EP0505606B2 - Procédé de décapage et de passivation de l'acier inoxydable sans utilisation de l'acide nitrique - Google Patents

Procédé de décapage et de passivation de l'acier inoxydable sans utilisation de l'acide nitrique Download PDF

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Publication number
EP0505606B2
EP0505606B2 EP91113628A EP91113628A EP0505606B2 EP 0505606 B2 EP0505606 B2 EP 0505606B2 EP 91113628 A EP91113628 A EP 91113628A EP 91113628 A EP91113628 A EP 91113628A EP 0505606 B2 EP0505606 B2 EP 0505606B2
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EP
European Patent Office
Prior art keywords
bath
pickling
maintain
acid
stainless steel
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
EP91113628A
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German (de)
English (en)
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EP0505606A1 (fr
EP0505606B1 (fr
Inventor
Marco Bianchi
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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, H 2 SO 4 , HF, H 2 O 2 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:
  • Fe 3+ ion content of the bath on preparing the bath, an Fe 3+ 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 2Fe 3+ + Fe ---> 3Fe 2+ , 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 H 2 O 2 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 H 2 O 2 is economically convenient, this never having been possible with known processes.
  • the pickling bath is prepared with an H 2 O 2 concentration of between 1 and 20 g/l, and preferably 2-5 g/l.
  • the continuous H 2 O 2 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 H 2 O 2 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 m 3 /m 3 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, austenitic.
  • 70 t of steel rod of average diameter 6 mm equivalent to about 5000 m 2 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 m 3 .
  • the initial pickling bath had the following composition:
  • 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.
  • H 2 SO 4 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 m 3 /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 Fe 3+ content of 60 g/l and an Fe 2+ content of 40 g/l.
  • 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 H 2 O 2 consumption), and the pollution problem posed by traditional nitric acid processes.

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (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)
  • Medicines Containing Material From Animals Or Micro-Organisms (AREA)
  • Detergent Compositions (AREA)

Claims (3)

  1. Procédé de décapage et de passivation d'acier inoxydable consistant à porter le matériau à traiter au contact d'un bain maintenu à une température comprise entre 30 et 70°C, et de préférence entre 45 et 55°C, et ayant la composition initiale suivante :
    a) H2SO4 au moins 150 g/l
    b) Fe3+ au moins 15 g/l
    c) HF au moins 40 g/l
    d) H2O2 (contenant des stabilisants connus) 1-20 g/l, et de préférence 2-5 g/l.
    e) additifs du type surfactif non ionique (émulsifiants, agents mouillants, lustrants) et du type inhibiteur d'attaque acide : environ 1 g/l au total ;
       en introduisant de manière continue dans ledit bain :
    un courant d'air d'au moins 3 m3/h par m3 de bain, en utilisant un dispositif distributeur approprié pour diffuser le courant dans la masse liquide;
    une quantité d'H2O2 stabilisé comprise entre 0,3 et 1 g/l par heure, régulée sur la base du potentiel redox du bain, qui doit être maintenu à ≥ 350 mV;
    et le cas échéant des quantités suffisantes de l'ingrédient e) pour maintenir sa concentration dans le bain à un niveau optimum ;
    et des quantités suffisantes des ingrédients a) et c) étant périodiquement apportées pour maintenir leur concentration dans le bain à des niveaux optima sur la base de l'analyse du bain, c'est-à-dire les valeurs d'acide libre et d'ion fluorure, et pour maintenir le pH du bain à moins de 1, et de préférence entre 0 et 0,5.
  2. Procédé selon la revendication 1, dans lequel les ions Fe3+ sont introduits dans le bain initial sous forme de sulfate ferrique.
  3. Procédé selon la revendication 1, réalisé en combinaison avec l'élimination partielle préalable des oxydes par une procédé connu.
EP91113628A 1991-03-29 1991-08-14 Procédé de décapage et de passivation de l'acier inoxydable sans utilisation de l'acide nitrique Expired - Lifetime EP0505606B2 (fr)

Applications Claiming Priority (2)

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

Publications (3)

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

Family

ID=11359360

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91113628A Expired - Lifetime EP0505606B2 (fr) 1991-03-29 1991-08-14 Procédé de décapage et de passivation de l'acier inoxydable sans utilisation de l'acide nitrique

Country Status (9)

Country Link
EP (1) EP0505606B2 (fr)
JP (1) JP2655770B2 (fr)
AT (1) ATE129753T1 (fr)
DE (2) DE69114265T3 (fr)
DK (1) DK0505606T3 (fr)
ES (1) ES2082063T5 (fr)
FI (1) FI101234B (fr)
GR (1) GR3018681T3 (fr)
IT (1) IT1245594B (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012024542A1 (de) * 2012-12-14 2014-06-18 Poligrat Gmbh Thixotropes Beizmittel

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1255655B (it) * 1992-08-06 1995-11-09 Processo di decapaggio e passivazione di acciaio inossidabile senza impiego di acido nitrico
IT1255855B (it) * 1992-10-12 1995-11-17 Cesare Pedrazzini Processo di decapaggio e di passivazione per lamiere di titanio in nastro, senza impiego di acido nitrico.
DE4237021C1 (de) * 1992-11-02 1994-02-10 Poligrat Gmbh Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels
DE4417284C2 (de) * 1993-05-24 1999-03-25 Alfred Schmitz Verfahren zum Beizen von Werkstücken aus hochlegierten Werkstoffen
DE69534340T2 (de) * 1994-09-26 2006-04-20 Steris Inc., Temecula Säurebehandlung von rostfreiem stahl
IT1276954B1 (it) * 1995-10-18 1997-11-03 Novamax Itb S R L Processo di decapaggio e di passivazione di acciaio inossidabile senza impiego di acido nitrico
FR2745301B1 (fr) * 1996-02-27 1998-04-03 Usinor Sacilor Procede de decapage d'une piece en acier et notamment d'une bande de tole en acier inoxydable
FR2772050B1 (fr) * 1997-12-10 1999-12-31 Imphy Sa Procede de decapage d'acier et notamment d'acier inoxydable
DE19755350A1 (de) * 1997-12-12 1999-06-17 Henkel Kgaa Verfahren zum Beizen und Passivieren von Edelstahl
EP0974682A1 (fr) * 1998-07-18 2000-01-26 Henkel Kommanditgesellschaft auf Aktien Procédé et dispositif pour le traitement chimique des surfaces métalliques
IT1302202B1 (it) 1998-09-11 2000-07-31 Henkel Kgaa Processo di decapaggio elettrolitico con soluzioni esenti da acidonitrico.
IT1303814B1 (it) * 1998-12-02 2001-02-23 Henkel Kgaa Apparecchiatura e metodo per controllare processi di decapaggio peracciaio.
DE10157340A1 (de) * 2001-11-22 2003-05-28 Sms Demag Ag Verfahren und Vorrichtung zum Behandeln der Oberflächen eines Metallstrangs, insbesondere zum Beizen eines Stahlbandes
DE10160318A1 (de) 2001-12-07 2003-06-18 Henkel Kgaa Verfahren zum Beizen von martensitischem oder ferritischem Edelstahl
US8192556B2 (en) 2002-10-15 2012-06-05 Henkel Kgaa Pickling or brightening/passivating solution and process for steel and stainless steel
EP1793016A1 (fr) * 2005-12-01 2007-06-06 Elpochem AG Composition d'ébavurage et de polissage pour des objets en acier carbone et la méthode chimique d'ébavurage et de polissage
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
GB2499000A (en) 2012-02-02 2013-08-07 Henkel Ag & Co Kgaa Aqueous acidic pickling solution with hydroxylamine accelerators
GB2508827A (en) 2012-12-11 2014-06-18 Henkel Ag & Co Kgaa Aqueous compositions and processes for passivating and brightening stainless steel surfaces
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
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
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
US20220220619A1 (en) * 2020-01-09 2022-07-14 Primetals Technologies Japan, Ltd. Method for pickling steel plate and pickling apparatus

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JPS549120A (en) * 1977-06-24 1979-01-23 Tokai Electro Chemical Co Method of controlling acid cleaning liquid for stainless steel
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
ATE121804T1 (de) * 1985-01-22 1995-05-15 Ugine Sa Verfahren zum säuren beizen von stahlen, insbesondere von rostfreien stahlen.
FR2587369B1 (fr) * 1985-09-19 1993-01-29 Ugine Gueugnon Sa Procede de decapage acide de produits en acier inoxydable

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012024542A1 (de) * 2012-12-14 2014-06-18 Poligrat Gmbh Thixotropes Beizmittel

Also Published As

Publication number Publication date
DE69114265T2 (de) 1996-04-18
EP0505606A1 (fr) 1992-09-30
IT1245594B (it) 1994-09-29
ES2082063T5 (es) 2003-11-01
DE505606T1 (de) 1994-02-03
GR3018681T3 (en) 1996-04-30
FI920580A0 (fi) 1992-02-12
ES2082063T3 (es) 1996-03-16
ATE129753T1 (de) 1995-11-15
FI920580A (fi) 1992-09-30
JP2655770B2 (ja) 1997-09-24
JPH04304391A (ja) 1992-10-27
FI101234B (fi) 1998-05-15
DE69114265T3 (de) 2004-08-05
EP0505606B1 (fr) 1995-11-02
DE69114265D1 (de) 1995-12-07
ITMI910879A0 (it) 1991-03-29
DK0505606T3 (da) 1995-12-04
ITMI910879A1 (it) 1992-09-29

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