US20040163671A1 - Degreasing composition useful for degreasing and/or decontaminating solid surfaces - Google Patents

Degreasing composition useful for degreasing and/or decontaminating solid surfaces Download PDF

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Publication number
US20040163671A1
US20040163671A1 US10/484,277 US48427704A US2004163671A1 US 20040163671 A1 US20040163671 A1 US 20040163671A1 US 48427704 A US48427704 A US 48427704A US 2004163671 A1 US2004163671 A1 US 2004163671A1
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Prior art keywords
degreasing
composition according
surfactant
composition
foam
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Abandoned
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US10/484,277
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English (en)
Inventor
Bruno Fournel
Laetitia Vauclair
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Orano Cycle SA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Commissariat a lEnergie Atomique CEA
Compagnie Generale des Matieres Nucleaires SA
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Assigned to COMMISSARIAT A L'ENERGIE ATOMIQUE, COMPAGNIE GENERALE DES MATIERES NUCLEAIRES reassignment COMMISSARIAT A L'ENERGIE ATOMIQUE ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: FOURNEL, BRUNO, VAUCLAIR, LAETITIA
Publication of US20040163671A1 publication Critical patent/US20040163671A1/en
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    • G—PHYSICS
    • G21—NUCLEAR PHYSICS; NUCLEAR ENGINEERING
    • G21F—PROTECTION AGAINST X-RADIATION, GAMMA RADIATION, CORPUSCULAR RADIATION OR PARTICLE BOMBARDMENT; TREATING RADIOACTIVELY CONTAMINATED MATERIAL; DECONTAMINATION ARRANGEMENTS THEREFOR
    • G21F9/00—Treating radioactively contaminated material; Decontamination arrangements therefor
    • G21F9/001—Decontamination of contaminated objects, apparatus, clothes, food; Preventing contamination thereof
    • G21F9/002—Decontamination of the surface of objects with chemical or electrochemical processes
    • 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
    • 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/003—Colloidal solutions, e.g. gels; Thixotropic solutions or pastes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/025—Cleaning or pickling metallic material with solutions or molten salts with acid solutions acidic pickling pastes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/085—Iron or steel solutions containing HNO3
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/10—Objects to be cleaned
    • C11D2111/14—Hard surfaces
    • C11D2111/16—Metals
    • 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
    • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
    • C11D2111/40—Specific cleaning or washing processes
    • C11D2111/42—Application of foam or a temporary coating on the surface to be cleaned

Definitions

  • the invention relates to a degreasing composition and also to a degreasing foam and gel which comprise the said composition.
  • the invention likewise relates to a method of degreasing and/or decontaminating a surface using the said degreasing composition, gel and/or foam.
  • the present invention finds application for example, though without being limited thereto, in the degreasing of surfaces, particularly of metallic surfaces such as those of instruments, components, floors, etc., of a plant for reprocessing spent nuclear fuels. These surfaces are or may be in contact with one or more fatty substances, which may be contaminated. It is therefore necessary to clean these surfaces regularly for the purpose of radioactive decontamination and/or sanitation.
  • tributyl phosphate TBP
  • HA high-activity
  • VHA very-high-activity
  • fatty substances which may be present on these surfaces are the breakdown products of TBP obtained by radiolysis of the solvent, such as dibutylphosphoric acid (HDBP), monobutylphosphoric acid (H 2 MBP) and the salts and complexes of these acids with metals such as uranium, plutonium and the metal cations which may be present during the reprocessing of nuclear waste and particularly of spent fuels.
  • HDBP dibutylphosphoric acid
  • H 2 MBP monobutylphosphoric acid
  • These surfaces may also be contaminated by uranium oxides and plutonium oxides and also by the nitrate compounds of these elements.
  • the document FR-A-2 781 809 [1] describes degreasing compositions which can be used for degreasing a metallic surface having been in contact with a solvent.
  • a solvent such as TBP and/or its derivatives, HDBP and H 2 MBP, and their salts and complexes, which comprises a basic medium such as sodium hydroxide solution in combination with two non-ionic surfactants.
  • This degreasing composition therefore uses a basic medium, which promotes chemical attack on the greases to be eliminated by the conventional saponification reaction.
  • the presence in this medium of the two surfactants allows the concentration of sodium hydroxide to be reduced and the spreading of the solution to be enhanced.
  • sodium hydroxide has the drawback of low compatibility with the glassy matrices for conditioning the ultimate waste obtained from the reprocessing of nuclear fuels.
  • the present invention specifically provides a degreasing composition which allows the drawbacks mentioned above to be removed, by virtue of the use of an acidic medium.
  • the liquid degreasing composition comprises an aqueous solution of an inorganic acid including:
  • At least one first, emulsifying non-ionic surfactant consisting of a polyethoxylated fatty alcohol
  • At least one second, wetting non-ionic surfactant consisting of a copolymer of ethylene oxide and propylene oxide.
  • the novelty of this composition therefore lies in the use of an inorganic acid, a solvent which is used little, if at all, in detergency.
  • nitric acid which is one of the acids used in nuclear fuel reprocessing installations.
  • the nitric acid concentration of the aqueous solution is selected such as to allow the dissolution therein of sufficient amounts of the first and second non-ionic surfactants.
  • the nitric acid concentration of the aqueous solution is from 0.1 to 5 mol.L ⁇ 1 .
  • the surfactants used are soluble in the nitric acid solution and are selected so as to allow a high level of solubilization of the TBP while at the same time resulting in a solution which has an appropriate cloud temperature and a controlled foaming effect.
  • the first, emulsifying non-ionic surfactant is a polyethoxylated fatty alcohol having, for example, the formula:
  • n is an integer ranging from 2 to 20 and R 1 is a saturated or unsaturated hydrocarbon chain having 9 to 18 carbon atoms.
  • n is an integer ranging from 6 to 15 and R 1 is an alkyl group of 11 to 13 carbon atoms.
  • a surfactant of this type mention may be made of the product sold by Goldschmidt (France) under the name Rewopal X 1207 L. It contains statistically from 6 to 15 oxyethylenated units per molecule and a carbon chain containing statistically 11 to 13 carbon atoms. This non-ionic surfactant possesses a high hydrophilic-lipophilic balance (HLB), of 12.5.
  • HLB hydrophilic-lipophilic balance
  • nitric medium its solubility is several tens of grams at 25° C., for example of the order of 80 g.L ⁇ 1 .
  • solubility is lower, of the order of 10 g.L ⁇ 1 .
  • the second, wetting non-ionic surfactant used in the composition of the invention allows the foamability of the surfactant system to be reduced and the micellization capacity of the surfactant system to be increased; it is selected from the class of block copolymers of ethylene oxide and propylene oxide.
  • These non-ionic surfactants are known for their good wetting properties and additionally they exhibit a cloud point, which makes it possible. to set a cloud temperature above which the system becomes perfectly non-foaming, by adjusting their concentration in the composition. This property is of advantage in safety terms, since it provides a simple means of controlling untimely foaming in the course of application on the industrial scale.
  • the degreasing of a surface consists in particular in solubilizing the substance or substances present on the surface to be degreased in micelles, which are formed by the combination of the surfactants in the aqueous solution. These micelles are formed in particular with the saturated or unsaturated, polyethoxylated fatty alcohol and contain the dissolved fatty substance(s).
  • the micelles are dynamic particles which form and disaggregate continuously in the solution.
  • concentration of one of the surfactants of the composition according to the invention is too low, in particular in relation to the amount of fatty substance(s) to be dissolved, the micelles are able to undergo dissociation and to release the fatty substance(s), which is (are) then redeposited on the degreased surfaces.
  • the dissociation of the micelles is visible and is manifested in the formation of clouding within the solution. This dissociation may take place when the composition according to the invention is saturated with fatty substance(s), and/or above a certain temperature.
  • the saturation of the composition according to the invention by a fatty substance may be demonstrated by measuring the “cloud point” of this composition.
  • the cloud point is expressed in degrees Celsius (° C.).
  • the cloud point of a non-ionic surfactant corresponds to partial dehydration of the hydrophilic chain, which is manifested, when the cloud point temperature is. reached, in phase separation, in other words the segregation of the surfactant.
  • the cloud point of the composition may be higher than the temperature used for degreasing, for example approximately 20° C., when degreasing is performed at ambient temperature or a temperature greater than 20° C.
  • a high cloud point moreover, translates into a high capacity for dissolution of a fatty substance. Measurement of the cloud point therefore makes it possible in particular to measure the degreasing efficiency of the composition according to the invention. This degreasing efficiency may also be measured by measuring the wettability of this surface.
  • the concentration of the second, wetting surfactant of the composition is selected to give a cloud point higher than the temperature at which degreasing will be performed.
  • the second, wetting surfactant is preferably made of a block copolymer of ethylene oxide and propylene oxide containing from 1 to 8 ethylene oxide units and from 3 to 12 propylene oxide units.
  • the proportion of each of the surfactants is determined as a function of the following criteria:
  • concentrations such that the total surfactant concentration of the composition is situated in the range from 1 to 20 g.L ⁇ 1 .
  • the amount of the first surfactant(s) is also preferable for the amount of the first surfactant(s) to be greater than that of the second surfactant(s).
  • the mass ratio of the first, emulsifying surfactant(s) to the second, wetting surfactant(s) is from 2 to 10, preferably around 4.
  • a third surfactant to the degreasing composition of the invention, this surfactant being composed, for example, of a phosphoric ester, for the purpose of reducing the foamability of the surfactant system.
  • This phosphoric ester may be of the formula C 5 H 17 OOP (OR 2 ) 2 , in which R 2 is a hydrocarbon group of 4 to 10 carbon atoms.
  • a third surfactant of this type mention may be made of the product sold by Quarré Chim under the name Victawet 12. It may be present in the composition at a concentration of from 0.1 to 3 g.L ⁇ 1 , for example 0.5 g.L ⁇ 1 .
  • TBP tributyl phosphate
  • TBP TBP at very low concentrations as an antifoam for highly selective applications associated with untimely foaming during the application of the treatment, especially during the transfer of the liquid compositions into the pumping elements of the plant. It may also be integrated at the point when the composition is manufactured.
  • This solution has the advantage, in the case of application to nuclear reprocessing, of not necessitating the addition of a chemical additive whose composition is different from those already present in the equipment.
  • the liquid degreasing composition of the invention is particularly advantageous since it provides solubilization both of the greases (TBP, HDBP and H 2 MBP and also, a priori, the U and Pu complexes of DBP and MBP) and of oxides, especially the oxides of uranium or of plutonium, and also of nitrate compounds which are obtained from these elements and are insoluble in a sodium hydroxide medium. It also provides for the solubilization of any corrosion products of the metallic surface, by carrying out treatment in a single step.
  • liquid degreasing composition of the invention may be used in this form and employed in a variety of ways, for example in the form of soak baths or by spraying.
  • liquid degreasing composition of the invention in the form of a foam, by combining it with a gas phase.
  • the foam one or more additives selected from those described in FR-A-2 679 458 [2].
  • Both the foam and the degreasing liquid can be used for degreasing and/or decontaminating a surface by contacting the surface with the foam or liquid in order to extract into the latter the products contaminating this surface.
  • the formulation may be used in the form of a foam and be circulated for containment cleaning. It may also be atomized by means of an applicator, for example a foam gun.
  • the formulation proposed and the proportions indicated are compatible with use of the product in foam form. Such use will take place, however, in the upper range of the concentrations indicated for the two principal surfactants.
  • the foamability of the system may also be enhanced or altered by adding other products like, for example, those described in reference [2].
  • destabilization can be obtained by adding Amonyl 675 SB, which is sold by SEPPIC (sulfo betaine) at up to 1.5% by mass.
  • SEPPIC sulfo betaine
  • the stability of the foam can be reinforced by adding a viscosity enhancer, for example xanthan gum, in proportions by mass of less than 0.2%.
  • the foam may also be employed as described in references [2] and [3].
  • contacting may be performed by circulating the foam within the containment. It is also possible to atomize the foam using an applicator, for example a foam gun, or else to use the techniques described in documents FR-A-2 679 458 [2] and FR-A-2 773 725 [3] in order to generate and apply the foam.
  • an applicator for example a foam gun
  • the degreasing composition in the form of a gel, by adding thereto a suitable inorganic viscosity enhancer such as alumina or silica.
  • the gel may be applied to the surface to. be decontaminated by means of an applicator, for example by brush or by atomization by means of a lance. It is also possible to use the techniques of decontamination described in documents FR-A-2 695 839 [4], FR-A-2 656 949 [5] and FR-A-2 717 709 [6].
  • the gel can be applied to the surface to be decontaminated by spraying with a gun, by soaking and allowing to drip dry, by packing or else using a brush. It can be subsequently removed from the surface by detaching it by simple rinsing with water, for example by means of a jet of water.
  • the gel is applied by spraying with a gun, for example under a pressure (Airless compressor) in the injector ranging from 500 to 1000 N.cm ⁇ 3 .
  • the invention likewise provides a method of decontaminating and/or degreasing a surface, which consists in contacting the surface with a liquid composition, a foam or a gel in accordance with the invention in order to extract the products contaminating this surface into this composition, foam or gel.
  • These contaminating products may be one or more of the following products: tributyl phosphate (TBP), dibutyl phosphoric acid (HDBP), monobutyl phosphoric acid (H 2 MBP) and their salts and complexes with uranium, plutonium and radioactive metals, and the oxides and nitrates of uranium and of plutonium.
  • TBP tributyl phosphate
  • HDBP dibutyl phosphoric acid
  • H 2 MBP monobutyl phosphoric acid
  • FIG. 1 is a diagram illustrating the change in the apparent solubility of TBP, S TBP (in g.L ⁇ 1 ), as a function of the nitric acid concentration of the medium (mol.L ⁇ 1 ), in the case of a nitric acid solution alone and in the case of a degreasing composition in accordance with the invention, composed of HNO 3 containing 8 g.L ⁇ 1 of Rewopal and 2 g.L ⁇ 1 of Antarox.
  • FIG. 2 is a diagram illustrating, for comparison, the change in the apparent solubility of TBP; S TBP (in g.L ⁇ 1 ), as a function of the NaOH concentration (mol.L ⁇ 1 ) of a composition comprising the same surfactants in the same concentrations as the composition of FIG. 1, HNO 3 being replaced by NaOH.
  • FIGS. 3 and 4 are curves illustrating the degreasing kinetics of a degreasing composition of the invention in a 1 M nitric medium (FIG. 3) and of a degreasing composition of the invention in a 5 M nitric medium (FIG. 4), i.e. the change in contact angle A c (°) as a function of the soak time t(s).
  • FIG. 5 is a histogram illustrating the effect of the degreasing compositions of the invention and the effect of a pure nitric acid solution or of a pure sodium hydroxide solution on the decontamination from americium of metallic surfaces, expressed in terms of 241 Am surface activity (Bq/cm 2 ) before and after decontamination.
  • TBP solubilization tests are therefore carried out in nitric acid solutions whose nitric acid concentrations vary from 0.5 to 5 M, containing the amounts of surfactants indicated above, by adding TBP to the composition until persistent clouding appears.
  • FIG. 1 illustrates the change in apparent solubility S TBP (in g.L ⁇ 1 ) as a function of the HNO 3 concentration (in mol.L ⁇ 1 ).
  • the level at which the surfactants are introduced is that of their capacity to remove hydrophobic deposits from solid surfaces, by virtue of their wetting and emulsifying properties.
  • the presence of these deposits of organic origin, even in a small quantity, may detract considerably from the conventional, hydrophilic-type treatments, by preventing their access to the entirety of the contaminated surfaces.
  • TBP as reference is justified because it constitutes the most hydrophobic deposit likely to be encountered in a nuclear fuel reprocessing plant.
  • TBP is solubilized in the micelles formed by the combination of surfactants in the composition. These micelles appear at surfactant concentrations greater than the critical micelle concentration (CMC).
  • CMC critical micelle concentration
  • the hydrophobic core of the micelle acts as a micro-reactor, allowing the solubilization of organic solvents.
  • the apparent solubility resulting from the incorporation of the organic material in the micelles is thus very much greater than the true solubility of TBP in the reference medium, as evident from FIG. 1.
  • Composition no. 1 1 M nitric acid, 8 g.L ⁇ 1 Rewopal and 2 g.L ⁇ 1 Antarox
  • Composition no. 2 5 M nitric acid, 8 g.L ⁇ 1 Rewopal and 2 g.L ⁇ 1 Antarox.
  • an initially clean plate of 304 L stainless steel is covered with a deposit composed of a mixture of TBP, HDBP and H 2 MBP in the following proportions by mass: TBP 70%, HDBP 18%, H2MBP 12%.
  • An indirect measurement of the initial contact angle is then carried out using a Krüss K12 plate tensiometer. The change in contact angle is subsequently followed after the plate has been soaked in the degreasing composition. A zero contact angle corresponds to ideal degreasing.
  • FIG. 3 illustrates the change in contact angle A c (in°) as a function of the soak time t (in s) of two plates in composition no. 1.
  • FIG. 4 illustrates the change in contact angle A c (in degrees) as a function of the soak time t (in seconds) for a number of tests conducted with composition no. 2.
  • TBP has a high antifoaming power owing to the hydrophobicity of this molecule.
  • the antifoaming power of TBP is evaluated in the case of the compositions of the invention in a nitric acid medium. This evaluation is performed using a column filled with solution into which air is introduced through a frit in order to form a foam. The experiment is stopped when a predetermined maximum duration has elapsed (in this case 280 seconds) or when the maximum available height on the column has been reached (in this case 26 cm). A determination is made of the maximum height of foam obtained or the time required to obtain it (Table 1, column 3) and of the time taken by the foam to fall by height equal to half the maximum height attained (Table 1, column 4). These tests are carried out with compositions no. 1 and no. 2 from the preceding example, by adding to them 0.6 or 0.05 g.L ⁇ 1 of TBP.
  • Composition no. 3 HNO 3 5 M, Antarox 2 g.L ⁇ 1 , Rewopal 8 g.L ⁇ 1
  • Composition no. 4 HNO 3 0.5 M, Antarox 2 g.L ⁇ 1 , Rewopal 8 g.L ⁇ 1
  • Composition no. 5 HNO 3 0.5 M, Antarox 2 g.L ⁇ 1 , Rewopal 8 g.L ⁇ 1
  • compositions of the invention are markedly superior to that of a concentrated nitric acid solution or a concentrated sodium hydroxide solution.

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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
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  • High Energy & Nuclear Physics (AREA)
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  • Food Science & Technology (AREA)
  • Detergent Compositions (AREA)
  • Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)
US10/484,277 2001-07-17 2002-07-16 Degreasing composition useful for degreasing and/or decontaminating solid surfaces Abandoned US20040163671A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR01/09519 2001-07-17
FR0109519A FR2827610B1 (fr) 2001-07-17 2001-07-17 Composition de degraissage utilisable pour le degraissage et/ou la decontamination de surfaces solides
PCT/FR2002/002524 WO2003008526A1 (fr) 2001-07-17 2002-07-16 Composition de degraissage utilisable pour le degraissage et/ou la decontamination de surfaces solides

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EP (1) EP1412464B1 (zh)
JP (1) JP2004535509A (zh)
CN (1) CN1244676C (zh)
AT (1) ATE311431T1 (zh)
DE (1) DE60207723T2 (zh)
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US11473036B2 (en) 2017-07-04 2022-10-18 Atotech Deutschland Gmbh Cleaning solution for cleaning metal surfaces

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FR2827610A1 (fr) 2003-01-24
ES2252507T3 (es) 2006-05-16
CN1555408A (zh) 2004-12-15
ATE311431T1 (de) 2005-12-15
FR2827610B1 (fr) 2005-09-02
JP2004535509A (ja) 2004-11-25
WO2003008526A1 (fr) 2003-01-30
EP1412464A1 (fr) 2004-04-28
RU2004104466A (ru) 2005-07-10
UA76161C2 (en) 2006-07-17
CN1244676C (zh) 2006-03-08
DE60207723D1 (de) 2006-01-05
DE60207723T2 (de) 2006-08-03

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