FR2858820A1 - Anti-corrosion compound for the preventive and curative treatment of metal reinforcement enclosed in mortar and concrete - Google Patents
Anti-corrosion compound for the preventive and curative treatment of metal reinforcement enclosed in mortar and concrete Download PDFInfo
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- FR2858820A1 FR2858820A1 FR0309939A FR0309939A FR2858820A1 FR 2858820 A1 FR2858820 A1 FR 2858820A1 FR 0309939 A FR0309939 A FR 0309939A FR 0309939 A FR0309939 A FR 0309939A FR 2858820 A1 FR2858820 A1 FR 2858820A1
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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
- C23F11/167—Phosphorus-containing compounds
- C23F11/1673—Esters of phosphoric or thiophosphoric acids
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5007—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing
- C04B41/5009—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with salts or salty compositions, e.g. for salt glazing containing nitrogen in the anion, e.g. nitrites
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
- C04B41/61—Coating or impregnation
- C04B41/65—Coating or impregnation with inorganic materials
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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
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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
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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
- C23F11/14—Nitrogen-containing compounds
- C23F11/141—Amines; Quaternary ammonium compounds
- C23F11/143—Salts of amines
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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
- C23F11/14—Nitrogen-containing compounds
- C23F11/144—Aminocarboxylic acids
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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
- C23F11/167—Phosphorus-containing compounds
- C23F11/1676—Phosphonic acids
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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
- C23F11/181—Nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/60—Agents for protection against chemical, physical or biological attack
- C04B2103/61—Corrosion inhibitors
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/20—Resistance against chemical, physical or biological attack
- C04B2111/26—Corrosion of reinforcement resistance
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Ceramic Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Structural Engineering (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
COMPOSITIONS ANTI-CORROSION DESTINEES AUX TRAITEMENTSANTI-CORROSION COMPOSITIONS FOR TREATMENTS
DES ARMATURES METALLIQUES INCLUSES DANS LES MORTIERS ET BETONS METAL FRONTS INCLUDED IN MORTAR AND CONCRETE
La présente invention a pour objet une composition anti-corrosion destinée aux traitements des armatures métalliques de renforcement des mortiers et béton, constituée par une combinaison anti-corrosion de base à laquelle on ajoute un additif spécifique pour les traitements préventifs et un autre additif spécifique pour les traitements curatifs. The subject of the present invention is an anti-corrosion composition intended for the treatment of reinforcing metal reinforcement of mortars and concrete, constituted by a basic anti-corrosion combination to which is added a specific additive for the preventive treatments and another specific additive for curative treatments.
La corrosion des armatures métalliques de renforcement des mortiers et bétons est un problème sérieux qui préoccupe depuis longtemps les spécialistes et qui est particulièrement présent dans les régions de montagne où l'on utilise des sels de fonte (chlorure de calcium) durant l'hiver; ou aux abords marins où règne une atmosphère saline. Corrosion of reinforcing metal reinforcement of mortars and concretes is a serious problem that has long been of concern to specialists and is particularly present in mountain regions where melt salts (calcium chloride) are used during the winter; or around the sea where there is a saline atmosphere.
Deux cas distincts doivent être pris en considération: - le traitement anti-corrosion préventif qui consiste à protéger les armatures métalliques contre l'installation et le développement des phénomènes de rouille conduisant aux dégâts de la corrosion. Two distinct cases must be taken into consideration: - the preventive anti-corrosion treatment, which consists in protecting the rebars against the installation and development of rust phenomena leading to corrosion damage.
Ce traitement est appliqué aux matériaux frais lors de leur préparation. This treatment is applied to fresh materials during their preparation.
Si au moment de leur mise en place ces matériaux présentent de bonnes caractéristiques rhéologiques (fluidité, étalement, plasticité) ils enroberont mieux les armatures métalliques; celles-ci en milieu alcalin seront ainsi mieux protégées. A fortiori si à une combinaison anticorrosion de base on associe un additif agent de rhéologie possédant luimême une bonne propension anti-rouille. If at the time of their introduction these materials have good rheological characteristics (fluidity, spreading, plasticity) they will better coat the metal frames; these in alkaline medium will be better protected. A fortiori if a basic anticorrosive combination is combined with a rheology additive additive itself having a good anti-rust propensity.
- le traitement anti-corrosion curatif qui consiste à des interventions sur mortiers ou bétons anciens, qui présentent des points de corrosion, dus le plus souvent, à l'apparition de micro-fissures dans les matériaux, et qui servent de vecteurs à l'oxygène et autres agents donnant naissance à la rouille, puis au développement des phénomènes de corrosion. II convient donc de les réduire voire les supprimer, et d'assurer une bonne protection contre de nouvelles agressions oxydatives. the curative anti-corrosion treatment which consists of interventions on old mortars or concretes, which present points of corrosion, most often due to the appearance of micro-cracks in the materials, and which serve as vectors for the oxygen and other agents giving rise to rust, then to the development of corrosion phenomena. It is therefore necessary to reduce or even eliminate them, and to ensure good protection against new oxidative aggressions.
L'intervention sur les matériaux durcis, anciens oblige à bien maîtriser la pénétration, la diffusion, la migration et le cheminement de la solution active au travers des micro-canaux, jusqu'au site à traiter où règne la corrosion. The intervention on hardened old materials requires a good control of penetration, diffusion, migration and the path of the active solution through the micro-channels, to the site to be treated where there is corrosion.
On a trouvé que l'on pouvait résoudre ces deux problèmes en associant à la même combinaison anti-corrosion de base des additifs spécifiques selon que l'on vise un traitement préventif, ou un traitement curatif. It has been found that both of these problems can be solved by combining the same basic anti-corrosion combination with specific additives depending on whether preventive treatment or curative treatment is being sought.
L'articulation de l'invention est donc la suivante: ^ une composition anti-corrosion de base à laquelle on associe: un additif agent de rhéologie pour les traitements préventifs un additif agent de mouillage étalement, diffusion, migration pour les traitements curatifs 50 The articulation of the invention is therefore as follows: a basic anti-corrosion composition to which is associated: a rheology agent additive for the preventive treatments an additive wetting agent spreading, diffusion, migration for curative treatments
DESCRIPTIONDESCRIPTION
A. Combinaison anti-corrosion de base al. L'utilisation d'agents réducteurs tel, en particulier du Nitrite de Sodium comme agent o anticorrosion des aciers est bien connu depuis longtemps. A. Basic anti-corrosion combination al. The use of reducing agents such as Sodium Nitrite as anti-corrosion agent for steels has been well known for a long time.
Dans le cadre de la présente invention, on a trouvé que les propriétés anti-rouille des solutions de Nitrite de Sodium, sont exacerbées et très sensiblement améliorées, lorsqu'elles contiennent, conjointement au nitrite un ou des agents complexants, polyfonctionnels actifs vis à vis des ions métalliques, sous forme de sels d'amines, notamment, entre autres, des sels de la Diméthyl Amino Ethanol, de l'éthyl 2 hexylamine, de la cyclohexylamine, de la morpholine, de la TEA, de: ^ L'acide amino tri méthylène phosphonique ^ L'acide 1 hydroxy éthylène 1,1 diphosphonique ^ L'acide hexamethylène diamine tétra (méthyl phosphonique) ^ L'acide diéthylène triamine penta (méthyl phosphonique) Et en particulier de: É L'acide éthylène diamine tétra (méthyl phosphonique) : In the context of the present invention, it has been found that the anti-rust properties of Sodium Nitrite solutions are exacerbated and very substantially improved when they contain, together with nitrite, one or more complexing agents, which are polyfunctional active against metal ions, in the form of amine salts, in particular, inter alia, salts of dimethyl amino ethanol, ethyl hexylamine, cyclohexylamine, morpholine, TEA, amino-methylene-phosphonic acid 1-hydroxy-ethylene-1,1-diphosphonic acid, hexamethylene-diamine tetra (methylphosphonic acid), diethylene triamine penta (methylphosphonic acid), and in particular ethylene diamine tetra ( methyl phosphonic):
O OO O
HO ii ll / OH P CH2 CH2 - P\ HO / OH N - CH2- CH2 N HO /OH P CH2 CH2P HO Il Il\OH ## STR2 ##
O OO O
Et également de: É l'acide Nitrilotriacétique: N-( CH2-COOH)3 sous forme de sel d'amines notamment de celles indiquées ci-dessus. And also: Nitrilotriacetic acid: N- (CH2-COOH) 3 in the form of amine salt, in particular from those indicated above.
^ En général le pourcentage de l'agent complexant est compris entre 3 et 10 %, exprimé en matière active, par rapport au nitrite de sodium. In general, the percentage of the complexing agent is between 3 and 10%, expressed as active material, relative to sodium nitrite.
Cet effet de synergie se traduit par une augmentation significative du pouvoir anti-rouille. Ainsi des essais comparatifs sur fibres métalliques ont montré qu'une solution aqueuse à 99.3% d'eau et 0.65% Nitrite de sodium + 0.05 % de sel de la Dimethyl amino ethanol de l'acide éthylène diamine tétra (méthyl phosphonique) avait un pouvoir anti-rouille pratiquement équivalent à une solution aqueuse à 98.8 % d'eau et 1.2 % de Nitrite de sodium. This synergistic effect results in a significant increase in anti-rusting power. Thus, comparative tests on metal fibers have shown that an aqueous solution containing 99.3% water and 0.65% sodium nitrite + 0.05% of the dimethyl amino ethanol salt of ethylene diamine tetra (methyl phosphonic acid) anti-rust virtually equivalent to an aqueous solution of 98.8% water and 1.2% sodium nitrite.
a2. La passivation des aciers par l'acide phosphorique, et ses dérivés est aussi bien connue depuis longtemps. a2. The passivation of steels by phosphoric acid and its derivatives is also well known for a long time.
Dans le cadre de l'invention, on a trouvé également que la combinaison d'un ester 5 phosphorique de formule générale: In the context of the invention, it has also been found that the combination of a phosphoric ester of general formula:
OO
o P OHo P OH
RO RORO RO
(ou R est une chaîne aliphatique, ou ramifiée, hydrocarbonée comportant quatre à dix huit atomes de carbone. Cette chaîne pouvant en outre être polyoxyéthylénée, et comporter trois à neuf motifs /OE sous forme de sel d'amines, notamment celles indiquées ci-avant au paragraphe a1, et d'un complexant polyfonctionnel, phosphonate sous forme d'un sel d'amines et notamment le sel de diméthyl amino éthanol de l'acide éthylène téta (méthyl phosphonique) avec un rapport 1-0.1, avait des propriétés antirouille supérieures de 30 à 35 % par rapport à celle de l'ester phosphorique seul, aux mêmes dosages d'utilisation (1%). (or R is an aliphatic or branched, hydrocarbon chain containing from four to eighteen carbon atoms, which chain may also be polyoxyethylenated, and comprise from three to nine units / EO in the form of an amine salt, in particular those indicated below. before at paragraph a1, and a polyfunctional complexing agent, phosphonate in the form of an amine salt and in particular the dimethylaminoethanol salt of ethylene tetra (methylphosphonic acid) with a 1 -0.1 ratio, had properties antirust 30 to 35% higher than that of the phosphoric ester alone, at the same dosages of use (1%).
a3. Dans le cadre de l'invention on a trouvé que si aux deux bases (a1-a2) décrites ci-avant, on ajoute un solvant bipolaire filmogène, on améliore sensiblement leur étalement, et on forme un film continu homogène qui se fixe sur les surfaces métalliques, améliorant ainsi leur protection antirouille. a3. In the context of the invention it has been found that if the two bases (a1-a2) described above are added, a film-forming bipolar solvent is added, their spreading is substantially improved, and a homogeneous continuous film is formed which is fixed on the metal surfaces, thus improving their rust protection.
Ce solvant filmogène est selon l'invention constitué par des esters Diméthyliques des diacides succinique, glutarique, adipique utilisés seuls séparément, ou en mélange, et 30 notamment par un mélange 20/60/20 de: CH3-OOC---CH2- CH2---COO CH3 diesters méthyliques de l'acide succinique CH3-OOC--- CH2- CH2- CH2---COO CH3 diesters méthyliques de l'acide glutarique CH3-OOC--- CH2- CH2- CH2- CH2---COO CH3 diesters méthyliques de l'acide adipique dont la plage de distillation est de 195- 225 C, et la tension superficielle, de 35.5 dynes/cm. According to the invention, this film-forming solvent is constituted by dimethyl esters of succinic, glutaric, and adipic diacids used alone, or as a mixture, and in particular by a 20/60/20 mixture of: CH3-OOC-CH2-CH2 --- COO CH3 succinic acid methyl diesters CH3-OOC --- CH2-CH2-CH2 --- COO CH3 glutaric acid methyl diesters CH3-OOC --- CH2-CH2-CH2-CH2-- -COO CH3 diesters methyl adipic acid whose distillation range is 195-225 C, and the surface tension, 35.5 dynes / cm.
Les combinaisons anti-corrosion de base revendiquées sont constituées de: - 60 à 75 % d'un agent réducteur tel le nitrite de sodium - 20 à 10 % d'un complexant polyfonctionnel phosphonate sel d'amine - 20 à 15 % d'un solvant filmogène bipolaire comme le Diester methylique d'un diacide Les 60 à 75 % de Nitrite de Sodium peuvent être remplacés par 60 à 75 % d'un sel d'amine d'un ester phosphorique, les autres constituants restant inchangés. The basic anti-corrosion combinations claimed are composed of: - 60 to 75% of a reducing agent such as sodium nitrite - 20 to 10% of a polyfunctional complexing agent phosphonate amine salt - 20 to 15% of a bipolar film-forming solvent such as the methyl diester of a diacid The 60 to 75% of sodium nitrite can be replaced by 60 to 75% of an amine salt of a phosphoric ester, the other constituents remaining unchanged.
D'autre part, les sels d'amines utilisés selon l'invention, sont obtenus en laissant libre, un 5o excès d'amine. Celui-ci entretient sur le site de traitement une ambiance aminée alcaline, ayant de bonnes propriétés de protection anti- rouille, notamment avec l'éthyl2 Hexylamine, et la cyclohexylamine qui forment avec l'eau, toujours présente, des azéotropes. On the other hand, the amine salts used according to the invention are obtained by leaving free an excess of amine. It maintains on the treatment site an alkaline amine atmosphere, having good anti-rust protection properties, especially with ethyl 2 hexylamine, and cyclohexylamine which form with water, always present, azeotropic.
Dans les compositions anti-corrosives, préventives et curatives le taux de l'amine laissée 55 libre se situe entre 2 et 10 %. In anticorrosive, preventive and curative compositions, the level of amine left free is between 2 and 10%.
B. Additifs à l'anti-corrosion de base pour l'obtention du produit destiné au traitement préventif Il s'agit de produits améliorant les caractéristiques rhéologiques des matériaux frais pour obtenir un meilleur enrobage des armatures métalliques. B. Basic anti-corrosion additives to obtain the product for the preventive treatment These are products that improve the rheological characteristics of the fresh materials in order to obtain a better coating of the metal reinforcements.
Ces adjuvants sont des dérivés anioniques, tensio-actifs dispersant, défloculant, plastifiant, fluidifiant qui selon l'invention sont utilisés sous forme de sels d'amines ce qui 10 leur confère une propension à l'effet anti-rouille, tels: - Les Lignosulfonates d'amines, et entre autres le lignosulfonate de triéthanolamine, de Diméthyl amino éthanol, de Cyclohexylamine, ou de l'Ethyl 2 Hexylamine. These adjuvants are anionic derivatives, dispersing, deflocculating, plasticizing and fluidizing surfactants which, according to the invention, are used in the form of amine salts, which gives them a propensity for the anti-rust effect, such as: Lignosulfonates of amines, and inter alia lignosulfonate triethanolamine, dimethyl amino ethanol, cyclohexylamine, or ethyl 2 hexylamine.
- Le Polynaphtalène sulfonate sous forme de sel d'amines notamment de celles mentionnées ci-avant. Polynaphthalene sulphonate in the form of amine salt, in particular from those mentioned above.
- Le Polymélamine formol sulfonate d'amines entre autres de celles déjà indiquées ci-avant. Polymelamine formol sulfonate of amines among others of those already indicated above.
Le taux de ces adjuvants spécifiques utilisés séparément ou en mélange, dans la solution anti-corrosive préventive est tel qu'au dosage de l'utilisation de celle-ci, il corresponde à 0.15 à 0.5 % (exprimé en matière active) d'adjuvant par rapport au poids du ciment mis en oeuvre. The level of these specific adjuvants used separately or in a mixture, in the anti-corrosive preventive solution is such that at the dosage of the use thereof, it corresponds to 0.15 to 0.5% (expressed as active ingredient) of adjuvant relative to the weight of the cement used.
Les compositions anti-corrosion, pour traitements préventifs, revendiquées comportent: - 30 à 40 % de la combinaison anti-corrosion de base - 70 à 60 % d'un dérivé tensio actif anionique, sous forme de sel d'amine ayant des propriétés, plastifiantes, fluidifiantes vis à vis des mortiers et bétons frais. The anti-corrosion compositions for preventive treatments claimed include: - 30 to 40% of the base anti-corrosion combination - 70 to 60% of anionic surfactant derivative, in the form of an amine salt having properties, plasticizers, fluidifying against mortars and fresh concretes.
C. Additifs à l'anti-corrosion de base pour l'obtention du produit destiné au traitement curatif Ce sont des produits destinés au mouillage, à l'étalement, à la pénétration, à la diffusion et 35 au cheminement des solutions anti-corrosives. C. Base Anti-Corrosion Additives for Curative Treatment Products These are products for wetting, spreading, penetration, diffusion and tracking of anti-corrosive solutions. .
c.1 Surfactants abaisseurs des tensions superficielle et interfaciale. c.1 Surfactants lowering surface and interfacial tensions.
On connaît l'importance des mécanismes de mouillage et de l'étalement d'une solution aqueuse sur la surface d'un solide. Ceux-ci dépendent de l'angle de raccordement aux frontières solide-liquide-air. La loi de WASHBURN donne la vitesse de pénétration d'un liquide dans un capillaire; tandis que l'équation de DUPRE et les propositions de HARKiNS permettent d'aborder les coefficients d'étalement et de tension d'adhésion. The importance of the wetting mechanisms and the spreading of an aqueous solution on the surface of a solid are known. These depend on the connection angle at the solid-liquid-air boundaries. The WASHBURN law gives the speed of penetration of a liquid into a capillary; while the DUPRE equation and the HARKiNS propositions make it possible to address the coefficients of spreading and adhesion tension.
La connaissance de ces phénomènes physiques, permet donc par l'utilisation de surfactants appropriés, de maîtriser les problèmes de diffusion, d'étalement et de cheminement des solutions actives anti- rouille, au travers des micro-structures des mortiers 5o et bétons durcis corrodés. The knowledge of these physical phenomena, allows by the use of appropriate surfactants, to control the problems of diffusion, spreading and routing of the active anti-rust solutions, through micro-structures corroded hardened mortars 5o and concretes .
Selon l'invention, les formulations anti-corrosion curatives comportent au moins un tensio-actif fluoro carboné, le plus souvent anionique. 5o According to the invention, the curative anti-corrosion formulations comprise at least one fluorocarbon surfactant, most often anionic. 5o
Ceux-ci ont des propriétés de surface exceptionnelles qui conduisent à abaisser la tension superficielle d'une solution aqueuse à 0.1 %o (0,1 pour mille) au dessous de 20 dynes/cm. Ces surfactants fluoro carbonés correspondent aux formules générales suivantes: F(CF2- CF2)x liés à divers groupements tels: - sulfonate CH2- CH2-SO3M - éthoxyle (CH2- CH2-O) xH ft - éthoxyle Phosphate (CH2- CH2-0)y P-(OH), - sulfure carboxylate CH2- CH2-S- CH2- CH2-COOH These have exceptional surface properties which lead to lowering the surface tension of an aqueous solution at 0.1% o (0.1 per thousand) below 20 dynes / cm. These fluoro carbonaceous surfactants correspond to the following general formulas: F (CF 2 -CF 2) x linked to various groups such as: - CH 2 -CH 2 -SO 3 M -sulfonate - ethoxyl (CH 2 -CH 2 -O) xH - ethoxyl Phosphate (CH 2 -CH 2 -0) P- (OH), - carboxylate sulfide CH2-CH2-S-CH2-CH2-COOH
OUOR
x=1à10 y=1 à2 z=2à1 y + z = 3 motifs M = métal: Sodium-Lithium-NH4- ou Amine Et en particulier dans le cadre de l'invention on utilisera: F(CF2CF2)z CH2- CH2-0)y P-(OH), 3o Sous forme de sels d'amines, entre autres des amines suivantes: Dimethylamino Ethanol, Ethyl2 Hexylamine, Cyclohexylamine, Morpholine, TEA ou encore: F(CF2- CF2)X CH2- CH2-S- CH2CH2-COO Li dont la tension superficielle en solution aqueuse à 0.02 % est de 20 dynes/cm. Ces deux produits présentent en outre une propension à l'effet anti-rouille. x = 1 to 10 y = 1 to 2 z = 2 to 1 y + z = 3 units M = metal: Sodium-Lithium-NH 4 - or Amine And in particular in the context of the invention use will be made of: F (CF 2 CF 2) z CH 2 -CH 2 0) y P- (OH), 3o In the form of amine salts, inter alia the following amines: Dimethylamino Ethanol, Ethyl2 Hexylamine, Cyclohexylamine, Morpholine, TEA or else: F (CF2-CF2) XCH2-CH2-S - CH2CH2-COO Li whose surface tension in 0.02% aqueous solution is 20 dynes / cm. These two products also have a propensity for the anti-rust effect.
Les compositions anti-corrosion pour traitements curatifs revendiquées comportent: - 95 à 99 % de la combinaison anti-corrosion de base - 5 à 1 % d'un surfactant fluoro carboné sous forme de sel d'amine ou de Lithium. The anti-corrosion compositions for claimed remedial treatments comprise: 95 to 99% of the base anti-corrosion combination; 5 to 1% of a fluoro carbonaceous surfactant in the form of an amine or lithium salt.
C2. Un solvant polaire favorisant la diffusion, la migration et le cheminement au travers des micro-fissures des matériaux des solutions actives anti-corrosives, pour atteindre les sites ou règne la corrosion. C2. A polar solvent promoting the diffusion, the migration and the path through the micro-fissures of the materials of the anti-corrosive active solutions, to reach the sites where corrosion reigns.
Selon l'invention on utilisera - Le Dimethylsulfoxyde (DMSO) CH3 CH3 S o qui a une tension de vapeur à 20 C de 0.417 m/m Hg Ou, et, - La Dimethylformamide CH3 NHCO CH3 dont la tension superficielle à 25 C est de 35 dynes/cm Ou encore, - Le Lactate d'Ethyl CH3 CH COO CH2 - CH3 1 According to the invention, use will be made of Dimethylsulfoxide (DMSO) CH 3 CH 3 S o which has a vapor pressure at 20 C of 0.417 m / m H 2 O 2, and Dimethylformamide CH 3 NHCO CH 3 whose surface tension at 25 ° C. is 35 dynes / cm Or, - Ethyl Lactate CH3 CH COO CH2 - CH3 1
OHOH
Ces produits étant utilisés seuls ou en mélange. These products are used alone or in mixture.
Les compositions anti-corrosion pour traitements curatifs revendiquées comportent: - 70 à 80 % de la combinaison anti-corrosion de base - 30 à 20 % d'un solvant polaire, tel notamment le Dimethylsulfoxyde favorisant leur diffusion et migration. The anti-corrosion compositions for curative treatments claimed comprise: - 70 to 80% of the base anti-corrosion combination - 30 to 20% of a polar solvent, such as Dimethylsulfoxide promoting their diffusion and migration.
EXEMPLESEXAMPLES
Les exemples mentionnés ci-après illustrent l'invention sans toutefois que celle-ci ne soit limitée à ces seules formulations. The examples mentioned below illustrate the invention without however being limited to these formulations alone.
Exemples 1 et 2:Examples 1 and 2:
Dans le tableau 1/5 présenté ci-après, sont mentionnés l'exemple 1 et l'exemple 2 qui correspondent à des produits, obtenus selon l'invention, destinés à des 5o traitements anti-corrosion préventifs. 10 In Table 1/5 presented below, are mentioned Example 1 and Example 2 which correspond to products, obtained according to the invention, intended for 5o preventive anti-corrosion treatments. 10
TABLEAU N 1/5TABLE N 1/5
Claims (2)
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0309939A FR2858820A1 (en) | 2003-08-14 | 2003-08-14 | Anti-corrosion compound for the preventive and curative treatment of metal reinforcement enclosed in mortar and concrete |
FR0407712A FR2858821A1 (en) | 2003-08-14 | 2004-07-09 | Anti-corrosion compound for the preventive and curative treatment of metal reinforcement enclosed in mortar and concrete |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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FR0309939A FR2858820A1 (en) | 2003-08-14 | 2003-08-14 | Anti-corrosion compound for the preventive and curative treatment of metal reinforcement enclosed in mortar and concrete |
Publications (1)
Publication Number | Publication Date |
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FR2858820A1 true FR2858820A1 (en) | 2005-02-18 |
Family
ID=34112772
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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FR0309939A Withdrawn FR2858820A1 (en) | 2003-08-14 | 2003-08-14 | Anti-corrosion compound for the preventive and curative treatment of metal reinforcement enclosed in mortar and concrete |
Country Status (1)
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FR (1) | FR2858820A1 (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3976494A (en) * | 1973-12-27 | 1976-08-24 | Onoda Cement Company, Ltd. | Process for inhibiting corrosion of iron or steel placed in cement products |
EP0474117A1 (en) * | 1990-09-04 | 1992-03-11 | IBC Manufacturing Company | Compositions |
GB2248612A (en) * | 1990-10-10 | 1992-04-15 | Ciba Geigy Ag | Corrosion inhibition |
EP0635463A1 (en) * | 1993-07-19 | 1995-01-25 | Sika AG, vorm. Kaspar Winkler & Co. | Additive preventing the corrosion of metals in building materials, method of making building materials using said corrosion inhibitor, and building material containing the corrosion inhibitor |
WO1996027695A2 (en) * | 1995-03-01 | 1996-09-12 | Sandoz Ltd. | A method for inhibiting corrosion of reinforced concrete |
-
2003
- 2003-08-14 FR FR0309939A patent/FR2858820A1/en not_active Withdrawn
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3976494A (en) * | 1973-12-27 | 1976-08-24 | Onoda Cement Company, Ltd. | Process for inhibiting corrosion of iron or steel placed in cement products |
EP0474117A1 (en) * | 1990-09-04 | 1992-03-11 | IBC Manufacturing Company | Compositions |
GB2248612A (en) * | 1990-10-10 | 1992-04-15 | Ciba Geigy Ag | Corrosion inhibition |
EP0635463A1 (en) * | 1993-07-19 | 1995-01-25 | Sika AG, vorm. Kaspar Winkler & Co. | Additive preventing the corrosion of metals in building materials, method of making building materials using said corrosion inhibitor, and building material containing the corrosion inhibitor |
US5916483A (en) * | 1993-07-19 | 1999-06-29 | Sika Ag, Vorm, Kaspar Winkler & Co. | Additive and a process for inhibiting the corrosion of metals in construction materials and constructions materials containing said additive |
WO1996027695A2 (en) * | 1995-03-01 | 1996-09-12 | Sandoz Ltd. | A method for inhibiting corrosion of reinforced concrete |
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