EP0609342B1 - Zusammensetzung zum stabilisieren anorganischer peroxidlösungen - Google Patents
Zusammensetzung zum stabilisieren anorganischer peroxidlösungen Download PDFInfo
- Publication number
- EP0609342B1 EP0609342B1 EP92922319A EP92922319A EP0609342B1 EP 0609342 B1 EP0609342 B1 EP 0609342B1 EP 92922319 A EP92922319 A EP 92922319A EP 92922319 A EP92922319 A EP 92922319A EP 0609342 B1 EP0609342 B1 EP 0609342B1
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- EP
- European Patent Office
- Prior art keywords
- composition according
- composition
- treatment
- stabilizing
- test
- 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.)
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- 239000000203 mixture Substances 0.000 title claims abstract description 85
- 150000002978 peroxides Chemical class 0.000 title claims abstract description 35
- 230000000087 stabilizing effect Effects 0.000 title claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 31
- 239000002184 metal Substances 0.000 claims abstract description 31
- 238000005554 pickling Methods 0.000 claims abstract description 30
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 11
- -1 aromatic amine compounds Chemical class 0.000 claims abstract description 10
- 230000002378 acidificating effect Effects 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract description 6
- 238000005498 polishing Methods 0.000 claims abstract description 5
- KYWMCFOWDYFYLV-UHFFFAOYSA-N 1h-imidazole-2-carboxylic acid Chemical class OC(=O)C1=NC=CN1 KYWMCFOWDYFYLV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims description 23
- 239000003381 stabilizer Substances 0.000 claims description 18
- 238000011282 treatment Methods 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 14
- 150000002739 metals Chemical class 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 230000008569 process Effects 0.000 claims description 9
- 230000001590 oxidative effect Effects 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 235000021317 phosphate Nutrition 0.000 claims description 7
- 239000000080 wetting agent Substances 0.000 claims description 7
- 239000002671 adjuvant Substances 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 235000005985 organic acids Nutrition 0.000 claims description 6
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 6
- 238000004381 surface treatment Methods 0.000 claims description 6
- 238000013019 agitation Methods 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 230000009849 deactivation Effects 0.000 claims description 4
- 150000002334 glycols Chemical class 0.000 claims description 4
- 229920000151 polyglycol Polymers 0.000 claims description 4
- 239000010695 polyglycol Substances 0.000 claims description 4
- CARFETJZUQORNQ-UHFFFAOYSA-N 1h-pyrrole-2-thiol Chemical group SC1=CC=CN1 CARFETJZUQORNQ-UHFFFAOYSA-N 0.000 claims description 3
- 150000001993 dienes Chemical class 0.000 claims description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 150000007824 aliphatic compounds Chemical group 0.000 claims description 2
- 150000001565 benzotriazoles Chemical class 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000002950 monocyclic group Chemical group 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 150000001491 aromatic compounds Chemical class 0.000 claims 1
- JXLHNMVSKXFWAO-UHFFFAOYSA-N azane;7-fluoro-2,1,3-benzoxadiazole-4-sulfonic acid Chemical compound N.OS(=O)(=O)C1=CC=C(F)C2=NON=C12 JXLHNMVSKXFWAO-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 abstract description 47
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 238000005282 brightening Methods 0.000 abstract 1
- 150000003852 triazoles Chemical class 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 47
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 19
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical class F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 17
- 230000009471 action Effects 0.000 description 13
- 239000000243 solution Substances 0.000 description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 229910000831 Steel Inorganic materials 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- 238000000354 decomposition reaction Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 3
- 239000002609 medium Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 229910000589 SAE 304 stainless steel Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 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
- 239000003945 anionic surfactant Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000003851 azoles Chemical class 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- 150000002222 fluorine compounds Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000004966 inorganic peroxy acids Chemical class 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- 125000001273 sulfonato group Chemical class [O-]S(*)(=O)=O 0.000 description 2
- 238000009736 wetting Methods 0.000 description 2
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001334 alicyclic compounds Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 description 1
- 235000011180 diphosphates Nutrition 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- ZODDGFAZWTZOSI-UHFFFAOYSA-N nitric acid;sulfuric acid Chemical compound O[N+]([O-])=O.OS(O)(=O)=O ZODDGFAZWTZOSI-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N nitrous oxide Inorganic materials [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 150000004968 peroxymonosulfuric acids Chemical class 0.000 description 1
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000004580 weight loss Effects 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
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
Definitions
- the present invention relates to a composition having high stabilizing properties, more particularly in the case of inorganic peroxides used in the context of industrial applications.
- It relates more particularly to a stabilizing composition of inorganic peroxides used in the pickling baths of metal surfaces.
- Strippers of the type mentioned generally contain nitric-hydrofluoric mixtures or mixtures of sulfuric-nitric and hydrofluoric acids, to which process correctors which may be surfactants have been added, in order to improve their wetting characteristics or inhibitors for standardize the chemical action.
- pickling baths have recently been proposed. which provide an alternative solution to traditional processes.
- the auxiliary mechanical action normally provides for the creation of turbulence in the pickling solution, either by stirring the liquid or by blowing air into the baths so as to promote the detachment of the oxides from the metal surfaces.
- the absence of nitric acid in these baths is compensated for by the presence of inorganic peroxides such as hydrogen peroxide.
- inorganic peroxides not only replaces the oxidizing action of nitric acid, but it also promotes pickling and passivation of the metal surface.
- control of the peroxides present in the baths should normally be carried out using redox measuring instruments which, as is known, are not only very expensive to purchase, but also have a limited longevity when they are used for this specific purpose.
- the baths containing peroxides also offer limited stability, due to the presence of metals which catalyze the decomposition of the peroxides.
- nitric acid-free baths allow for the moment to considerably reduce the degree of pollution, on the other hand, it is necessary either to operate at temperatures generally higher than the temperatures usual, either to carry out costly modifications of the equipment, the latter having to be equipped with means for heating and agitating the baths or means for blowing air into these same baths, and therefore providing for automatic control and permanent peroxide contained in the pickling mixture.
- peroxidized chemical attack compositions of effective metals must contain a certain amount of 3-amino-1,2,4-triazole, a constituent which acts both as an accelerator of chemical attack and as stabilizer (page 2, lines 20 to 26).
- an important objective of the present invention is to produce a composition having high stabilizing properties, and this, more particularly with regard to the inorganic peroxides used in the context of industrial applications, this composition having to be able to stabilize peroxides while avoiding undesirable decompositions of these same peroxides in the presence of metals, even in high concentrations, and more specifically in the context of acid pickling processes replacing nitric mixtures.
- Another important objective of the present invention is to provide a composition offering high stabilizing properties and capable of increasing the oxidation action of peroxides, more particularly hydrogen peroxide in contact with surfaces metallic, and this by means of an oxidation-dissolution action of oxides which is extremely rapid, even at room temperature.
- Another important objective of the present invention consists in producing a composition offering high stabilizing properties and which is capable of providing a pickling system which would replace the nitric acid baths currently used, without however the need to modify the equipment used and without reducing the treatment time at the same temperature.
- Another objective - and not least - of the present invention is to provide a composition with high stabilizing properties which makes it possible to eliminate the heating of the solutions and to eliminate their agitation as well as the permanent control of the level of peroxides contained in the baths. .
- the invention relates to a stabilizing composition for inorganic peroxides intended for baths for the surface treatment of metal parts, according to which it comprises at least one activating agent selected from benzotriazoles, imidazole and carboxyimidazoles or their derivatives.
- composition with high stabilizing properties in particular for the inorganic peroxides used in the context of 'applications industrial.
- inorganic peroxides is intended to denote hydrogen peroxide, inorganic peracids and their salts, more particularly perboric, perphosphoric and persulfuric acids and their alkali or alkaline earth metal salts, as well as peroxides of alkali and alkaline earth metals such as sodium, calcium and magnesium peroxides.
- hydrogen peroxide or inorganic peracids are used. Very good results have been obtained with hydrogen peroxide.
- surface treatment of metal parts is intended to denote the treatment of metal parts using a bath comprising one or more acidic compounds and one or more oxidizing compounds, in particular with a view to stripping them by removing the oxides covering their surface, or passivate them or improve the surface finish, more particularly to polish them and / or perform a polishing treatment.
- the composition is intended to be incorporated into the surface treatment baths of metal parts. It generally does not itself contain peroxide, which is added to the treatment bath independently.
- the stabilizing action of peroxides and their capacity to accelerate deoxidation depend on the composition of the baths in which the traditional standard nitric-hydrofluoric mixture is replaced, as regards the nitric part, by oxygenated water in the H2O2-HNO3 molar proportion of 1/2 to 2/1 but preferably 1/1, while the acid part of the nitric acid is replaced by sulfuric acid in the HNO3-H2SO4 molar proportion of 1 / 2 to 2.5 / 1, but preferably 1 / 1.3.
- the acid part with regard to sulfuric acid may be replaced, in whole or in part, by inorganic acids of phosphoric, sulfamic or other type, insofar as they do not cause a negative interaction with the stabilizer of the hydrogen peroxide or peroxide.
- the hydrofluoric part can for its part comprise at least one compound chosen from fluorinated acids or fluorinated salts and the percentage is maintained within the usual standard values that are known.
- the bath thus obtained requires the presence of a peroxide stabilizing agent in the proportion of 1/100 to 1/1, but preferably from 1/30 to 1/2, depending on the peroxide used.
- the stabilizing agent used for the baths of these compositions and which constitutes the object of the present invention can comprise, in addition to the activating agent at least, another compound chosen from stabilizing agents, the solvent compounds of the stabilizing agent, oxidation catalysts, wetting agents capable of resisting in an oxidizing acid environment, optionally phosphates or phosphonates as co-adjuvants for precipitation and deactivation of dissolved metals, and finally, inorganic and / or organic acids as product standardizers.
- the composition also comprises at least one stabilizing agent.
- the stabilizing agent in particular, it may comprise one or more aromatic or cyclic rings or one or more aliphatic chains. It can also contain at least one group chosen from hydroxyl, carboxylic, sulfonate and phosphate groups.
- the term “sulfonate and phosphate groups” is intended to denote here both the sulfonic and phosphoric groups and their salts. It can also contain at least one group chosen from esters, ethers, dienes, azoles, mercapto-azoles or combinations thereof.
- the stabilizing agent may comprise at least one compound selected from mono or polycyclic aromatic or alicyclic compounds and aliphatic compounds substituted by at least one group chosen from the groups hydroxyls, carboxyls, sulfonates, phosphates, esters, ethers, dienes, azoles and mercapto-azoles. Good results have been obtained with compounds substituted by sulfonate (or sulfonic) groups and phosphates (or phosphoric) groups or mixtures thereof. P-Toluene sulfonic acid is well suited.
- compositions according to the invention can comprise at least one solvent compound for the stabilizing agent.
- the solvent compound also called dissolving part of the stabilizing agent described above can include alcohols, glycols, polyethers, dimethylformamide, N-methylpyrrolidone, ketones, polyglycols, esters, low-weight condensates molecular or organic groups characterized by a reasonable solubility in water, resistant in an acidic environment and having a good dissolving power of the organic components used as stabilizing agents and having zero or low solubility in water or in inorganic acids at use concentrations.
- the solvent compound of the stabilizing agent preferably comprises at least one compound selected from alcohols, glycols and polyglycols.
- the solvent compound can also contain, in admixture with said alcohols, glycols and / or polyglycols at least one adjuvant chosen from dimethylformamide and N-methylpyrrolidone.
- the solvent compound can include polyesters, ketones, esters, low molecular weight condensates or organic groups with good water solubility and resistance in an acidic medium.
- the activating agent which can also also be used independently of the stabilizing agents or solvent compounds mentioned above, comprises cyclic, aromatic amine components, derivatives of imidazoles and / or carboxy-imidazoles, and / or aliphatic amines.
- compositions according to the invention can also contain at minus one compound chosen from oxidation catalysts made up of metals and wetting agents resistant in an oxidizing acid medium.
- the oxidation catalysts can comprise at least one metal belonging to the first, second, third or fourth group. These are present in a percentage varying from 2 to 20,000 ppm and preferably from 10 to 3,000 ppm.
- group is meant a group which corresponds to a family represented in the same column of the periodic table of the elements.
- the metals of group 3 have proved to be interesting and good results have been obtained with aluminum.
- the composition may also comprise at least one wetting agent stable in oxidizing acid medium, that is to say an agent capable of modifying the surface tension at the solid / liquid interface in order to improve the wetting of metal parts by the treatment bath.
- This wetting agent should be selected from those which are chemically inert in the presence of an acidic and oxidizing aqueous solution and, in particular, acidic aqueous solutions of peroxides.
- wetting agents capable of resisting in an oxidizing acid environment consist of nonionic, anionic, amphoteric or cationic condensates or fluorinated derivatives, or a mixture of these. Good results have been obtained with fluorinated anionic surfactants and ethylene glycol condensates with alkylphenols and their mixtures.
- the pickling bath constituted in this way and having the stabilizing agent described above can operate from a pH equal to 2.5 and up to a pH of 0.0, but usually it operates at a pH below 1.3.
- the pickling bath can operate at pH values equal to or less than 0.3.
- the stabilizing composition reduces the oxidation potential of the iron / nickel / chromium sub-oxides and catalyze their oxidation, thereby promoting the transformation into soluble oxides.
- the presence in a pickling bath of the stabilizing composition which is the subject of the present invention makes it possible to carry out pickling in a time and at extremely competitive temperatures compared to the baths currently used.
- composition according to the invention it is also possible to incorporate precipitation additives and, consequently, deactivation of the dissolved metals originating from the dissolution of the oxides or from the surface part of the metal part under the action of the treatment bath.
- adjuvants can be soluble inorganic or organic salts whose anion combines with the cation of the metal or metals dissolved in the bath to form a salt whose solubility product is very low under the conditions prevailing in the bath, for example less than 10 ⁇ 5 gram ion.
- the composition can also comprise at least one compound chosen from phosphates and phosphonates as co-adjuvants for precipitation and deactivation of dissolved metals and inorganic and organic acids as treatment-leveling agents. These are used to standardize the product.
- the precipitation co-adjuvants can be chosen from phosphates and phosphonates of all types. Pyrophosphates are well suited.
- the stripping action obtained through the use of the composition having high stabilizing properties and which is the subject of the present invention normally does not require any agitation of the baths or of the elements which are immersed therein.
- the invention therefore therefore also relates to methods for treating metallic surfaces, more particularly stainless steel surfaces in the presence of the stabilizing compositions described above using at least one inorganic peroxide at acid pH. This treatment is then followed by at least one rinsing. During at least one of the treatment or rinsing phases, agitation of the bath can be obtained using ultrasound.
- variable doses of the various active compounds and in particular of acid, of inorganic peroxides and of stabilizing composition according to the invention can be used. It is thus possible to use 0.1 to 5 moles and preferably 0.5 to 3 moles of peroxidized compound per liter of solution.
- the amount of acid is added to maintain the pH at the desired values.
- the acids which can be used for this purpose mention may be made of sulfuric acid which is particularly suitable. It can be used in combination with fluorides and for example with hydrofluoric acid in variable ratios. In this case, the sulfuric acid / hydrofluoric acid weight ratios generally do not exceed 500 and, more often than not, 100. Likewise these ratios are generally not less than 0.1 and, most often, not less than 1.
- the invention also relates to the use of the composition described above for the preparation of a pickling, passivating, polishing and / or polishing bath for metals.
- a typical composition includes: 98% sulfuric acid from 4 to 300 g / l 100% hydrogen peroxide from 0.2 to 100 g / l hydrofluoric acid from 0.5 to 10 g / l stabilizing composition from 0.2 to 30 g / l where the standard stabilizing composition consists of: p-toluene sulfonic acid 10 N-methylpyrrolidone 22 ethylene glycol 5 benzotriazole + imidazole (about 50% - 50%) 3 aluminum +++ 3 fluorinated anionic surfactant 0.5 (FC R 95: registered trademark of 3M company) ethylene oxide and octylphenol condensate 5 pyrophosphate ion 4 sulfuric acid 10 citric acid 2 water complement to 100
- Stability tests were then carried out by incorporating into the mixture, consisting of 180 g / l of sulfuric acid, 40 g / l of H2O2 and 30 g / l of hydrofluoric acid, an amount of 8 g / l of AISI 304 steel and then relating the H2O2 content to the initial values.
- composition of the invention having high stabilizing properties and more particularly in the case of inorganic peroxides used in the context of industrial applications, offers many advantages of all kinds.
- the temperatures of use of pickling baths appear to be equal to or really lower than the temperatures which are those of baths based on nitric and hydrofluoric acid and therefore, highly polluting.
- composition having important stabilizing properties, object of the present invention By using in a bath the composition having important stabilizing properties, object of the present invention, there is no emission of nitrous vapors, and the emission of acids, for example fluorides, is itself extremely reduced.
- Intergranular corrosion is also eliminated, among other things, and the process can be adapted to different types of stainless steels such as, for example, steels from the AISI 400 series (pickling is generally difficult with traditional systems). or still, the steels of the AISI 300 series. It is understood that the compositions according to the invention are also well suited for the treatment of other types of stainless steels.
- the use of the stabilizing composition described above makes it possible in particular to considerably reduce the consumption of inorganic peroxide, more particularly hydrogen peroxide, while allowing equal or really lower pickling times. , even up to 50%, compared to the stripping times required in the case of traditional baths.
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- Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Detergent Compositions (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- ing And Chemical Polishing (AREA)
Claims (13)
- Zusammensetzung zum Stabilisieren anorganischer Peroxide, die für Bäder zur Behandlung der Oberfläche von Metallteilen bestimmt ist, dadurch gekennzeichnet, daß sie wenigstens ein unter den Benzotriazolen, Imidazol und den Carboxyimidazolen oder ihren Derivaten ausgewähltes Aktivierungsmittel umfaßt.
- Zusammensetzung gemäß Anspruch 1, dadurch gekennzeichnet, daß sie außerdem wenigstens einen Stabilisator umfaßt.
- Zusammensetzung gemäß Anspruch 2, dadurch gekennzeichnet, daß sie außerdem wenigstens ein Lösungsmittel für den Stabilisator umfaßt.
- Zusammensetzung gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß sie außerdem einen Oxidationskatalysator umfaßt, der wenigstens ein zu den Gruppen I bis IV des Periodensystems gehörendes Metall umfaßt.
- Zusammensetzung gemäß einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß sie außerdem wenigstens ein Benetzungmittel enthält, das in oxidierendem saurem Medium stabil ist.
- Zusammensetzung gemäß Anspruch 2, dadurch gekennzeichnet, daß der Stabilisator wenigstens eine Verbindung umfaßt, die unter den mono- oder polyzyklischen aromatischen oder alizyklischen Verbindungen und den aliphatischen Verbindungen, die mit wenigstens einer unter den Hydroxyl-, Carboxyl-, Sulfonat-, Phosphat-, Ester-, Ether-, Dien-, Azol- und Mercaptoazolgruppen ausgewählten Gruppe substituiert sind, ausgewählt ist.
- Zusammensetzung gemäß einem der Ansprüche 3 bis 6, dadurch gekennzeichnet, daß das Lösungsmittel wenigstens eine unter Alkoholen, Glykolen und Polyglykolen ausgewählte Verbindung umfaßt.
- Zusammensetzung gemäß Anspruch 7, dadurch gekennzeichnet, daß das Lösungsmittel außerdem wenigstens einen unter Dimethylformamid und N-Methylpyrrolidon ausgewählten Hilfsstoff umfaßt.
- Zusammensetzung gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß sie außerdem wenigstens eine unter Phosphaten und Phosphonaten ausgewählte Verbindung als Co-Hilfsstoff zum Ausfällen und zur Desaktivierung von gelösten Metallen und anorganische und organische Säuren als Egalisiermittel für die Behandlung umfaßt.
- Verwendung der Zusammensetzung gemäß einem der Ansprüche 1 bis 9 für die Herstellung eines Beiz-, Glanz- oder Polierbads für Metalle.
- Verfahren zur Behandlung von metallischen Oberflächen, dadurch gekennzeichnet, daß man sie mit wenigstens einem anorganischen Peroxid bei einem sauren pH in Gegenwart von Zusammensetzungen gemäß einem der Ansprüche 1 bis 9 behandelt.
- Verfahren gemäß Anspruch 11, dadurch gekennzeichnet, daß man nach der Behandlung wenigstens einmal spült.
- Verfahren gemäß einem der Ansprüche 11 oder 12, dadurch gekennzeichnet, daß im Verlauf wenigstens einer der Phasen der Behandlung oder des Spülens das Bad mit Hilfe von Ultraschall bewegt wird.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
ITMI91284 | 1991-10-25 | ||
ITMI912845A IT1251431B (it) | 1991-10-25 | 1991-10-25 | Composto ad elevate caratteristiche stabilizzanti particolarmente per perossidi inorganici utilizzati in applicazioni industriali |
PCT/EP1992/002442 WO1993008317A1 (fr) | 1991-10-25 | 1992-10-23 | Composition stabilisante de solutions de peroxydes inorganiques |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0609342A1 EP0609342A1 (de) | 1994-08-10 |
EP0609342B1 true EP0609342B1 (de) | 1996-05-08 |
Family
ID=11360958
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Application Number | Title | Priority Date | Filing Date |
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EP92922319A Expired - Lifetime EP0609342B1 (de) | 1991-10-25 | 1992-10-23 | Zusammensetzung zum stabilisieren anorganischer peroxidlösungen |
Country Status (11)
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US (1) | US5538152A (de) |
EP (1) | EP0609342B1 (de) |
JP (1) | JPH07500378A (de) |
KR (1) | KR100249061B1 (de) |
BR (1) | BR9206668A (de) |
CA (1) | CA2121691A1 (de) |
DE (1) | DE69210622T2 (de) |
ES (1) | ES2089573T3 (de) |
FI (1) | FI100727B (de) |
IT (1) | IT1251431B (de) |
WO (1) | WO1993008317A1 (de) |
Families Citing this family (28)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2941948B2 (ja) * | 1994-09-26 | 1999-08-30 | カルゴン ベスタル, インコーポレイテッド | ステンレス鋼酸処理 |
WO1998011777A1 (en) * | 1996-09-18 | 1998-03-26 | Cottrell, Ltd. | Hydrogen peroxide disinfecting and sterilizing compositions |
US5958147A (en) * | 1997-05-05 | 1999-09-28 | Akzo Nobel N.V. | Method of treating a metal |
US6068879A (en) * | 1997-08-26 | 2000-05-30 | Lsi Logic Corporation | Use of corrosion inhibiting compounds to inhibit corrosion of metal plugs in chemical-mechanical polishing |
EP0945527A1 (de) * | 1998-03-24 | 1999-09-29 | Henkel Corporation | Wässerige, desoxidierende Zusammensetzung, Verfahren zu deren Herstellung und Verfahren zur Desoxidierung und Ätzung von Aluminium |
EP2194570A1 (de) * | 1998-12-28 | 2010-06-09 | Hitachi Chemical Co., Ltd. | Materialien für eine Reinigungsflüssigkeit für Metall, Reinigungsflüssigkeit für Metall, Herstellungsverfahren dafür und Reinigungsverfahren damit |
US6117250A (en) * | 1999-02-25 | 2000-09-12 | Morton International Inc. | Thiazole and thiocarbamide based chemicals for use with oxidative etchant solutions |
US6444140B2 (en) | 1999-03-17 | 2002-09-03 | Morton International Inc. | Micro-etch solution for producing metal surface topography |
US20030178391A1 (en) * | 2000-06-16 | 2003-09-25 | Shipley Company, L.L.C. | Composition for producing metal surface topography |
US20040099637A1 (en) * | 2000-06-16 | 2004-05-27 | Shipley Company, L.L.C. | Composition for producing metal surface topography |
DE60215629T2 (de) | 2001-04-09 | 2007-09-06 | AK Steel Properties, Inc., Middletown | Verfahren zum beizen von rostfreiem stahl unter verwendung von wasserstoffperoxid |
ES2311598T3 (es) * | 2001-04-09 | 2009-02-16 | Ak Steel Properties, Inc. | Aparato y procedimiento para eliminar peroxido de hidrogeno de un liquido de decapado residual. |
CA2443687C (en) | 2001-04-09 | 2009-08-11 | Vijay N. Madi | Hydrogen peroxide pickling of silicon-containing electrical steel grades |
TW591089B (en) * | 2001-08-09 | 2004-06-11 | Cheil Ind Inc | Slurry composition for use in chemical mechanical polishing of metal wiring |
US6953389B2 (en) * | 2001-08-09 | 2005-10-11 | Cheil Industries, Inc. | Metal CMP slurry compositions that favor mechanical removal of oxides with reduced susceptibility to micro-scratching |
DE10156624B4 (de) * | 2001-11-17 | 2005-10-27 | Robert Bosch Gmbh | Verfahren und Beizlösung zum Abreinigen von Belägen eines Stahl-Werkstückes |
KR20030050026A (ko) * | 2001-12-18 | 2003-06-25 | 백운규 | 화학기계적 연마용 슬러리, 이들 슬러리의 제조방법 및이들 슬러리를 이용한 화학기계적 연마방법 |
DE10346192B4 (de) * | 2003-10-02 | 2009-08-06 | Thyssenkrupp Presta Teccenter Ag | Verfahren zum Entrosten von Formteilen und Verwendung des Verfahrens |
KR100795364B1 (ko) * | 2004-02-10 | 2008-01-17 | 삼성전자주식회사 | 반도체 기판용 세정액 조성물, 이를 이용한 세정 방법 및도전성 구조물의 제조 방법 |
KR20050110470A (ko) * | 2004-05-19 | 2005-11-23 | 테크노세미켐 주식회사 | 반도체 기판용 세정액 조성물, 이를 이용한 반도체 기판세정방법 및 반도체 장치 제조 방법 |
EP1793016A1 (de) * | 2005-12-01 | 2007-06-06 | Elpochem AG | Polier- und Entgratungsmittel für Werkstücke aus Kohlenstoffstahl und Verfahren zum chemischen Polieren und Entgraten |
CA2767805A1 (en) * | 2009-07-06 | 2011-01-13 | Prestone Products Corporation | Methods and composition for cleaning a heat transfer system having an aluminum component |
GB2508827A (en) | 2012-12-11 | 2014-06-18 | Henkel Ag & Co Kgaa | Aqueous compositions and processes for passivating and brightening stainless steel surfaces |
JPWO2018142810A1 (ja) * | 2017-01-31 | 2019-11-14 | 三菱瓦斯化学株式会社 | 殺菌用過酸化水素水溶液 |
US11678433B2 (en) | 2018-09-06 | 2023-06-13 | D-Wave Systems Inc. | Printed circuit board assembly for edge-coupling to an integrated circuit |
US11647590B2 (en) | 2019-06-18 | 2023-05-09 | D-Wave Systems Inc. | Systems and methods for etching of metals |
US12033996B2 (en) | 2019-09-23 | 2024-07-09 | 1372934 B.C. Ltd. | Systems and methods for assembling processor systems |
CA3081989A1 (en) | 2020-06-05 | 2021-12-05 | Fluid Energy Group Ltd. | Stable nitric acid blends and uses thereof |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE710733C (de) * | 1937-10-16 | 1941-09-19 | Schering Ag | Verfahren zum Beizen von Eisen und Eisenlegierungen |
DE1190292B (de) * | 1959-08-04 | 1965-04-01 | Huettenwerk Oberhausen Ag | Verfahren und Vorrichtung zum Polieren von Schliffen fuer metallographische Untersuchungen |
JPS5221460B1 (de) * | 1971-04-26 | 1977-06-10 | ||
JPS5120972B1 (de) * | 1971-05-13 | 1976-06-29 | ||
JPS5332341B2 (de) * | 1973-03-27 | 1978-09-07 | ||
US3945865A (en) * | 1974-07-22 | 1976-03-23 | Dart Environment And Services Company | Metal dissolution process |
SE400581B (sv) * | 1974-12-13 | 1978-04-03 | Nordnero Ab | Bad for kemisk polering av koppar och dess legeringar |
SE400575B (sv) * | 1974-12-13 | 1978-04-03 | Nordnero Ab | Bad for betning av koppar och dess legeringar |
EP0015002B1 (de) * | 1979-02-22 | 1984-04-18 | The Wellcome Foundation Limited | 1-substituierte Imidazol-Derivate und deren Salze, Verfahren zu ihrer Herstellung und sie enthaltende pharmazeutische Formulierungen |
FR2513258A1 (fr) * | 1981-09-21 | 1983-03-25 | Dart Ind Inc | Solution aqueuse de peroxyde d'hydrogene stabilisee au 3-amino-1,2,4-triazole et son procede de stabilisation |
JPS58197277A (ja) * | 1982-05-08 | 1983-11-16 | Mitsubishi Gas Chem Co Inc | 金属の化学的溶解処理液 |
US4462861A (en) * | 1983-11-14 | 1984-07-31 | Shipley Company Inc. | Etchant with increased etch rate |
US4510018A (en) * | 1984-02-21 | 1985-04-09 | The Lea Manufacturing Company | Solution and process for treating copper and copper alloys |
US4875973A (en) * | 1988-07-27 | 1989-10-24 | E. I. Du Pont De Nemours And Company | Hydrogen peroxide compositions containing a substituted aminobenzaldehyde |
US4875972A (en) * | 1988-07-27 | 1989-10-24 | E. I. Du Pont De Nemours And Company | Hydrogen peroxide compositions containing a substituted oxybenzene compound |
US4915781A (en) * | 1988-07-27 | 1990-04-10 | E. I. Du Pont De Nemours And Company | Stabilized hydrogen peroxide compositions |
JP2800020B2 (ja) * | 1989-04-18 | 1998-09-21 | 東海電化工業株式会社 | 錫又は錫合金の化学溶解剤 |
JP2995667B2 (ja) * | 1990-11-27 | 1999-12-27 | 東海電化工業株式会社 | 銅を含む酸性過酸化水素水溶液の安定化法 |
-
1991
- 1991-10-25 IT ITMI912845A patent/IT1251431B/it active IP Right Grant
-
1992
- 1992-10-23 DE DE69210622T patent/DE69210622T2/de not_active Expired - Fee Related
- 1992-10-23 KR KR1019940701353A patent/KR100249061B1/ko not_active IP Right Cessation
- 1992-10-23 WO PCT/EP1992/002442 patent/WO1993008317A1/fr active IP Right Grant
- 1992-10-23 ES ES92922319T patent/ES2089573T3/es not_active Expired - Lifetime
- 1992-10-23 EP EP92922319A patent/EP0609342B1/de not_active Expired - Lifetime
- 1992-10-23 JP JP5507462A patent/JPH07500378A/ja active Pending
- 1992-10-23 US US08/211,964 patent/US5538152A/en not_active Expired - Fee Related
- 1992-10-23 BR BR9206668A patent/BR9206668A/pt not_active Application Discontinuation
- 1992-10-23 CA CA002121691A patent/CA2121691A1/fr not_active Abandoned
-
1994
- 1994-04-22 FI FI941893A patent/FI100727B/fi active
Also Published As
Publication number | Publication date |
---|---|
JPH07500378A (ja) | 1995-01-12 |
CA2121691A1 (fr) | 1993-04-29 |
KR100249061B1 (ko) | 2000-04-01 |
DE69210622D1 (de) | 1996-06-13 |
US5538152A (en) | 1996-07-23 |
FI941893A0 (fi) | 1994-04-22 |
DE69210622T2 (de) | 1996-11-28 |
WO1993008317A1 (fr) | 1993-04-29 |
IT1251431B (it) | 1995-05-09 |
FI941893A (fi) | 1994-06-01 |
ES2089573T3 (es) | 1996-10-01 |
ITMI912845A1 (it) | 1993-04-25 |
ITMI912845A0 (it) | 1991-10-25 |
EP0609342A1 (de) | 1994-08-10 |
FI100727B (fi) | 1998-02-13 |
BR9206668A (pt) | 1995-10-24 |
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