Classifications

• • 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
  • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
  • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
• • 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
  • C04B28/14—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 calcium sulfate cements
• • 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
  • C04B28/14—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 calcium sulfate cements
  • C04B28/145—Calcium sulfate hemi-hydrate with a specific crystal form
  • C04B28/147—Calcium sulfate hemi-hydrate with a specific crystal form beta-hemihydrate

Definitions

• the invention relates dry gypsum compositions, in particular for preparing foamed gypsum compositions. Additional aspects of the invention are related to a method for producing a foamed gypsum composition, a foamed gypsum composition obtainable with the method, and a foam body obtainable from the foamed gypsum composition. Furthermore, the invention is concerned with the use of a foamed gypsum composition or a foam body for thermal insulation, phonic insulation, fire protection, as a brick, as a panel, as cavity filling compound, as an injection grout, as insulation screed and/or as insulation facade render.
• mineral binder compositions are widely used, in particular in the form of mortar and concrete compositions based on cement and aggregates comprising sand and/or gravel.
• mineral binder compositions can be adapted to achieve certain desired properties or functionalities.
• mortars e.g. based on lime, which are in particular adapted to fill cavities, e.g. in modular constructions.
• Such kind of mortars typically feature a high fluidity in order to facilitate the filling process.
• a commercially available fire resistant mortar comprises for example cement as mineral binder in combination with fire retardant additives, e.g. alumina hydrates capable of releasing water and delaying fire propagation.
• Another mortar for fire protection comprises gypsum in combination with special lightweight aggregates, such as perlite, vermiculite, and expanded glass.
• special interest are lightweight mineral binder compositions since they can be formulated to have several properties or functionalities combined, e.g. thermal insulation and fire protection.
• the gas phase present in foamed mortars or concretes may be introduced by mechanical foaming in the presence of the respective gas, or it can be introduced by chemical foaming, whereby gas generating substances, e.g. aluminum powder, in the compositions liberate the gas upon contact with water.
• gas generating substances e.g. aluminum powder
• Hybrid foam which is obtained by initially producing a mixture comprising at least one mineral binder, at least one polymer comprising monomer units derived from at least one ethylenically unsaturated monomer or from a combination of polyisocyanates and polyols and/or polyamines, and water. This mixture is subsequently mixed with an aqueous foam comprising water and a surface-active substance to obtain the hybrid foam.
• the lightweight mineral binder compositions should be as easy and safe to handle as possible.
• the lightweight mineral binder compositions should be suitable for different purposes and applications, in particular for thermal and phonic insulations as well as fire protection.
• the improved lightweight mineral binder compositions should have beneficial chemical and mechanical properties, especially in terms of shrinkage, setting behavior and/or freeze thawing.
• the core of the present invention is related to a dry gypsum composition, in particular for preparing foamed gypsum compositions, comprising: a) 10 - 50 wt.-% of a gypsum based binder; b) 30 - 60 wt.% of aggregates, optionally comprising lightweight aggregates; c) 1 - 15 wt.-%, especially 2 - 9 wt.%, of a foaming agent capable of producing carbon dioxide; d) 0.5 - 10 wt.%, especially 1 - 6 wt.%, of an acidic agent, capable of reacting with the foaming agent under aqueous conditions for generation of carbon dioxide; whereby the proportions are given with respect to the total weight of the dry gypsum composition.
• the inventive composition is a dry mix.
• the dry gypsum composition is essentially free of water or an amount of water is below 1 wt.%, in particular below 0.5 wt.%, especially below 0.1 wt.% or below 0.01 wt.%, with respect to the total weight of the dry gypsum composition.
• the dry gypsum composition does not comprise any water.
• the foaming agent in combination with the acidic agent will generate non-hazardous CO2 bubbles during and after the mixing of the dry gypsum composition with water. The bubble generation typically starts right after mixing with water.
• the dry gypsum composition can be prepared, pumped, conveyed and applied with standard equipment.
• the composition is fully self-foaming and this even without the use of problematic foaming agents in the form of metals, such as e.g. aluminum. There is thus no need to separately prepare and mix in an additional foam component when preparing the dry gypsum composition with water for application.
• dry gypsum composition lightweight compositions and hardened bodies can be produced without need for lightweight aggregates.
• the setting time can easily be adjusted, e.g. from 30 min to 1 hour, depending on the application. This allows to avoid the use of molds in case of filling cavities during casting.
• compressive strengths after 2 days from 0.5 to 4 MPa, especially 2 to 3 MPa can be achieved when densities of the foam bodies are in the range of 80 to 900 kg/m 3 , especially 400 to 700 kg/m 3 After 28 days, the compressive strength can reach up to 4 MPa, especially up to 5 MPa, at densities as low as 500 kg/m 3 , especially as low as 200 kg/m 3 .
• the inventive composition provides anti shrinkage benefits.
• the dry gypsum composition can be used as a multipurpose composition.
• the viscosity of the processable gypsum composition can be adapted easily, such that the processable composition is suitable for casting or for vertical applications.
• the inventive dry gypsum compositions can in particular be used for:
• a first aspect of the present invention is directed to a dry gypsum composition, in particular for preparing foamed gypsum compositions, comprising: a) 10 - 50 wt.-% of a gypsum based binder; b) 30 - 60 wt.% of aggregates, optionally comprising or consisting of lightweight aggregates; c) 1 - 15 wt.-%, especially 2 - 9 wt.%, of a foaming agent capable of producing carbon dioxide; d) 0.5 - 10 wt.%, especially 1 - 6 wt.%, of an acidic agent, capable of reacting with the foaming agent under aqueous conditions for generation of carbon dioxide; whereby the proportions are given with respect to the total weight of the dry gypsum composition.
• gypsum refers to any known form of gypsum, in particular calcium sulfate dihydrate, calcium sulfate a-hemihydrate, calcium sulfate 0-hemihydrate, a blend of calcium sulfate a-hemihydrate and calcium sulfate 0- hemihydrate, calcium sulfate anhydrite or mixtures thereof.
• a blend of calcium sulfate a-hemihydrate and calcium sulfate 0-hemihydrate in particular is a blend of 50 - 90 wt.%, especially 60 - 80 wt.%, of calcium sulfate a- hemihydrate with 10 - 50 wt.%, especially 20 - 40 wt.%, of calcium sulfate 0- hemihydrate.
• the blend comprises 70 wt.% of calcium sulfate a- hemihydrate and 30 wt.% calcium sulfate 0-hemihydrate.
• Gypsum can be obtained from different sources, such as e.g. gypsum from natural sources, gypsum from flue gas desulphurization (FGD gypsum), phosphogypsum, pyro gypsum, and/or fluoro gypsum.
• sources such as e.g. gypsum from natural sources, gypsum from flue gas desulphurization (FGD gypsum), phosphogypsum, pyro gypsum, and/or fluoro gypsum.
• all the components of the dry gypsum composition are solid, e.g. in the form of powders and/or particulates.
• Liquid substances, if present, preferably are provided as impregnation of solid particles.
• all of the components are intermixed.
• the foaming agent preferably is a solid, especially in the form of a powder and/or particulates.
• the foaming agent is a carbonate and/or bicarbonate salt, in particular CaCOs, Na2CO3, and/or NaHCOs, most preferably NaHCOs.
• CaCOs CaCOs
• Na2CO3, and/or NaHCOs NaHCOs
• NaHCOs NaHCOs
• These are solid substances, which in dry state are chemically stable in the dry gypsum compositions. Nevertheless, they effectively produce carbon dioxide upon contact with an acidic agent and water. Thereby, the reaction products do not negatively affect the dry gypsum composition. However other substances can be used as well.
• the acidic agent has a pK a value in the range of 2 - 5, especially 3 - 4.
• the "pK a " is meant to be the negative logarithm of the acid dissociation constant.
• Such acidic agents are able to react with the foaming agent in a gentle but nevertheless effective manner in order to produce suitable and evenly distributed bubbles of CO2 in the gypsum composition after mixing with water. Nevertheless, for specific applications, acidic agents with pKa values outside this ranges might be suitable as well.
• the acidic agent preferably is a solid, especially in the form of a powder and/or particulates.
• aluminum salts in dry state are chemically highly stable in the inventive dry gypsum compositions while being very suitable for activating carbon dioxide production upon contact with the foaming agent in aqueous media. Furthermore, reaction products do not negatively affect the dry gypsum composition. However other substances can be used as well.
• the foaming agent is a carbonate and/or bicarbonate salt, in particular CaCOs, Na2CO3, and/or NaHCOs, most preferably NaHCOs
• the acidic agent is an aluminum salt, especially an aluminum sulfate, in particular Al2(SO4)3, most preferably Al2(SO4)3 ⁇ 18 H2O.
• the combination of NaHCOs as foaming agent and of Al2(SO4)3, most preferably Al2(SO4)3 ⁇ 18 H2O, as acidic agent is especially preferred. This is because in this case six equivalents of CO2 are formed per mol of Al2(SO4)3 whereas only three equivalents are formed per mol of Al2(SO4)3 when CaCOs or Na2COs are used as foaming agent. The formation of more CO2 leads to a better foaming.
• the gypsum based binder comprises or consists of calcium sulfate hemihydrate, in particular calcium sulfate a-hemihydrate and/or calcium sulfate p- hemihydrate.
• the gypsum based binder with respect to the total amount of gypsum based binder, preferably includes at least 70 wt.% calcium sulfate hemihydrate, even more preferably at least 90 wt.% calcium sulfate hemihydrate.
• the gypsum based binder comprises or consists of a blend of calcium sulfate a-hemihydrate and calcium sulfate p-hemihydrate.
• the blend comprises 50 - 90 wt.%, especially 60 - 80 wt.%, of calcium sulfate a-hemihydrate and 10 - 50 wt.%, especially 20 - 40 wt.%, of calcium sulfate p-hemihydrate.
• the blend comprises 70 wt.% of calcium sulfate a-hemihydrate and 30 wt.% calcium sulfate 0-hemihydrate.
• Such kind of gypsum based binders turned out to be beneficial for obtaining a high water resistance.
• the gypsum based binder may comprise or consist of gypsum from different sources, e.g. gypsum from natural sources, flue gas desulphurization (FGD) gypsum, phosphogypsum, pyro gypsum, and/or fluoro gypsum.
• sources e.g. gypsum from natural sources, flue gas desulphurization (FGD) gypsum, phosphogypsum, pyro gypsum, and/or fluoro gypsum.
• FGD flue gas desulphurization
• the composition further comprises 0.1 - 10 wt.%, in particular 1 - 8 wt.% or 3 - 7 wt.%, of a further mineral binder, especially selected from Portland cement, aluminate cement, sulphoaluminate cement, latent hydraulic and/or pozzolanic binder materials, and/or hydrated lime.
• a further mineral binder especially selected from Portland cement, aluminate cement, sulphoaluminate cement, latent hydraulic and/or pozzolanic binder materials, and/or hydrated lime.
• Preferred Portland cement is according to standard EN 197, in particular of type CEM I.
• alumina cement stands in particular for a cement with an aluminum content, measured as AI2O3, of at least 30 wt.%, especially at least 35 wt.%, in particular 35 - 58 wt.%.
• the alumina cement is alumina cement according to standard EN 14647.
• the sulphoaluminate cement is calcium sulphoaluminate cement.
• the further mineral binder comprises aluminate cement, sulphoaluminate cement and/or Portland cement.
• Portland cements in particular improve the surface resistance of foam bodies prepared from the inventive dry gypsum compositions.
• Aluminate cement and sulphoaluminate cement especially accelerate the hardening process.
• Aggregates preferably comprise sand, quartz, gravel, and/or lightweight aggregates.
• the aggregates comprise sand.
• a particle size of the aggregates in particular is from 0.01 - 10 mm, especially 0.05 - 5 mm, preferably 0.1 - 4 mm, in particular 0.15 - 2 mm.
• the proportion of the aggregates is from 40 - 55 wt.%.
• the term "lightweight aggregates” stands in particular for aggregates with a particle density ⁇ 2'000 kg/m 3 , preferably ⁇ 1'500 kg/m 3 ’ especially ⁇ 1'250 kg/m 3
• the particle density of an aggregate is the ratio between the mass of the particle material and the volume occupied by the individual particles. This volume includes the pores within the particle but does not include voids between the particles.
• Lightweight aggregates in particular are selected from wood particles, plastic particles, rubber particles, cork particles, inorganic particles, layered particles, hollow particles and/or porous particles.
• the lightweight particles are present as a powder.
• the lightweight aggregates are selected from vermiculite, perlite and/or expanded glass, e.g. expanded glass available under the tradename Poraver®.
• Most preferred lightweight aggregates are vermiculite and/or expanded glass, especially expanded glass available under the tradename Poraver®.
• the composition preferably comprises 1 - 30 wt.%, especially 10 - 25 wt.% of a filler, preferably calcium carbonate filler.
• a particle size of the filler in particular is ⁇ 150 pm, especially ⁇ 100 pm.
• Fillers can be used to improve thixotropic properties. However, fillers are optional.
• the calcium carbonate filler has a larger particle size as compared to the calcium carbonate foaming agent.
• the calcium carbonate filler has a particle size of between 10 - 150 pm and the calcium carbonate foaming agent has a particle size of below 10 pm, for example of between 0.2 - 10 pm.
• the size of particles having a size below 0.1 mm according to sieve analysis can be determined by laser diffraction as described in ISO 13320:2009.
• a particle size of non-spherical or irregular particles is represented by the equivalent spherical diameter of a sphere of equivalent volume.
• the lower values of the ranges given for the particle size represent D10 values whereas the upper values of the ranges given for the particle size represent D90 values.
• 10% of the particles have a lower particle size than the lower value of a range, whereas 10% of the particles have a larger particle size than the upper value of a range.
• the dry gypsum composition may further comprise 0.001 - 1 wt.%, especially 0.01 - 0.1 wt.-% of a gypsum accelerator, especially calcium sulfate dihydrate. This allows for reducing the setting and/or hardening times, which is especially beneficial in casting applications since de-molding is possible at earlier times.
• a gypsum accelerator especially calcium sulfate dihydrate.
• the dry composition comprises 0.1 - 10 wt.%, especially 0.5 - 5 wt.% of a water redispersible polymer.
• a water redispersible polymer is present in the form of a powder.
• the polymer helps to stabilize the bubbles in the foamed gypsum composition.
• the polymer improves the brittleness and smoothness of the surface of foam bodies produced from foamed gypsum composition.
• the water redispersible polymer is a homopolymer or copolymer based on one or more monomers selected from vinyl ester, vinyl acetate, vinyl alcohol, vinyl chloride, vinyl laureate, acrylic acid, acrylate, methacrylic acid, methacrylate, methylmethacrylate, acrylonitrile, styrene, butadiene, ethylene or mixtures thereof.
• highly preferred are copolymers based on styrene and butadien.
• the polymer is selected from poly(vinyl acetate-ethylene), poly(vinyl acetate-ethylene-methylmethacrylate), poly(vinyl acetate-ethylene-vinylester), poly(vinyl acetate-ethylene-acrylic acid ester), poyl(vinyl acetate-ethylene-vinyl laureate), poly(vinyl acetate-vinyl versate), poly(acrylic ester-acrylonitrile), poly(acrylic ester-styrene butadiene), poly(styrene-butadiene) or mixtures thereof.
• Highly preferred as the water redispersible polymer is poly(styrene-butadiene).
• the composition preferably comprises 0.001 - 5 wt.%, especially 0.1 - 2 wt.%, of at least one additive selected from the group of polysaccharide- based viscosity modifiers and precipitated amorphous silica.
• Polysaccharide- based viscosity modifiers are in particular selected from starch ethers and/or diutan gum. These substances, in particular in combination, help to prevent coalescence of the gas bubbles in the foamed composition. Starch ethers are further beneficial for equilibrating the speed of expansion during foaming.
• the composition may additionally comprises 0.001 - 1 wt.% of a plasticizer, especially selected from the group of lignosulfonates, gluconates, naphthalenesulfonates, melamine sulfonates, vinyl copolymers and/or polycarboxylates.
• a plasticizer is beneficial for obtaining a desired flowability of the foamed gypsum composition.
• the plasticizer is different from the above described water redispersible polymer.
• the composition preferably comprises 0.001 - 5 wt.%, especially 0.1 - 2 wt.%, of at least one hydrophobizing agent.
• the hydrophobizing agent is selected from silanes, siloxanes, siliconates, silicones, and/or fatty acids.
• Suitable silanes, siloxanes, siliconates, and silicones are commercially available from various suppliers, e.g. from Sika (Switzerland) under the tradename Sikagard®.
• fatty acids are stearic acid, oleic acid, caprylic acid, capric acids and mixtures thereof.
• other hydrophobizing agents can be used as well.
• the dry gypsum composition comprises fibers, in particular mineral, plastic and/or cellulose fibers.
• Mineral fibers are highly preferred.
• a proportion of the fibers is preferably from 0.001 - 3 wt.%, in particular 0.01 - 2.5 wt.%, especially 1 - 2 wt.%, with respect to the weight of the dry gypsum composition.
• a length of the fibers is for example 0.5 - 1'000 pm.
• inventive dry gypsum compositions do not require other foaming agents than claimed, different types of foaming agents, e.g. aluminum powder, can be used in addition for special applications.
• the dry gypsum composition comprises: a) 10 - 50 wt.-% of a gypsum based binder, especially comprising calcium sulfate a-hemihydrate and/or calcium sulfate 0-hemihydrate; b) 30 - 60 wt.% of aggregates comprising sand, quartz, gravel and/or lightweight aggregates, whereby the lightweight aggregates, if present, in particular are selected from vermiculite and/or expanded glass, e.g.
• a further aspect of the present invention is directed to a method for producing a foamed gypsum composition comprising the steps of (i) providing a dry gypsum composition as described above and (ii) mixing the dry gypsum composition with water. This results in a processable foamed gypsum composition.
• water is used with a proportion of 20 - 40 parts by weight per 100 parts by weight of the dry gypsum composition.
• water is added in a proportion of 22 - 27 parts by weight.
• water is added in a proportion of 30 - 37 parts by weight.
• the method preferably does not comprise any mechanical and/or physical foaming. However, if desired, such methods can be applied in addition.
• the method further comprises a step of hardening the dry gypsum composition mixed with water or the foamed gypsum composition, respectively. Thereby, a foam body is obtained.
• foam bodies can e.g. be in the form of a casted body, a brick, a panel, a coating on a substrate, a screed, a wall, a floor, a wall barrier, a floor barrier and/or a ceiling.
• Another aspect of the present invention is directed to a foamed gypsum composition obtainable by the method as described above.
• the foamed gypsum composition is a processable foamed gypsum composition.
• Such compositions can be casted and/or applied on substrates.
• foam bodies obtainable by hardening the foamed gypsum composition described above.
• foam bodies can e.g. be in the form of a casted body, a brick, a panel, a coating on a substrate, a screed, a wall, a floor, a wall barrier, a floor barrier and/or a ceiling.
• the foam body has a density of 20 - 900 kg/m 3 , in particular 30 - 800 kg/m 3 , especially 40 - 600 kg/m 3 , preferably 50 - 500 kg/m 3 .
• a first inventive use is directed to the use of a foaming agent capable of producing carbon dioxide in combination with an acidic agent, capable of reacting with the foaming agent under aqueous conditions for generation of the carbon dioxide, for producing a foamed gypsum composition.
• a foaming agent and an acidic agent as described above are used.
• a second inventive use is directed to the use of a foamed gypsum composition or of a foam body as described above for modular construction, repair work, precasting, thermal insulation, phonic insulation, as attic insulation foams, for roofing insulation, fire protection, as a brick, as a panel, as cavity filling compound, as an injection grout, as an insulation screed, as light insulation screed and/or as insulation facade render.
• the foamed gypsum composition or the foam body as described above can specifically be used to:
• protective corrosion inhibitors such as e.g. sodium benzoate and/or potassium nitrite.
• the foamed gypsum composition or the foam body can easily be removed by hydroblasting during the deconstruction phase.
• the foamed gypsum composition or the foam body as described above can be used as fire protection of walls, ceilings and facades of buildings or tunnels, especially in the form of floor barriers and/or wall barriers to retard fire propagation in buildings or tunnels.
• Bricks or panels can be aesthetic bricks or panels, optionally colored, for interior use.
• Phonic insulation and/or thermal insulation can be realized by bricks made of the foamed gypsum composition or by applying the foamed gypsum composition by in situ placing on job sites, especially by vertical and/or horizontal application.
• inventive foamed gypsum compositions can be used as replacement of known systems, such as e.g. systems based on YTONG or Xella technology.
• the foamed gypsum composition When used as repair mortar, can in particular be used for filling small volumes such as cracks.
• the foamed gypsum compositions can easily achieve densities below 800 kg/m 3 with compressive strength of 2 to 4 MPa. Thereby, the addition of aluminate cement allows to produce screeds, which are walkable already after 24 hours.
• Figure 1 shows the results of water resistance testing of foam bodies prepared with pure CaSCM [3-hemihydrate (“£” in figure 1 ), pure CaSCM a-hemihydrate (“a” in figure 1 ), and a mixture of CaSCM [3+a hemihydrate (“[3+a“ in figure 1 ) respectively.
• compositions C1 - C6 were prepared by intermixing the solid components in a standard mixer.
• the dry gypsum compositions C1 - C6 were mixed with water (proportions given in table 2) to produce foamed gypsum compositions that were allowed to harden into foam bodies HC1 - HC6.
• Table 2 Foamed compositions and foam bodies produced with inventive dry gypsum compositions.
• the pot life was about 30 min for all compositions. After 30 min the compositions started thickening and could for example be applied as repair mortars on vertical surfaces. The time of workability, where the applied composition can be corrected or adjusted, is about 60 min.
• Foam bodies HC4 were completely immersed in a water bath at 23°C for 28 days. No signs of deterioration were visible after that time (see figure 1 - foam body designated “(3 + a”). This is a proof for good water resistance.
• Two further foam bodies were produced in the same way as HC4 with the only difference that in one case pure CaSCMa-hemihydrate was used while in the other case pure CaSCM [3- hemihydrate was used instead of the mixture of [3+a hemihydrate. After storage under water both foam bodies showed visible signs of deterioration (see figure 1 - foam bodies designated “

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• Curing Cements, Concrete, And Artificial Stone (AREA)

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• 2021
  • 2021-08-12 EP EP21191058.3A patent/EP4134355A1/de not_active Withdrawn
• 2022
  • 2022-08-05 WO PCT/EP2022/072054 patent/WO2023016934A1/en not_active Ceased
  • 2022-08-05 EP EP22764331.9A patent/EP4384487A1/de active Pending

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