EP2697346A1 - Procédé de traitement de protection des métaux à base de composition hydrosoluble d'huile(s) végétale(s) saponifiée(s), et produits et compositions obtenus - Google Patents
Procédé de traitement de protection des métaux à base de composition hydrosoluble d'huile(s) végétale(s) saponifiée(s), et produits et compositions obtenusInfo
- Publication number
- EP2697346A1 EP2697346A1 EP12724704.7A EP12724704A EP2697346A1 EP 2697346 A1 EP2697346 A1 EP 2697346A1 EP 12724704 A EP12724704 A EP 12724704A EP 2697346 A1 EP2697346 A1 EP 2697346A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- solution
- product
- composition
- corrosion
- weight
- 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.)
- Ceased
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0073—Anticorrosion compositions
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
- C09D5/086—Organic or non-macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11C—FATTY ACIDS FROM FATS, OILS OR WAXES; CANDLES; FATS, OILS OR FATTY ACIDS BY CHEMICAL MODIFICATION OF FATS, OILS, OR FATTY ACIDS OBTAINED THEREFROM
- C11C1/00—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids
- C11C1/02—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils
- C11C1/025—Preparation of fatty acids from fats, fatty oils, or waxes; Refining the fatty acids from fats or fatty oils by saponification and release of fatty acids
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/042—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on anionic surface-active compounds and soap
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D10/00—Compositions of detergents, not provided for by one single preceding group
- C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
- C11D10/045—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap based on non-ionic surface-active compounds and soap
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D9/00—Compositions of detergents based essentially on soap
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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
- C23F11/10—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 organic inhibitors
- C23F11/12—Oxygen-containing compounds
- C23F11/124—Carboxylic acids
- C23F11/126—Aliphatic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
- C11D1/143—Sulfonic acid esters
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
Definitions
- the present invention relates to the technical field of anticorrosive chemistry and in particular for applications of corrosion inhibitors, in the "coating” ("coating"), the temporary protection or not of metals, anticorrosive fluids, and more generally, in all areas where corrosion activity is sought on metals.
- This type of treatment process should be easy to apply and non-toxic.
- the coating must also be easy to remove from the parts without producing additional pollution, altering the surface condition of the supports, or discomfort during their handling.
- Oily or semi-oily compositions obtained by mixing water and mineral oil in emulsion are called "white emulsions". These solutions often contain a corrosion inhibitor as in US Pat. No. 4,342,596.
- More complex emulsions comprising mineral paraffins, amides, alcohols and surfactants described in US Pat. No. 4,479,981. can also be used (patent WO 06/070083 A1).
- Other temporary protective coatings are obtained by spraying, on the surface to be protected from atmospheric air, water-soluble compositions obtained by mixing polyoxyalkylene glycols and alkyl derivatives of succinic anhydride, such as the composition described in US Pat. U.S. Patent 5,316,696.
- the coatings formed are presented as having good stability and may be a good barrier to atmospheric oxidation, but result in the formation of an oily and liquid film on the surface of the parts, and many liquid effluents and volatile organic compounds in the workshops, often difficult to process.
- carboxylic acid or carboxylate salt compositions have been patented as an inhibitor of atmospheric corrosion.
- the carboxylic acids used are linear acids of chemical formula:
- the thin films formed with these solutions have the advantage of having a "dry appearance" of being easily removable from the surface and generating little pollution. They are described by EP 0556 087A1.
- the linear carboxylic acids of formula CH 3 (CH 2 ) n - 2 COOH and the associated carboxylate ions, with or without unsaturations, are compounds of interest for forming "dry" films ( or non-oily) on metals.
- two industrial constraints currently impose limiting these processes to the use of short chain carboxylic acids, less than or equal to 10-12 carbons:
- complex formulations based on surfactant and / or co-solvent often cause problems of stability of the baths in service such as phase separations (demixing), solid deposits in the bottom of the tank, or bacterial developments.
- films "liquid” or formed from short-chain carboxylic acids have a limited resistance to corrosion under atmospheric corrosion conditions commonly encountered during storage. metal parts under cover or during transport. Indeed, the moisture recovery in the stacks of parts leads to severe differential aeration conditions and corrosion inside the stack.
- the industrial conditions of use require that the solution can dry in the open air without causing the appearance of corrosion products (red rust on iron bases or white rust on galvanized products or tarnishing on copper products or based on aluminum).
- the objective technical problem is therefore to use, if possible, carboxylic acids and / or carboxylate salts with long carbon chains (HC n with n> 14) in order to to increase the stability of the protective film in fully aqueous formulations, that is to say without any co-solvent or any of the now-regulated defects of the prior art AND provided they are used in the context of a formulation and a method which avoids the aforementioned drawbacks.
- These formulations should also be prepared concentrated (for transport and storage) and then be easily diluted in water.
- the merit of the invention is, moreover, to have overcome the prejudgment which was attached a priori to the solution developed below by a process and totally original compositions.
- the present invention aims to meet this technical challenge from saponification products in general, provided that they meet the above criteria, including aqueous reaction medium and long chain carboxylic acids, we do not duplicate not here.
- This approach had never been attempted or considered in the state of the art. It relates more particularly, according to a clearly preferred but non-limiting mode, an innovative saponification process in dilute medium, a corresponding saponification product, said saponification process preferably employing reagents from eco-resources, including oils plant.
- This saponification process makes it possible to prepare in aqueous solvent concentrated solutions of carboxylic acids with long carbon chains up to 250 g / l (HC n with n> 14) usable for the targeted treatment.
- This process referred to as a "one-pot process" requires a single reactor in which reagents are added successively, and requires no separation, purification or transfer of material steps.
- no addition of organic solvents or co-solvents (still sometimes called humectants) is necessary to achieve the desired viscosity.
- This method of forming a "dry” anti-corrosion film is done by simple application on the metal surfaces or “metals” (immersion, spraying or coating) of a totally aqueous solution (without organic solvent and surfactant). active), prepared from this method of saponification in a diluted medium.
- This "dry” film has anti-corrosion properties on metals due to its insoluble nature in water and hydrophobic (weak wettability).
- the present invention comprises the innovative saponification process, as well as the application of the anti-corrosion solution obtained, and the solution or protection composition used / applied, and their applications to anticorrosion.
- the fatty substances are hydrolysed in an alkaline medium with a base, usually sodium hydroxide (NaOH) or potassium hydroxide (KOH), at a temperature of between 30 ° C. and 80 ° C. .
- a base usually sodium hydroxide (NaOH) or potassium hydroxide (KOH)
- NaOH sodium hydroxide
- KOH potassium hydroxide
- the elevated temperature serves to accelerate the saponification reaction.
- the saponification of fatty substances produces glycerol and a mixture of carboxylates (sodium or potassium) which constitutes the soap.
- composition in particular concentrated aqueous solution (up to 250 g / l of carboxylic acids containing from 14 to 22 carbons, that is to say having stable "C14-C22" chains and liquid (viscosity ⁇ 150 cPo to 20 ° C).
- oils are generally composed of a mixture of chain length products that may be different from one another.
- C14-C22 will be understood to mean oils or mixtures of oils comprising either only C14 to C22 chains or very predominantly C14-C22 chains, especially preferably greater than or equal to 80%, preferably greater than or equal to 90%, and more preferably greater than or equal to 95%, the only criterion being that, according to the invention, an extremely clear solution is obtained extremely preferably stable and concentrated saponification product incorporating said carboxylate chains. It is therefore possible to tolerate a small percentage, preferably a very small percentage, in the starting oil (s), for example, C12 or C10, or, in theory, C24 or C26.
- oils in particular C22, C24, C26 but throughout the present application including the claims will be used only the term “oils” for simplicity.
- the object of the present invention is therefore to develop a composition, a product and a method for the anticorrosion treatment of metal parts (hereinafter "metals") by application of an aqueous solution obtained by saponification, and in particular saponification of vegetable oil, diluted medium.
- metal parts hereinafter "metals”
- the term "metals” means the group formed by iron and its alloys; Copper and its alloys; Aluminum and its alloys, Zinc and its alloys; Lead and its alloys; tin and its alloys; including all of these partially oxidized or corroded metals.
- the aqueous solution applied is obtained by dilution between 0.2 and 30% by weight of a concentrated solution obtained by saponification in a dilute medium of vegetable oil (s).
- the method of manufacture (by saponification according to the invention) of the concentrated solution (or composition) must be rapid, “reproducible”, that is to say be able to be industrialized, and lead to a product with a pH and a viscosity conform to industry standards.
- the concentrated solution of the product or composition must be chemically stable without the addition of organic and / or surfactant co-solvents, and be biologically stable, without the addition of bactericidal compounds having a toxic character.
- the dilute aqueous solution applied to the metal surfaces must be allowed to air-dry at room temperature or hot air on the parts without rinsing. It must allow corrosion protection in conventional atmospheric conditions under shelter (alternation of dry and wet periods) and in stacking conditions of metal parts generating corrosion phenomena by differential aeration.
- the present invention therefore relates to a method of anticorrosion treatment from a solution developed from a saponification process, and in particular a very preferred saponification process, described hereinafter in detail, and completely innovative.
- the first subject of the invention is the anticorrosion composition for "metals", characterized in that it consists or comprises at least one saponification product of at least one vegetable oil, or mixture of vegetable oils (or, so to speak equivalent throughout this application, “composition”) and the “one-pot” process (or extremely preferred implementation in a single reactor) allowing the manufacture of a concentrated saponified solution (in other words product derived from saponification) without the stages of maturation, storage, recovery that required a lot of time.
- the process is carried out at atmospheric pressure, at a temperature between 70 ° C and 99.9 ° C (boiling limit at atmospheric pressure) and without the use of water vapor, and uses at least one vegetable oil as a product of departure.
- the Applicant has considered a large number of different oils (including Sweet Almond, Peanut, avocado, Shea, Flax, Olive, Sunflower, Palm, Rapeseed, Apricot Kernels, Corn, Ricin), used alone or in combination. mixed.
- oils including Sweet Almond, Peanut, Avocado, Shea, Flax, Olive, Sunflower, Palm, Rapeseed, Apricot Kernels, Corn, Ricin
- the Applicant has finally selected the use of castor oil which alone (among the oils tested) and surprisingly, allows to obtain a sufficiently concentrated solution, limpid and stable.
- a quantity of vegetable oil (between 15 and 35% by weight of the final mixture) is mixed with a potassium hydroxide solution (between 5 and 20% by weight of the final mixture).
- the mixture is heated under constant stirring at a temperature between 70 ° C and 99.9 ° C (boiling limit at atmospheric pressure) at atmospheric pressure, for 15 to 30 min.
- the temperature chosen in the different steps of the process is between 95 ° C. and 99.9 ° C., very preferably it is between 85 ° C. and 95 ° C., and finally, less preferably, it is between 70 ° C and 85 ° C still at atmospheric pressure.
- the final mixture (which is the product or composition according to the invention) is completely transparent, directly has the desired viscosity (about 100 to 150cPo).
- the saponification is complete (no rise of oil appears), and the saponification product in solution is excessively stable over time (more than 12 months without addition of organic co-solvent or surfactant).
- the total process (instead of the 15 days required for the prior art) is carried out in a single reactor on a working day at most.
- the set is therefore very different from the prior art of saponification, and totally innovative.
- the product obtained is also innovative by the absence of solvent and other advantageous properties.
- the solution thus created may be supplemented with oxidizing or accelerating agents such as nitrite salts. nitrates, persulfates, perborates, percarbonates or hydrogen peroxide. It will be preferred to add 1 to 20% by weight of hydrogen peroxide for its non-toxic nature and harmless to the environment.
- a wetting agent selected from the group consisting of anionic surfactants such as alkylsulfates and nonionic surfactants such as ethoxylated compounds of the fatty alcohol type and alkylphenols, facilitating the spreading solution on metal surfaces (example: 1% lauryl sulphate), and / or
- an additional compound having corrosion inhibiting properties such as the triazol derivatives chosen from the group consisting of benzotriazoles, tolyltriazoles and alkyltriazoles. (example: 1% tolyltriazole), and / or
- the skilled person may also add from 0.2 to 20% by weight of an oxidizing compound or accelerator.
- the method according to the invention therefore leads to a "final mixture” which is the “product according to the invention”, which becomes a “composition according to the invention” after the possible additions above. It may be of great interest to work the concentration of said composition, in particular dilute it to the usual application concentration in anti-corrosion.
- the invention also covers the "products" and “compositions” obtained by the process according to the invention with the possible addition of subsequent additives as described above.
- the second object of the invention is the method of depositing and forming the protective film on the metal surfaces from said concentrated composition. It consists in diluting the said solution between 0.2 and 30% by weight in water, bringing the solution thus formed into contact with the metal surface for residence times ranging from 10 seconds to 24 hours, to drain the so-called solution and then dry the said surface in the open air or under a possibly heated air stream.
- any means will be used, in particular watering, spraying or immersion.
- the film thus obtained is in the form of a non-oily dry film which does not stick and which leaves no dirt on the hands during the handling of the metal parts and which protects them from atmospheric corrosion.
- a third object of the invention is the use of these concentrated compositions to form dry films for the particular protection against corrosion of metal surfaces or "metals” including iron and its alloys; Copper and its alloys; Aluminum and its alloys, Zinc and its alloys; Lead and its alloys; tin and its alloys; including all of these partly corroded metals.
- metal surfaces or "metals” including iron and its alloys; Copper and its alloys; Aluminum and its alloys, Zinc and its alloys; Lead and its alloys; tin and its alloys; including all of these partly corroded metals.
- step d) an acidic compound such as a carboxylic acid or borax.
- an acidic compound such as a carboxylic acid or borax.
- Benzoic acid is preferred because it provides bactericidal properties, very useful for the preservation of the final product, on the other hand it increases the effectiveness on corrosion.
- Other acids having little or no influence at low concentration on the anticorrosion properties, can be used as including heptanoic acid, undecylenic acid, benzoic acid, etc.
- Figure 1 which consists of Figures 1a-1d shows the measurement of corrosion potential (1a and 1b) and corrosion rates by the polarization resistance method (1c and 1d) in ASTM-free water or with solutions 1, 2, or 3 of Table 1.
- Figure 2 which consists of Figures 2a to 2c, shows the results of the test DIN 51360 (black areas correspond to corroded areas).
- Figure 2a shows the visual result of the degree of rust without the additive.
- Figure 2b shows the visual result of the degree of rust with solution 1
- Figure 2c shows the visual result of the degree of rust with solution 4
- Figure 3 consists of Figures 3a to 3c.
- Figure 3a shows an experimental setup of the tight packet test.
- Figure 3b shows the macroscopic appearance of the galvanized steel after 20 days in a humidotherm chamber for plates rinsed with water without additive.
- Figure 3c shows the macroscopic appearance of the galvanized steel after 20 days in the humidotherm chamber for plates rinsed with water with 5% of solution 2 (the black areas correspond to the corroded areas).
- Table 1 Possible compositions for 1000 g of solution.
- the three formulations 1 to 3 lead to concentrated liquid solutions, clear and completely dilutable in water, without any other addition.
- ASTM corrosive water
- Test solutions are prepared by diluting inhibiting solutions (solution 1 to 3 in Table 1) in ASTM water; no agent nor basic nor acid is added to the mixtures, all of which have a so-called "natural" pH between 8 and 8.5.
- the corrosion potential makes it possible to evaluate the enninozation of the material in contact with the water added with inhibitors, and the polarization resistance is inversely proportional to the corrosion rate expressed in ⁇ / year.
- the polarization resistance is increased by a factor of 100 in the presence of the solutions; the corrosion rate of the steel is therefore reduced by a factor of 100 in ASTM water.
- potassium heptanoate used at this low concentration (about 10 3 mol / l in solution 6 to 5%) does not provide sufficient corrosion protection with a polarization resistance between 50 to 100 ka.cm 2
- benzoic acid in solution 3 makes it possible to form a more noble protective film on the surface of the metal and to improve its protection.
- This standard is intended to simulate the application of inhibitory formula on steel parts, and then the natural drying in the open air of this formula.
- the principle of the test is to soak iron chips on a filter paper placed in a petri dish; after two hours the paper is removed, rinsed and dried. The degree of corrosion is evaluated in relation to any traces of rust on the filter paper using standard references.
- the corrosive solution to which solutions 1 to 3 will be mixed is composed of 3.58 mmol / L CaCl 2 , 6H 2 O and 3.58 mmol / L MgSO 4 , 7H 2 O.
- This example is intended to demonstrate that the treatment of a zinc-coated steel sheet with the aid of the solution 4 according to the invention protects the sheet against the risks of corrosion, in particular "punctures" inside the sheet. stacks due to moisture retention phenomenon.
- immersion, spraying or coating may be used; thanks in general to the use of an ink roller in contact with the metal.
- test pieces After application of the solution, the test pieces are drained and then stacked 5 by
- This tight packing test recreates the containment that exists when stacking metal parts during transport or storage.
- the sheet metal specimens are dried and any traces of corrosion are noted visually.
- the result of the test is obtained by raising the number of successive cycles before the corrosion traces appear within the stack. When the number of cycles recorded is greater than 20, the resistance against corrosion in stacking is in line with expectations.
- the plates rinsed with water added with 5% of solution 2 only show very slight tarnish after 2 days of stacking. under pronounced differential aeration conditions between the inside and the outside of the stack.
- the treatment of metals according to the invention application can greatly reduce the wettability of the metal surfaces.
- the wettability of a material is measured by the contact angle, ⁇ , only with a drop of water ( Figure 5).
- Figure 5 shows the definition of the contact angle ⁇ formed by a drop of water placed on a surface.
- this angle is greater than 90 ° (generally between 90 ° and 120 °)
- the surface is hydrophobic (the contact surface between water and the material is small) and when it is less than 90 °, the surface is hydrophilic (the contact surface between water and the material is high).
- the treated surface of zinc still has a very hydrophobic character, because of a nanometric layer of size crystals of the order of 100 nm. This layer of entangled and insoluble crystals makes it possible to trap air and maintain long-lasting hydrophobic properties on the surface of the metal. This hydrophobic effect or "lotus effect" of the treated metal surface is maintained after several days in a corrosive condition.
- Example 2 serves the same purpose as Example 1 applied to aluminum alloys, in particular Al-Cu alloys. Indeed, in industrial water circuits, these alloys have a significant sensitivity to localized corrosion phenomena ("pitting") due to the presence of copper-rich particles within them.
- the 1% assay of solution 2 shows less effective anticorrosion properties than the 5% assay.
- the limited ennoblement and the decrease of the current density between -0.5 V and -0.1 V with this assay may be sufficient in practice in the case of industrial waters with little corrosive effect.
- Table No. 4 below lists the tests carried out by the Applicant with different oils tested. These tests were carried out according to the method of the invention.
- these pastes have substantially the same anti-corrosion power on metals and may optionally be used in certain domestic applications, or certain industrial applications where the quality is the properties obtained with castor oil would not be required.
- formulations according to the invention are intended to illustrate the anticorrosive effectiveness of the formulations according to the invention in the case of previously oxidized metals.
- the formulations can be used as basic electrolyte in the so-called clogging process of anodized aluminum.
- electrolyte Anoseal 1000 poses problems of hydiene and safety due to the presence of Ni 2+ in the solution.
- the invention also covers all the embodiments and all the applications which will be directly accessible to the person skilled in the art upon reading the present application, and of his own knowledge.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1101131A FR2974112B1 (fr) | 2011-04-13 | 2011-04-13 | Procede de traitement de protection des metaux a base de composition hydrosoluble d'huile(s) vegetale(s) saponifiee(s), et produits et compositions obtenus. |
PCT/IB2012/000714 WO2012140488A1 (fr) | 2011-04-13 | 2012-04-06 | Procédé de traitement de protection des métaux à base de composition hydrosoluble d'huile(s) végétale(s) saponifiée(s), et produits et compositions obtenus |
Publications (1)
Publication Number | Publication Date |
---|---|
EP2697346A1 true EP2697346A1 (fr) | 2014-02-19 |
Family
ID=46197621
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP12724704.7A Ceased EP2697346A1 (fr) | 2011-04-13 | 2012-04-06 | Procédé de traitement de protection des métaux à base de composition hydrosoluble d'huile(s) végétale(s) saponifiée(s), et produits et compositions obtenus |
Country Status (3)
Country | Link |
---|---|
EP (1) | EP2697346A1 (fr) |
FR (1) | FR2974112B1 (fr) |
WO (1) | WO2012140488A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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WO2016176795A1 (fr) * | 2015-05-03 | 2016-11-10 | 南通长航船舶配件有限公司 | Revêtement antirouille pour bateau |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL38983C (fr) * | 1933-03-08 | |||
US4342596A (en) | 1980-04-10 | 1982-08-03 | Conner Alvin James Sen | Non-petroleum based metal corrosion inhibitor |
US4479981A (en) | 1982-05-03 | 1984-10-30 | Ashland Oil, Inc. | Water-borne hard coating compositions and processes therefor |
GB9009625D0 (en) | 1990-04-30 | 1990-06-20 | Ici Plc | Composition |
DE69325828D1 (de) | 1992-02-14 | 1999-09-09 | Atochem Elf Sa | Verwendung zur inhibierung der Kupferkorrosion einer Zusammensetzung bestehend aus Heptansoiuce oder dessen Derivate und Natriumtetraborat. |
FR2822852B1 (fr) | 2001-03-27 | 2003-12-12 | Usinor | Procede de traitement par carboxylatation de surfaces metalliques |
GB0501825D0 (en) * | 2004-10-26 | 2005-03-09 | Unilever Plc | Liquid cleansing compositions |
FR2880034A1 (fr) | 2004-12-23 | 2006-06-30 | Usinor Sa | Composition aqueuse de protection et de lubrification |
FR2904829B1 (fr) * | 2006-08-08 | 2012-10-05 | Total France | Compositions a base d'acides carboxyliques pour protection temporaire de surfaces metalliques et films secs obtenus a partir desdites compositions |
-
2011
- 2011-04-13 FR FR1101131A patent/FR2974112B1/fr active Active
-
2012
- 2012-04-06 EP EP12724704.7A patent/EP2697346A1/fr not_active Ceased
- 2012-04-06 WO PCT/IB2012/000714 patent/WO2012140488A1/fr active Application Filing
Non-Patent Citations (2)
Title |
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None * |
See also references of WO2012140488A1 * |
Also Published As
Publication number | Publication date |
---|---|
FR2974112A1 (fr) | 2012-10-19 |
FR2974112B1 (fr) | 2013-05-03 |
WO2012140488A1 (fr) | 2012-10-18 |
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