EP0501867B1 - Procédé de décapage de matériaux en acier tels que les aciers inoxydables et les aciers alliés - Google Patents
Procédé de décapage de matériaux en acier tels que les aciers inoxydables et les aciers alliés Download PDFInfo
- Publication number
- EP0501867B1 EP0501867B1 EP92400471A EP92400471A EP0501867B1 EP 0501867 B1 EP0501867 B1 EP 0501867B1 EP 92400471 A EP92400471 A EP 92400471A EP 92400471 A EP92400471 A EP 92400471A EP 0501867 B1 EP0501867 B1 EP 0501867B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- bath
- acid
- concentration
- iron
- steels
- 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
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 11
- 239000010959 steel Substances 0.000 title claims abstract description 11
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 7
- 238000005530 etching Methods 0.000 title claims 2
- 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 14
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 238000004090 dissolution Methods 0.000 claims abstract description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-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
- 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
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 239000000956 alloy Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 43
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 23
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 150000001875 compounds Chemical class 0.000 claims description 10
- 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
- 230000015572 biosynthetic process Effects 0.000 claims description 5
- 239000007789 gas Substances 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
- 238000011065 in-situ storage 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
- 230000001105 regulatory effect Effects 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 abstract 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract 1
- 235000011054 acetic acid Nutrition 0.000 abstract 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 235000019253 formic 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
- 238000005554 pickling Methods 0.000 description 20
- -1 iron aluminate Chemical class 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 235000014692 zinc oxide Nutrition 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
- 229910001092 metal group alloy Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 229910015475 FeF 2 Inorganic materials 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
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 229910052864 hemimorphite Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000012549 training Methods 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
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910000851 Alloy steel Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910015372 FeAl Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 150000004645 aluminates Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical class [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000470 constituent Substances 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
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 150000004760 silicates Chemical class 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
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 method of pickling and descaling of stainless steel materials and / or alloy steel, and in particular over-stripping allowing elimination of an internal oxidation layer located on the surface of the materials, under the scale.
- the oxidation layer internal is formed when the solubility of oxygen is very low, about 100 ppm, at particularly low partial pressure below the scale, on the surface of the 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 (FeAl 2 O 4 ), the formation of these compounds being detrimental to the good performance of the materials in service.
- iron aluminate FeAl 2 O 4
- the oxidation of the material before pickling as a result of more or less weathering significant of the underlying metal or metal alloy generates surface dechromination thereafter a modification, in composition, of the healthy metal.
- 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 HNO 3 and 10 to 50 g / l of HF, the overblasting bath being used at a temperature above 40 ° C.
- Such a method allows, in use at a temperature above 60 ° C, the pickling of the layer affected by internal oxidation.
- This process has the drawback, on the one hand, of lead to intense release of oxide vapor or particularly toxic nitrogen dioxide and, on the other hand, to generate releases of compounds nitrates, some of which are particularly toxic.
- FR-A-2 587 369 also describes a pickling process for stainless steel products in which a compound pickling bath is used essentially a hydrofluoric acid bath and of water, in a concentration of less than 50 g / l in which dissolves iron into ferric iron and iron ferrous and the ferric iron content is maintained at at least 15 g / l by oxidation of the bath.
- the active pickling agent is the ferric ion Fe 3+ , the acid solution containing H + ions being essentially a vector allowing maintenance in proportion of the ions Fe 2+ and Fe 3+ in the form of complexes, by controlling the redox potential of said pickling bath.
- This process has the disadvantage, when the product surface is sensitive to the formation of a internal oxidation layer, for example during a long-term annealing, not to eliminate this layer.
- GB-A-2 000 196 describes a pickling process at 50 ° C with a solution containing 5% hydrofluoric acid, 50 g / l ferric sulfate and 30 g / l ferrous sulfate and maintaining the potential oxidation-reduction of the bath to a value of +300 mV per addition of hydrogen peroxide and acid to the bath sulfuric.
- the subject of the invention is a method of pickling of metallic materials such as steels stainless and alloy steels allowing in addition to pickling of calamines, a controlled over-stripping of a internal oxidation layer.
- Maintaining the desired value of the redox potential can be obtained by introduction or in situ training in the bath an oxidizing gas chosen from air, ozone, oxygen or by adding compounds to the bath chosen from hydrogen peroxide, persalts, mineral and organic peracids, or any other oxygen source.
- an oxidizing gas chosen from air, ozone, oxygen or by adding compounds to the bath chosen from hydrogen peroxide, persalts, mineral and organic peracids, or any other oxygen source.
- the concentration of ferric iron (which found in complexed state) is usually 20 to 100 g / l.
- the bath temperature is from 40 to 80 ° C.
- FIG. unique represents the sectional image of an oxide layer on which the different compounds of constitution.
- 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 Fe 2 O 3 of a layer 3 of Fe 3 O 4 , of a layer 4 of FeO.
- this set 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, ( SiO 2 , 2FeO); (Al 2 O 3 , 3FeO).
- control of these parameters is ensured in particular, on the one hand, by measuring a potential REDOX 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 / cm 2 .
- 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, protruding and dissolving agent of the silicates present in the layer of internal oxidation.
- the mixed complexes formed between Fe ++ and Fe +++ are of the Fe 2 F 5 nH 2 O type, n being between 2 and 10.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- ing And Chemical Polishing (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9102222 | 1991-02-25 | ||
| 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. |
| 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 EP0501867A1 (fr) | 1992-09-02 |
| EP0501867B1 true EP0501867B1 (fr) | 1999-01-07 |
Family
ID=26228531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP92400471A Expired - Lifetime EP0501867B1 (fr) | 1991-02-25 | 1992-02-24 | Procédé de décapage de matériaux en acier tels que les aciers inoxydables et les aciers alliés |
Country Status (9)
Families Citing this family (15)
| 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 | |
| DE4237021C1 (de) * | 1992-11-02 | 1994-02-10 | Poligrat Gmbh | Mittel zum Beizen der Oberfläche von Chromnickelstählen und Chromstählen sowie Verwendung des Mittels |
| IT1276955B1 (it) | 1995-10-18 | 1997-11-03 | Novamax Itb S R L | Processo di decapaggio e passivazione di acciaio inossidabile senza impiego di acido nitrico |
| US5724668A (en) * | 1995-11-07 | 1998-03-03 | Electronic Power Research Institute | Method for decontamination of nuclear plant components |
| 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 |
| US20040140288A1 (en) * | 1996-07-25 | 2004-07-22 | Bakul Patel | Wet etch of titanium-tungsten film |
| IT1297076B1 (it) | 1997-11-24 | 1999-08-03 | Acciai Speciali Terni Spa | Metodo per il decapaggio di prodotti in acciaio |
| DE19755350A1 (de) * | 1997-12-12 | 1999-06-17 | Henkel Kgaa | Verfahren zum Beizen und Passivieren von Edelstahl |
| 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 (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 |
| 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 |
| 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 |
| IT202000005848A1 (it) | 2020-03-19 | 2021-09-19 | Tenova Spa | Processo per decapare e/o passivare un acciaio inossidabile. |
Family Cites Families (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2474526A (en) * | 1940-06-15 | 1949-06-28 | Monsanto Chemicals | Picking of stainless steels |
| US2337062A (en) * | 1942-04-07 | 1943-12-21 | Solar Aircraft Co | Pickling solution and method |
| US2564549A (en) * | 1945-07-02 | 1951-08-14 | Albert R Stargardter | Pickling treatment |
| US2856275A (en) * | 1956-11-20 | 1958-10-14 | Amchem Prod | Chemical treatment of refractory metal surfaces |
| US3310435A (en) * | 1963-11-18 | 1967-03-21 | Dravo Corp | Process for continuous pickling of steel strip and regeneration of the contact acid |
| AU471215B2 (en) * | 1972-02-22 | 1976-04-15 | Seat belt retractor | |
| JPS549120A (en) * | 1977-06-24 | 1979-01-23 | Tokai Electro Chemical Co | Method of controlling acid cleaning liquid for stainless steel |
| DE3105508A1 (de) * | 1981-02-14 | 1982-09-02 | Metallgesellschaft Ag, 6000 Frankfurt | Beiz- und entrostungspaste fuer metalle |
| JPS5839234B2 (ja) * | 1981-10-26 | 1983-08-29 | 住友金属工業株式会社 | 鋼線材の酸洗脱スケ−ル方法 |
| US4608091A (en) * | 1982-01-11 | 1986-08-26 | Enthone, Incorporated | Peroxide selective stripping compositions and method |
| DE3222532A1 (de) * | 1982-06-16 | 1983-12-22 | Arno 5042 Erftstadt Kuhlmann | Verfahren und mittel zum sauren beizen von austenitischen edelstaehlen |
| FR2539140A1 (fr) * | 1983-01-07 | 1984-07-13 | Ugine Kuhlmann | Stabilisation de solutions aqueuses contenant du peroxyde d'hydrogene, de l'acide fluorhydrique et des ions metalliques |
| FR2551465B3 (fr) * | 1983-09-02 | 1985-08-23 | Gueugnon Sa Forges | Procede de decapage acide des aciers inoxydables et solution acide pour sa mise en oeuvre |
| FR2560893B1 (fr) * | 1984-03-09 | 1986-09-12 | Snecma | Bain de decapage chimique pour pieces en alliage resistant a chaud |
| EP0188975B8 (fr) * | 1985-01-22 | 2002-01-09 | Ugine S.A. | Procédé pour le décapage acide des aciers, et notamment des aciers inoxydables |
| US5154774A (en) * | 1985-09-19 | 1992-10-13 | Ugine Aciers De Chatillon Et Gueugnon | Process for acid pickling of stainless steel products |
| FR2587369B1 (fr) * | 1985-09-19 | 1993-01-29 | Ugine Gueugnon Sa | Procede de decapage acide de produits en acier inoxydable |
| US5292374A (en) * | 1988-11-15 | 1994-03-08 | Maschinenfabrik Andritz Actiengesellschft | Process and plant for pickling stainless steel strip |
| DE3937438C2 (de) * | 1989-02-23 | 1998-01-29 | Wilfried Simmer | Verfahren zum Beizen von Stahl |
| FR2657888B1 (fr) * | 1990-02-08 | 1994-04-15 | Ugine Aciers | Procedes de decapage de materiaux en acier inoxydable. |
| US5354383A (en) * | 1991-03-29 | 1994-10-11 | Itb, S.R.L. | Process for pickling and passivating stainless steel without using nitric acid |
-
1991
- 1991-02-25 FR FR9102222A patent/FR2673200A1/fr active Granted
-
1992
- 1992-02-24 DK DK92400471T patent/DK0501867T3/da active
- 1992-02-24 AT AT92400471T patent/ATE175452T1/de active
- 1992-02-24 DE DE69228080T patent/DE69228080T2/de not_active Expired - Lifetime
- 1992-02-24 EP EP92400471A patent/EP0501867B1/fr not_active Expired - Lifetime
- 1992-02-24 ES ES92400471T patent/ES2127208T3/es not_active Expired - Lifetime
- 1992-02-24 FI FI920787A patent/FI99031C/fi not_active IP Right Cessation
-
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
Also Published As
| Publication number | Publication date |
|---|---|
| FR2673200B1 (enrdf_load_stackoverflow) | 1995-03-03 |
| FI920787L (fi) | 1992-08-26 |
| GR3029688T3 (en) | 1999-06-30 |
| EP0501867A1 (fr) | 1992-09-02 |
| ATE175452T1 (de) | 1999-01-15 |
| US5690748A (en) | 1997-11-25 |
| FI920787A0 (fi) | 1992-02-24 |
| FR2673200A1 (fr) | 1992-08-28 |
| ES2127208T3 (es) | 1999-04-16 |
| FI99031C (fi) | 1997-09-25 |
| DE69228080T2 (de) | 1999-05-20 |
| DK0501867T3 (da) | 1999-08-30 |
| FI99031B (fi) | 1997-06-13 |
| DE69228080D1 (de) | 1999-02-18 |
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