE69114265D1 (de) 1995-12-07
JP2655770B2 (ja) 1997-09-24
JPH04304391A (ja) 1992-10-27
DE69114265T2 (de) 1996-04-18
ES2082063T3 (es) 1996-03-16
FI920580A (fi) 1992-09-30
ITMI910879A0 (it) 1991-03-29
ITMI910879A1 (it) 1992-09-29
DE69114265T3 (de) 2004-08-05
GR3018681T3 (en) 1996-04-30
ES2082063T5 (es) 2003-11-01
EP0505606B2 (de) 2003-02-26
FI920580A0 (fi) 1992-02-12

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