EP4143144A1 - Procédé de production de particules composites thermo-isolantes, particules composites et leur utilisation - Google Patents

Procédé de production de particules composites thermo-isolantes, particules composites et leur utilisation

Info

Publication number
EP4143144A1
EP4143144A1 EP21724210.6A EP21724210A EP4143144A1 EP 4143144 A1 EP4143144 A1 EP 4143144A1 EP 21724210 A EP21724210 A EP 21724210A EP 4143144 A1 EP4143144 A1 EP 4143144A1
Authority
EP
European Patent Office
Prior art keywords
silica
airgel
composite particles
particulate material
porous particulate
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.)
Pending
Application number
EP21724210.6A
Other languages
German (de)
English (en)
Inventor
Kurt SCHÜMCHEN
Julian FASOLA
Andreas Gabriel
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.)
Interbran Raw Materials GmbH
Original Assignee
Interbran Raw Materials GmbH
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Interbran Raw Materials GmbH filed Critical Interbran Raw Materials GmbH
Publication of EP4143144A1 publication Critical patent/EP4143144A1/fr
Pending legal-status Critical Current

Links

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
    • C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
    • C04B40/0028—Aspects relating to the mixing step of the mortar preparation
    • C04B40/0039—Premixtures of ingredients
    • C04B40/0042—Powdery mixtures
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1003—Non-compositional aspects of the coating or impregnation
    • C04B20/1007—Porous or lightweight coatings
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/1055—Coating or impregnating with inorganic materials
    • C04B20/1074—Silicates, e.g. glass
    • 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
    • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
    • C04B20/10—Coating or impregnating
    • C04B20/12—Multiple coating or impregnating
    • 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
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/20—Resistance against chemical, physical or biological attack
    • C04B2111/28—Fire resistance, i.e. materials resistant to accidental fires or high temperatures

Definitions

  • the present invention relates to the technical field of thermal insulation, in particular thermal insulating additives for binder systems.
  • the present invention relates to a method for producing heat-insulating composite particles and the composite particles obtainable with the method.
  • the present invention relates to the use of the composite particles for the production of building materials and dry building material mixtures which contain the composite particles.
  • the invention also relates to plastering mortar compositions which contain the dry building material mix or the composite particles and a thermal insulation board obtainable therefrom.
  • heat-insulating aggregates in particular lightweight aggregates. Due to their porosity, the aggregates improve the thermal conductivity of the resulting building materials, in particular of mortar and plaster.
  • the lightweight aggregates used are usually highly porous materials such as expanded vermiculite or expanded perlite.
  • Expanded perlite is often used as a surcharge due to its good mechanical strength, general availability and low acquisition costs.
  • mineral systems in particular expanded perlite, have a disadvantage compared to plastic-based thermal insulation materials in that they have high thermal conductivities in comparison, so that thin insulation systems based exclusively on mineral systems, such as perlite, are not accessible.
  • silica aerogels in particular, which can significantly reduce the thermal conductivity of mineral insulation systems, but these are often not sufficiently mechanically resilient to be able to be introduced into industrially manufactured dry building materials and applied by machine.
  • fumed silica Another, in principle good thermal insulation material is fumed silica, which, however, only has extremely small particle sizes and is also relatively expensive to purchase, so that fumed silica is seldom used as the sole additive. Furthermore, when fumed silica is used as an additive in mineral binder systems, in particular lime-cement binders, a deterioration in the thermal insulation properties is often observed.
  • EP 2 576 929 B1 describes a thermal insulation powder mixture which has at least one silica and at least one fiber material with a fiber diameter of 1 to 50 ⁇ m and optionally foamed or expanded powders such as perlite. The powder mixtures are pressed in order to obtain moldings.
  • EP 3490 954 B1 describes a method for producing a hydrophobic silica-containing thermal insulation material, in which hydrophilic and hydrophobic silica are crosslinked by means of a silicon-based binder, for example a silane or silazane, and the mixture is then pressed into molded bodies.
  • a silicon-based binder for example a silane or silazane
  • silica aerogels are also suitable in principle as excellent thermal insulation materials, as they have a very high porosity and a pore volume of up to 99.8%.
  • silica aerogels have the major disadvantage that they can only be mechanically stressed to a limited extent and are therefore destroyed by the forces acting during mixing or mixing when they are introduced into building material mixtures for thermal insulation purposes.
  • the production of aerogels is complex, so that their use is always associated with significantly increased costs.
  • the state of the art therefore still lacks heat-insulating materials which have improved heat-insulating properties compared to conventional mineral aggregates, are preferably in particle form and a large number of inorganic binder systems can be incorporated easily and flexibly.
  • a heat-insulating system which, for example, can be incorporated into dry mixes of conventional inorganic binders, in particular cement-containing binders, and which can then be processed like conventional mortars or plasters.
  • One object of the present invention is thus to be seen in avoiding, or at least reducing the disadvantages associated with the prior art, as outlined above.
  • thermo insulation material which has improved thermal insulation properties compared to conventional thermal insulation materials such as expanded perlite.
  • Another object of the present invention is to provide a thermal insulation material which can be incorporated easily and without problems into a large number of inorganic binder systems and which can be produced inexpensively.
  • the subject matter of the present invention according to a first aspect of the present invention is thus a method for producing heat-insulating composite particles according to claim 1; further advantageous refinements of this aspect of the invention are the subject of the related subclaims.
  • the present invention according to a second and third aspect of the present invention further relates to composite particles according to the invention according to claim 18 or 19.
  • the present invention according to a fourth aspect of the present invention also further provides the use of the composite material according to the invention according to claim 20.
  • Yet another subject matter of the present invention according to a fifth aspect of the present invention is a dry building material mix according to claim 21.
  • Yet another subject matter of the present invention according to a sixth aspect of the present invention is a plaster mortar according to claim 22.
  • the present invention again further provides a thermal insulation panel according to claim 23.
  • weight or quantity-related percentages are selected by the person skilled in the art in such a way that the total result is 100%.
  • the present invention - according to a first aspect of the present invention - is thus a method for producing heat-insulating composite particles, wherein a porous particulate material is mixed with deagglomerated silica and / or with airgel, preferably deagglomerated silica.
  • porous particles such as expanded perlite
  • the mixture forms a layer of silica or airgel on the surface of the porous particulate material, the porous material is coated with the silica and / or the airgel, so to speak.
  • silica when silica is used, it is prevented that silica is incorporated into the when incorporated into an inorganic binder system Pores of a binder system or in gaps between aggregates and thus leads to a compression of the particular inorganic binder system, whereby its thermal conductivity is improved.
  • silica is used, which is preferred within the scope of the invention, it is essential that the silica is deagglomerated before mixing with the particulate material.
  • Silica is usually in the form of agglomerates in the high micrometer to millimeter range. If these agglomerates are incorporated into insulation systems or mixed with aggregates, they are deposited in the pores of the binder system or in gaps between aggregates, so that overall a deterioration in the thermal insulation properties is observed.
  • the porous particulate material serves as a carrier material.
  • the result is composite particles with a core / filling structure which have significantly improved thermal insulation properties compared to the carrier material used, the material of the core.
  • the composite particles obtainable with the method according to the invention when incorporated into mineral insulation systems, have a positive effect on the mechanical properties of the resulting cured systems, in particular of plasters and mortars, so in particular the compressive strength and the tendency to crack are significantly improved.
  • silica and / or airgel are used to produce the composite particles, the use of silica being preferred. If a silica is used, it has proven useful if the silica is selected from pyrogenic silica, precipitated silica and mixtures thereof, preferably pyrogenic silica.
  • porous particulate material As far as the porous particulate material is concerned, a large number of materials, in particular porous particles, come into consideration here. However, inorganic or mineral materials are preferably used.
  • the porous particulate material, in particular carrier material can have both closed pores and open pores. Closed pores - also known as closed porosity - are closed inside the material and have no connection to the environment. In contrast to closed pores, open pores end on the outer surface of the material and are therefore in contact with the environment.
  • composite particles with improved thermal insulation are accessible in a simple and inexpensive manner, which can be incorporated easily and flexibly into a large number of binder systems, in particular inorganic binder systems.
  • the composite particles obtainable with the method according to the invention can preferably be incorporated into cement-containing binder systems and thus used for the production of plastering mortars, in particular thermal insulation plasters, or thermal insulation boards, for example for interior construction.
  • a special feature of the composite particles obtainable with the method according to the invention is in particular that they are preferably free of further fibers, i.e. contain at most fibers based on silica and / or airgel, preferably silica, preferably pyrogenic silica.
  • the composite materials according to the invention do not have to be admixed with further fibers, in particular glass fibers or mineral fibers, for stabilization.
  • hydrophobic and hydrophilic silicas and / or aerogels or silicas and / or aerogels with different hydrophobicity, the hydrophobic properties of the resulting Adjust composite particles in a targeted manner. In this way it is possible to obtain composite particles which are adapted to a high degree to the particular binder system and the intended use.
  • the compounds summarized under the name "silica” in the context of the present invention are polycondensation products of orthosilicic acid Si (OH) 4 , the empirical formula of which converges to S1O2, ie silicon dioxide, as condensation progresses.
  • the silicas used in the context of the present invention are therefore often also referred to as silicon dioxides.
  • Polysilicic acids are divided into precipitated silica - also called precipitated silicon dioxide - and pyrogenic silica - also called pyrogenic silicon dioxide - according to the way they are produced. Both precipitated silicas and pyrogenic silicas are synthetic amorphous silicon dioxides.
  • Precipitated silica is usually obtained by the polycondensation reaction of sodium silicate solution after acidification with mineral acids, whereby water glass, i.e. a water-containing polysilicic acid, is formed first, which is then condensed to amorphous colloidal particles and dried.
  • Pyrogenic silica is generally formed by the reaction of silicon tetrachloride SiCU in an oxyhydrogen flame, i.e. in an ignited mixture of elemental hydrogen and elemental oxygen.
  • Both precipitated silicas and pyrogenic silicas are colorless powders with a low bulk density and a large specific surface.
  • Precipitated silicas and pyrogenic silicas are often used for similar purposes and are used as fillers, for example to improve the mechanical resistance of coatings.
  • Pyrogenic silica is usually more mechanically resilient than precipitated silica and has a higher density: Pyrogenic silica usually has BET specific surfaces of 20 to 600 m 2 / g and densities of about 2.2 g / cm 3 .
  • the primary particle size is usually Usually between 5 and 60 nm, while the particle size of the aggregated primary particles usually varies in the range from a few 100 nm to approx. 2 mm.
  • Precipitated silica has a BET specific surface area in the range from 30 to 800 m 2 / g with a density of 1.9 to 2.1 g / cm 3 .
  • the primary particle size is between 50 and 100 nm, while the particle size of the agglomerated primary particles is 1 to 50 ⁇ m.
  • all specific BET surface areas are preferably determined in accordance with DIN ISO 9277: 2003-05.
  • pyrogenic silicas are preferably used.
  • hydrophilic silicas or also hydrophobic silicas are used.
  • Hydrophilic silicas can be incorporated more easily and more homogeneously into inorganic binder systems, in particular plaster mortar systems, the components of which often consist of hydrophilic mineral components.
  • hydrophilic silica is to be understood as meaning a silica which has as few, preferably no, organic groups, in particular no alkyl groups, but is preferably terminated with polar chemical groups, in particular silanol groups.
  • Hydrophilic substances usually refer to polar organic or inorganic substances which are readily miscible with water. This also applies, for example, to solid systems, which are referred to as hydrophilic if they are well wetted by water.
  • Hydrophobically modified silicas are modified with organic groups, in particular with alkylsilanes, in order to reduce the hydrophilicity of unmodified silicic acid and, for example, to increase the compatibility of the silicas with organic systems.
  • organic groups in particular with alkylsilanes
  • hydrophilic and hydrophobic silica or mixtures thereof are used in order to increase the hydrophilicity or hydrophobicity of the composite particles obtainable with the method according to the invention for the respective application purpose or to tailor the binder system into which they are to be incorporated.
  • aerogels are highly porous solids, the volume of which consists of pores up to 99.8% by volume.
  • silicate-based aerogels or hybrid aerogels containing silicon dioxide and a further component are used, the use of silicate-based aerogels being preferred.
  • Silicate-based aerogels so-called silica aerogels, are derived from orthosilicic acid H 4 Si0 4 and its condensation products. They are highly porous solids with a pore volume of generally 95 to 99.8% by volume, based on the total volume of the airgel. Due to their high porosity, aerogels are poor conductors of heat and sound and are therefore of interest for the development of insulation materials.
  • Aerogels in particular also silica aerogels, can be both hydrophilic and hydrophobic.
  • a hydrophobic treatment is often carried out as part of the airgel synthesis in order to enable water or polar organic solvents to be removed from the pores of the airgel without the pore structure of the airgel being destroyed.
  • the hydrophobization is often done with silanes or siliconates.
  • both hydrophilic and hydrophobic aerogels in particular silica aerogels, or their can be used within the scope of the invention
  • Mixtures are used.
  • Mixtures of aerogels and silicas can also be used. However, the best results are obtained when silicas, in particular fumed silicas, are used.
  • the porous particulate material is selected from mineral materials.
  • porous particulate material is selected from the group consisting of volcanic rock, perlite, in particular expanded perlite, vermiculite, in particular expanded vermiculite, pumice, foam and expanded glass, expanded clay, expanded slate, tuff , Lava gravel, lava sand, and their mixtures.
  • porous particulate material is selected from the group consisting of perlite, in particular expanded perlite, vermiculite, in particular expanded vermiculite, pumice, foam and expanded glass, expanded clay, expanded slate, tuff, and mixtures thereof.
  • the porous particulate material is selected from the group consisting of perlite, in particular expanded perlite, and vermiculite, in particular expanded vermiculite, and mixtures thereof.
  • the porous particulate material is perlite, in particular expanded perlite.
  • Specially expanded perlite is available inexpensively in large quantities and has long been tried and tested as a heat-insulating additive that is open to water vapor diffusion for mineral binder systems, in particular for cement-containing binder systems.
  • the particle size of the porous particulate material used can vary within wide ranges. In the context of the present invention, however, it has proven useful if the porous particulate material has absolute particle sizes in the range from 0.01 to 7 mm, in particular from 0.05 to 4 mm, preferably 0.1 to 3.5 mm, preferably 0.15 to 3 mm, particularly preferably 0.2 to 2.5 mm.
  • the porous particulate material to have pores with pore sizes in the range from 0.05 to 800 ⁇ m, in particular 0.1 to 700 ⁇ m, preferably 0.5 ⁇ m to 500 ⁇ m, preferably 1 ⁇ m to 300 ⁇ m, particularly preferably 2 to 200 ⁇ m. Pore sizes in the range mentioned seem to be particularly suitable for anchoring a coating made of silica and / or airgel.
  • the composite particles obtainable by the process according to the invention are concerned, their particle size can also vary within wide ranges. However, it has generally proven useful if the composite particles have absolute particle sizes in the range from 0.01 to 10 mm, in particular 0.1 to 8 mm, preferably 0.15 to 5 mm, preferably 0.2 to 4 mm, particularly preferably 0 , 25 to 3 mm.
  • Particles with the aforementioned particle sizes can easily be incorporated as additives into commercially available binder systems, in particular cement- or lime-based binder systems.
  • the composite particles in bulk generally have a thermal conductivity at 25 ° C. in the range from 0.020 to 0.045 W / (mK), in particular 0.022 to 0.040 W / (mK), preferably 0.024 to 0.038 W / (mK), preferably 0.026 up to 0.035 W / (mK), particularly preferably 0.028 to 0.035 W / (mK).
  • porous particulate materials in particular expanded perlite
  • pyrogenic silica By mixing or coating porous particulate materials, in particular expanded perlite, with pyrogenic silica, a significant reduction in thermal conductivity can be achieved compared to pure carrier materials, such as expanded perlite, which has thermal conductivity values of approx. 0.040 at 25 ° C up to 0.045 W / (mK).
  • the composite particles have a bulk density in the range from 30 to 150 kg / m 3 , in particular 40 to 100 kg / m 3 , preferably 50 to 80 kg / m 3 , preferably 70 to 80 kg / m 3 .
  • the composite particles obtainable with the method according to the invention are thus suitable for use as lightweight aggregates, with they also have good thermal insulation properties due to their low density and high porosity.
  • the composite particles have the combustibility A1 or A2 according to DIN 4102.
  • the composite particles obtainable by the process according to the invention can thus be incorporated into a large number of binder systems without increasing the combustibility of the system.
  • a further advantage of the composite particles obtainable according to the invention can be seen in the fact that they consist of inorganic mineral materials which, on the one hand, are non-combustible and, on the other hand, have good water vapor permeability and consequently counteract the formation of mold when used in or on buildings.
  • the porous particles are mixed or coated with silica and / or airgel, preferably silica.
  • silica or airgel a large number of silicas and / or aerogels can be used here.
  • the silica or the airgel have a specific surface area (BET) of more than 20 ⁇ g, in particular more than 50 ⁇ g, preferably more than 80 ⁇ g, particularly preferably more than 100 m 2 / g.
  • BET specific surface area
  • the silica or the airgel has a specific surface area (BET) in the range from 20 to 500 m 2 / g, in particular 50 to 450 m 2 / g, preferably 80 to 450 m 2 / g, preferably 100 to 400 m 2 2 / g.
  • BET specific surface area
  • the present invention preferably provides for the silica in aqueous dispersion with 4% by weight of silica, based on the dispersion, to have a pH in the range from 3 to 7, in particular 4 to 6 .
  • the silica is deagglomerated before mixing with the particulate materials, since corresponding composite particles can only be obtained with deagglomerated silica.
  • the pyrogenic silica after deagglomeration, has particle sizes in the range from 5 to 250 ⁇ m, in particular 10 to 200 ⁇ m, preferably 15 to 180 ⁇ m, preferably 20 to 150 ⁇ m, particularly preferably 25 to 100 ⁇ m, having.
  • aerogels are preferably used without deagglomeration in order to prevent extensive destruction of the airgel particles.
  • the silica is deagglomerated with the introduction of high shear forces or, for example, also by sieving. If the silica is deagglomerated by introducing high shear forces, it has proven useful if the silica is used at shear rates of more than 20 m / s, in particular more than 30 m / s, preferably more than 40 m / s, preferably more than 50 m / s, is deagglomerated.
  • deagglomeration is preferably achieved by sieving, in particular by means of a vibrating sieve.
  • the silica used according to the invention is in the form of silica granules before deagglomeration.
  • the silica granules generally have particle sizes in the range from 0.1 to 3 mm, in particular 0.2 to 2 mm.
  • the silica Before deagglomeration, the silica usually has a tamped density in the range from 20 to 200 g / l, preferably 30 to 150 g / l, preferably 40 to 100 g / l.
  • the particulate materials as well as the silica and / or the airgel are mixed. It is particularly preferred in the context of the present invention if the porous particulate material and the silica or the airgel carefully, in particular with little low mechanical stress, can be mixed. As the applicant has found, it is completely sufficient if the porous particulate materials are coated with the silica and / or the airgel by careful or gentle mixing. This leads to the formation of, in particular, fibrous structures made of silica and / or airgel on the surface of the porous particles, which on the one hand adhere to the pores and the other surface of the particles or interlock there and on the other hand adhere and interlock with one another.
  • the porous particulate material and the silica or the airgel are mixed with the introduction of low shear forces.
  • Particularly good results are obtained in this context if the porous particulate material and the silica or the airgel with a shear rate of not more than 5 m / s, in particular not more than 3 m / s, preferably not more than 2 m / s, preferably not more than 1 m / s, are mixed.
  • the duration for which the particulate materials and the silica or airgel are mixed can vary within wide ranges, in particular depending on the respective conditions and the layer thickness of silica and / or airgel to be achieved on the particulate carrier material .
  • porous particulate material and the silica or the airgel are mixed for at least 1 minute, in particular at least 2 minutes, preferably at least 5 minutes, preferably at least 10 minutes.
  • porous particulate material and the silica or the airgel over a period of 1 minute to 2 hours, in particular 2 minutes to 1.5 hours, preferably 5 minutes to 1 hour, preferably 10 minutes to 1 hour.
  • the porous particulate material is preferably coated with the silica and / or the airgel.
  • the porous particulate material by mixing the silica or the airgel with the porous particulate material apparently fibrous structures made of silica and / or airgel formed on the surface of the porous carrier material, which are anchored to the surface of the particles or hook there as well as hook with each other, so that gradually a - albeit uneven and not completely closed - layer of silica and / or airgel is formed on the particulate material.
  • the coating with the silica and / or the airgel is varied in the range from 5 to 600 ⁇ m, in particular 5 to 500 ⁇ m, preferably 8 to 400 ⁇ m, preferably 10 to 300 ⁇ m.
  • the layer thicknesses can be varied in particular by adjusting the ratio of the starting materials to one another and also the mixing time or the repetition of the mixing process. Composite particles specially tailored to the respective application can be obtained.
  • the ratio in which the porous particulate material and the silica and / or the airgel are mixed can likewise vary within wide ranges, depending on which layer thicknesses are to be achieved. In the context of the present invention, however, it has proven useful if the porous particulate material and the silica or the airgel in a volume-related ratio of porous particulate material to silica or airgel in the range from 4: 1 to 1:30, in particular 3: 1 to 1:20, preferably 2: 1 to 1:15, preferably 1.5: 1 to 1:10, can be mixed.
  • porous particulate material and the silica or the airgel are in a weight-related ratio of porous particulate material to silica or airgel in the range from 0.1: 1 to 40: 1, in particular 0.2: 1 up to 30: 1, preferably 0.3: 1 to 20: 1, preferably 0.5: 1 to 20: 1, can be mixed.
  • the porous particulate material is mixed with different silicas and / or aerogels, in particular silicas, preferably pyrogenic silicas.
  • the different silicas or aerogels can be silicas or aerogels with different physical or chemical properties, in particular with different particle sizes or different densities, but also with different rather hydrophilicity.
  • the porous particulate material is first mixed with a hydrophilic silica and / or a hydrophilic airgel, and then the coated particles thus obtained are mixed again with a hydrophobic silica and / or a hydrophobic airgel will.
  • the silicas used must in any case be deagglomerated before use.
  • a hydrophilic silica and / or a hydrophilic airgel By initially using a hydrophilic silica and / or a hydrophilic airgel, a good bond between the coating and the usually mineral and hydrophilic carrier material can be achieved to obtain hydrophobized particles.
  • the porous particulate material and the silica or the airgel are mixed several times.
  • the multiple mixing processes are carried out one after the other.
  • layer thicknesses of the coating with silica and / or airgel can be adjusted in a targeted manner.
  • the porous particulate material and the silica or the airgel 2 to 10 times, in particular 2 to 7 times, preferably 2 to 5 times, preferably 2 to 3 times, particularly preferably 2 times, mixed.
  • the porous particulate material is coated several times with the silica and / or the airgel.
  • porous particulate material is applied twice to 10 times, in particular 2 to 7 times, preferably 2 to 5 times, preferably 2 to 3 times, particularly preferably 2 times times, is coated with silica and / or airgel.
  • each coating is carried out with a layer thickness in the range from 2 to 200 ⁇ m, in particular from 3 to 150 ⁇ m, preferably from 5 to 100 ⁇ m, preferably from 5 to 80 ⁇ m.
  • the multiple coating processes are preferably carried out in such a way that the aforementioned total thicknesses for the coating are retained.
  • a layer of hydrophilic silica or hydrophilic airgel is first applied to the porous particulate material and then a layer of hydrophobic silica or hydrophobic airgel is applied, it has proven useful if the ratio - either by weight or based on volume - from hydrophilic to hydrophobic silica or airgel in the range from 10: 1 to 1: 4, in particular 8: 1 to 1: 2, preferably 7: 1 to 1: 1, preferably 5: 1 to 1: 1.
  • the porous particulate material is mixed with an IR scattering agent before, during or after mixing with the silica and / or the airgel.
  • An IR scattering agent also called an IR opacifier, is a substance, in particular in particle form, which minimizes the infrared permeability of the composite particles and thus prevents the transfer of heat by radiation as far as possible.
  • the infrared radiation is preferably reflected or diffusely scattered by the IR scattering means.
  • the IR scattering agents can, for example, be mixed together with the silica or the airgel and the porous particulate material.
  • IR scattering agents prior to mixing with the silica or to mix the airgel with the porous material or to mix the composite particles, ie after the porous particulate material has been mixed with the silica or the airgel, with the IR scattering agent; good results are always achieved.
  • the thermal conductivity of the composite particles can be further reduced by using the IR scattering agent.
  • the IR diffuser can also be selected from a variety of materials.
  • the IR scattering agent is selected from the group consisting of carbon, in particular carbon black and / or graphite, silicon carbide, llmenite, zirconium silicate, iron oxide, titanium dioxide, zirconium oxide, manganese oxide, iron titanate and mixtures thereof.
  • the IR scattering agent is selected carbon, in particular carbon black and / or graphite, and silicon carbide.
  • the amount in which the IR scattering agent is used this can also be varied depending on the results to be achieved in each case.
  • the IR scattering agent is used in an amount of 0.01 to 20% by weight, in particular 0.02 to 18% by weight, preferably 0.03 to 14% by weight. %, preferably 0.04 to 12% by weight, particularly preferably 0.05 to 10% by weight, based on the total amount of porous particulate material and silica or airgel, is used.
  • small amounts of IR scattering agent are sufficient to further reduce the thermal conductivity of the material obtained.
  • porous particulate material and the IR scattering agent are mixed carefully, i.e. with the introduction of low shear forces. It is preferably provided that the porous particulate material and the IR scattering agent are mixed under the same conditions as the porous particulate material and the silica or the airgel.
  • the porous particulate material and the IR scattering agent have a shear rate of not more than 5 m / s, in particular not more than 3 m / s, preferably not more than 2 m / s, preferably not more than 1 m / s, are mixed.
  • further additives in particular processing aids, are also mixed with the other starting materials.
  • this is preferably not provided, so that preferably only two materials, namely the porous particulate material and silica or airgel or three materials, namely porous particulate material, silica or airgel and IR scattering medium, are used to produce the composite particles.
  • the silica or the airgel it can of course be provided that several types of silica or airgel are used, as described above.
  • the method is carried out in such a way that
  • silica is deagglomerated
  • a porous particulate material is mixed, in particular coated, with the deagglomerated silica and optionally airgel.
  • the particulate porous material and the silica or the airgel are mixed with the introduction of low thrust forces. It is also particularly possible that several coating processes are carried out with the silica or the airgel, in particular also with different silicas or aerogels, a hydrophilic silica or a hydrophilic airgel being used initially in a first coating step and one in a subsequent step hydrophobic silica or a hydrophobic airgel.
  • 1 shows a composite particle according to the invention with a core made of expanded perlite which is coated with graphite and hydrophilic fumed silica
  • 2 shows a composite particle according to the invention with a core made of expanded perlite, which is first coated with hydrophilic silica and graphite and then with hydrophobic fumed silica.
  • Another object of the present invention - according to a second aspect of the present invention - is a composite particle obtainable by the method described above.
  • the further invention - according to a third aspect of the present invention - is a composite particle which is obtainable in particular by the method described above, the composite particles having a core made of a porous material and a shell, in particular a coating, containing silica and / or airgel, in particular silica.
  • the composite particle preferably consists of a core made of a porous material and a shell (coating) which contains silica or airgel and optionally an IR scattering agent.
  • the composite particles have a thermal conductivity at 25 ° C in the range from 0.020 to 0.045 W / (mK), in particular 0.022 to 0.040 W / (mK), preferably 0.024 to 0.038 W / (mK) , preferably 0.026 to 0.035 W / (mK), particularly preferably 0.0328 to 0.035 W / (mK).
  • Another subject of the present invention - according to a fourth aspect of the present invention - is the use of the aforementioned composite particles for the production of building materials, in particular of Insulating materials, such as insulating plaster, insulation boards or thermal insulation composite systems, preferably thermal insulation boards.
  • Insulating materials such as insulating plaster, insulation boards or thermal insulation composite systems, preferably thermal insulation boards.
  • the composite particles according to the invention are outstandingly suitable for use in all types of insulation systems and can be used there in particular as a substitute for plastics or purely mineral-based insulation materials.
  • Another object of the present invention - according to a fifth aspect of the present invention - is a dry building material mixture containing the aforementioned composite particles.
  • the dry building material mix is preferably suitable for the production of plaster mortars and insulating plasters, but for the production of molded bodies, such as thermal insulation boards.
  • the dry building material mix usually has the composite particles in amounts of 10 to 90% by weight, in particular 10 to 70% by weight, preferably 15 to 65% by weight, preferably 20 to 60% by weight, particularly preferably 30 to 50% by weight .-%, based on the dry mix of building materials.
  • the dry building material mix has at least one binder composition, the dry building material mix preferably having only one binder composition.
  • the dry building material mixture contains the binder composition in amounts of 5 to 80% by weight, in particular 15 to 70% by weight, preferably 30 to 60% by weight, preferably 35 to 55% by weight. -%, particularly preferably 40 to 50% by weight, based on the dry building material mixture.
  • the binder composition has at least one cement-based binder, preferably cement, preferably Portland cement, particularly preferably white cement.
  • cement-based binders means that they set hydraulically, ie by adding water, and form particularly resilient and permanent solid systems.
  • the binder composition contains the cement-based binder in amounts of 1 to 79% by weight, in particular 3 to 50% by weight, preferably 5 to 40% by weight, preferably 8 to 30% by weight. %, particularly preferably 10 to 25% by weight, based on the dry building material mixture.
  • the binder composition has at least one lime-based binder, in particular hydraulic lime and / or hydrated lime, preferably hydraulic lime.
  • Hydrated lime is calcium hydroxide Ca (OH) 2, which is obtained from quicklime (CaO) by dry adsorption.
  • Hydraulic lime is calcium hydroxide Ca (OH) 2 to which small amounts of a hydraulic binder, in particular cement, are added.
  • the binder composition contains the lime-based binder in amounts of 1 to 79% by weight, in particular 5 to 60% by weight, preferably 10 to 50% by weight, preferably 15 to 45% by weight, particularly preferably 20 to 40% by weight, based on the dry building material mix.
  • the binder composition contains the lime-based binder in amounts of 1 to 79% by weight, in particular 5 to 60% by weight, preferably 10 to 50% by weight, preferably 15 to 45% by weight, particularly preferably 20 to 40% by weight, based on the dry building material mix.
  • the binder composition has at least one cement-based binder and at least one lime-based binder, in particular in the aforementioned amounts.
  • the ratio of cement-based binder to lime-based binder can also vary within wide ranges.
  • the ratio of cement-based binder to lime-based binder in the range from 5: 1 to 1:10, in particular 3: 1 to 1: 8, preferably 1: 1 to 1: 5, preferably 1: 2 to 1: 3.
  • the dry building material mixture contains fibers, in particular inorganic, preferably mineral fibers.
  • fibers can further increase the strength and mechanical resistance of the resulting materials.
  • inorganic fibers in particular mineral inorganic fibers, is preferred.
  • the fibers are selected from calcium silicate fibers, glass fibers, wollastonite fibers, carbon fibers, carbon nanotubes and mixtures thereof. It is particularly preferred in the context of the present invention if the fibers are selected from calcium silicate fibers, glass fibers, wollastonite fibers and mixtures thereof. Particularly good results are obtained when the fibers are calcium silicate fibers.
  • the dry building material mix is based on the fibers in amounts of 0.1 to 5% by weight, in particular 0.2 to 2% by weight, preferably 0.2 to 1% by weight the dry building material mix.
  • the dry building material mixture contains at least one additive, in particular at least one additive.
  • the additive is selected from the group of liquefiers, thickeners, retarders, accelerators, stabilizers (stabilizers), rheology control agents, additives to adjust the water retention capacity (water retention agents), dispersants, sealants, air entrainment agents and mixtures thereof .
  • the dry building material mixture usually contains the additive in amounts of 0.01 to 10% by weight, in particular 0.1 to 5% by weight, preferably 0.3 to 3% by weight, preferably 0.5 to 1% by weight, based on the dry building material mix.
  • the dry building material mix contains
  • the dry building material mix according to the invention has a bulk density in the range 80 to 650 kg / m 3 , in particular 90 to 600 kg / m 3 , preferably 100 to 500 kg / m 3 , preferably 110 to 400 kg / m 3 .
  • Another object of the present invention - according to a sixth aspect of the present invention - is a plaster mortar, in particular re an insulating plaster, obtainable from the aforementioned dry mix of building materials and / or containing the aforementioned composite particles.
  • plaster mortar is mixed with water in amounts of 70 to 300% by weight, in particular 80 to 250% by weight, preferably 90 to 200% by weight, based on the Dry building material mix, is available.
  • the plaster mortar according to the invention can be made up and also processed like a conventional plaster mortar known from the prior art.
  • the hardened plaster mortar has a water vapor diffusion resistance number m, determined according to DIN EN ISO 12542, in the range from 2 to 9, in particular 3 to 7, preferably 4 to 6.
  • m water vapor diffusion resistance number
  • the plaster mortar according to the invention is characterized in that it is open to diffusion and moisture can be released from the masonry to the environment, which counteracts the formation of mold and algae and also increases the durability of the thermal insulation system.
  • the hardened plaster mortar usually has a thermal conductivity in the range from 0.030 to 0.55 W / (mK), in particular 0.035 to 0.042 W / (mK), preferably 0.035 to 0.040 W / (mK).
  • another subject matter of the present invention - is a molded body, in particular a thermal insulation board, obtainable from the aforesaid dry building material mix or the aforesaid plaster mortar and / or containing the aforesaid composite particles.
  • the shaped body is particularly characterized in that it preferably has a thermal conductivity in the range from 0.030 to 0.55 W / (mK), in particular 0.035 to 0.042 W / (mK), preferably 0.035 to 0.040 W / (mK).
  • the thickness of the shaped body according to the invention in particular the thermal insulation board, is concerned, it can vary within wide ranges. In the context of the present invention, however, particularly good results are obtained when the shaped body has a thickness in the range from 1 to 20 cm, in particular from 1.5 to 15 cm, preferably from 1.5 to 10 cm, preferably from 2 to 8 cm.
  • 40 l of expanded perlite with particle sizes between 0.6 and 2.5 mm are placed in a tumble mixer with a capacity of 200 liters.
  • the perlite has a bulk density of approx. 50 g / l and a thermal conductivity of 40 mW / (mK).
  • hydrophilic fumed silica with a tamped density of 50 g / l, a BET surface area of approx. 380 m 2 / g and a vibrating sieve with a mesh size of 2 mm are sieved to break up the agglomerates.
  • the deagglomerated silica is then added to the mixture of graphite and perlite and mixed for a further 10 minutes at 250 revolutions / minute in a tumble mixer. Hydrophilic composite particles are obtained.
  • FIG. 1 shows a light microscope image of a particle of expanded perlite coated with hydrophilic fumed silica and graphite.
  • Fig. 1 it can be seen that the surface and in particular the pores of the expanded perlite are covered with pyrogenic silica and that fiber-like or structures are formed on the surface of the perlite, which adhere firmly to there.
  • the composite particles coated with hydrophilic fumed silica obtained under 1. are mixed with 4 l of hydrophobic fumed silica with a tamped density of 60 g / l and a BET surface area of approx. 220 m 2 / g.
  • the hydrophobic fumed silica was also sieved beforehand with a vibrating sieve with a mesh size of 2 mm in order to break up the agglomerates.
  • hydrophobic pyrogenic silica After the hydrophobic pyrogenic silica has been added to the hydrophilic composite particles, mixing is continued for 10 minutes at a speed of 250 revolutions / minute in a tumble mixer.
  • Approx. 50 l of hydrophobized, coated pearlite particles with a bulk density of approx. 70 g / l and a thermal conductivity of 31 mW / (mK) are obtained.
  • FIG. 2 shows a light microscope image of a composite particle according to the invention which is obtained after the process has ended, i.e. which is first mixed with graphite and hydrophilic silica and then mixed with hydrophobic silica.
  • hydrophilic and the hydrophobic composite particles according to the invention can be incorporated into binder systems in an outstanding manner.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Silicon Compounds (AREA)
  • Thermal Insulation (AREA)

Abstract

L'invention concerne un procédé de production de particules composites thermo-isolantes et les particules composites pouvant être obtenues par ce procédé, ainsi que leur utilisation. Le procédé est caractérisé en ce que, dans le but de produire des particules composites thermo-isolantes, un matériau particulaire poreux, tel que, par exemple, de la roche volcanique, de la perlite (expansée), de la vermiculite (expansée), de la pierre ponce, du verre cellulaire et du verre expansé, de l'argile expansée, de l'ardoise expansée, du tuf, du gravier de lave, du sable de lave, est mélangé avec de l'acide silicique désaggloméré, par exemple de l'acide de silice pyrogénée et/ou précipitée, et/ou avec un aérogel, le matériau particulaire poreux étant de préférence revêtu de l'acide silicique et/ou de l'aérogel.
EP21724210.6A 2020-04-30 2021-04-30 Procédé de production de particules composites thermo-isolantes, particules composites et leur utilisation Pending EP4143144A1 (fr)

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PCT/EP2021/061393 WO2021219847A1 (fr) 2020-04-30 2021-04-30 Procédé de production de particules composites thermo-isolantes, particules composites et leur utilisation

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CN114315248B (zh) * 2021-12-29 2023-03-17 上海暖丰保温材料有限公司 一种混凝土砌块及其制备方法
CN114621016B (zh) * 2022-03-18 2023-03-14 安徽碳鑫科技有限公司 一种耐火保温材料的制备工艺
CN115368048B (zh) * 2022-09-19 2023-07-14 河南建筑材料研究设计院有限责任公司 一种改性膨胀珍珠岩及其制备方法和应用

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EP3138826B1 (fr) * 2015-09-02 2018-10-17 Interbran Systems AG Mélange sec contenant silice pyrolyse pour matériau de construction et enduit ignifugé en découlant
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