EP3411466B1 - Verfahren zum reinigen eines durch partikel kontaminierten substrats - Google Patents

Verfahren zum reinigen eines durch partikel kontaminierten substrats Download PDF

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Publication number
EP3411466B1
EP3411466B1 EP17713716.3A EP17713716A EP3411466B1 EP 3411466 B1 EP3411466 B1 EP 3411466B1 EP 17713716 A EP17713716 A EP 17713716A EP 3411466 B1 EP3411466 B1 EP 3411466B1
Authority
EP
European Patent Office
Prior art keywords
cleaning
particles
polymer
polymer matrix
substrate according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP17713716.3A
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English (en)
French (fr)
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EP3411466A1 (de
Inventor
Mathias REYNES
Simon Clavaguera
Sylvie MOTELLIER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique CEA
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
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Publication of EP3411466A1 publication Critical patent/EP3411466A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B08—CLEANING
    • B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
    • B08B7/00—Cleaning by methods not provided for in a single other subclass or a single group in this subclass
    • B08B7/0014—Cleaning by methods not provided for in a single other subclass or a single group in this subclass by incorporation in a layer which is removed with the contaminants
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3765—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in liquid compositions
    • 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
    • C11D2111/12—Soft surfaces, e.g. textile
    • 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

Definitions

  • the present invention relates to a method for cleaning a surface having been contaminated with particles, for example metal oxide nanoparticles.
  • the field of use of the present invention relates in particular to the decontamination of metal, glass, plastic or ceramic surfaces.
  • nanoparticles in fields as varied as health, microelectronics, energy, or cosmetics requires studying the possible health or environmental impact that these nanoparticles are likely to generate.
  • nanoparticles whose quantity marketed each year is estimated at about 11.5 million tons, include carbon black (9.6.10 6 t), synthetic amorphous silica (1.5.10 6 t), aluminum oxide (200,000 t), barium titanate (15,000 t), titanium dioxide (10,000 t), cerium oxide (10,000 t), and zinc oxide (8,000 t).
  • acidic or basic solutions, surfactants, powders or abrasive creams is particularly suitable for cleaning hard surfaces such as ceramics, metals, plastics or glass. This is particularly the case when the surfaces are not flat.
  • peelable materials are of interest for cleaning large areas. Indeed, the solid residue containing the particles contaminating the surface can be easily handled and removed, in particular by peeling a single large film or brushing followed by suction.
  • the peeling of a single large film is particularly suitable for smooth and flat surfaces while brushing followed by suction is applicable to any type of surface.
  • the document US 2002/0160224 describes a treatment for cleaning and treating surfaces such as ceramic, steel, plastic, glass or external surfaces of a vehicle.
  • This treatment also comprises the deposition of a hydrophilic polymer remaining on the cleaned surface so as to avoid the formation of traces during drying.
  • the document US 2010/0313907 describes a method for removing contaminants using magnetic nanoparticles.
  • the application of a magnetic field thus makes it possible to simultaneously remove the magnetic nanoparticles and the contaminants to which they are linked.
  • the document FR 2 891 470 describes a gel for decontaminating surfaces contaminated with radioactive particles.
  • This gel can be aspirated after drying. It is obtained from a colloidal gelling solution containing surfactants and corrosive products for recovering the contaminants in the solidified gel. This document therefore describes the use of colloidal solutions to decontaminate soiled surfaces.
  • US 5681399 discloses a method for removing stains from a coated surface by forming a film on the coated surface.
  • the document JP 59189200 discloses a method of cleaning a substrate by forming a coating of a dispersion of a copolymer.
  • the document US 2010/0120647 discloses a method for removing particles from a substrate by forming a layer on the surface.
  • the prior art includes many methods for cleaning various types of surfaces by wet wiping and peelable film deposition.
  • the Applicant has developed an inexpensive alternative, thanks to a polymer matrix for trapping particles contaminating a substrate.
  • the present invention makes it possible to clean a substrate whose surface is polluted by particles by the action of a polymer matrix which can be a microgel which, after drying, forms a varnish trapping the particles in the polymer matrix. Particles present or adsorbed on solid surfaces are impregnated into the polymer matrix. The varnish can then be peeled off the surface of the substrate.
  • a polymer matrix which can be a microgel which, after drying, forms a varnish trapping the particles in the polymer matrix. Particles present or adsorbed on solid surfaces are impregnated into the polymer matrix. The varnish can then be peeled off the surface of the substrate.
  • the particles, and in particular the nanoparticles then no longer present a risk because they are trapped in a polymer matrix.
  • the group C 1 -C 22 denotes a hydrocarbon group comprising 1 to 22 carbon atoms, preferably 1 to 8 carbon atoms.
  • C 1 -C 22 may comprise heteroatoms (O, N, S for example) and / or at least one aromatic group.
  • C 1 -C 22 is advantageously a linear or branched alkyl group.
  • the C 1 -C 22 group may in particular be a methyl, ethyl, isopropyl, butyl, hexyl, 2-ethylhexyl, lauryl or strearyl-type alkyl.
  • the counterion is advantageously a cation of an alkali metal or an ammonium, in particular a quaternary ammonium.
  • the substrate that can be cleaned by the method according to the invention can be made of a material chosen from the group comprising plastic; metals ; metal oxides; the textile ; glass ; and ceramics.
  • a substrate the contaminated part of which has a smooth surface, that is to say a surface whose roughness (average of the depths of the micro geometric defects of the surface) is advantageously less than 1 ⁇ m, in particular in the case of a metal substrate.
  • the substrate generally corresponds to a surface of a unit for producing or handling nanoparticle-type particles.
  • the particles trapped according to the invention have a size advantageously between 1 and 1000 nanometers, more advantageously between 1 and 100 nanometers. Their aggregates and agglomerates may be larger.
  • the particles are metal particles, metal oxide particles or carbon-based particles. It may especially be TiO 2 , SiO 2 , Al 2 O 3 , CeO 2 or Ag particles.
  • the carbon-based particles may be carbon nanotubes, graphene, carbon black, or nanocellulose.
  • the first step of the process according to the invention consists in depositing a polymer matrix on the substrate to be cleaned, and more particularly on a surface of the substrate being contaminated by the presence of particles.
  • the deposition of the polymer matrix may in particular be carried out by manual deposition of drops, by spraying, or by coating, for example with a brush.
  • the polymer matrix used is advantageously in the form of a microgel.
  • a microgel corresponds to gel particles whose size is between 0.1 and 100 micrometers, the size corresponding to the largest dimension of the gel, that is to say the diameter for spherical particles.
  • the polymer matrix has, before the formation of the varnish, a weight ratio polymer / water advantageously between 1 and 75%, more preferably between 5 and 50%.
  • the acrylic monomer is acrylamide or methacrylamide.
  • the radical polymerization is carried out conventionally in the presence of a radical polymerization initiator consisting of an initiator preferably chosen from the family of azo initiators and peroxides.
  • a radical polymerization initiator consisting of an initiator preferably chosen from the family of azo initiators and peroxides.
  • preferred initiators include azobisisobutyronitrile (AIBN) and potassium persulfate (KPS).
  • the polymer for forming the polymer matrix is crosslinked with at least one crosslinking agent.
  • the crosslinking of the polymer is generally carried out in the presence of a crosslinking agent during the polymerization of the acrylic monomer or monomers.
  • the crosslinking agent is advantageously a compound having at least two vinyl functional groups such as N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, dihydroxyethylene bisacrylamide, N, N'-bisacryloylpiperazine, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, glycerin triacrylate, divinylbenzene, vinylsulfone or carbodiimidesglycol dimethacrylate, advantageously N, N'-methylene-bisacrylamide.
  • vinyl functional groups such as N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, dihydroxyethylene bisacrylamide, N, N'-bisacryloylpiperazine, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate, glycerin triacrylate, divinylbenzene, vinylsulfone or carbodiimidesglycol dimeth
  • the crosslinking agent represents 0.01 to 20 mol%, relative to the acrylic monomer (s), more advantageously 0.5 to 5 mol%.
  • the polymer matrix can also comprise chelating functions that can promote the cleaning of certain (nano) particles.
  • the polymer matrix may comprise catechol or thiol functions, especially for the removal of (nano) metal particles such as (nano) particles of silver or gold.
  • the polymer matrix may be obtained in the presence of at least one surfactant. It may especially be one or more anionic, cationic, zwitterionic and / or nonionic surfactants. These surfactants can be used alone or in a mixture of two or more.
  • the surfactant may be chosen from the following groups: alkylbenzene sodium sulphonates, sodium alkyl sulphonates, polyoxyethylene sodium alkyl ether sulphonates, polyoxyethylene alkyl ether, polyoxyethylene glycol and polyoxypropylene glycol.
  • the surfactant is preferably sodium 1,4-bis (2-ethylhexoxy) -1,4-dioxobutane-2-sulfonate (AOT; CAS 577-11-7 ); sodium dodecyl sulfate (SDS; CAS 151-21-3 ) or the nonionic surfactant corresponding to the CAS 9003-11-6 .
  • the surfactant used may have unsaturations thus rendering it polymerizable.
  • agent (s) surfactant (s) represent (s) advantageously between 0.1 and 10% by weight of the polymer matrix (water + polymer + crosslinking agent if appropriate), more preferably less than 0.1 to 5 %% by weight of the polymer matrix.
  • the nature of the surfactant also makes it possible to modify the polymer matrix.
  • the polymer matrices, and more particularly in the form of microgels, containing the surfactants having the following CAS numbers CAS 9003-11-6 , CAS 151-21-3 and CAS 577-11-7 have a decreasing size.
  • the impregnation, or even the migration, of the particles within the polymer matrix takes place between the polymer matrix deposition and the varnish formation stages, that is to say during the drying of the polymer matrix, by evaporation. some water.
  • the polymer matrix is in the aqueous phase devoid of an organic solvent, drying has the advantage of not producing volatile organic compounds.
  • the removed particles can be treated in conventional nanoscale solid waste management channels while limiting the volume of effluent to be treated.
  • the drying of the polymer matrix may in particular be carried out at atmospheric pressure and at a relative humidity which may be between 20 and 70%.
  • the formation of the varnish is advantageously obtained after 1 to 72 hours at this temperature, more advantageously between 2 and 24 hours.
  • the drying step can be accelerated, for example by increasing the temperature and / or lowering the pressure.
  • the particles are then trapped in the varnish formed by drying the polymer matrix.
  • the varnish is in the form of a polymer film on the surface of the substrate. It is advantageously removed by tearing.
  • the formation of the varnish by drying the polymer matrix may be accompanied by cracking.
  • the removal of the varnish can be facilitated by manual mechanical action, by using a brush, a vacuum or compressed air. This optional means makes it possible to eliminate any residues of varnish.
  • the polymer matrix used in the present invention does not require a rinsing solvent.
  • the removal of the varnish is carried out without water.
  • the process according to the invention makes it possible to eliminate the majority of the particles by using a single deposit of polymer matrix.
  • the various process steps can be repeated, especially in the face of large quantities of particles to be removed.
  • a process comprising two consecutive sequences (polymer matrix / varnish / elimination) each making it possible to eliminate 90% of particles, could correspond to a total decontamination efficiency of 99%.
  • the present invention may in particular be used to clean instruments, equipment, vehicles, or surfaces in industry and research. It may also concern the restoration of monuments, works of art or an intervention after a disaster, for example after a fire that has resulted in the deposition of smoke particles or soot.
  • MG1-MG4 polymeric matrices according to the invention (MG1-MG4) of polymethacrylamide were prepared from the polymers P1-P4 obtained according to the following procedure and according to the conditions of Table 1.
  • the methacrylamide is polymerized by radical radical polymerization in the presence of a radical initiator and optionally a crosslinking agent and a surfactant.
  • a radical initiator for this purpose, an aqueous solution containing methacrylamide ( CAS 79-39-0 ), N, N'-methylene-bis-acrylamide and a surfactant is prepared and degassed for several hours with argon.
  • an aqueous solution containing the radical initiator is prepared and degassed for several hours with argon.
  • the polymer thus obtained is precipitated and then centrifuged after the addition of methanol.
  • the polymer is purified by dialysis for 4 to 5 days.
  • microgel thus produced is dried at 70 ° C under vacuum and can be stored dry at room temperature for several years.
  • microgel Before each use, the microgel is suspended in heated water (5 to 50% by weight of microgel) until the optimum viscosity for easy application.
  • the molar percentages (mol%) are expressed relative to the amount of methacrylamide monomer.
  • the suspension of TiO 2 used has a concentration of 1 g / L in water .
  • a 10 ⁇ L deposit is made on the substrate which is then dried on a hot plate at 50 ° C.
  • microgel (MG1 to MG4) is solubilized in hot deionized water (approximately 50 ° C), then a few drops are pipetted onto the substrate to cover an area of approximately 1 cm 2 in the center of which the TiO 2 deposition was performed.
  • the substrate is protected from dust at ambient temperature / pressure / humidity for 48 hours. At the end of these 48 hours, the microgel looks like a shell that comes off almost alone in one piece.
  • the glass slide has not undergone treatment.
  • Example CE-2 a drop of deionized water was deposited on the glass slide. This drop of water, of the same volume as the microgels of Examples INV-1 to INV-3, was then dried before being subjected to a mechanical action simulating the detachment of the varnish as in Examples INV-1 to INV-3. 3.
  • examples INV-1 to INV-3 according to the invention, a drop of a saturated aqueous solution of microgel was deposited on the glass slide. After drying, a slight mechanical action was applied to the blade so as to finish the peeling of the varnish formed by the dried microgel.
  • microgels drastically improves the cleaning of the substrate, 80 to 90% of the nanoparticles being removed (INV-1 to INV-3) in one step.
  • Table 2 polystyrene substrate cleaning protocols. Trial Treatment % of particles removed Solution Drying Mechanical action EC-3 - - - ⁇ 1% EC-4 water - Yes 39.8 INV-4 microgel MG4 Yes Yes 95.2
  • the polystyrene plate has not undergone treatment.
  • Example CE-4 In counter-example CE-4, a drop of deionized water was deposited on the polystyrene plate. This drop of water, of the same volume as the microgel of Example INV-4, was then dried before being subjected to a mechanical action simulating the detachment of the varnish as in Example INV-4.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (10)

  1. Verfahren zum Reinigen eines durch Partikel kontaminierten Substrats, das die folgenden Schritte umfasst:
    - Abscheiden einer Wasser und ein Polymer umfassenden Polymermatrix auf der Oberfläche des Substrats, wobei das Polymer aus Einheiten besteht, die von einem oder mehreren Acrylmonomeren abgeleitet sind, die die Formel CH2=CR1-C(=0)-R2 haben und gegebenenfalls mindestens eines Vernetzungsmittels
    mit

            R1 = H oder CH3

            R2 = NH2; NHR3; NR3 2; oder OR3

            R3 = H oder eine Gruppe auf Kohlenwasserstoffbasis mit 1 bis 22 Kohlenstoffatomen;

    - Imprägnieren der Partikel in die Polymermatrix;
    - Ausbilden eines Lackes durch Trocknen der Polymermatrix;
    - Entfernen des Lacks und der im Lack eingeschlossenen Partikel ohne Spüllösung.
  2. Verfahren zum Reinigen eines Substrats gemäß Anspruch 1, dadurch gekennzeichnet, dass das Substrat aus einem Material besteht, das aus der Gruppe ausgewählt wird, zu der Kunststoff, die Metalle, die Metalloxide, Textil, Glas und Keramik gehören.
  3. Verfahren zum Reinigen eines Substrats gemäß Anspruch 1 oder 2, dadurch gekennzeichnet, dass es sich bei den Partikeln um Metallpartikel, Metalloxid-Partikel oder um Partikel auf Kohlenstoffbasis handelt;
    wobei die Größe der Partikel dabei zwischen 1 und 100 nm liegt.
  4. Verfahren zum Reinigen eines Substrats gemäß einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Polymermatrix vor Bildung des Lacks ein Masseverhältnis Polymer/ Wasser zwischen 1 und 75%, besser zwischen 5 und 50% enthält.
  5. Verfahren zum Reinigen eines Substrats gemäß Anspruch 1 bis 4, dadurch gekennzeichnet, dass das Acrylmonomer aus der Gruppe ausgewählt wird, zu der (Meth)acrylamid ; (Meth)acrylsäure, (Meth)acrylsäuresalzen, (Meth)acrylsäuresters; N-alkylacrylamide und ihre Mischungen gehören.
  6. Verfahren zum Reinigen eines Substrats gemäß einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass das Polymer mit einem Vernetzungsmittel vernetzt wird.
  7. Verfahren zum Reinigen eines Substrats gemäß einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass das Polymer mit einem Vernetzungsmittel vernetzt wird, das mindestens 0,01 bis 20 mol%, besser noch 0,5 bis 5 mol%, bezogen auf das (die) Acryl-Monomer(e) darstellt.
  8. Verfahren zum Reinigen eines Substrats gemäß einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Polymermatrix in Anwesenheit mindestens eines tensioaktiven Wirkstoffs hergestellt wird.
  9. Verfahren zum Reinigen eines Substrats gemäß einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Polymermatrix in Anwesenheit mindestens eines tensioaktiven Wirkstoffs hergestellt wird, der aus den folgenden Gruppen ausgewählt wird: Alkylbenzen-Natriumsulfonate, Natriumalkylsulfonate, Polyoxyethylen-Natrium-alkylethersulfonate, Polyoxyethylen-Alkylether, Polyoxyethylen-Glykol und Polyoxypropylen-Glykol.
  10. Verfahren zum Reinigen eines Substrats gemäß einem der Ansprüche 1 bis 9 dadurch gekennzeichnet, dass die Bildung des Lacks bei einer Temperatur zwischen 5 und 50°C erfolgt.
EP17713716.3A 2016-03-22 2017-02-28 Verfahren zum reinigen eines durch partikel kontaminierten substrats Active EP3411466B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1652435A FR3049202B1 (fr) 2016-03-22 2016-03-22 Procede de nettoyage d'un substrat contamine par des particules
PCT/FR2017/050437 WO2017162945A1 (fr) 2016-03-22 2017-02-28 Procede de nettoyage d'un substrat contamine par des particules

Publications (2)

Publication Number Publication Date
EP3411466A1 EP3411466A1 (de) 2018-12-12
EP3411466B1 true EP3411466B1 (de) 2019-09-04

Family

ID=55863085

Family Applications (1)

Application Number Title Priority Date Filing Date
EP17713716.3A Active EP3411466B1 (de) 2016-03-22 2017-02-28 Verfahren zum reinigen eines durch partikel kontaminierten substrats

Country Status (3)

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EP (1) EP3411466B1 (de)
FR (1) FR3049202B1 (de)
WO (1) WO2017162945A1 (de)

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4341687A (en) 1979-09-25 1982-07-27 Tokyo Shibaura Denki Kabushiki Kaisha Peelable film-forming urethane/isocyanate paints
JP3046918B2 (ja) * 1994-10-17 2000-05-29 クレオール株式会社 塗装面の洗浄方法
US7267728B2 (en) 2001-01-30 2007-09-11 The Procter & Gamble Company System and method for cleaning and/or treating vehicles and the surfaces of other objects
GB0404326D0 (en) * 2004-02-27 2004-03-31 Reckitt Benckiser Uk Ltd Method and apparatus
GB0517471D0 (en) * 2005-08-26 2005-10-05 Reckitt Benckiser Uk Ltd Surface treatment process and applicator
FR2891470B1 (fr) 2005-10-05 2007-11-23 Commissariat Energie Atomique Gel aspirable pour la decontamination de surfaces et utilisation
US8845812B2 (en) 2009-06-12 2014-09-30 Micron Technology, Inc. Method for contamination removal using magnetic particles
DE102014104238A1 (de) * 2014-03-26 2015-10-01 Washtec Holding Gmbh Fahrzeugwaschanlage und Verfahren zur Reinigung von Fahrzeugen und Reinigungsmittel

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
FR3049202A1 (fr) 2017-09-29
WO2017162945A1 (fr) 2017-09-28
FR3049202B1 (fr) 2022-03-04
EP3411466A1 (de) 2018-12-12

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