EP0658636A1 - Corrosion inhibitor for metallic material, such as steel - Google Patents
Corrosion inhibitor for metallic material, such as steel Download PDFInfo
- Publication number
- EP0658636A1 EP0658636A1 EP94470040A EP94470040A EP0658636A1 EP 0658636 A1 EP0658636 A1 EP 0658636A1 EP 94470040 A EP94470040 A EP 94470040A EP 94470040 A EP94470040 A EP 94470040A EP 0658636 A1 EP0658636 A1 EP 0658636A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- corrosion inhibitor
- alkali metal
- solution
- steel
- sheet
- 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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Classifications
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- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
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- 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
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- 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
- C23C22/68—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 solutions with pH between 6 and 8
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- 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
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/18—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using inorganic inhibitors
- C23F11/187—Mixtures of inorganic inhibitors
- C23F11/188—Mixtures of inorganic inhibitors containing phosphates
Definitions
- the invention relates to the field of corrosion inhibitors with which the surface of metals, in particular steel, is coated, prior to their storage.
- corrosion inhibitors are used by steelmakers to coat, together with oils, the surface of the steel sheets after they are rolled and before they are wrapped in coils and shipped to the customer who ordered them.
- These corrosion inhibitors have the function of passivating the surface of the product (in the case of passivating inhibitors, based, for example on nitrites) by forming a protective film therein, or of forming compounds which precipitate on the surface of the product and forming therein a film protective (in the case of non-passivating inhibitors, based, for example, on phosphates), or to cause neutralization or alkalization of the medium surrounding the surface and adsorption (case of organic inhibitors based on amines).
- These inhibitors can also serve as lubricants during the subsequent operations of work hardening of the sheet.
- Inhibitors containing both sodium nitrite NaNO2 and azoles have been shown to work protection of steel sheets. However, they cannot be used on sheets of which only one side is coated and comprises, for example, a deposit of a zinc-nickel alloy, since the contact during winding between this coating and the inhibitor deposited on the bare face of the neighboring coil causes the appearance of spots on the zinc-nickel layer. However, they do not risk generating nitrosamines during a possible subsequent heating of the sheet, unlike amines. Since nitrosamines are known for their carcinogenic properties, such a possibility of formation should be avoided.
- the object of the invention is to propose a corrosion inhibitor which can be used on steel sheets coated on only one of their faces, without this inhibitor damaging the coated face and generating toxic compounds during heating. ulterior.
- the subject of the invention is an inhibitor of the corrosion of a metallic material, such as steel, of the type constituted by an aqueous solution containing an alkali metal nitrite, characterized in that said solution contains 0, 01 to 0.3 mol / l of an alkali metal nitrite, 0.01 to 0.3 mol / l of an alkali metal phosphate, and phosphoric acid in an amount sufficient to maintain the pH of said solution, measured at room temperature, between 6.9 and 7.2.
- the invention consists in jointly adding an alkali metal phosphate and phosphoric acid to known inhibitors based on sodium nitrite, in well-defined proportions, in such a way that one obtains a neutral, non-aggressive solution for the surface coated with zinc-nickel single-sided sheets.
- the inventors have found that the appearance of spots on the zinc-nickel coating of the coated face of the sheets whose bare face is protected by sodium nitrite inhibitors was due to the pronounced basicity and the absence of a buffer medium. of these inhibitors. Their pH is around 9 to 11, which causes alkaline corrosion of the coating by the formation of zincates.
- the idea behind the invention is that it is possible to avoid this alkaline corrosion by buffering the inhibitor at a neutral pH, compatible with the passivation of iron. This can be achieved by adding a buffer salt to the sodium nitrite.
- a mixture of sodium phosphate Na3PO4 and phosphoric acid H3PO4 is particularly indicated (sodium can be replaced by another alkali metal such as potassium).
- nitrite ions and phosphate ions have synergistic effects in their anti-corrosion action, the former acting as neutralizing inhibitors and the latter as passivating inhibitors.
- the corrosion inhibitor according to the invention is an aqueous solution of an alkali metal nitrite at a concentration of 0.01 to 0.3 mol / l, and an alkaline phosphate at a concentration of 0.01 to 0 , 3 mol / l, and also containing phosphoric acid at a concentration such that it imposes on the solution a pH of between 6.9 and 7.2 measured at room temperature. It is also desirable that the molar concentrations of alkali metal nitrite ions and alkaline phosphate ions should not differ by more than 20%.
- a non-ionic or anionic wetting agent such as a phosphoric ester
- a non-ionic or anionic wetting agent such as a phosphoric ester
- an anti-foaming agent it is desirable to add an anti-foaming agent.
- the amounts added can be, for example, from 1 to 5 ml / l of wetting agent and from 0.2 to 1 ml / l of antifoam.
- Different modes of application of the inhibitor can be envisaged, for example using dewatering rollers between which the sheet runs, and the lower parts of which soak in tanks containing the solution containing the inhibitor.
- These drain rollers must apply, for example, 1 to 2 ml of solution per m2 of sheet metal (on each side concerned by the treatment), corresponding to an amount of sodium of 2 to 6 mg / m2. It is understood that one can, as desired, coat the two faces of the sheet or only the bare face.
- this corrosion inhibitor is not limited to the protection of coated sheets on a single face by a zinc-nickel alloy, which is only a preferential application, but it is applicable to the protection of any steel sheet, even other metallic materials.
Abstract
Description
L'invention concerne le domaine des inhibiteurs de corrosion dont on enduit la surface des métaux, notamment de l'acier, préalablement à leur stockage.The invention relates to the field of corrosion inhibitors with which the surface of metals, in particular steel, is coated, prior to their storage.
Différentes solutions renfermant des inhibiteurs de corrosion sont utilisées par les sidérurgistes pour enduire, conjointement aux huiles, la surface des tôles d'acier après leur laminage et avant leur conditionnement en bobines et leur expédition chez le client qui les a commandées. Ces inhibiteurs de corrosion ont pour fonction de passiver la surface du produit (cas des inhibiteurs passivants, à base, par exemple de nitrites) en y formant un film protecteur, ou de former des composés précipitant à la surface du produit et y formant un film protecteur (cas des inhibiteurs non passivants, à base, par exemple, de phosphates), ou de provoquer une neutralisation ou une alcalinisation du milieu avoisinant la surface et une adsorption (cas des inhibiteurs organiques à base d'amines). Ces inhibiteurs peuvent également servir de lubrifiants lors des opérations ultérieures d'écrouissage de la tôle.Different solutions containing corrosion inhibitors are used by steelmakers to coat, together with oils, the surface of the steel sheets after they are rolled and before they are wrapped in coils and shipped to the customer who ordered them. These corrosion inhibitors have the function of passivating the surface of the product (in the case of passivating inhibitors, based, for example on nitrites) by forming a protective film therein, or of forming compounds which precipitate on the surface of the product and forming therein a film protective (in the case of non-passivating inhibitors, based, for example, on phosphates), or to cause neutralization or alkalization of the medium surrounding the surface and adsorption (case of organic inhibitors based on amines). These inhibitors can also serve as lubricants during the subsequent operations of work hardening of the sheet.
Cette protection des tôles par de tels inhibiteurs est particulièrement nécessaire dans le cas des tôles d'acier qui ont été revêtues par électrodéposition sur une seule de leurs faces. D'une part, au cours des différentes étapes liées à ce traitement, la tôle est en contact avec différents liquides qui peuvent être agressifs pour la face non revêtue s'ils ne sont pas, par la suite, totalement éliminés : les solutions de dégraissage et d'avivage, l'électrolyte, les fluides de rinçage... De plus l'atmosphère de la ligne d'électrodéposition est chargée de sels d'électrolyte et d'acide. Toutes les conditions sont donc réunies pour nécessiter un traitement de la face non revêtue de la tôle par un inhibiteur de corrosion, afin d'éviter sa piqûration pendant le stockage de la bobine.This protection of the sheets by such inhibitors is particularly necessary in the case of steel sheets which have been coated by electrodeposition on only one of their faces. On the one hand, during the various stages linked to this treatment, the sheet is in contact with different liquids which can be aggressive for the uncoated face if they are not subsequently completely eliminated: degreasing solutions and brightening, electrolyte, rinsing fluids ... In addition, the atmosphere of the plating line is charged with electrolyte salts and acid. All the conditions are therefore met to require treatment of the uncoated face of the sheet with a corrosion inhibitor, in order to avoid its pitting during storage of the coil.
Les inhibiteurs contenant à la fois du nitrite de sodium NaNO₂ et des azoles ont prouvé leur efficacité pour la protection des tôles d'acier. Ils ne sont cependant pas utilisables sur les tôles dont une seule face est revêtue et comporte, par exemple, un dépôt d'un alliage zinc-nickel, car le contact lors du bobinage entre ce revêtement et l'inhibiteur déposé sur la face nue de la spire voisine provoque l'apparition de taches sur la couche de zinc-nickel. Ils ne risquent toutefois pas de générer des nitrosamines lors d'un éventuel réchauffage ultérieur de la tôle, contrairement aux amines. Les nitrosamines étant connues pour leurs propriétés carcinogènes, une telle possibilité de formation doit être évitée.Inhibitors containing both sodium nitrite NaNO₂ and azoles have been shown to work protection of steel sheets. However, they cannot be used on sheets of which only one side is coated and comprises, for example, a deposit of a zinc-nickel alloy, since the contact during winding between this coating and the inhibitor deposited on the bare face of the neighboring coil causes the appearance of spots on the zinc-nickel layer. However, they do not risk generating nitrosamines during a possible subsequent heating of the sheet, unlike amines. Since nitrosamines are known for their carcinogenic properties, such a possibility of formation should be avoided.
Le but de l'invention est de proposer un inhibiteur de corrosion pouvant être utilisé sur les tôles d'acier revêtues sur une seule de leurs faces, sans que cet inhibiteur ne détériore la face revêtue et ne génère des composés toxiques lors d'un chauffage ultérieur.The object of the invention is to propose a corrosion inhibitor which can be used on steel sheets coated on only one of their faces, without this inhibitor damaging the coated face and generating toxic compounds during heating. ulterior.
A cet effet, l'invention a pour objet un inhibiteur de la corrosion d'un matériau métallique, tel que l'acier, du type constitué par une solution aqueuse renfermant un nitrite de métal alcalin, caractérisé en ce que ladite solution renferme 0,01 à 0,3 mol/l d'un nitrite de métal alcalin, 0,01 à 0,3 mol/l d'un phosphate d'un métal alcalin, et de l'acide phosphorique à raison d'une quantité suffisante pour maintenir le pH de ladite solution, mesuré à température ambiante, entre 6,9 et 7,2.To this end, the subject of the invention is an inhibitor of the corrosion of a metallic material, such as steel, of the type constituted by an aqueous solution containing an alkali metal nitrite, characterized in that said solution contains 0, 01 to 0.3 mol / l of an alkali metal nitrite, 0.01 to 0.3 mol / l of an alkali metal phosphate, and phosphoric acid in an amount sufficient to maintain the pH of said solution, measured at room temperature, between 6.9 and 7.2.
Comme on l'aura compris, l'invention consiste à rajouter conjointement un phosphate d'un métal alcalin et de l'acide phosphorique aux inhibiteurs connus à base de nitrite de sodium, dans des proportions bien déterminées, de telle manière qu'on obtienne une solution neutre, non agressive pour la face revêtue des tôles monoface zinc-nickel.As will be understood, the invention consists in jointly adding an alkali metal phosphate and phosphoric acid to known inhibitors based on sodium nitrite, in well-defined proportions, in such a way that one obtains a neutral, non-aggressive solution for the surface coated with zinc-nickel single-sided sheets.
Les inventeurs ont constaté que l'apparition de taches sur le revêtement de zinc-nickel de la face revêtue des tôles dont la face nue est protégée par les inhibiteurs au nitrite de sodium était due à la basicité prononcé et à l'absence de milieu tampon de ces inhibiteurs. Leur pH est d'environ 9 à 11, ce qui provoque une corrosion alcaline du revêtement par formation de zincates. L'idée à la base de l'invention est qu'il est possible d'éviter cette corrosion alcaline en tamponnant l'inhibiteur à un pH neutre, compatible avec la passivation du fer. Ceci peut être réalisé en ajoutant au nitrite de sodium un sel tampon. Un mélange de phosphate de sodium Na₃PO₄ et d'acide phosphorique H₃PO₄ est particulièrement indiqué (le sodium pouvant être remplacé par un autre métal alcalin tel que le potassium). En effet, les ions nitrite et les ions phosphate ont des effets synergiques dans leur action anti-corrosion, les premiers agissant comme inhibiteurs neutralisants et les seconds comme inhibiteurs passivants.The inventors have found that the appearance of spots on the zinc-nickel coating of the coated face of the sheets whose bare face is protected by sodium nitrite inhibitors was due to the pronounced basicity and the absence of a buffer medium. of these inhibitors. Their pH is around 9 to 11, which causes alkaline corrosion of the coating by the formation of zincates. The idea behind the invention is that it is possible to avoid this alkaline corrosion by buffering the inhibitor at a neutral pH, compatible with the passivation of iron. This can be achieved by adding a buffer salt to the sodium nitrite. A mixture of sodium phosphate Na₃PO₄ and phosphoric acid H₃PO₄ is particularly indicated (sodium can be replaced by another alkali metal such as potassium). Indeed, nitrite ions and phosphate ions have synergistic effects in their anti-corrosion action, the former acting as neutralizing inhibitors and the latter as passivating inhibitors.
Le fait de prévoir un milieu tampon accompagnant l'inhibiteur de corrosion s'accorde bien avec l'exécution d'un rinçage acide préalablement à l'enduction de la tôle, et avec la présence éventuelle d'ions K⁺, Zn ²⁺ et Ni ²⁺ dans l'atmosphère de la halle d'électrodéposition et de bobinage. Il est, pour cela, impératif que le tampon impose un pH non inférieur à 6,5, mesuré à température ambiante (donc sur l'inhibiteur mis en solution aqueuse et non encore appliqué sur la tôle).The fact of providing a buffer medium accompanying the corrosion inhibitor agrees well with the execution of an acid rinse before coating the sheet, and with the possible presence of ions K⁺, Zn ²⁺ and Ni ²⁺ in the atmosphere of the electroplating and winding hall. For this, it is imperative that the buffer impose a pH not less than 6.5, measured at room temperature (therefore on the inhibitor put in aqueous solution and not yet applied to the sheet).
L'inhibiteur de corrosion selon l'invention est une solution aqueuse d'un nitrite de métal alcalin à une concentration de 0,01 à 0,3 mol/l, et d'un phosphate alcalin à une concentration de 0,01 à 0,3 mol/l, et renfermant également de l'acide phosphorique à une concentration telle qu'elle impose à la solution un pH compris entre 6,9 et 7,2 mesuré à température ambiante. Il est également souhaitable que les concentrations molaires en ions alcalins du nitrite et en ions alcalins du phosphate ne diffèrent pas de plus de 20 %. A titre d'exemple, de très bons résultats ont été obtenus avec une solution renfermant 6 g/l de nitrite de sodium, 10 g/l de phosphate de sodium Na₃PO₄, 12H₂O, la quantité d'acide phosphorique permettant d'ajuster le pH à 7, et un agent mouillant non ionique.The corrosion inhibitor according to the invention is an aqueous solution of an alkali metal nitrite at a concentration of 0.01 to 0.3 mol / l, and an alkaline phosphate at a concentration of 0.01 to 0 , 3 mol / l, and also containing phosphoric acid at a concentration such that it imposes on the solution a pH of between 6.9 and 7.2 measured at room temperature. It is also desirable that the molar concentrations of alkali metal nitrite ions and alkaline phosphate ions should not differ by more than 20%. For example, very good results have been obtained with a solution containing 6 g / l of sodium nitrite, 10 g / l of sodium phosphate Na₃PO₄, 12H₂O, the quantity of phosphoric acid allowing the pH to be adjusted. to 7, and a nonionic wetting agent.
On a testé son efficacité en appliquant sur une tôle non huilée une solution corrosive d'ions chlorure, en huilant le métal et en le soumettant à des cycles comportant successivement 8 heures d'exposition à une atmosphère humide et 16 heures d'exposition à une atmosphère sèche. Après 68 heures d'un tel traitement, on observe deux fois moins de piqûres sur la tôle lorsqu'elle a été revêtue d'une solution de cet inhibiteur préalablement à l'application de la solution corrosive.Its effectiveness was tested by applying a corrosive solution of chloride ions to an unoiled sheet, oiling the metal and subjecting it to cycles comprising successively 8 hours of exposure to a humid atmosphere. and 16 hours of exposure to a dry atmosphere. After 68 hours of such treatment, two times less pitting is observed on the sheet when it has been coated with a solution of this inhibitor before applying the corrosive solution.
Optionnellement, on peut ajouter à cette solution d'inhibiteur un agent mouillant non ionique ou anionique, tel qu'un ester phosphorique. On pallie ainsi la mauvaise mouillabilité de la couche de zinc-nickel, et ce, sans utiliser de produits à base d'amines dans l'inhibiteur. Conjointement à l'agent mouillant, il est souhaitable d'ajouter un anti-mousse. Les quantités ajoutées peuvent être par exemple, de 1 à 5 ml/l d'agent mouillant et de 0,2 à 1 ml/l d'anti-mousse.Optionally, a non-ionic or anionic wetting agent, such as a phosphoric ester, can be added to this inhibitor solution. This compensates for the poor wettability of the zinc-nickel layer, without using amine-based products in the inhibitor. In addition to the wetting agent, it is desirable to add an anti-foaming agent. The amounts added can be, for example, from 1 to 5 ml / l of wetting agent and from 0.2 to 1 ml / l of antifoam.
L'application de l'inhibiteur s'inscrit dans le schéma suivant :
- électrozingage de la tôle sur une de ses faces par un alliage zinc-nickel ;
- rinçage acide, puis rinçage à l'eau déminéralisée de la tôle ;
- application de la solution d'inhibiteur ;
- séchage de la tôle, entraînant l'évaporation de l'eau ;
- huilage de la tôle ;
- bobinage de la tôle, et stockage ou expédition de la bobine.
- electrogalvanizing of the sheet on one of its faces by a zinc-nickel alloy;
- acid rinsing, then rinsing with demineralized water from the sheet;
- application of the inhibitor solution;
- sheet drying, causing water to evaporate;
- oiling of the sheet;
- winding of the sheet, and storage or shipping of the reel.
Différents modes d'application de l'inhibiteur sont envisageables, par exemple à l'aide de rouleaux essoreurs entre lesquels défile la tôle, et dont les parties inférieures trempent dans des bacs contenant la solution renfermant l'inhibiteur. Ces rouleaux essoreurs doivent appliquer par exemple 1 à 2 ml de solution par m² de tôle (sur chaque face concernée par le traitement), correspondant à une quantité de sodium de 2 à 6 mg/m². Il est entendu qu'on peut, au choix, revêtir les deux faces de la tôle ou seulement la face nue.Different modes of application of the inhibitor can be envisaged, for example using dewatering rollers between which the sheet runs, and the lower parts of which soak in tanks containing the solution containing the inhibitor. These drain rollers must apply, for example, 1 to 2 ml of solution per m² of sheet metal (on each side concerned by the treatment), corresponding to an amount of sodium of 2 to 6 mg / m². It is understood that one can, as desired, coat the two faces of the sheet or only the bare face.
Bien entendu, cet inhibiteur de corrosion n'a pas un usage limité à la protection des tôles revêtues sur une seule face par un alliage zinc-nickel, qui n'est qu'une application préférentielle, mais il est applicable à la protection de toute tôle d'acier, voire d'autres matériaux métalliques.Of course, this corrosion inhibitor is not limited to the protection of coated sheets on a single face by a zinc-nickel alloy, which is only a preferential application, but it is applicable to the protection of any steel sheet, even other metallic materials.
Claims (5)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9315196A FR2713669B1 (en) | 1993-12-14 | 1993-12-14 | Corrosion inhibitor of a metallic material, such as steel. |
FR9315196 | 1993-12-14 |
Publications (2)
Publication Number | Publication Date |
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EP0658636A1 true EP0658636A1 (en) | 1995-06-21 |
EP0658636B1 EP0658636B1 (en) | 1999-12-29 |
Family
ID=9454040
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP94470040A Expired - Lifetime EP0658636B1 (en) | 1993-12-14 | 1994-11-21 | Corrosion protecting process for steel sheet, plated on one side with a Zn-Ni allog |
Country Status (9)
Country | Link |
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US (1) | US5567354A (en) |
EP (1) | EP0658636B1 (en) |
JP (1) | JP3398724B2 (en) |
KR (1) | KR100358219B1 (en) |
AT (1) | ATE188264T1 (en) |
CA (1) | CA2137837A1 (en) |
DE (1) | DE69422377T2 (en) |
ES (1) | ES2141813T3 (en) |
FR (1) | FR2713669B1 (en) |
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US6585933B1 (en) | 1999-05-03 | 2003-07-01 | Betzdearborn, Inc. | Method and composition for inhibiting corrosion in aqueous systems |
US20070001150A1 (en) * | 2005-06-29 | 2007-01-04 | Hudgens Roy D | Corrosion-inhibiting composition and method of use |
US20070152191A1 (en) * | 2005-12-29 | 2007-07-05 | Trahan David O | Corrosion inhibitors |
US8178078B2 (en) | 2008-06-13 | 2012-05-15 | S.C. Johnson & Son, Inc. | Compositions containing a solvated active agent suitable for dispensing as a compressed gas aerosol |
US8287841B2 (en) | 2010-06-18 | 2012-10-16 | S.C. Johnson & Son, Inc. | Aerosol odor eliminating compositions containing alkylene glycol(s) |
RU2571243C1 (en) * | 2014-06-06 | 2015-12-20 | Общество с ограниченной ответственностью "Научно-производственное объединение ЕВРОХИМ" | Inhibitor for protection of reaction equipment from corrosion |
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CH668265A5 (en) * | 1985-09-09 | 1988-12-15 | Lonza Ag | METHOD FOR THE PRODUCTION OF LUBRICANTS IN POWDERED TO PASTOESE FORM. |
US4717490A (en) * | 1986-09-30 | 1988-01-05 | Chevron Research Company | Synergistic combination of alkali metal borates, sulfur compounds, phosphites and neutralized phosphates |
DE4228470A1 (en) * | 1992-08-27 | 1994-03-03 | Henkel Kgaa | Process for phosphating steel strips galvanized on one side |
-
1993
- 1993-12-14 FR FR9315196A patent/FR2713669B1/en not_active Expired - Fee Related
-
1994
- 1994-11-21 EP EP94470040A patent/EP0658636B1/en not_active Expired - Lifetime
- 1994-11-21 DE DE69422377T patent/DE69422377T2/en not_active Expired - Fee Related
- 1994-11-21 AT AT94470040T patent/ATE188264T1/en not_active IP Right Cessation
- 1994-11-21 ES ES94470040T patent/ES2141813T3/en not_active Expired - Lifetime
- 1994-11-22 US US08/346,188 patent/US5567354A/en not_active Expired - Fee Related
- 1994-12-12 CA CA002137837A patent/CA2137837A1/en not_active Abandoned
- 1994-12-13 KR KR1019940034009A patent/KR100358219B1/en not_active IP Right Cessation
- 1994-12-14 JP JP33308594A patent/JP3398724B2/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
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FR1080119A (en) * | 1952-06-03 | 1954-12-07 | Standard Oil Dev Co | Corrosion inhibition |
GB1182247A (en) * | 1966-07-01 | 1970-02-25 | Lorant Joseph John | Improvements in or relating to the Surface Treatment of Metals. |
US3522093A (en) * | 1967-02-27 | 1970-07-28 | Chem Cleaning & Equipment Serv | Processes of cleaning and passivating reactor equipment |
FR2098832A5 (en) * | 1970-07-20 | 1972-03-10 | Gallay Futs Metalliques | |
JPS52110242A (en) * | 1976-03-08 | 1977-09-16 | Nippon Paint Co Ltd | Antirust treating method for steel members |
Non-Patent Citations (1)
Title |
---|
DATABASE WPI Week 7743, Derwent World Patents Index; AN 77-76772Y * |
Also Published As
Publication number | Publication date |
---|---|
KR100358219B1 (en) | 2003-01-24 |
FR2713669B1 (en) | 1996-01-05 |
JPH0835083A (en) | 1996-02-06 |
DE69422377D1 (en) | 2000-02-03 |
ATE188264T1 (en) | 2000-01-15 |
DE69422377T2 (en) | 2000-08-24 |
CA2137837A1 (en) | 1995-06-15 |
EP0658636B1 (en) | 1999-12-29 |
JP3398724B2 (en) | 2003-04-21 |
KR950018670A (en) | 1995-07-22 |
US5567354A (en) | 1996-10-22 |
FR2713669A1 (en) | 1995-06-16 |
ES2141813T3 (en) | 2000-04-01 |
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