WO2024115577A1 - Matériau de protection thermique ablatif à base biologique ayant une fonction mécanique - Google Patents

Matériau de protection thermique ablatif à base biologique ayant une fonction mécanique Download PDF

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Publication number
WO2024115577A1
WO2024115577A1 PCT/EP2023/083564 EP2023083564W WO2024115577A1 WO 2024115577 A1 WO2024115577 A1 WO 2024115577A1 EP 2023083564 W EP2023083564 W EP 2023083564W WO 2024115577 A1 WO2024115577 A1 WO 2024115577A1
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Prior art keywords
thermal protection
protection material
binder
fibers
bio
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PCT/EP2023/083564
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German (de)
English (en)
Inventor
Raphaela Elisa GÜNTHER
Holger Unbehaun
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Technische Universitaet Dresden
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Technische Universitaet Dresden
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Priority to EP23817072.4A priority Critical patent/EP4626999A1/fr
Publication of WO2024115577A1 publication Critical patent/WO2024115577A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/16—Materials undergoing chemical reactions when used
    • C09K5/18—Non-reversible chemical reactions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B64—AIRCRAFT; AVIATION; COSMONAUTICS
    • B64G—COSMONAUTICS; VEHICLES OR EQUIPMENT THEREFOR
    • B64G1/00—Cosmonautic vehicles
    • B64G1/22—Parts of, or equipment specially adapted for fitting in or to, cosmonautic vehicles
    • B64G1/52—Protection, safety or emergency devices; Survival aids
    • B64G1/58—Thermal protection, e.g. heat shields
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02K—JET-PROPULSION PLANTS
    • F02K9/00—Rocket-engine plants, i.e. plants carrying both fuel and oxidant therefor; Control thereof
    • F02K9/97—Rocket nozzles
    • F02K9/974—Nozzle- linings; Ablative coatings

Definitions

  • the invention relates to thermal protection using materials made from renewable raw materials, whereby in addition to heat protection, good mechanical properties or the absorption of loads also play a role, so that use in space travel may be considered.
  • Ablative thermal protection means that the material sacrifices itself when exposed to heat and carries away the heat energy, for example by burning up, flaking off or releasing cooling gases. This form of thermal protection is of great interest in space travel, for example.
  • Ablation is a physical process that takes place on the surface of the thermal protection material. It is described as the removal of a material by the action of heat (T > approx. 1000 °C), in which particles are decomposed by evaporation, flaking off or other erosive processes through direct contact with a hot reactor surface or plasma flow. In relation to the surface of the thermal protection material, this means: The hot material particles and material melts that have been removed from the material surface by the action of heat are carried away by the surrounding free flow. The surface is cooled as the warm ablation products are carried away. This type of cooling is called ablative cooling.
  • Cork materials are widely used for ablative thermal protection. These are usually glued to carrier materials as flexible, pliable panels and are used only for thermal insulation. Such materials are made from cork granulate with the addition of a binding agent. Cork is also only available in very limited quantities.
  • Cork-based TPS do not yet meet the mechanical requirements for structural materials in aerospace.
  • Seaweed fibers have a long tradition in the insulation of buildings. They are used as dried fibers.
  • DE 199 54 474 C1 discloses insulation materials made from biogenic raw materials for building interiors - that is, aimed at thermal insulation and soundproofing. Mechanical stabilization plays no role here.
  • DE 20 2005 012 457 U1 discloses seaweed Noise protection elements.
  • DE10017202A1 also describes seaweed for heat and sound insulation for buildings. The strength values mentioned are very low.
  • DE 10 2020 001 467 A1 discloses insulating bricks with an insulating material, such as wood fiber or seagrass fiber.
  • the insulating bricks preferably do not contain any binding agent.
  • CH452885A describes a process for producing a coated synthetic board and synthetic boards obtained by the process.
  • a polyurethane coating compound is applied to a board, whereby the board exudes moisture.
  • It can be a wood fiber board.
  • Synthetic boards contain, for example, wood fibers (description) with or without a synthetic binder.
  • seaweed for example, can also be used as a lignocellulose material.
  • DE 103 41 205 A1 and DE 20320953 U1 describe a molded body made of biodegradable material and a process for its production, in which seaweed is fibrillated by mechanical or thermomechanical defibration and pressed into materials with the addition of synthetic or natural binding agents.
  • the molded body is intended for use in furniture construction, the packaging and automotive industries or in interior design.
  • Insulating molded bodies made of wood fiber are described in EP 1 247 916 B1.
  • EP3540027A1 describes the use of tannin-based flame retardants in natural fibre materials.
  • the object of the invention is to provide a material made largely from renewable raw materials, which protects against heat or shields against heat and at the same time mechanical strength.
  • the invention is intended to enable use in space travel or other areas where ecology, thermal protection or mechanical protection play a role. This includes, for example, rocket stages and their components that are not recovered after use and remain in nature.
  • the invention is intended to enable the use of materials containing wood and seaweed as ablative and structural material in space travel.
  • the amount of binding agents required should be as minimal as possible.
  • Structural materials are materials that meet mechanical strength requirements for components.
  • the invention relates to the use of 1-year-old saltwater plant fibers for producing a bio-based ablative thermal protection material with increased strength for aerospace, in particular the thermal protection material according to the invention described below, for example (in aerospace) as external heat protection or for hot structures, e.g. in the combustion chamber of engines.
  • the invention also relates to a bio-based (i.e. largely produced from renewable raw materials) ablative thermal protection material with increased strength for aerospace, containing a mixture of a binder and natural fibers, wherein the natural fibers are selected from: a) wood fibers and b) 1-year-old saltwater plant fibers, wherein
  • the binder preferably an isocyanate-based binder
  • the binder is contained in the mixture in a proportion of 6-12% dwpaser (i.e. 6-12% by weight based on the dry mass of the fibres), and
  • the weight ratio of wood fibre to 1-year-old saltwater plant fibre is 30:70, with a maximum deviation of ⁇ 20% by weight (this means that the weight ratio is in the range of 10-50:50-90 with a maximum deviation).
  • Matture means that the natural fibres and the binding agent are mixed almost homogeneously.
  • “1-year-old saltwater plants” are marine plants with cellulose structures with a high salt content. They are annual. These include, for example, seagrass or plants from the plant family Zosteraceae, in particular the genus Zostera:
  • Nanozostera mucronata Hartog
  • Tomi. & Posl. Taxon 50: 433
  • o Nanozostera muelleri Irmisch ex Asch.
  • Tomi. & Posl. Taxon 50: 433
  • o Nanozostera noltii Hornern.
  • Tomi. & Posl. Taxon 50: 433
  • o Nanozostera novazelandica Setch.
  • Tomi. & Posl. Taxon 50: 433 (2001).
  • “dwpaser” means the weight percentage based on the dry weight of all fibers in the mixture of natural fibers. It is therefore a weight percentage.
  • the weight ratio of 30:70 is the same as a ratio of 30 wt% to 70 wt%.
  • Binders can be, for example: phenolic resins, urea-melamine resins, mineral-based binders (such as water glass, silanes), isocyanate-based binders (such as PMDI), bio-based binders (such as starch, proteins, lignin).
  • the binder is particularly preferably an isocyanate-based binder.
  • isocyanate-based binder is one that hardens due to the isocyanate groups it contains. It is also included that the binder can contain other reactive groups in addition to the isocyanate groups that were also involved in the hardening of the binder. However, for the purposes of the invention, at least 50% of the reactive groups that are involved in the hardening are isocyanate groups.
  • the invention further relates to plates containing the bio-based ablative thermal protection material according to the invention with increased strength, with a bulk density of 300 to 1200 kg/m 3 , particularly preferably in the range of 850-900 kg/m 3 .
  • the invention also relates to the use of 1-year-old saltwater plant fibers for producing the bio-based thermal protection material according to the invention with increased strength, in particular in the following process according to the invention.
  • the subject matter is also a process for producing the bio-based thermal protection material according to the invention with increased strength, comprising the steps:
  • the invention surprisingly showed that 1-year-old saltwater plant fibers, such as seaweed, alone (i.e. without wood) yield a higher residue after heating to 1000°C than other materials, such as oak bark, cork granules or wood fiber (see Fig. 3).
  • the thermal protection material according to the invention is suitable as a paneling material for components that are exposed to high thermal stress, for example in aerospace.
  • the ratio between wood fiber and the fibers of the 1-year-old saltwater plants and the proportion of the binder have a positive influence.
  • a surprising advantage of the combination according to the invention has also been found to be that the strength is higher than if, for example, only wood fibers were used. This results in a thermal protection material, i.e. a material with heat-shielding properties, which also has increased strength and does not contain cork.
  • thermal protection material according to the invention and seagrass fiber materials in general, have significantly lower densities than glass fiber reinforced plastics or metals such as stainless steel and thus the component weight can be significantly reduced, but the mechanical requirements are still met.
  • the binder is contained in the mixture of the thermal protection material according to the invention with a proportion of 9-12% dw fiber, particularly preferably with 11-12% dw fiber .
  • the annual saltwater plant fibers are selected from seagrass fibers and fibers of the plant family Zosteraceae. Seagrass is one of the annual plants.
  • its salt content is optimal for use in the thermal protection material according to the invention and yet the salt does not interfere with the hardening of the isocyanate-based binder in the corresponding proportion of 6-12% dw fiber .
  • Particularly preferred seaweed (at least 70% by weight) is of the Zostera marina variety, especially at least 95% by weight. It can also belong exclusively to this variety.
  • a preferred embodiment is one in which the binder is PMDI.
  • PMDI is a technical mixture of methylene diphenyl isocyanates and aromatic polyisocyanates.
  • the proportion of the binder (in the mixture) is in the range of 9.5-10.5% dw fiber , particularly preferably the binder is PMDI.
  • the wood fibers have a fiber length of 0.5-6 mm, in particular even 1-3 mm. This fiber length of the wood fibers is advantageously particularly favorable in combination with the 1-year-old saltwater plants in the ratio of 30:70 according to the invention.
  • the thermal protection material contains a flame retardant.
  • a flame retardant This can be, for example, inorganic, halogenated or nitrogen-based flame retardants as well as organic phosphorus compounds and combinations thereof.
  • the thermal protection material contains phosphate-based flame retardants, particularly preferably a flame retardant based on phosphated plant material, e.g. tannin (according to EP 3540027 B1), as in embodiment 1.
  • phosphate-based flame retardants particularly preferably a flame retardant based on phosphated plant material, e.g. tannin (according to EP 3540027 B1), as in embodiment 1.
  • the flame retardants are preferably used in a proportion of 6-12 wt.%.
  • the thermal protection material contains a tannin-based flame retardant in a proportion of 6-12 wt.%.
  • these ingredients are sensibly distributed homogeneously in the mixture according to the invention. In the process according to the invention, they are therefore added during the mixing step.
  • the thermal protection material according to the invention contains a hydrophobic agent (for example oil, wax, paraffin or paraffin-based hydrowax) and a tannin-based flame retardant (for example based on phosphated tannin), wherein the 1-year-old saltwater plant fibers are seaweed fibers and wherein the binder is PMDI and wherein the ratio of PMDI hydrophobic agent to tannin-based flame retardant is 10:1:10, each wt.% based on dw fiber (ie on the dry weight of all fibers, in particular the wood fibers and the seaweed fibers), in each case with a relative deviation of ⁇ 5% based on the respective value of the individual component.
  • a hydrophobic agent for example oil, wax, paraffin or paraffin-based hydrowax
  • a tannin-based flame retardant for example based on phosphated tannin
  • the individual component therefore means the wood fibre, or the seaweed fibre, or the PMDI or... etc.
  • the thermal protection material contains a paraffin-containing hydrophobic agent.
  • it contains cork and/or bark, with bark being present in a proportion of 15-20% by weight.
  • the high thermal resilience is supported in particular by adding the bark.
  • these have a bulk density in the range of 300 to 1200 kg/m 3 , particularly preferably in the range of 850-900 kg/m 3 .
  • the thickness of the plates according to the invention can be in the range from 0.5 to 200 mm, particularly preferably in the range from 0.5 to 30 mm. This thickness has proven to be particularly suitable for providing sufficient heat protection combined with sufficient mechanical strength.
  • the natural fibers are preferably obtained by shredding and breaking down debarked wood chips, e.g. using the TMP process (thermo-mechanical pulp).
  • Seaweed for example, can be bought or collected on the beach and then shredded after drying, e.g. by chopping or grinding.
  • Fig. 1 shows a test specimen produced according to the invention (embodiment 1) during a test of the thermal load capacity in the Huels arc heater (left: general test setup, top right: tip of a test specimen made of oak, bottom right: tip of a test specimen according to embodiment 1 after 120 seconds.
  • Fig. 2a and Fig. 2b show the temperature curve at the tip of these two test specimens from Fig. 1.
  • Tables 1, 2 and 3 show the measured values.
  • the test of the bulk density is carried out in accordance with the invention in accordance with DIN EN 323.
  • the bending strength and the bending modulus of elasticity were determined in accordance with DIN EN 310:1993.
  • the transverse tensile strength was determined in accordance with DIN EN 319:1993.
  • the tensile strength was determined in accordance with DIN 52377.
  • a bio-based thermal protection material is produced from 30% by weight wood fiber and 70% by weight seaweed fiber.
  • the binding agent PMDI is added at 10% by weight and a paraffin-containing hydrophobing agent (Sasol Hydrowax Pro A18) at 1% by weight.
  • a tannin-based flame retardant (according to patent EP 3540027 B1, embodiment 1, based on phosphated tannin) is also added at 10% by weight.
  • the additives and binding agent are dosed based on the atro mass (absolutely dry) of the fiber materials.
  • the fiber materials are mixed in a plowshare mixer.
  • the two additives and the binding agent are sprayed onto the individual fibers (fluidized bed) during the mixing process.
  • the material is then processed in a hot press to form panels with a bulk density in the range of 800 to 950 kg/m 3.
  • the thickness of the panels is 20 to 22 mm.
  • the plates are then ground to a thickness of 20 mm and a leading edge geometry is milled out.
  • the fin leading edge is installed in tail units and is subjected to both thermal stress (temperatures up to 2500 °C) and mechanical stress (multi-axis bending stress) due to deformation of the tail units during use.
  • Example 2 Analogous to example 1 + additional bark
  • a bio-based thermal protection material is produced from 30% by weight wood fiber and 70% by weight seaweed fiber.
  • the binding agent PMDI is added at 10% by weight, bark (ground oak bark) at 15% by weight and a paraffin-containing hydrophobing agent (Sasol Hydrowax Pro A18) at 1% by weight.
  • a tannin-based flame retardant (according to patent EP 3540027 B1, embodiment 1) is also added at 10% by weight.
  • the dosage of additives and binding agent is based on the atro mass (absolutely dry) of the fiber materials.
  • the fiber materials are mixed in a plowshare mixer.
  • the two additives and the binding agent are sprayed onto the individual fibers (fluidized bed) during the mixing process.
  • the material is then pressed in a hot press to form panels with a Bulk density in the range of 800 to 950 kg/m 3 is processed.
  • the thickness of the plates is 20 to 22 mm.
  • the plates are then ground to a thickness of 20 mm and a leading edge geometry is milled out.
  • the fin leading edge is installed in tail units and is subject to both thermal stress (temperatures up to 2500 °C) and mechanical stress (multi-axial bending stress) due to deformation of the tail units during the use phase.
  • the material manufactured according to a mixture from embodiment 1, is processed into a plate and used as a paneling material/coating material on the surfaces of components to protect substructures from thermal stress or as a solid material, for example on tank structures, nose radii/nose tips (nose cone), housings and bases.
  • a comparison example without seaweed and without flame retardants with 100% wood fiber was also investigated.
  • the components PMDI hydrophobic agent were added to the wood fiber in a ratio of 10:1 (each wt. %), each based on dw fiber .
  • the bio-based thermal protection material without seaweed and without flame retardants does not provide the desired thermal resistance.
  • the bending modulus of elasticity is the ratio of the applied stress to the deflection in a bending test. It is a measure of the stiffness of the material in the elastic range.
  • the tensile strength describes the maximum mechanical tensile stress that a material can withstand before failure. “Mechanical stability/strength” means greater ability to withstand acting forces; a lower modulus of elasticity also makes the material resilient to different thermal expansion coefficients of the surrounding materials.
  • thermogravimetric analysis was carried out in the measuring range of 25 °C - 1000 °C.
  • TGA thermogravimetric analysis
  • the change in the mass of a test specimen is determined as a function of temperature and time. It provides information about the carbonization yield and the pyrolytic behavior of a material.
  • the test specimens are each arranged symmetrically in a test crucible in a test carousel, which is located in the oven of the thermogravimetric analyzer TGA 701 from LECO.
  • test specimens were pre-dried in an oven for around 18 hours so that any residual moisture could escape from the material.
  • the test specimens were then placed in the crucibles, ensuring that they were symmetrically positioned to one another within the test carousel.
  • the test specimens were heated in the TGA test device from 25 °C to 105 °C at a temperature increase of 15 K/min.
  • the test specimens were then heated from 105 °C to 1000 °C at 40 K/min.
  • the test device determined the mass of the test specimens. The measurement was carried out under a nitrogen atmosphere with a volume flow of 3.5 l/min.
  • Table 2 TGA measurements of the bio-based thermal protection material from Example 1 compared to a conventional thermal protection material made of cork and one made of oak bark
  • GRP glass fiber reinforced plastic
  • stainless steel have been used so far (Table 3). Due to their high density, high weight and high thermal conductivity, their substitution is being sought.
  • the arc-heated test facilities LBK of the DLR Cologne are certified by the ESA (European Space Agency) as a European key facility for the testing and qualification of thermal protection systems.
  • the L2K system is equipped with a Huels type arc furnace for gas mass flows between 5 and 75 g/s. With a maximum output of 1.4 MW, moderate specific enthalpies of up to 10 MJ/kg are achieved at a gas mass flow of 50 g/s, which corresponds to a pressure of about 1500 hPa. Air, nitrogen, argon or mixtures, e.g. for Mars (CO2/N2) or Titan atmospheres (N2/CH4) are used as working gases. Hypersonic free jet velocities are achieved by a convergent-divergent nozzle. The expansion part of the nozzle is conical with a half-angle of 12°. Various neck diameters from 14 mm to 29 mm are available and can be combined with nozzle outlet diameters of 50 mm, 100 mm and 200 mm. This allows the structure of the system to be effectively adapted to the requirements of a specific test campaign.
  • test specimens made from the selected materials consist entirely of solid material.
  • the materials that showed the least deterioration were tested three times. This increased the reliability of the test.
  • the materials tested multiple times include the samples
  • Execution example 1 (corresponds to the sample from execution example 1).
  • test specimens do not have temperature sensors integrated into the sample structure.
  • the sample geometry used results from the defined leading edge geometry.
  • the test specimens are clamped in a cooled sample holder that is fixed in the test chamber of the L2K.
  • a water-based cooling system ensures even heat dissipation from the sample holder during the measurements and guarantees a firm hold under the applied thermal loads.
  • Fig. 1 shows the boundary layer that forms around the test specimen.
  • the mechanical surface erosion of ablation, the chipping and removal of a particle of material carried away from the test specimen by the free plasma stream can be seen.
  • test specimen tips from embodiment 1 (Fig. 1 bottom right) and from solid oak (Fig. 1 top right) are shown on the right side of Fig. 1.
  • use 2 the glowing, continuously degrading test specimen tip and the formation of melt beads from the resins and mineral components contained therein can be seen.
  • the tip of the oak specimen degrades irregularly compared to Example 1 and does not form a straight front edge.
  • the pointed shape of the oak specimen cannot be maintained over the test period of 120 s. Separation of porous carbon and solid material is visible on the upper part of the test specimen.
  • Fig. 2a and Fig. 2b show the corresponding temperature profiles (measurement using a 2-color pyrometer) at the sample tip (Fig. 2a: sample with oak tip, Fig. 2b: embodiment 1).
  • the temperature initially rises from 1500 °C to a maximum of 2300 °C and remains relatively constant over the test period.
  • the exemplary embodiment 1 according to the invention is compared with the comparative example 3a of the patent application (wood fiber, flame retardant, hydrophobic agent) and a variant of the comparative example (3b) without flame retardant. It can be seen that the exemplary embodiment according to the invention leads to a much higher thermal resistance at 1000 °C, namely 42 mass%.
  • Example 1 The use of a material using seaweed and flame retardants (FR) leads to an increase in thermal resistance under the given conditions. The proportion of the remaining material is approximately 42% by mass. - Compare Example 3: Without seaweed but with the use of FR, the proportion of remaining material is only about 35% by mass.
  • FR flame retardants
  • a test specimen according to Example 1 retains its shape at 2500°C after a test period of 120 seconds. The pointed shape and straight front edge of the test specimen were retained throughout the entire test period.

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Abstract

L'invention concerne un matériau de protection thermique ablatif d'origine biologique, constitué de matières premières renouvelables, dans lequel, en plus de la protection thermique, de bonnes propriétés mécaniques, plus précisément une capacité de support de charge, jouent un rôle et par conséquent une utilisation dans le secteur aérospatial est possible. L'invention porte sur l'utilisation de fibres de plantes halophytes d'un an d'âge pour produire un matériau de protection thermique ablatif d'origine biologique ayant une résistance accrue pour le secteur aérospatial. L'invention porte également sur le matériau de protection thermique d'origine biologique ayant une résistance accrue, contenant un mélange d'un liant et de fibres naturelles choisies parmi a) les fibres de bois et b) les fibres de plantes halophytes d'un an d'âge, - le liant étant présent à une teneur de 6 à 12% dw fibres , et - le rapport pondéral de fibres de bois : fibres de plantes halophytes d'un an d'âge étant de 30 : 70, dans chaque cas avec un écart maximal de ± 20% en poids. L'invention concerne aussi un procédé de production du matériau de protection thermique ablatif d'origine biologique. L'invention concerne également des panneaux fabriqués par ce procédé.
PCT/EP2023/083564 2022-12-02 2023-11-29 Matériau de protection thermique ablatif à base biologique ayant une fonction mécanique Ceased WO2024115577A1 (fr)

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Application Number Priority Date Filing Date Title
EP23817072.4A EP4626999A1 (fr) 2022-12-02 2023-11-29 Matériau de protection thermique ablatif à base biologique ayant une fonction mécanique

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DE102022132031.6 2022-12-02
DE102022132031.6A DE102022132031B4 (de) 2022-12-02 2022-12-02 Verwendung von 1-Jahres-Salzwasserpflanzenfasern zur Herstellung eines biobasierten ablativen Thermalschutzmaterials für die Luft- und Raumfahrt

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US4507165A (en) * 1982-09-15 1985-03-26 Hercules Incorporated Elastomer insulation compositions for rocket motors
FR2556738A1 (fr) * 1983-12-16 1985-06-21 Ferrazzini Patrick Materiau agglomere a haut degre d'ininflammabilite
DE10017202A1 (de) 2000-04-06 2000-09-21 Fasa Gmbh Seegras-Dämmstoff-Bauelement
DE19954474C1 (de) 1999-11-12 2001-05-10 Amt Kluetzer Winkel Dämmmaterial aus biogenen Rohstoffen als Schütt-, Matten- und Plattendämmung für den Innenausbau von Gebäuden
CN1387607A (zh) * 1999-09-08 2002-12-25 埃里安特技术体系股份有限公司 火箭发动机用的弹性体化酚醛树脂烧蚀性隔热物
DE10341205A1 (de) 2003-09-04 2005-04-07 Technische Universität Dresden Formkörper aus biologisch abbaubarem Material und Verfahren zu dessen Herstellung
DE20320953U1 (de) 2003-09-04 2005-09-01 Technische Universität Dresden Formkörper aus biologisch abbaubarem Material
DE202005012457U1 (de) 2005-08-08 2005-12-15 FASA GmbH Gesellschaft für Management, Innovation und Consulting Seegras Lärmschutzelement
EP1247916B1 (fr) 2001-03-01 2006-08-09 Glunz Ag Elément isolant, en particulier plaque isolante en fibres de bois
EP3540027A1 (fr) 2018-03-13 2019-09-18 Technische Universität Dresden Agent ignifuge et procédé de production d'agent ignifuge ainsi que son utilisation
DE102020001467A1 (de) 2020-03-06 2021-09-09 Berhard Eggerdinger Dämmziegel

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Publication number Priority date Publication date Assignee Title
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