EP0505606B2 - Process for pickling and passivating stainless steel without using nitric acid - Google Patents
Process for pickling and passivating stainless steel without using nitric acid Download PDFInfo
- 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
- Authority
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 43
- 230000008569 process Effects 0.000 title claims abstract description 41
- 238000005554 pickling Methods 0.000 title claims abstract description 34
- 229910001220 stainless steel Inorganic materials 0.000 title claims abstract description 8
- 239000010935 stainless steel Substances 0.000 title claims abstract description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title description 12
- 229910017604 nitric acid Inorganic materials 0.000 title description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002253 acid Substances 0.000 claims abstract description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000003112 inhibitor Substances 0.000 claims abstract description 5
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 4
- 229910001447 ferric ion Inorganic materials 0.000 claims description 13
- 239000000463 material Substances 0.000 claims description 13
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 9
- 239000000654 additive Substances 0.000 claims description 8
- -1 Fe3+ ions Chemical class 0.000 claims description 7
- 239000003381 stabilizer Substances 0.000 claims description 5
- 238000004458 analytical method Methods 0.000 claims description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 3
- 239000003995 emulsifying agent Substances 0.000 claims description 3
- 239000000080 wetting agent Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000004615 ingredient Substances 0.000 claims 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 claims 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 claims 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims 1
- 235000011149 sulphuric acid Nutrition 0.000 abstract description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 25
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 238000007664 blowing Methods 0.000 description 4
- 229910001448 ferrous ion Inorganic materials 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000009533 lab test Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 229910021653 sulphate ion Inorganic materials 0.000 description 3
- 239000001117 sulphuric acid Substances 0.000 description 3
- 238000013019 agitation Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 239000012286 potassium permanganate Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000011265 semifinished product Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 159000000009 barium salts Chemical class 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002843 nonmetals Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000035755 proliferation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229960001922 sodium perborate Drugs 0.000 description 1
- YKLJGMBLPUQQOI-UHFFFAOYSA-M sodium;oxidooxy(oxo)borane Chemical compound [Na+].[O-]OB=O YKLJGMBLPUQQOI-UHFFFAOYSA-M 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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.
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)
- Medicines Containing Material From Animals Or Micro-Organisms (AREA)
- Detergent Compositions (AREA)
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 EP0505606A1 (en) | 1992-09-30 |
| EP0505606B1 EP0505606B1 (en) | 1995-11-02 |
| EP0505606B2 true EP0505606B2 (en) | 2003-02-26 |
Family
ID=11359360
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP91113628A Expired - Lifetime EP0505606B2 (en) | 1991-03-29 | 1991-08-14 | Process for pickling and passivating stainless steel without using nitric acid |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0505606B2 (fi) |
| JP (1) | JP2655770B2 (fi) |
| AT (1) | ATE129753T1 (fi) |
| DE (2) | DE69114265T3 (fi) |
| DK (1) | DK0505606T3 (fi) |
| ES (1) | ES2082063T5 (fi) |
| FI (1) | FI101234B (fi) |
| GR (1) | GR3018681T3 (fi) |
| IT (1) | IT1245594B (fi) |
Cited By (1)
| 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)
| 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 |
| WO1996009899A1 (en) * | 1994-09-26 | 1996-04-04 | E.R. Squibb & Sons, Inc. | Stainless steel acid treatment |
| 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 (de) * | 1998-07-18 | 2000-01-26 | Henkel Kommanditgesellschaft auf Aktien | Verfahren zur chemischen Behandlung von Metalloberflächen und dazu geeignete Anlage |
| 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 |
| ES2350095T3 (es) | 2002-10-15 | 2011-01-18 | HENKEL AG & CO. KGAA | Solución y procedimiento de decapado para acero inoxidable. |
| EP1793016A1 (de) * | 2005-12-01 | 2007-06-06 | Elpochem AG | Polier- und Entgratungsmittel für Werkstücke aus Kohlenstoffstahl und Verfahren zum chemischen Polieren und Entgraten |
| 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 |
| EP3951014B1 (en) * | 2020-01-09 | 2024-05-22 | Primetals Technologies Japan, Ltd. | Method for pickling steel plate and pickling apparatus |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
1991
- 1991-03-29 IT ITMI910879A patent/IT1245594B/it active IP Right Grant
- 1991-08-14 ES ES91113628T patent/ES2082063T5/es not_active Expired - Lifetime
- 1991-08-14 EP EP91113628A patent/EP0505606B2/en not_active Expired - Lifetime
- 1991-08-14 DK DK91113628.1T patent/DK0505606T3/da active
- 1991-08-14 DE DE69114265T patent/DE69114265T3/de not_active Expired - Lifetime
- 1991-08-14 AT AT91113628T patent/ATE129753T1/de not_active IP Right Cessation
- 1991-08-14 DE DE91113628T patent/DE505606T1/de active Pending
- 1991-10-04 JP JP3284206A patent/JP2655770B2/ja not_active Expired - Lifetime
-
1992
- 1992-02-12 FI FI920580A patent/FI101234B/fi not_active IP Right Cessation
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1996
- 1996-01-17 GR GR960400082T patent/GR3018681T3/el unknown
Cited By (1)
| 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 |
|---|---|
| FI920580A0 (fi) | 1992-02-12 |
| ITMI910879A0 (it) | 1991-03-29 |
| ATE129753T1 (de) | 1995-11-15 |
| FI101234B (fi) | 1998-05-15 |
| EP0505606A1 (en) | 1992-09-30 |
| JP2655770B2 (ja) | 1997-09-24 |
| JPH04304391A (ja) | 1992-10-27 |
| DE69114265D1 (de) | 1995-12-07 |
| DE505606T1 (de) | 1994-02-03 |
| IT1245594B (it) | 1994-09-29 |
| DE69114265T3 (de) | 2004-08-05 |
| EP0505606B1 (en) | 1995-11-02 |
| DK0505606T3 (da) | 1995-12-04 |
| ES2082063T3 (es) | 1996-03-16 |
| FI920580A (fi) | 1992-09-30 |
| ITMI910879A1 (it) | 1992-09-29 |
| GR3018681T3 (en) | 1996-04-30 |
| DE69114265T2 (de) | 1996-04-18 |
| ES2082063T5 (es) | 2003-11-01 |
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