ITRM20000679A1 - PROCEDURE FOR THE PASSIVATION OF STAINLESS STEEL BAND WITH CHROMIUM-FREE PASSIVATION FILM. - Google Patents
PROCEDURE FOR THE PASSIVATION OF STAINLESS STEEL BAND WITH CHROMIUM-FREE PASSIVATION FILM. Download PDFInfo
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- ITRM20000679A1 ITRM20000679A1 IT2000RM000679A ITRM20000679A ITRM20000679A1 IT RM20000679 A1 ITRM20000679 A1 IT RM20000679A1 IT 2000RM000679 A IT2000RM000679 A IT 2000RM000679A IT RM20000679 A ITRM20000679 A IT RM20000679A IT RM20000679 A1 ITRM20000679 A1 IT RM20000679A1
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- Prior art keywords
- passivation
- steel band
- chromium
- free
- bath
- Prior art date
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- 238000002161 passivation Methods 0.000 title claims description 65
- 238000000034 method Methods 0.000 title claims description 43
- 229910001220 stainless steel Inorganic materials 0.000 title 1
- 239000010935 stainless steel Substances 0.000 title 1
- 230000008569 process Effects 0.000 claims description 34
- 229910000831 Steel Inorganic materials 0.000 claims description 25
- 239000010959 steel Substances 0.000 claims description 25
- 239000005028 tinplate Substances 0.000 claims description 14
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- 239000003973 paint Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- MEYVLGVRTYSQHI-UHFFFAOYSA-L cobalt(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Co+2].[O-]S([O-])(=O)=O MEYVLGVRTYSQHI-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- BBJSDUUHGVDNKL-UHFFFAOYSA-J oxalate;titanium(4+) Chemical compound [Ti+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O BBJSDUUHGVDNKL-UHFFFAOYSA-J 0.000 claims description 2
- 235000013324 preserved food Nutrition 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 235000015393 sodium molybdate Nutrition 0.000 claims description 2
- 239000011684 sodium molybdate Substances 0.000 claims description 2
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 2
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 claims description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims 4
- 235000003270 potassium fluoride Nutrition 0.000 claims 2
- 239000011698 potassium fluoride Substances 0.000 claims 2
- 235000013305 food Nutrition 0.000 claims 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 10
- 239000011651 chromium Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- 230000010287 polarization Effects 0.000 description 8
- 238000011282 treatment Methods 0.000 description 6
- 239000003792 electrolyte Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 239000007979 citrate buffer Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000004611 spectroscopical analysis Methods 0.000 description 3
- 239000003440 toxic substance Substances 0.000 description 3
- JHWIEAWILPSRMU-UHFFFAOYSA-N 2-methyl-3-pyrimidin-4-ylpropanoic acid Chemical compound OC(=O)C(C)CC1=CC=NC=N1 JHWIEAWILPSRMU-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910020491 K2TiF6 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- SQTLECAKIMBJGK-UHFFFAOYSA-I potassium;titanium(4+);pentafluoride Chemical compound [F-].[F-].[F-].[F-].[F-].[K+].[Ti+4] SQTLECAKIMBJGK-UHFFFAOYSA-I 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical class [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000009993 protective function Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- 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
- C23C22/40—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 molybdates, tungstates or vanadates
-
- 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
- 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
- C23C22/46—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 oxalates
-
- 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
- C23C22/48—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 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/58—Treatment of other metallic material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
- C25D9/10—Electrolytic coating other than with metals with inorganic materials by cathodic processes on iron or steel
Description
DESCRIZIONE DELL'INVENZIONE INDUSTRIALE dal titolo: "PROCEDIMENTO PER LA PASSIVAZIONE DI BANDA DI ACCIAIO STAGNATA CON FILM DI PASSIVAZIONE SENZA CROMO" DESCRIPTION OF THE INDUSTRIAL INVENTION entitled: "PROCEDURE FOR THE PASSIVATION OF TIN-PLATED STEEL BAND WITH CHROME-FREE PASSIVATION FILM"
La presente invenzione si riferisce al settore dei trattamenti per passivare la banda d'acciaio stagnata con film di passivazione senza cromo, al fine di migliorare l'impatto ambientale delle relative tecnologie. The present invention refers to the sector of treatments for passivating the tin-plated steel band with passivation film without chromium, in order to improve the environmental impact of the related technologies.
Come è noto, prima dell'utilizzo finale gli acciai rivestiti devono essere passivati, se il loro impiego è allo stato tal-quale, oppure subire un trattamento di superficiale per migliorare l'adesione di eventuali rivestimenti o per migliorare talune prestazioni, quale ad esempio la resistenza alla corrosione. As is known, before final use, coated steels must be passivated, if their use is in the state as such, or undergo a surface treatment to improve the adhesion of any coatings or to improve certain performances, such as for example resistance to corrosion.
Allo stato attuale di evoluzione della tecnologia, i più comuni trattamenti di passivazione, o conversione superficiale, utilizzano soluzioni che contengono cromo sotto forma di bicromato di sodio. In the current state of evolution of technology, the most common passivation treatments, or surface conversion, use solutions that contain chromium in the form of sodium dichromate.
Questi trattamenti sono finalizzati sia alla "conversione" del substrato metallico con funzione protettiva in ambienti blandamente aggressivi, sia alla preparazione della superficie al fine di migliorare l'adesione di successivi strati protettivi . These treatments are aimed both at the "conversion" of the metal substrate with protective function in mildly aggressive environments, and at the preparation of the surface in order to improve the adhesion of subsequent protective layers.
Il rivestimento di passivazione può essere considerato composto da una miscela di prodotti di corrosione del substrato metallico e di svariate specie ridotte che derivano dal bagno di conversione. Esempi tipici di trattamento di passivazione sono sistemi basati su cromati e fosfati, i quali rappresentano una considerevole fetta di mercato dei processi e prodotti di conversione superficiale. The passivation coating can be considered to be composed of a mixture of corrosion products of the metal substrate and of various reduced species deriving from the conversion bath. Typical examples of passivation treatment are systems based on chromates and phosphates, which represent a considerable market share of surface conversion processes and products.
Le principali tecniche di passivazione prevedono la semplice immersione del prodotto da passivare oppure l'applicazione ad esso di una corrente catodica che spesso permette di avere tempi di formazione più rapidi. The main passivation techniques involve the simple immersion of the product to be passivated or the application to it of a cathodic current which often allows for faster formation times.
La necessità di migliorare l'impatto ambientale e la severità delle leggi che disciplinano il trattamento di sostanze tossiche, quali ad esempio i metalli pesanti e, di conseguenza, la necessità di trattare le acque di lavaggio e gli esausti, ha creato l'esigenza di un trattamento di passivazione delle superfici metalliche totalmente privo di sostanze tossiche. The need to improve the environmental impact and the severity of the laws governing the treatment of toxic substances, such as heavy metals and, consequently, the need to treat washing water and waste, has created the need to a passivation treatment of metal surfaces totally free of toxic substances.
La banda d'acciaio stagnata viene ad esempio convenzionalmente passivata con soluzioni a base di sali di cromo (bicromato di sodio, Na2Cr207). Dato che il cromo è ritenuto una sostanza ad elevata tossicità con gravi problemi di impatto ambientale, si pone il problema di sostituire la passivazione a base di cromo con passivazioni altrettanto efficaci a base di soluzioni prive di cromo. The tin-plated steel band is, for example, conventionally passivated with solutions based on chromium salts (sodium dichromate, Na2Cr207). Given that chromium is considered a highly toxic substance with serious problems of environmental impact, the problem arises of replacing the chromium-based passivation with equally effective passivations based on chromium-free solutions.
La presente invenzione rappresenta una risposta a questa esigenza. E1 infatti oggetto della presente invenzione un procedimento per la passivazione di banda d'acciaio stagnata con film di passivazione senza cromo, caratterizzato dal fatto di comprendere l'operazione di immergere, eventualmente applicando una corrente catodica, la banda stagnata in un bagno di passivazione comprendente almeno un sale di un metallo di transizione scelto tra cobalto, titanio, zirconio e molibdeno. The present invention represents a response to this need. In fact, the subject of the present invention is a process for the passivation of tinplate steel with chromium-free passivation film, characterized in that it comprises the operation of immersing, possibly by applying a cathode current, the tinplate in a passivation bath comprising at least one salt of a transition metal selected from cobalt, titanium, zirconium and molybdenum.
In una forma di realizzazione dell'invenzione, il bagno di passivazione è una soluzione acquosa di solfato di cobalto eptaidrato In an embodiment of the invention, the passivation bath is an aqueous solution of cobalt sulphate heptahydrate
fluoruro di titanio e potassio e nitrato di sodio (NaN03). In una variante di questo procedimento, le caratteristiche di processo sono le seguenti: composizione del bagno di passivazione espressa in grammi/litro titanium potassium fluoride and sodium nitrate (NaN03). In a variant of this procedure, the process characteristics are the following: composition of the passivation bath expressed in grams / liter
la restante parte essendo acqua; temperatura del bagno 50-65°C; densità della corrente catodica 0,10-0,15 A/dm2; e tempo di esposizione 1-5 secondi. the remainder being water; bath temperature 50-65 ° C; cathode current density 0.10-0.15 A / dm2; and exposure time 1-5 seconds.
In una seconda forma di realizzazione del procedimento secondo l'invenzione, il bagno di passivazione è una soluzione acquosa di fluoruro di titanio e potassio e nitrato di sodio In a second embodiment of the process according to the invention, the passivation bath is an aqueous solution of titanium-potassium fluoride and sodium nitrate
In una variante di questo procedimento, le In a variant of this procedure, the
caratteristiche di processo sono le seguenti: composizione del bagno di passivazione espressa in grammi/litro process characteristics are the following: composition of the passivation bath expressed in grams / liter
la restante parte essendo acqua; temperatura del bagno 50-60°C; densità della corrente catodica 0,10-0,15 A/dm2; e tempo di esposizione 10-30 secondi. the remainder being water; bath temperature 50-60 ° C; cathode current density 0.10-0.15 A / dm2; and exposure time 10-30 seconds.
In una terza forma di realizzazione della presente invenzione, il bagno di passivazione è una soluzione acquosa contenente solfato di zirconio. In una variante di questo procedimento, le caratteristiche di processo sono le seguenti: composizione del bagno di passivazione In a third embodiment of the present invention, the passivation bath is an aqueous solution containing zirconium sulfate. In a variant of this process, the process characteristics are the following: composition of the passivation bath
la restante parte essendo acqua; temperatura del bagno 50-60°C; densità della corrente catodica 0,1-0,2 A/dm2 e tempo di esposizione 5-10 secondi. the remainder being water; bath temperature 50-60 ° C; cathode current density 0.1-0.2 A / dm2 and exposure time 5-10 seconds.
In una quarta forma di realizzazione secondo la presente invenzione, il bagno di passivazione è una soluzione acquosa contenente ossalato di titanio. In una variante di questo procedimento, le caratteristiche di processo sono le seguenti: composizione del bagno di passivazione espressa in grammi/litro (g/1) In a fourth embodiment according to the present invention, the passivation bath is an aqueous solution containing titanium oxalate. In a variant of this procedure, the process characteristics are the following: composition of the passivation bath expressed in grams / liter (g / 1)
la restante parte essendo acqua; temperatura del bagno nell'intervallo compreso fra 50 e 65°C; densità della corrente catodica 0,1-0,2 A/dm2 e tempo di esposizione 5-10 secondi. the remainder being water; bath temperature in the range from 50 to 65 ° C; cathode current density 0.1-0.2 A / dm2 and exposure time 5-10 seconds.
In una quinta forma di realizzazione secondo la presente invenzione, il bagno di passivazione è una soluzione acquosa contenente molibdato di sodio. In una variante di questo procedimento, le caratteristiche di processo sono le seguenti: composizione del bagno di passivazione espressa in g/i In a fifth embodiment according to the present invention, the passivation bath is an aqueous solution containing sodium molybdate. In a variant of this process, the process characteristics are the following: composition of the passivation bath expressed in g / i
la restante parte essendo acqua; temperatura del bagno 40-45°C; densità della corrente catodica 0,1-0,15 A/dm2 e tempo di esposizione 5-10 secondi . the remainder being water; bath temperature 40-45 ° C; cathode current density 0.1-0.15 A / dm2 and exposure time 5-10 seconds.
E' anche oggetto della presente invenzione una banda d'acciaio stagnata, passivata con il procedimento descritto in precedenza. The present invention also relates to a tin-plated steel band, passivated with the process described above.
Oggetto della presente invenzione è anche una banda d'acciaio stagnata, passivata con il procedimento descritto in precedenza, verniciata con vernici senza cromo. The subject of the present invention is also a tin-plated steel band, passivated with the process described above, painted with chrome-free paints.
E' infine oggetto della presente invenzione l'uso della banda d'acciaio stagnata, passivata e verniciata senza uso di cromo, per la produzione di scatolame per alimenti. Finally, the subject of the present invention is the use of the tin-plated steel band, passivated and painted without the use of chromium, for the production of canned food.
Si è data finora della presente invenzione una descrizione di carattere generale. Con l'aiuto delle seguenti figure e dell'esempio verrà ora fornita una descrizione più dettagliata di sue particolari forme di realizzazione finalizzate a farne meglio comprendere scopi, caratteristiche, vantaggi e modalità di applicazione. Up to now, a general description of the present invention has been given. With the help of the following figures and the example, a more detailed description of its particular embodiments will now be provided, aimed at making them better understand the purposes, characteristics, advantages and methods of application.
La figura 1 mostra le curve di polarizzazione potenziodinamiche in tampone di citrato, a pH 6, velocità di scansione 0,2 mV/s, 50°C, per una banda stagnata, non passivata (curva punteggiata), passivata con soluzione a base di cromo (curva tratteggiata) , e passivata secondo 11invenzione (curva continua) con le seguenti caratteristiche di processo: bagno di passivazione contenente un 15 g/1 di Figure 1 shows the potentiodynamic polarization curves in citrate buffer, at pH 6, scanning rate 0.2 mV / s, 50 ° C, for a tinplate, non-passivated (dotted curve), passivated with solution based on chromium (dashed curve), and passivated according to the invention (continuous curve) with the following process characteristics: passivation bath containing 15 g / 1 of
(elettrolita 1); temperatura del bagno 50°C; densità di corrente applicata 0,15 A/dm2; e tempo di esposizione 1 secondo. (electrolyte 1); bath temperature 50 ° C; applied current density 0.15 A / dm2; and 1 second exposure time.
La figura 2 mostra le curve di polarizzazione potenziodinamiche in tampone di citrato, a pH 6,0, velocità di scansione 0,2 mV/s, 50°C, per banda stagnata, non passivata (curva punteggiata), passivata con soluzioni a base di cromo (curva tratteggiata), passivata secondo l'invenzione (curva continua) con le seguenti caratteristiche di processo: bagno di passivazione contenente 15 g/1 di K2TiF6 e 5 g/1 di NaN03 (elettrolita 2); temperatura del bagno 50°C; densità di corrente applicata 0,14 A/dm2; tempo di esposizione 30 secondi. Figure 2 shows the potentiodynamic polarization curves in citrate buffer, at pH 6.0, scanning rate 0.2 mV / s, 50 ° C, for tinplate, non-passivated (dotted curve), passivated with solutions based chromium (dashed curve), passivated according to the invention (continuous curve) with the following process characteristics: passivation bath containing 15 g / 1 of K2TiF6 and 5 g / 1 of NaN03 (electrolyte 2); bath temperature 50 ° C; applied current density 0.14 A / dm2; exposure time 30 seconds.
La figura 3 mostra uno spettro EDS (X-ray Dispersive Energy Spectrometry Measurements) di una banda stagnata non trattata, da sottoporre al procedimento di passivazione secondo l'invenzione. Figure 3 shows an EDS spectrum (X-ray Dispersive Energy Spectrometry Measurements) of an untreated tinplate, to be subjected to the passivation process according to the invention.
Le figure 4 e 5 mostrano i profili GDOS (Glow Discharge for Optical Emission Spectrochemical Analysis) per campioni passivati rispettivamente con l'elettrolita 1 e con l'elettrolita 2 secondo l 'invenzione. Figures 4 and 5 show the GDOS profiles (Glow Discharge for Optical Emission Spectrochemical Analysis) for samples passivated respectively with the electrolyte 1 and with the electrolyte 2 according to the invention.
ESEMPIO EXAMPLE
Una banda stagnata da sottoporre al procedimento di passivazione secondo l’invenzione viene caratterizzata con la tecnica EDX (X-ray Dispersive Energy Spectrometry Measurements). Il relativo spettro, mostrato in figura 3, rivela la presenza di stagno come elemento massivo e di ferro. Il contenuto di cromo, evidenziato mediante spettroscopia ad assorbimento atomico, è compreso nell'intervallo 0,58 - 0,67 mg/m2. A tinplate to be subjected to the passivation process according to the invention is characterized with the EDX (X-ray Dispersive Energy Spectrometry Measurements) technique. The relative spectrum, shown in figure 3, reveals the presence of tin as a massive element and of iron. The chromium content, highlighted by atomic absorption spectroscopy, is in the range 0.58 - 0.67 mg / m2.
Questa banda stagnata viene sottoposta a passivazione secondo l'invenzione, in soluzione acquosa a 50°C contenente 15 g/1 di K2TiF6 e 5 g/1 di NaN03, con densità di corrente catodica pari a 0,14 A/dm2 e tempo di esposizione 30 secondi. This tinplate is subjected to passivation according to the invention, in aqueous solution at 50 ° C containing 15 g / 1 of K2TiF6 and 5 g / 1 of NaN03, with a cathode current density equal to 0.14 A / dm2 and exposure 30 seconds.
Il comportamento alla corrosione di campioni di banda stagnata così passivata viene studiato mediante curve di polarizzazione potenziodinamiche e prove di esposizione in soluzione di cloruro di sodio (30 g/1) per 24 ore a 25°C. The corrosion behavior of tinplate samples thus passivated is studied by means of potentiodynamic polarization curves and exposure tests in sodium chloride solution (30 g / 1) for 24 hours at 25 ° C.
Le curve di polarizzazione potenziodinamiche vengono costruite mediante misure fatte con una cella di vetro convenzionale a 25°C in soluzione saturata con azoto puro. Il controelettrodo è un foglio di platino e, come elettrodo di riferimento, viene usato un elettrodo a calomelano saturo (SCE). L'elettrolita è un tampone di citrato, pH 6,0. La velocità di scansione è 0,2 mV/s. Le curve di polarizzazione vengono iniziate dopo la stabilizzazione del potenziale di corrosione (circa 90 minuti) . La figura 2 mostra la curva di polarizzazione potenziodinamica della banda stagnata passivata come descritto in precedenza (curva continua), in confronto alle curve di polarizzazione potenziodinamica di banda stagnata non passivata (curva punteggiata) e banda stagnata passivata con soluzione a base di cromo (curva tratteggiata) . Potentiodynamic polarization curves are constructed by measurements made with a conventional glass cell at 25 ° C in a solution saturated with pure nitrogen. The counter electrode is a platinum foil and a saturated calomel electrode (SCE) is used as the reference electrode. The electrolyte is a citrate buffer, pH 6.0. The scanning speed is 0.2mV / s. The polarization curves are initiated after stabilization of the corrosion potential (approximately 90 minutes). Figure 2 shows the potentiodynamic polarization curve of the passivated tinplate as described above (continuous curve), in comparison to the potentiodynamic polarization curves of non-passivated tinplate (dotted curve) and passivated tinplate with chromium-based solution (curve dotted) .
Il risultato dei test di esposizione conferma i risultati ottenuti dalle curve di polarizzazione. I campioni passivati secondo la forma di realizzazione dell'invenzione descritta in precedenza presentano un ottimo comportamento. The result of the exposure tests confirms the results obtained from the polarization curves. The passivated samples according to the embodiment of the invention described above exhibit excellent behavior.
La superficie di campioni di banda stagnata passivata come indicato in precedenza è stata analizzata con le tecniche SEM (Scanning Electron Microscopy) , EDS (X-ray Dispersive Energy Spectrometry Measurements), GDOS (Glow Discharge for Optical Emission Spectrochemical Analysis)( il cui profilo è mostrato in figura 4, e XPS (X-ray Photoelectron Spectroscopy). I risultati di queste analisi di superficie evidenziano caratteristiche paragonabili a quelle delle superiici di banda stagnata passivata con soluzioni a base di cromo. The surface of passivated tinplate samples as indicated above was analyzed with SEM (Scanning Electron Microscopy), EDS (X-ray Dispersive Energy Spectrometry Measurements), GDOS (Glow Discharge for Optical Emission Spectrochemical Analysis) techniques (whose profile is shown in figure 4, and XPS (X-ray Photoelectron Spectroscopy) .The results of these surface analyzes show characteristics comparable to those of the passivated tinplate surfaces with chromium-based solutions.
Claims (15)
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2000RM000679A IT1316032B1 (en) | 2000-12-19 | 2000-12-19 | PROCEDURE FOR THE PASSIVATION OF STAINLESS STEEL BAND WITH CHROMIUM-FREE PASSIVATION FILM. |
| AU2002225326A AU2002225326A1 (en) | 2000-12-19 | 2001-12-19 | Process for the passivation of tinned stainless steel strip with a chrome-free passivation film |
| PCT/IT2001/000643 WO2002050341A2 (en) | 2000-12-19 | 2001-12-19 | Process for the passivation of tinned stainless steel strip with a chrome-free passivation film |
| EP01994948A EP1368515A2 (en) | 2000-12-19 | 2001-12-19 | Process for the passivation of tinned stainless steel strip with a chrome-free passivation film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| IT2000RM000679A IT1316032B1 (en) | 2000-12-19 | 2000-12-19 | PROCEDURE FOR THE PASSIVATION OF STAINLESS STEEL BAND WITH CHROMIUM-FREE PASSIVATION FILM. |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| ITRM20000679A0 ITRM20000679A0 (en) | 2000-12-19 |
| ITRM20000679A1 true ITRM20000679A1 (en) | 2002-06-19 |
| IT1316032B1 IT1316032B1 (en) | 2003-03-26 |
Family
ID=11455067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| IT2000RM000679A IT1316032B1 (en) | 2000-12-19 | 2000-12-19 | PROCEDURE FOR THE PASSIVATION OF STAINLESS STEEL BAND WITH CHROMIUM-FREE PASSIVATION FILM. |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1368515A2 (en) |
| AU (1) | AU2002225326A1 (en) |
| IT (1) | IT1316032B1 (en) |
| WO (1) | WO2002050341A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2484381C (en) | 2004-10-08 | 2013-03-19 | Anne Marie Sedgwick | Supporting device |
| DE102009044982A1 (en) * | 2009-09-24 | 2011-03-31 | Stefan Dameron | Process for electroplating and passivation |
| CN102268664B (en) * | 2011-07-28 | 2013-04-17 | 顺德职业技术学院 | Chromium-free passivating solution used for black passivation treatment of zinc plating and preparation method thereof |
| CN104562029A (en) * | 2014-12-26 | 2015-04-29 | 江苏新华明机械制造实业有限公司 | Surface treatment process for framework stamping part of high-frequency tuner |
| CN109975340A (en) * | 2017-12-26 | 2019-07-05 | 上海梅山钢铁股份有限公司 | The Microstructural Analysis of aluminium plating zinc plate chromium-free deactivation film thickness |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4298404A (en) * | 1979-09-06 | 1981-11-03 | Richardson Chemical Company | Chromium-free or low-chromium metal surface passivation |
| US4444601A (en) * | 1979-09-06 | 1984-04-24 | Richardson Chemical Company | Metal article passivated by a bath having an organic activator and a film-forming element |
| JPS5698480A (en) * | 1980-01-11 | 1981-08-07 | Kobe Steel Ltd | Rust preventive treatment of galvanized steel material |
| DK187391D0 (en) * | 1991-11-15 | 1991-11-15 | Inst Produktudvikling | PROCEDURE FOR THE TREATMENT OF ZINC COATED MATERIALS AND TREATMENT SOLUTION FOR USE BY THE PROCEDURE |
| GB2298870B (en) * | 1995-03-13 | 1998-09-30 | British Steel Plc | Passivation treatment of tinplate |
| DE19745801A1 (en) * | 1997-10-16 | 1999-04-22 | Henkel Kgaa | Method for coating metals with organic film-former solutions or dispersions containing corrosion inhibitor pigment precursors |
-
2000
- 2000-12-19 IT IT2000RM000679A patent/IT1316032B1/en active
-
2001
- 2001-12-19 WO PCT/IT2001/000643 patent/WO2002050341A2/en not_active Application Discontinuation
- 2001-12-19 AU AU2002225326A patent/AU2002225326A1/en not_active Abandoned
- 2001-12-19 EP EP01994948A patent/EP1368515A2/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| EP1368515A2 (en) | 2003-12-10 |
| IT1316032B1 (en) | 2003-03-26 |
| WO2002050341A3 (en) | 2003-09-25 |
| ITRM20000679A0 (en) | 2000-12-19 |
| WO2002050341A2 (en) | 2002-06-27 |
| AU2002225326A1 (en) | 2002-07-01 |
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