EP0501867A1 - Verfahren zum Beizen von Stahlwerkstoffen wie z.B. rostfreien und legierten Stählen - Google Patents

Verfahren zum Beizen von Stahlwerkstoffen wie z.B. rostfreien und legierten Stählen Download PDF

Info

Publication number: EP0501867A1
Authority: EP; European Patent Office
Prior art keywords: acid; bath; concentration; chosen; iron
Prior art date: 1991-02-25
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

EP92400471A

Other languages

English (en)

French (fr)

Other versions

EP0501867B1 (de

Inventor

Dominique Henriet

René Ledey

Didier Paul

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.)

USINOR SA

Original Assignee

Ugine SA

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.)

1991-02-25

Filing date

1992-02-24

Publication date

1992-09-02

1992-02-24 Application filed by Ugine SA filed Critical Ugine SA

1992-09-02 Publication of EP0501867A1 publication Critical patent/EP0501867A1/de

1999-01-07 Application granted granted Critical

1999-01-07 Publication of EP0501867B1 publication Critical patent/EP0501867B1/de

2012-02-24 Anticipated expiration legal-status Critical

Status Expired - Lifetime legal-status Critical Current

Links

239000000463 material Substances 0.000 title claims abstract description 23
238000000034 method Methods 0.000 title claims abstract description 21
229910000831 Steel Inorganic materials 0.000 title claims abstract description 10
239000010959 steel Substances 0.000 title claims abstract description 10
229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 7
238000005530 etching Methods 0.000 title 1
230000003647 oxidation Effects 0.000 claims abstract description 20
238000007254 oxidation reaction Methods 0.000 claims abstract description 20
VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 18
CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 15
238000006243 chemical reaction Methods 0.000 claims abstract description 14
239000002253 acid Substances 0.000 claims abstract description 13
QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 11
230000008569 process Effects 0.000 claims abstract description 11
229910052751 metal Inorganic materials 0.000 claims abstract description 9
238000004090 dissolution Methods 0.000 claims abstract description 8
JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 8
NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 7
BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 7
UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 6
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 6
229910001447 ferric ion Inorganic materials 0.000 claims abstract description 6
239000001257 hydrogen Substances 0.000 claims abstract description 6
229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
239000011159 matrix material Substances 0.000 claims abstract description 6
229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 5
HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 5
OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 3
229910045601 alloy Inorganic materials 0.000 claims abstract description 3
239000000956 alloy Substances 0.000 claims abstract description 3
229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 3
235000019253 formic acid Nutrition 0.000 claims abstract description 3
230000009467 reduction Effects 0.000 claims abstract description 3
XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
238000005554 pickling Methods 0.000 claims description 20
KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 13
229910052742 iron Inorganic materials 0.000 claims description 10
MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
150000001875 compounds Chemical class 0.000 claims description 9
QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
239000001301 oxygen Substances 0.000 claims description 7
229910052760 oxygen Inorganic materials 0.000 claims description 7
239000007789 gas Substances 0.000 claims description 4
230000001590 oxidative effect Effects 0.000 claims description 4
230000008030 elimination Effects 0.000 claims description 3
238000003379 elimination reaction Methods 0.000 claims description 3
CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 2
238000010952 in-situ formation Methods 0.000 claims description 2
229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
239000011707 mineral Substances 0.000 claims description 2
150000004967 organic peroxy acids Chemical class 0.000 claims description 2
235000011054 acetic acid Nutrition 0.000 abstract 1
235000011007 phosphoric acid Nutrition 0.000 abstract 1
239000001117 sulphuric acid Substances 0.000 abstract 1
235000011149 sulphuric acid Nutrition 0.000 abstract 1
-1 iron aluminate Chemical class 0.000 description 7
150000002500 ions Chemical class 0.000 description 6
239000002184 metal Substances 0.000 description 6
230000015572 biosynthetic process Effects 0.000 description 5
235000014692 zinc oxide Nutrition 0.000 description 5
229910052804 chromium Inorganic materials 0.000 description 4
239000011651 chromium Substances 0.000 description 4
FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 4
229910001092 metal group alloy Inorganic materials 0.000 description 3
GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
229910052782 aluminium Inorganic materials 0.000 description 2
XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
229940105847 calamine Drugs 0.000 description 2
239000003795 chemical substances by application Substances 0.000 description 2
239000000470 constituent Substances 0.000 description 2
238000010494 dissociation reaction Methods 0.000 description 2
230000005593 dissociations Effects 0.000 description 2
SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 2
229910052864 hemimorphite Inorganic materials 0.000 description 2
238000007654 immersion Methods 0.000 description 2
150000002739 metals Chemical class 0.000 description 2
239000000203 mixture Substances 0.000 description 2
229910017604 nitric acid Inorganic materials 0.000 description 2
229910052710 silicon Inorganic materials 0.000 description 2
239000010703 silicon Substances 0.000 description 2
239000010935 stainless steel Substances 0.000 description 2
231100000331 toxic Toxicity 0.000 description 2
230000002588 toxic effect Effects 0.000 description 2
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
239000011787 zinc oxide Substances 0.000 description 2
CPYIZQLXMGRKSW-UHFFFAOYSA-N zinc;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Zn+2] CPYIZQLXMGRKSW-UHFFFAOYSA-N 0.000 description 2
MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
229910000851 Alloy steel Inorganic materials 0.000 description 1
VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
230000004075 alteration Effects 0.000 description 1
150000004645 aluminates Chemical class 0.000 description 1
PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
238000000137 annealing Methods 0.000 description 1
UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
229910052681 coesite Inorganic materials 0.000 description 1
230000000536 complexating effect Effects 0.000 description 1
229910052593 corundum Inorganic materials 0.000 description 1
229910052906 cristobalite Inorganic materials 0.000 description 1
230000001627 detrimental effect Effects 0.000 description 1
238000011161 development Methods 0.000 description 1
238000009792 diffusion process Methods 0.000 description 1
229910001448 ferrous ion Inorganic materials 0.000 description 1
229910001691 hercynite Inorganic materials 0.000 description 1
UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
230000007774 longterm Effects 0.000 description 1
238000012423 maintenance Methods 0.000 description 1
238000005259 measurement Methods 0.000 description 1
239000007769 metal material Substances 0.000 description 1
238000005272 metallurgy Methods 0.000 description 1
235000010755 mineral Nutrition 0.000 description 1
230000004048 modification Effects 0.000 description 1
238000012986 modification Methods 0.000 description 1
150000002828 nitro derivatives Chemical class 0.000 description 1
JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
150000004760 silicates Chemical class 0.000 description 1
239000000377 silicon dioxide Substances 0.000 description 1
235000012239 silicon dioxide Nutrition 0.000 description 1
238000003756 stirring Methods 0.000 description 1
229910052682 stishovite Inorganic materials 0.000 description 1
239000000126 substance Substances 0.000 description 1
238000006467 substitution reaction Methods 0.000 description 1
230000009466 transformation Effects 0.000 description 1
229910052905 tridymite Inorganic materials 0.000 description 1
229910001845 yogo sapphire Inorganic materials 0.000 description 1

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
- 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
- C23G1/08—Iron or steel

Definitions

the present invention relates to a process for pickling and descaling stainless steel and / or alloy steel materials, and in particular for over-pickling allowing the elimination of an internal oxidation layer located on the surface of the materials, under the scale.
the internal oxidation layer is formed when the solubility of oxygen is very low, that is to say about 100 ppm, under a low partial pressure, particularly below the scale, on the surface of metals or metal alloys. .
the internal oxidation results in the formation of oxides of the residual or addition elements, more oxidizable than iron such as aluminum and / or silicon, these elements entering into the formation. of compounds such as iron aluminate, (FeAl2O4), the formation of these compounds being detrimental to the good performance of the materials in service.
iron aluminate FeAl2O4
the oxidation of the material before pickling as a result of the more or less significant alteration of the metal or of the underlying metal alloy, generates surface dechromization subsequently causing a modification, in composition, of the healthy metal. .
the pickling and / or descaling processes make it possible to remove the layers of scale but do not always have the specific properties to remove the layers affected by internal oxidation.
the products are immersed in over-pickling baths composed of nitric acid and hydrofluoric acid in a proportion of 60 to 160 g / l of HNO3 and 10 at 50 g / l of HF, the overblasting bath being used at a temperature above 40 ° C.
Such a method allows, when used at a temperature above 60 ° C., the pickling of the layer affected by internal oxidation.
This process has the disadvantage, on the one hand, of leading to an intense release of particularly toxic oxide or nitrogen dioxide vapor and, on the other hand, of generating releases of nitro compounds, some of which are particularly toxic.
FR-A-2 5887 369 also describes a process for pickling stainless steel products in which a pickling bath is used which is essentially composed of a hydrofluoric acid and water bath, in a concentration of less than 50 g / l in which iron is dissolved in ferric iron and ferrous iron and the content of ferric iron is maintained at least 15 g / l by oxidation of the bath.
the active pickling agent is the ferric ion Fe3+, the acid solution containing H+ ions being essentially a vector allowing maintenance in proportion of the Fe2+ and Fe3 en ions in the form of complexes, by controlling the redox potential of said pickling bath.
This process has the disadvantage, when the surface of the product is sensitive to the formation of a internal oxidation layer, for example during long-term annealing, not to eliminate this layer.
the subject of the invention is a method of pickling metallic materials such as stainless steels and alloy steels which, in addition to pickling calamines, also control over-stripping of an internal oxidation layer.
Maintaining the desired value of the redox potential can be obtained by the introduction or the in situ formation in the bath of an oxidizing gas chosen from air, ozone, oxygen or by addition to the bath of compounds chosen from hydrogen peroxide, persalts, mineral and organic peracids, or any other source of oxygen.
an oxidizing gas chosen from air, ozone, oxygen or by addition to the bath of compounds chosen from hydrogen peroxide, persalts, mineral and organic peracids, or any other source of oxygen.
its volume is generally between 10 and 100 g / m2 of material surface.
the acid concentration of the bath is generally at least 5% by weight.
its concentration is advantageously from 40 to 150 g / l.
the concentration of ferric iron (which is in the complexed state) is generally 20 to 100 g / l.
the bath temperature is advantageously from 40 to 80 ° C.
FIG. single represents the sectional image of an oxide layer on which the various constituent compounds are materialized.
Fig. single is shown in section an oxide layer.
the various constituent compounds which are present there demonstrate the influence of oxygen and its partial pressure on the chemical form of said compounds.
a layer 2 of Fe2O3, of a layer 3 of Fe3O4, of a layer 4 of FeO Under this assembly forming the oxide layer, also called calamine, there sometimes appears a so-called internal oxidation layer which has a composition close to that of healthy metal, but which is enriched with inclusive oxidized compounds.
elements of this internal oxidation layer releases elements of constitution such as silicon and aluminum, very sensitive to oxygen, which forms compounds, such as, for example, iron silicates and aluminates, ( SiO2, 2FeO); (Al2O3, 3FeO).
the control of said parameters is ensured in particular, on the one hand, by the measurement of a REDOX potential and, on the other hand, by the release of hydrogen.
the Fe+++ / Fe++ ratio is maintained at a value between 1 and 10 and preferably at a value of 4 by measuring the REDOX potential maintained at 200 mV / Ag / AgCl.
the amount of hydrogen resulting from reaction (b) is 2 ml / cm2.
Hydrofluoric acid is introduced into the bath to maintain a concentration of 80 g / l.
the acid concentration is a determining factor in the over-stripping reaction, because it generates H+ ions, complexing Fe+++ and Cr+++ ions, over-active and dissolving agent of the silicates present in the layer of internal oxidation.
the mixed complexes formed between Fe++ and Fe+++ are of the Fe2F5 nH2O type, n being between 2 and 10.

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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)
ing And Chemical Polishing (AREA)
Pressure Welding/Diffusion-Bonding (AREA)

EP92400471A 1991-02-25 1992-02-24 Verfahren zum Beizen von Stahlwerkstoffen wie z.B. rostfreien und legierten Stählen Expired - Lifetime EP0501867B1 (de)

Applications Claiming Priority (3)

Application Number	Priority Date	Filing Date	Title
FR9102222A FR2673200A1 (fr)	1991-02-25	1991-02-25	Procede de surdecapage de materiaux en acier tels que les aciers inoxydables et les aciers allies.
FR9102222		1991-02-25
US08/150,254 US5690748A (en)	1991-02-25	1993-11-10	Process for the acid pickling of stainless steel products

Publications (2)

Publication Number	Publication Date
EP0501867A1 true EP0501867A1 (de)	1992-09-02
EP0501867B1 EP0501867B1 (de)	1999-01-07

Family

ID=26228531

Family Applications (1)

Application Number	Title	Priority Date	Filing Date
EP92400471A Expired - Lifetime EP0501867B1 (de)	1991-02-25	1992-02-24	Verfahren zum Beizen von Stahlwerkstoffen wie z.B. rostfreien und legierten Stählen

Country Status (9)

Country	Link
US (1)	US5690748A (de)
EP (1)	EP0501867B1 (de)
AT (1)	ATE175452T1 (de)
DE (1)	DE69228080T2 (de)
DK (1)	DK0501867T3 (de)
ES (1)	ES2127208T3 (de)
FI (1)	FI99031C (de)
FR (1)	FR2673200A1 (de)
GR (1)	GR3029688T3 (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
DE4237021C1 (de) *	1992-11-02	1994-02-10	Poligrat Gmbh	Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels
EP0769574A1 (de)	1995-10-18	1997-04-23	NOVAMAX ITB s.r.l.	Verfahren zum Beizen und Passivieren von rostfreiem 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
WO1999027162A1 (en) *	1997-11-24	1999-06-03	Acciai Speciali Terni S.P.A.	Method for pickling steel products
WO1999031296A1 (de) *	1997-12-12	1999-06-24	Henkel Kommanditgesellschaft Auf Aktien	Verfahren zum beizen und passivieren von edelstahl
EP0859671A4 (de) *	1995-11-07	2001-01-24	Electric Power Res Inst	Verfahren zur dekontaminierung von komponenten eines kernkraftwerkes
IT202000005848A1 (it)	2020-03-19	2021-09-19	Tenova Spa	Processo per decapare e/o passivare un acciaio inossidabile.

Families Citing this family (8)

* 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
US20040140288A1 (en) *	1996-07-25	2004-07-22	Bakul Patel	Wet etch of titanium-tungsten film
GB9807286D0 (en) *	1998-04-06	1998-06-03	Solvay Interox Ltd	Pickling process
USH2087H1 (en) *	1998-05-19	2003-11-04	H. C. Starck, Inc.	Pickling of refractory metals
DE19833990A1 (de) *	1998-07-29	2000-02-10	Metallgesellschaft Ag	Beizmittel für Edelstähle
EP1980650A1 (de) *	2007-04-05	2008-10-15	Kerma S.A.	Nitrat- und Peroxydfreie Beizzusammensetzung und Verfahren zur Umsetzung einer solchen Zusammensetzung
CN109234746A (zh) *	2018-11-12	2019-01-18	江阴祥瑞不锈钢精线有限公司	一种不锈钢丝的酸洗工艺方法
JP7176137B2 (ja) *	2020-01-09	2022-11-21	ＰｒｉｍｅｔａｌｓＴｅｃｈｎｏｌｏｇｉｅｓＪａｐａｎ株式会社	鋼板の酸洗方法及び酸洗装置

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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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1991
- 1991-02-25 FR FR9102222A patent/FR2673200A1/fr active Granted
1992
- 1992-02-24 DE DE69228080T patent/DE69228080T2/de not_active Expired - Lifetime
- 1992-02-24 ES ES92400471T patent/ES2127208T3/es not_active Expired - Lifetime
- 1992-02-24 DK DK92400471T patent/DK0501867T3/da active
- 1992-02-24 AT AT92400471T patent/ATE175452T1/de active
- 1992-02-24 FI FI920787A patent/FI99031C/fi not_active IP Right Cessation
- 1992-02-24 EP EP92400471A patent/EP0501867B1/de not_active Expired - Lifetime
1993
- 1993-11-10 US US08/150,254 patent/US5690748A/en not_active Expired - Lifetime
1999
- 1999-03-12 GR GR990400772T patent/GR3029688T3/el unknown

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DE4237021C1 (de) *	1992-11-02	1994-02-10	Poligrat Gmbh	Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels
EP0769574A1 (de)	1995-10-18	1997-04-23	NOVAMAX ITB s.r.l.	Verfahren zum Beizen und Passivieren von rostfreiem Stahl ohne Salpetersäure
EP0859671A4 (de) *	1995-11-07	2001-01-24	Electric Power Res Inst	Verfahren zur dekontaminierung von komponenten eines kernkraftwerkes
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
WO1999027162A1 (en) *	1997-11-24	1999-06-03	Acciai Speciali Terni S.P.A.	Method for pickling steel products
US6500328B1 (en)	1997-11-24	2002-12-31	Acciai Speciali Terni S.P.A.	Method for pickling steel products
WO1999031296A1 (de) *	1997-12-12	1999-06-24	Henkel Kommanditgesellschaft Auf Aktien	Verfahren zum beizen und passivieren von edelstahl
IT202000005848A1 (it)	2020-03-19	2021-09-19	Tenova Spa	Processo per decapare e/o passivare un acciaio inossidabile.

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ATE175452T1 (de)	1999-01-15
FI920787L (fi)	1992-08-26
FI99031B (fi)	1997-06-13
ES2127208T3 (es)	1999-04-16
FI920787A0 (fi)	1992-02-24
FR2673200A1 (fr)	1992-08-28
DK0501867T3 (da)	1999-08-30
EP0501867B1 (de)	1999-01-07
GR3029688T3 (en)	1999-06-30
FR2673200B1 (de)	1995-03-03
DE69228080T2 (de)	1999-05-20
FI99031C (fi)	1997-09-25
US5690748A (en)	1997-11-25
DE69228080D1 (de)	1999-02-18

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Publication	Publication Date	Title
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Bolann et al.	1990	On the limited ability of superoxide to release iron from ferritin
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