Classifications

• • 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, as well as to a degreasing gel and foam which comprise said composition.
• the invention also relates to a method for degreasing and / or decontaminating a surface using said composition, said gel and / or said degreasing foam.
• the present invention finds for example, but is not limited to, an application in the degreasing of surfaces, in particular of metallic surfaces such as apparatuses, components, grounds, etc. of a factory for reprocessing of irradiated 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 regularly clean these surfaces for the purpose of sanitation and / or radioactive decontamination.
• one of these substances is a solvent called tributylphosphate (TBP) which is used in the extraction cycles of radioactive metals such as uranium and plutonium. During these extraction cycles, this solvent acquires a particularly important radiochemical activity, since it can contain up to a few tens of grams. uranium and / or plutonium per liter. This solvent can then become a high activity solvent (HA solvent) or a very high activity solvent (THA solvent).
• HA solvent high activity solvent
• THA solvent very high activity solvent
• the presence of these HA and THA solvents on some of the components of irradiated fuel reprocessing plants such as mixer-settlers, extraction columns, etc. often leads to the formation of particularly organophilic metal surfaces which promote fatty deposits later. These fatty deposits are almost insensitive to rinsing with conventional aqueous solutions used in reprocessing and therefore require specific treatment.
• fatty substances likely to be found on these surfaces are the degradation 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 metal cations which may be present during the reprocessing of nuclear waste and in particular of spent fuel.
• HDBP dibutylphosphoric acid
• H 2 MBP monobutylphosphoric acid
• These surfaces can also be contaminated by uranium and plutonium oxides as well as nitrates compounds of these elements.
• Document FR-A-2 781 809 [1] describes degreasing compositions which can be used to degrease a metal surface having been in contact with a solvent such as TBP and / or its HDBP and H 2 MBP derivatives and their salts and complex, which includes a basic medium such as sodium hydroxide, combined with two nonionic surfactants.
• a solvent such as TBP and / or its HDBP and H 2 MBP derivatives and their salts and complex, which includes a basic medium such as sodium hydroxide, combined with two nonionic surfactants.
• This degreasing composition thus uses a basic medium which promotes a chemical attack on the fats to be eliminated by the conventional saponification reaction.
• This medium of the two surfactants makes it possible to reduce the sodium hydroxide concentration and to improve the spreading of the solution.
• the use of a basic medium has the drawback, in the nuclear field, of leading to the formation of hydroxides of radioactive metals, in particular plutonium hydroxide, which risks re-depositing on the metal surface. Therefore, it is necessary to carry out additional treatments to dissolve these hydroxides, for example by acid treatments.
• soda has the disadvantage of being not very compatible with vitreous matrices for packaging ultimate waste from the reprocessing of nuclear fuels.
• the present invention specifically relates to a degreasing composition which makes it possible to eliminate the drawbacks mentioned above, thanks to the use of an acid medium.
• the liquid degreasing composition comprises an aqueous solution of an inorganic acid, containing:
• At least one first nonionic emulsifying surfactant consisting of a polyethoxylated fatty alcohol
• At least one second nonionic wetting surfactant consisting of a copolymer of ethylene oxide and propylene oxide.
• the originality of this composition lies in the use of an inorganic acid, solvent which is little or not used in detergency.
• nitric acid which is part of the acids used in nuclear fuel reprocessing plants.
• concentration of nitric acid in the aqueous solution is chosen so as to be able to dissolve in it sufficient quantities of the first and second nonionic surfactants.
• the nitric acid concentration of the aqueous solution is 0.1 to 5 mol. L "1 .
• the surfactants used are soluble in the nitric acid solution and are chosen so as to allow high solubilization of the TBP, while leading to a solution having an appropriate cloud temperature and a controlled foaming effect.
• the first nonionic emulsifying surfactant is a polyethoxyl fatty alcohol, for example corresponding to the formula:
• 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 marketed by Goldschmidt (France) under the names RE OPAL X 1207 L. It statistically comprises 6 to 15 oxyethylenated units per molecule and a carbon chain comprising statistically 11 to 13 carbon atoms.
• This nonionic surfactant has a high hydrophilic-lipophilic balance (HLB) value of 12.5.
• nitric medium In 5 M nitric medium, its solubility is several tens of grams at 25 ° C., for example of the order of 80 gL "1. In more concentrated nitric medium, for example 15 M, the solubility is lower, by 1 'order of 10 gL "1 .
• the second nonionic wetting surfactant used in the composition of the invention makes it possible to reduce the foamability of the surfactant system and to increase the micellization capacity of the surfactant system; it is chosen from the family of block copolymers of ethylene oxide and of propylene.
• These non-ionic surfactants are known for their good wetting properties and they also have 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 advantageous in terms of safety because it provides a simple means of controlling untimely foaming during application on an industrial scale.
• Degreasing a surface consists in particular in dissolving in the micelles formed by the association of surfactants in the aqueous solution, the substance (s) present on the surface to be degreased.
• These micelles are formed in particular with fatty alcohol, saturated or unsaturated, polyethoxyl and contain (the) fatty substance (s) solubilized (s).
• Micelles are dynamic particles that form and disintegrate constantly in the solution.
• the concentration of one of the surfactants of the composition according to the invention is too low, in particular relative to the amount of fatty substance (s) to be dissolved, the micelles can dissociate and release the substance (s) ( s) oily (s) which then redeposit (s) on degreased surfaces.
• the dissociation of the micelles is visible and results in the formation of a cloud in the solution.
• This dissociation can occur when the composition according to the invention is saturated with fatty substance (s), and / or from a certain temperature.
• the saturation of the composition according to the invention with a fatty substance can be demonstrated by measuring the "cloud point" of this composition.
• the cloud point is expressed in degrees Celsius (° C).
• the cloud point of a nonionic surfactant corresponds to a partial dehydration of the hydrophilic chain, and this results, if the temperature of the cloud point is reached, by the phase separation, that is to say the demixing surfactant. If the cloud point reaches room temperature, this can lead to redeposition of the fatty substance on the degreased surfaces at room temperature. It is therefore preferable for the cloud point of the composition to be higher than the temperature used for degreasing, for example around 20 ° C., when the degreasing is carried out at ambient temperature or a temperature above 20 ° C. A high cloud point also indicates a high capacity for dissolving a fatty substance.
• the 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 can also be measured by measuring the wettability of this surface.
• the concentration of the second wetting surfactant of the composition is chosen to obtain a cloud point higher than the temperature at which the degreasing will be carried out.
• the second wetting surfactant preferably consists of a block copolymer of ethylene oxide and propylene oxide comprising from 1 to 8 ethylene oxide units and from 3 to 12 propylene oxide units.
• ANTAROX FM 33 As an example of a block copolymer of this type which can be used in the invention, mention may be made of the product sold by Rhodia under the name ANTAROX FM 33.
• the proportion of each of the surfactants is determined according to the following criteria:
• concentrations are preferably chosen such that the total concentration of surfactants in the composition is in the range from 1 to 20 gL "1 .
• the mass ratio of the first emulsifying surfactant (s) to the second wetting surfactant (s) is from 2 to 10, preferably about 4.
• a third surfactant can be added to the degreasing composition of the invention, constituted for example by a phosphoric ester, in order to reduce the foamability of the surfactant system.
• This phosphoric ester can correspond to the formula C 5 H 17 OOP (OR 2 ) 2 in which R 2 is a hydrocarbon group of 4 to 10 carbon atoms.
• 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 marketed by Quarré
• the foamability of the surfactant system can also be reduced by adding to the composition 0 to 0.5 gL "1 of tributyl phosphate (TBP) to take advantage of the high anti-foaming power due to the hydrophobicity of the molecule. TBP.
• TBP can therefore be used at very low concentrations as an anti-foaming agent for very specific applications linked to untimely foaming during the application of the treatment, in particular during the transfer of the liquid compositions into the pumping organs of the plant. It can also be incorporated from the manufacture of the composition.
• This solution has the advantage, in the case of an application to nuclear reprocessing, of not requiring the addition of a chemical additive of composition different from those already present in the equipment.
• the liquid degreasing composition of the invention is particularly advantageous because it allows the simultaneous solubilization of fats (TBP, HDBP, H 2 MBP as well, a priori as the U and Pu complexes of DBP and MBP) and of oxides in especially uranium or plutonium oxides as well as nitrates compounds derived from these elements and insoluble in soda medium. It also makes it possible to ensure the solubilization of any corrosion products of the metal surface, by carrying out the treatment in a single step.
• the liquid degreasing composition of the invention can be used in this form and used in various ways, for example in the form of soaking baths or by spraying.
• One can also use the liquid degreasing composition of the invention in the form of a foam by associating it with a gaseous phase.
• one or more additives chosen from those described in FR-A-2 679 458 [2] can be added to the foam.
• Both the foam and the degreasing liquid can be used for degreasing and / or decontaminating a surface, by bringing the surface into contact with the foam or the liquid in order to extract therefrom the products contaminating this surface.
• the formulation can be used in the form of foam and circulated for cleaning the enclosure.
• the proposed formulation and the proportions indicated are compatible with the use of the product in the form of foam. However, we will place our in the upper range of the concentrations indicated for the two main surfactants.
• the foamability of the system can also be reinforced or altered by adding third-party products such as, for example, those described in reference [2]. Thus, destabilization may be obtained by adding Amonyl 675 SB marketed by SEPPIC (sulfo betaine) up to 1.5% by mass.
• SEPPIC sulfo betaine
• the stability of the foam can be reinforced by the addition of a viscosant, for example xanthan gum in mass proportions of less than 0.2%.
• the implementation of the foam can also be carried out as described in references [2] and [3].
• the contacting can be carried out by circulating the foam in the enclosure. It is also possible to spray the foam using an applicator, for example a foam cannon, or else to use the techniques described in documents FR-A-2 679 458 [2] and FR-A-2 773 725 [ 3] to generate and apply the foam.
• the degreasing composition in the form of gel, by adding to it an appropriate inorganic viscosifying agent such as alumina or silica.
• the gel can be applied to the surface to be decontaminated using an applicator, for example with a brush or by spraying with a lance.
• an applicator for example with a brush or by spraying with a lance.
• the gel can be applied to the surface to be decontaminated by spraying with a spray gun, by soaking and draining, by packaging or even by means of a brush. It can then be removed from the surface by peeling it off with a simple water rinse, for example by means of a water jet.
• the gel is applied by spraying with a gun, for example under a pressure (AIRLESS compressor) at the level of the injector ranging from 500 to 1000 N.cm "2.
• the invention also relates to a decontamination process and / or degreasing a surface which consists in bringing the surface into contact with a liquid composition, a foam or a gel in accordance with the invention, in order to extract from this composition, this foam or this gel, the products contaminating this surface .
• contaminating products can be one or more of the following products: tributyl phosphate (TBP), dibutylphosphoric acid (HDBP), monobutylphosphoric acid (H 2 MBP) and their salts and complexes of uranium, plutonium and radioactive metals, and oxides and nitrates of uranium and plutonium.
• TBP tributyl phosphate
• HDBP dibutylphosphoric acid
• H 2 MBP monobutylphosphoric acid
• FIG. 1 is a diagram illustrating the evolution of the apparent solubility of TBP, S TBP (in gL “1 ) as a function of the concentration of nitric acid in the medium (mol.L “ 1 ), in the case of a solution nitric acid alone and in the case of a composition of degreasing according to the invention consisting of HN0 3 containing 8 gL "1 of RE OPAL and 2 gL " 1 of ANTAROX.
• FIG. 2 is a diagram illustrating for comparison the evolution of the apparent solubility of TBP, S TB p (in gL “1 ) as a function of the NaOH concentration (mol.L “ 1 ) of a composition comprising the same surfactants at the same concentrations as the composition of FIG. 1, replacing HN0 3 with NaOH.
• FIGS. 3 and 4 are curves illustrating the degreasing kinetics of a degreasing composition of the invention in 1 M nitric medium (FIG. 3) and of a degreasing composition of the invention in 5 M nitric medium (FIG. 4), or the evolution of the contact angle A c (°) as a function of the soaking time t (s).
• FIG. 5 is a histogram illustrating the effect of the degreasing compositions of the invention and the effect of a solution of pure nitric acid or of a solution of pure sodium hydroxide on the decontamination in americium of metal surfaces, expressed in surface activity 241 Am (Bq / cm 2 ) before and after decontamination.
• nitric acid concentration of a degreasing composition of the invention comprising 8 gL "1 of the first surfactant, REWOPAL X1207 L, and 2 gL " 1 of the second surfactant ANTAROX FM 33 is studied. So tests are carried out on the solubilization of TBP in nitric acid solutions whose nitric acid concentrations vary from 0.5 to 5 M, which contain the amounts given above of surfactants, by adding TBP in the composition up to 'at the onset of a persistent disorder.
• FIG. 1 illustrates the evolution of the apparent solubility S TB p (in gL “1 ) as a function of the concentration of HN0 3 (in mol.L “ 1 ). It is thus noted that in both cases the maximum apparent solubility is observed for an acid concentration of the order of 1 mol.L “1 , and that the gain due to the addition of surfactants to the composition of the invention is by a factor of 12 compared to the nitric medium alone.
• TBP is dissolved in the micelles formed by the combination of surfactants in the composition. These micelles appear for surfactant concentrations higher than the critical micelle concentration (CMC).
• CMC critical micelle concentration
• the hydrophobic core of the micelle acts as a microreactor allowing the solubilization of organic solvents. The apparent solubility resulting from the incorporation of the organic matter in the micelles is then much higher than the true solubility of TBP in the reference medium, as it appears from FIG. 1.
• composition No. 1 1 M nitric acid, REWOPAL
• a stainless steel blade 304 L initially clean is covered with a deposit composed of a mixture of TBP, HDBP and H 2 MBP in the following mass proportions: TBP 70%, HDBP 18%, H2MBP 12%.
• An indirect measurement of initial contact angle is then carried out using a Krùss K12 type blade tensiometer. The evolution of the contact angle is then followed after soaking the blade in the degreasing composition. A zero contact angle corresponds to perfect degreasing.
• FIG. 3 illustrates the evolution of the contact angle A c (in °) as a function of the soaking time t
• FIG. 4 illustrates the evolution of the contact angle A c (in degrees) as a function of the soaking time t (in seconds) for several tests carried out with composition No. 2.
• the initial mass of the deposit was 45 + 4 mg.
• Example 3 Reduction of foaming by adding a third-party product
• the presence of TBP has a strong anti-foaming power.
• the anti-foaming power of TBP is evaluated. This evaluation is carried out using a column filled with solution into which air is introduced through a frit to form a foam. The experiment is stopped when a predefined maximum time is reached (here 280 seconds) or when the maximum height available on the column is reached (here 26 cm). The maximum height of foam obtained or the time necessary to obtain it is determined (Table 1, 3rd column) as well as the time taken by the foam to fall from a height equal to half the maximum height reached (Table 1, 4th column). These tests are carried out with compositions no. 1 and no. 2 of the previous example by adding 0.6 or 0.05 gL "1 of TBP to them.
• Example 4 Decontamination of metal parts contaminated with americium 241
• the parts contaminated with americium-241 are immersed in the following degreasing compositions:
• Composition No. 3 HN0 3 5M, ANTAROX 2 gL "1 ,
• REWOPAL 8 gL -1 Composition No. 4 HN0 3 0.5 M, ANTAROX 2 gL "1 ,
• the tests are carried out with different initial activity levels in 241 Am.
• the final surface activity is then determined in 241 Am (in Bq / cm 2 ) of the parts after this treatment.
• the results obtained are given in the form of a histogram in FIG. 5, which also indicates the initial surface activity of the parts in 241 Am (in Bq / cm 2 ).
• the decontamination factor FD is determined, ie the ratio of the initial activity to the final activity of the parts. The values obtained are given in FIG. 5.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Organic Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Metallurgy (AREA)
• Mechanical Engineering (AREA)
• Materials Engineering (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Electrochemistry (AREA)
• Dispersion Chemistry (AREA)
• Food Science & Technology (AREA)
• Physics & Mathematics (AREA)
• General Engineering & Computer Science (AREA)
• High Energy & Nuclear Physics (AREA)
• Detergent Compositions (AREA)
• Cleaning And De-Greasing Of Metallic Materials By Chemical Methods (AREA)

Applications Claiming Priority (3)

Publications (2)

Family

ID=8865597

Family Applications (1)

Country Status (11)

Families Citing this family (10)

Family Cites Families (25)

• 2001
  • 2001-07-17 FR FR0109519A patent/FR2827610B1/fr not_active Expired - Fee Related
• 2002
  • 2002-07-16 WO PCT/FR2002/002524 patent/WO2003008526A1/fr active IP Right Grant
  • 2002-07-16 CN CNB028182081A patent/CN1244676C/zh not_active Expired - Fee Related
  • 2002-07-16 AT AT02764987T patent/ATE311431T1/de not_active IP Right Cessation
  • 2002-07-16 DE DE60207723T patent/DE60207723T2/de not_active Expired - Fee Related
  • 2002-07-16 UA UA2004010351A patent/UA76161C2/uk unknown
  • 2002-07-16 JP JP2003514071A patent/JP2004535509A/ja active Pending
  • 2002-07-16 RU RU2004104466/04A patent/RU2004104466A/ru not_active Application Discontinuation
  • 2002-07-16 ES ES02764987T patent/ES2252507T3/es not_active Expired - Lifetime
  • 2002-07-16 US US10/484,277 patent/US20040163671A1/en not_active Abandoned
  • 2002-07-16 EP EP02764987A patent/EP1412464B1/de not_active Expired - Lifetime

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events