EP1851181A1

EP1851181A1 - Moldable material consisting of articles coated with a coating material and use thereof for producing molded elements

Info

Publication number: EP1851181A1
Application number: EP05818161A
Authority: EP
Inventors: Gerhard Melcher
Original assignee: Individual
Current assignee: Individual
Priority date: 2004-12-29
Filing date: 2005-12-20
Publication date: 2007-11-07
Also published as: WO2006069411A1; AT501586B1; AT501586A1

Abstract

The invention concerns an expansible, hardenable and moldable material consisting of particles coated with a coating material. In the molded element produced with said material, the particles are mechanically in contact with one another and the void volume between the particles is filled with foam in an adjustable manner. This enables the mechanical and isolating properties of the particulate structure to be associated with the mechanical and isolating properties of the hardened foam material. The expanded and hardened material is particularly suitable for applications as isolating material, fireproof material and for high-temperature applications.

Description

Molding composition consisting of coated with coating particles and their use for the production of moldings

State of the art

The invention relates to the field of molding compositions and molding production based on the binding of particles by coating compositions.

Coating compositions, such as, for example, cement paste, are used for point-wise cementing, in particular of coarse-grained particles, such as gravel or expanded clay particles, e.g. in porous concrete with maximum retention of void volume between the particles. The aim of the use of these coating compositions is usually to produce cost-effective moldings with low specific weight and better insulation behavior.

However, this type of bonding does not allow to achieve either the high strengths of normal concrete or the low densities comparable with foams, which are necessary for optimum insulation or fire protection properties. The partial filling of the void volume between, for example, coarse-grained particles with foams-in order to achieve higher strengths by enlarging the cementing surface of the coarse-grained particles-fails because of the low green strength of the foams. The often supported by a shaking process filling process of shapes or cavities causes a demixing of existing particles and coating mass total mass, so that located at different heights fillers are unevenly sheathed and thus inhomogeneously bound.

If foam compositions are used and if these are added, for example, to coarse-grained particles, then these compositions have all the negative properties of foam compounds. They are difficult to fill in molds without air pockets and also do not have the strength properties of the framework of mutually supporting, coarse-grained, such as pressure-stable particles, such as those present in porous concrete. On the other hand, if foam is allowed to form in a mold, it is necessary to provide an excess of foam in order to guarantee complete filling of the mold. This thus requires either pressure-resistant forms or shapes with foam outlet openings, which often leads to contamination and as a result to necessary cleaning processes. Furthermore, in the case of molds with large heights, the different hydrostatic pressure of the foam mass often results in considerable differences in density and thus inhomogeneous properties in the molded body. In addition to inorganic particles, such as gravel, pumice, expanded clay, expanded mica, expanded glass, pearlite, etc., organic particles, such as polystyrene particles, are also used. They are coated with cement and various other materials such as water glass, glue, etc. and used mainly for screeds and plasters (DE 296 23 459 Ul).

In AT 407526 B, for example, in AT 407526 B a very thin coating of particles with clay mineral-containing earths, such as clay, loam, marl, but also cement, lime, gypsum or the like is proposed in order to achieve the lowest possible densities for good insulating properties of screeds. In DE 197 14729 Al the sheathing of fiber materials is described. Organic binders, such as bitumen, are used as binders for foam granules for underbody masses (EP 0 947 480 B).

Coating compositions are also used in the pellet production of inorganic building materials. Here, light particles, such as perlite or distended vermiculite, either in a melting process with solid shells (JP 7291685 A) or in the case of the use of glass with a foamed crust (JP 61236643 A) are coated. The use of a mixture of phenolic resin and rock flour as a coating composition is described in JP 56160368 A.

Description of the invention

The object of the invention is, using a coating composition for organic and inorganic particles, in particular coarse particles, to describe a method for the production of moldings in which particles are combined with foam compositions, wherein

1) the scaffolding of the particles is maintained in mutual mechanical contact,

2) the foam mass fills the void volume between the particles either completely or at least partially to an adjustable extent,

3) even with large filling heights uniformly dense shaped bodies are obtained, and

4) in the case of a process-dependent shaking process no segregation of coating composition and particles takes place, so the coating composition is adjustable to the process-related requirements.

1. General principle

Surprisingly, it has been found that the object of this invention can be met by means of special coating compositions. The filling of the void volume between the particles, in particular coarse particles by foam masses is important not only for the strength of the bonding of the particles, but also for the insulation and fire protection properties. The heat transfer is based on heat conduction through the material framework, on convection through the air in the material scaffold and on radiation. The filling of continuous cavities, in particular between coarse-grained particles with a cured foam mass hinders convection and radiant heat conduction and thus improves the insulation and fire protection properties of the molding.

According to the invention, coating compositions have been developed for particles, in particular for coarse-particle particles, which are produced from one or more components and which adhere to the particles in the process of filling the particles coated with the coating composition into a mold, into a cavity or their application to a surface without ripping off even with relatively large layer thicknesses and process-related vibration. This process will hereinafter be referred to as a molding process. The coating composition either begins to foam after this shaping process or is made to foam or it has begun to foam and crosslink at high reactivity already during the mixing process and the molding process. In the latter case, the viscosity of the coating composition already increases during the mixing and shaping process compared to the originally used in the individual components viscosity.

The foaming mass thus fills the void volume between the particles. A movement of the particle skeleton by the resulting foam is partly due to the weight of the particles and on the other hand by their mutual tension and support, which can be enhanced, for example, by a vibration process or a pressing process, prevented. Even if the coating composition has already begun to foam before or during the molding process, this is compared to the void volume slight still uncured foam volume fraction by the weight of the particles and their mutual tension (the pressure applied to the coating composition, which is between the direct contact surfaces of the Particle is, corresponds) pressed into the void volume between the particles and foams and hardens there further. Between the particle contact surfaces thus remains a solid, substantially unfoamed coating mass layer, from which the resulting gas has escaped into the void volume. It is therefore possible to use also much lighter particles than the density of the cured and foamed coating composition, for example to combine polystyrene particles with cement slurry or distended Vermiculilparükel with water glass as coating compositions. In these cases, it is possible according to the invention that substantially the foamed and cured coating composition assumes the mechanical strength of the molding and the particles improve the insulating properties.

2. Quantity and properties of the coating composition

The amount of the coating composition to be used, based on a defined amount or a defined volume of particles, is calculated firstly from the void volume between the particles, secondly from the desired foam density to be set and thirdly from the fill level of the void volume to be set. In the case of a single-grain distribution of particles - idealized as the cubic closest packing - a space filling (Vjςu _ge i / V _Gesa m _t ) ^of 0.74 results purely geometrically in the unit cell - and thus independent of the particle size - and thus a void volume of 26% by volume. If particle size mixtures or strongly irregular particle shapes or fines are used, the void volume must be determined experimentally. This is done, for example, by filling the void volume of a defined volume of a sample of the particles with fine Bauxitmehl. Taking into account the bulk density of the bauxite meal, the void volume can be calculated from the weight increase of the sample filled with bauxite flour.

Foam density, curing and foaming rates can be adjusted for the selected binder according to the prior art by selecting the amount and type of foaming agent and curing agent and the reaction conditions.

Furthermore, the flow behavior of the coating composition is important. It is intended, on the one hand, to ensure as light and uniform a distribution of the mass on the surface of the particles as possible during the mixing process and, on the other hand, to guarantee a stable adhesion of the coating mass to the particle surface during the shaping process of the coated particles. The coating composition is thus adjusted to whether a vibration process takes place and how strong and long it must be carried out and in which layer thickness the coating composition is applied to the particles. The layer thickness results from the amount of the coating composition and the specific surface area of the particles. The amount of Coating mass, in turn, is calculated from the void volume, the foam density to be set and the fill level of the void volume to be set.

One can distinguish the following four cases:

1. If the coating composition has the properties of a Newtonian liquid, the initial viscosity shall already be high enough, with a value of at least 100 mPa.s to 500 mPa.s, or more of 500 mPa.s to 5000 mPa.s , or preferably from 5000 mPa.s to 50 000 mPa.s is favorable.

2. If the coating composition has the properties of a non-Newtonian liquid, it is preferable to adjust thixotropic (see Example 1), in particular selecting pseudoplastic compositions which have a high apparent viscosity at rest, which decreases with increasing shear rate and increasing stirring time.

3. Third, the reactivity of the coating composition, ie its hardening and foaming behavior, can be adjusted so that it already has high viscosity in the molding process due to the incipient crosslinking of the coating composition and / or an incipient foaming process. (See Example 2, based on the procedure described in AT 400840 B, in which the composition is additionally thixotropic.) Supporting this process is that foams themselves have thixotropic properties, which contributes to the rigidity of the foaming coating composition itself.

4. Any possible combinations of the three cases 1, 2, and 3.

The necessary rheological behavior, ie the sag resistance of the coating composition is thus determined quite substantially by the layer thickness on the filler. Thus, for coarse-grained particles with large specific surface areas or for particles with very small particle size, a low viscosity is possible because the coating composition is present in very thin layers and does not sink even with strong shaking, while for coarse-grained particles with smooth closed surfaces (eg gravel) the stability of the coating mass layer is essential.

The determination of the theological properties of liquids is state of the art and it is only in part to refer to some methods. A determination of the flow path can be made in accordance with DIN 16916 Part 2. The use of a Brookfield viscometer in accordance with ASTM D 2196 or an assessment of the flow inclination using a level and Ablaufprüfrakels (Erichsen (Germany)) according to DIN 55677 or ASTM D 4400 are further methods. It is, for example, according to DIN 55677 according to point 7.2 relatively easy to set with the aid of finely ground, inexpensive platelet-shaped fillers in coating thicknesses solid layer thicknesses of 1 000 microns to 1 300 microns and above.

Since the conditions of production, the types of moldings to be produced and fillable cavities are many, it can only be said that the coating compositions can be adjusted by their rheological properties (viscosity and in particular thixotropy) and their reactivity to the corresponding process conditions for a person skilled in the art.

3. Used raw materials

As particles, both inorganic and organic particles or mixtures thereof, preferably with a particle size of 1 mm to 24 mm, to 50 mm or a maximum of 100 mm, in particular the industrially available particle size ranges, such as those between 4 mm and 12 mm, or preferably of 2 mm to 4 mm, 4 mm to 8 mm, 8 mm to 12 mm, 8 mm to 16 mm or 12 mm to 20 mm, or mixtures thereof or any other particle size ranges or selected in these areas Einkornzusammensetzungen be used. As inorganic coarse-grained particles, for example, particles with compact surfaces, such as glass beads, corundum hollow spheres, gravel, various rock particles, such as gypsum, etc., can be used, as well as foamed or porous particles such as expanded clay, expanded glass, expanded, Perlite, expanded mica, distended vermiculite, volcanic rock particles, tuff, pumice, etc. or high-temperature-resistant particles of, for example, corundum, chamotte, molochite, etc. Organic particles may be, for example, cork particles, wood chips, foam particles, particles from various recycling materials, polystyrene particles, etc., ie consist of substances that contribute to Group of organic polymers belong. Furthermore, organic or inorganic microspheres or nanospheres are suitable, such as, for example, polystyrene, PMMA or aluminum oxide, glass or quartz. Microspheres of diameter 0.2 to 0.6 mm, for example of hafnium oxide and zirconium oxide, can also be used for high-temperature applications, for example.

Absorbency, porosity and specific surface area of the particles are essential for the adjustment of the coating composition. For example, if you use materials such as expanded clay, slate, or distended vermiculite so specifically the absorbency of the material (in particular the material moisture) and the specific surface to be considered.

The coating compositions, which may be predominantly inorganic or predominantly organic in nature, consist of: a) a binder.

The binders can be both organic, such as polyesters, polyurethane, acrylates, epoxy resins, bituminous materials, etc., as well as inorganic, such as phosphate-based, such as solutions of predominantly primary phosphates of magnesium, calcium, aluminum, preferably A, aluminum monophosphate, such Water glass base, such as solutions of sodium or potassium silicates of various concentrations, cement-based, such as calcium silicate (Portland cement) or Calziumaluminatbasis, or gypsum-based, Sorrelzementbasis, etc. or chemically possible mixtures thereof. b) a hardening substance, wherein the curing takes place after the foaming process or simultaneously with this; Also, for example, hardening and foaming substance may be identical. As such, for the organic binders in question, for example, isocyanates, peroxides, epoxides, etc. in question, for inorganic binders substances are used, such as for aluminum monophosphate soluble polyvalent metal oxides, and their carbonates, for water glass in particular acid-splitting hydrolyzing substances or reactive metal oxides , for cement and gypsum water acts as a hardening substance, in sorrel cement magnesium oxide is hardened by magnesium salts, such as their chloride or sulfate. c) A gas-evolving foam-forming substance.

These may be, for example, ammonium carbonates or alkali metal carbonates, polyvalent metal carbonates, water in the case of polyisocyanates, aluminum powder, organic or inorganic peroxides, sodium perborate, hydrogen peroxide, etc. d) optionally inorganic ground fillers, such as kaolin, chalk, slate, mica, quartz, etc. and / or optionally also fine to coarse-grained hydrates, such as gypsum, gypsum, magnesium sulfate hydrate, Aluminiumumsulfathy-, alums, etc. or organic fillers, such as starch, sugar, etc. included. Preference is given to particles with anisotropic form, ie with platelet or needle-shaped structures. used, which themselves form thixotropic suspensions. Another advantage of platelet fillers is that they stabilize the wall structure of the foam bubbles. e) Optionally flame retardants, such as hydrates of salts, for example sulfates, such as gypsum, Epsom salt, various phosphates, such as MgHPθ ₄ .3H ₂ θ, MgHPOφVBbO, or pyrophosphates or hydroxides of aluminum, magnesium, calcium, etc. (These can both finely ground or used as coarse-grained fillers.) f) optionally reinforcing fillers, such as inorganic or organic fibers, for example glass fibers, wood fibers, pulp fibers, plastic fibers, or rod-shaped fillers, such as wollastonite. g) optionally thixotropic substances, such as hydrophilic or hydrophobic colloidal or fumed silica, synthetic polymers having ionic and / or other associating groups, such as homopolymers and copolymers of acrylic acid, their alkali and ammonium salts, smectites, organically modified bentonites, Montmorillonites, carboxymethylcellulose and water-soluble melamine-formaldehyde resins or urea derivative resins, gelatin, hydroxypropylmethylcellulose, ethylene oxides and propylene oxide copolymers, etc., h) optionally various additives, such as wetting agents, flow aids, retarders (retarders for cement, etc) i) and optionally water-binding substances, in particular when using aqueous binders such as calcium sulfate, magnesium sulfate, aluminum sulfate, various phosphates or pyrophosphates of alkali metals, magnesium and calcium which form hydrates (as described in AT 408347 B) or water-reactive substances.

4. The procedure and the process parameters

The process consists essentially of three stages:

4.1. Preparation of the coating composition and coating of the particles with it

The coating composition can either be prepared in advance in a separate vessel and be applied as such in a mixer to the particles, or alternatively it is applied to the particles by stepwise application of the individual components to the particle surface. surfaces produced in the mixer. Depending on the reactivity of the coating composition and the type of particles, slow or fast-running mixers can be used in continuous or discontinuous mixing processes. In general, it is sufficient if the coating composition covers the surface of the particles almost completely or at least partially. In practice, there are hardly any completely round particles with uniform outer surfaces. Since the coating composition in the mixing process is primarily distributed only on the mutual contact surfaces of the particles, in some cases sub-surfaces of the particles remain uncoated. However, this is irrelevant to the overall process. It is essential that a virtually homogeneous distribution of the coating composition takes place during the foaming and curing process in the molding.

The stepwise application of the coating composition is recommended with a high reactivity of the coating composition, wherein only in the last step, shortly before the shaping process, the reactive hardener and foaming component is applied to the particles.

It is particularly advantageous if the setting and foaming process already begins during the mixing and shaping process, the reactivity of the mixture, ie holding time, rise time, setting time, compression time, being tuned to the overall process, as described, for example, in patent AT 400 840 B is described. This is particularly favorable for the timing of a production process, since it keeps stand times and curing times as short as possible. However, the overall foaming process must be calculated so that the mechanical breakdown of the foam during the mixing process by the particles proceeds as a precrosslinking process of the coating composition, in which the binder is partially crosslinked to larger molecular units, and by the remaining unreacted hardener / foamer quantity to the desired degree of filling of the void volume between the particles comes. This procedure requires exact adherence to well-defined mixing times (See Example 2).

It is also advantageous when using aqueous binder systems, such as in aqueous phosphate solutions, as described in AT 408347 B, to use water-binding substances that cause internal drying. As such are for example in question:

• oxides, such as cements (tricalcium silicate, calcium aluminates, etc.), CaO, etc.

Sulphates, such as the sulphates of calcium, aluminum, and the vitriol-forming sulphates of copper, manganese, magnesium, zinc, iron, cobalt and nickel, or double salts of these sulphates with potassium or ammonium sulphate or alum

• Phosphates and pyrophosphates of alkali metals, magnesium and calcium

• Various other water-binding substances, such as metals that react to form hydrogen or inorganic or organic esters and other hydrating or water-binding substances, such as physically water-absorbing substances such as phyllosilicates or the like.

In this connection, reference is explicitly made to the teaching described in AT 408347 B, where the foaming masses produced on the basis of phosphate are characterized in that the inorganic foam product which is produced by the mixing together of two or more components, of which at least one is liquid and acidic and water, phosphates or phosphoric acid as a binder and at least one second component containing polyvalent cations in an acid-reactive form, characterized in that it contains a water-binding substance in a substantial amount for binding the water contained in the foam mass ,

This principle can subsequently also be applied to other aqueous systems, for example those based on waterglass, since any reactive water-binding substances added as solids often have no time to react to any appreciable extent with the unreacted binder in the preferably short reaction times recommended here.

Naturally, the drying rate must be matched to the curing and foaming behavior of the coating composition. Drying may therefore only take place after foaming and hardening.

Such compositions, which subsequently contain water of hydration in bound form, are particularly suitable for use in closed molds or composites, such as fire doors or panels with metallic outer layers, since the chemically bound water, unlike the physically bound, in the long term to the fire protection property the hardened mass contributes. It is also advisable to add such hydrates as fillers to the coating compositions and thus to adjust any fire resistance classes via the chemically bound water content.

The dosage of the coating composition takes place in such a way that the void volume between the fillers is filled either substantially completely (to a maximum of 100%) in order to avoid possible coating mass leakage (lathering) from the mold or cavity in the course of curing and foaming, or at a lower adjusted percentage such as 10%, 20%, 50%, 75% or 90% of the void volume.

If, while maintaining the contact of the particles with each other, a guaranteed complete (100%) filling of the void volume by means of foam is desired, a foam amount which is greater than that required for the filling of the entire void volume is also possible. In this case, the mold is to be filled with the coated particles and it must be provided for the resulting, the void volume exceeding foam amount, foam outlet openings in the mold or pressure-resistant forms are used. It is thus possible to adapt the properties of the molded article produced in a wide range to the requirements in terms of strength, elasticity, thermal insulation, fire protection, etc. Naturally, the selection of raw materials is essential for the properties of the final product.

4.2. Shaping process of coated with the coating composition particles

The molding process of the coating composition coated particles by filling into a mold, into a cavity, or by applying to a surface can be done rapidly within seconds or slowly within minutes. During or after this process, a densification process, for example by vibration or by a pressing process, can be used to achieve a uniform dense arrangement of the particles, for example in the cubic closest packing.

4.3. Foaming, curing and optionally drying the foamed and cured mass

After the forming process of the coated particles, the coating composition is at rest. It can now be brought to a predetermined extent for foaming and either at the same time or shortly thereafter for curing. The foaming and curing process can either take place automatically at room temperature, usually under exothermic conditions or can be started and carried out by heating, for example, with thermal energy with heating devices or with microwave or high-frequency energy.

When using aqueous binders, as is generally known for concrete and gypsum, drying to achieve ultimate strength is essential. In addition to the already described method of internal drying by hydrate formation is probably the least expensive Me¬

li method by evaporating the physically bound water. The porous structure of the hardened and foamed mass present here permits accelerated drying in the form of a separate process stage by sucking air through the shaped body, in particular with heating of the shaped body. This method of sucking air is particularly advantageous in closed by outer surfaces moldings, such as fire doors, as this their uniform flow can be achieved. In this case, this is nothing more than a simulation of slowly changing air by a change of temperature (day / night) in a physically bonded moisture-containing fire door from which when heated with water vapor saturated air is transported through the air expansion to the outside and cooling from the outside unsaturated fresh air is sucked in. Depending on the environmental conditions, significant quantities of physically bound water (subject to changes in the fire protection properties of the fire door) can be transported outwards over the course of years.

If you use these masses, for example, for insulating underbody masses in place in buildings, so you can bring them by conventional microwave-drying for foaming and drying. Alternatively, self-foaming and self-hardening coating compositions, for example according to Example 2, are also possible for these cases, wherein a subsequent slow drying process can be carried out by air drying.

It is therefore generally advantageous if the process of foaming and curing occasionally by a simultaneous or subsequent drying process, either by hydrate formation either at room temperature or at elevated temperature, wherein a temperature range of 30 ⁰ C to 90 ⁰ C, preferably at 40 ⁰ C to 75 ⁰ C, is complied with, or slowly by adding air through the molding or by standing in the air is completed automatically expiring.

As a result, a filled with the cured and foamed mass mold, a filled cavity or a demolded body is obtained which has homogeneous properties even at large dimensions and filling heights and consists of particles and foam masses that at least partially fill the void volume between the particles.

5. Application areas

It is possible to distinguish between the application of the composition and the application of the molded articles produced therefrom. The main application areas include the Areas of thermal insulation and sound insulation as insulating material and the areas of fire protection and high-temperature applications.

In the construction industry, there are a variety of applications of the mass for filling cavities. For example, it is possible to produce vibration-proof insulation with very low densities, for example made of polystyrene. The coated with coating mass particles can be blown into a cavity, where they are then connected by the foam to a long-term stable vibration insensitive molding. It is advantageous, for example, if the particles in this use are already coated with a part of the coating composition, are transported as such to a construction site and, on the spot, quantity-related subcomponents for curing and foaming are admixed continuously or discontinuously. In analogous form, such compositions can be used, for example, for screeds.

The use of moldings in the construction industry may take the form of insulation or fire protection panels and any other molded parts or part of composite elements. Such composite elements can by connecting to other components of mineral materials, such as element in precast chimneys, as insulation in prefabricated house walls and ceiling elements, or in combination with other example thin-walled, such as metallic outer layers, such as in fire doors, panels, door frames, and the like be formed. In this case, the moldings remain parts of the composite element. In this context, it is to be regarded as a considerable advantage that you can produce from silos and, for example, for fire doors no plate storage and no plate blanks needed.

Such materials can be used for example as insulation in household appliances, such as refrigerators, dishwashers or insulation in ovens and heating systems for industry, commerce and household. When using the corresponding high-temperature-resistant particles, such as corundum hollow spheres, and selecting high-temperature-resistant binders, for example based on aluminum phosphate such materials and moldings for the high temperature range from 600 ⁰ C to 2200 ⁰ C, preferably in the range of 900 ⁰ C to 1450 ⁰ C and from 1450 ⁰ C to 1750 ⁰ C, can be used. Spezialan- Punctures result from the use of organic or inorganic microspheres or nanospheres. They can be bound together by coating compositions to hardened masses with defined cavities, which can be used for example as a filter or carrier material. Furthermore, packaging materials, for example on a purely organic basis, can thus be produced inexpensively.

The invention thus relates to the particles coated with the coating composition, the method of foaming, curing and shaping, furthermore the cured and foamed composition, for example a shaped body which is obtainable by the curing of the composition according to the invention, and an article or component, in particular composite elements with, for example, metallic outer layers, such as panels, metal doors, fire doors, etc., which contain a filling of the moldings obtainable with the composition according to the invention.

The invention will be explained in the following examples, without being limiting, in part. It is always possible for a person skilled in the art to use any substance of his choice according to the information according to the invention.

6. Examples

Example 1.

Gravel and thixotropic cement slurry with aluminum powder as foaming agent

Example of a slow-curing and foaming thixotropic coating composition at room temperature, which is applied to coarse-grained particles with a smooth surface.

Experimental procedure:

5 000 g of gravel with a grain size of 4 mm to 20 mm are coated with a coating mass consisting of 520 g Portland cement + 380 g water + 2 g wetting agent / foam stabilizer + 7.5 g HDK N20 + 7 g standard aluminum powder coated particles are filled with shaking into a mold. Cement hardening and foaming are carried out at room temperature. The molded body has a density of about 1.8 kg / l when dry.

Remarks:

• Particles: The particulate ballast has a bulk density of 1.6 kg / 1 and an experimentally determined void volume of 40 volume percent. Approximately one 50% filling of the void volume [(5000 g / 1600 g / l). 0.4. 0.5 = 0; 625 I)] are about 600 g of a foam material having a density of 0.97 g / cm ³ in the cured state, is required (0.97 g / cm ³ 625 cm ³ = 606 g)..

Coating composition: The cement slurry used as the coating composition was adjusted to a layer thickness of more than 1 300 μm with highly dispersed silica HDK N 20 (Wacker-Chemie GmbH, Germany) with respect to its drainage tendency according to DIN 55677 according to 7.2. For example, SB3 (Heidelberger Zementwerke) was used as wetting agent / foam stabilizer. The foamer used was standard aluminum powder Slurry N30 No. 53199 / G from Eckart GmbH & Co. KG, (Germany).

• Procedure: The mass was shaken into a mold for about 5 seconds. The entire foaming process takes place due to the sluggish reaction of the aluminum powder used in the vibrated mass in the mold.

Example 2

Expanded clay and rapidly reacting coating compound based on aluminum monophosphate with internal drying

This is an example of coarse-grained porous particles having a fast-reacting, thixotropically-adjusted coating composition with internal drying.

Experimental procedure:

18 liters (5.9 kg) of expanded clay particle size 8 mm to 12 mm (Leca 8/12 from Leca- Liapore Baustoffe GmbH, Germany) are mixed with 590 g of water in a rapidly running mixer (10 seconds with a mixing tool speed of 50 U / min) evenly before the start of the experiment.

[Alternatively, 18 liters (2.5 kg) of expanded glass of particle size 8 - 16 mm from Dennert / Poverver GmbH (Germany).]

Subsequently, the following coating mass components are added in steps 1 to 3 with mixing times of 10 seconds and a mixing tool speed of 50 rpm.

1st addition: 620 g of aluminum monophosphate solution (Fabutit705 from Chemische Fabrik Budenheim, Germany)

2nd addition: 1570 g of anhydrous magnesium sulfate (K & S, Germany) 3. Addition: 1340 g of aluminum monophosphate premixed with 700 g of slate meal with a particle size of 90 μm

4. Addition: Hardener / foaming mixture consisting of 147 g of magnesium oxide and 100 g Omyacarb 15 (Omya, Germany). The addition of the hardener / foaming ergemisches takes place with a mixing time of 5 seconds and a speed of the mixing tool of 100 rev / min.

The coarse-grained expanded clay particles coated with the coating composition are filled into a sheet-metal mold under vibration for 10 seconds. The foamed and cured clay based on expanded clay has a density of 0.61 g / cm ³ . The alternative example with expanded glass particles gave a density of 0.356 g / cm ³ .

Remarks:

• Particles: As particles, expanded clay particles with a bulk density of 320 kg / m ³ and an experimentally determined void volume of 51 volume percent are used. Due to the absorbency of the expanded clay, it is recommended to set a defined material moisture content by adding 10% water by weight. [Alternatively: non-absorbent expanded glass particles with a bulk density of 140 kg / m ³ and an experimentally determined void volume of 45% by volume.]

Coating composition: This example describes the preparation of a hardened and foamed composition suitable for fire protection and follows the stoichiometric theory of almost complete neutralization of the secondary hydrogen atoms of the phosphoric acid groups described in AT 400 840 B / EP 0741 677. The method of internal water binding by anhydrous magnesium sulfate is described in patent AT 408 347 B. The amount of bound water (water of hydration) can be widely controlled by the addition of other hydrated fillers (e.g., gypsum, epsom salt) and contributes significantly to the fire protection properties. Furthermore, the addition of various additives, e.g. Wetting agent, occasionally recommended.

Process: The process parameters are particularly important because of the reactivity of the coating composition. In the mixing time of 5 seconds of the last addition stage about 2/3 of the hardener / foaming mixture used are implemented. The resulting in this mixing time foam is essentially crushed. The reacted parts of the hardener / foaming mixture cause above all a pre-crosslinking of the coating composition and thus an increase in viscosity, so that even a strong vibration of 10 seconds in the molding process does not lead to segregation between coating composition and particles. At an estimated fill level of void volume (20 liters, 0.51 = 10.2 liters) of 2/3 and a coating weight of 4477 g, an estimated foam density of (4477 g / ((2/3) .10.2 liters) is obtained ) = 0.66 g / cm 3. The resulting hardened mass is well suited for filling composite elements with metallic outer layers because of its excellent adhesion to metal surfaces and its high mechanical strength.

Example 3. Vermiculite and water glass as coating mass

Example of coarse particles with high specific surface area (expanded vermiculite). In a gentle, slow-running mixing process, the coating composition is applied. Foaming and hardening are started by microwave heating.

Experimental procedure:

20 g of distended vermiculite are mixed intimately with a mixture of 30 g of water glass 50/49 (50% by weight) + 1.2 g of sodium perborate (ground) + 7 g of Fabutit 277. The coated particles are placed by hand into a mold, lightly compressed and then heated with microwave energy at about 90 ⁰ C. This gives a molding density of 0.25 g / cm ³ to 0.27 g / cm ³ .

Remarks:

• Particles: Particles used are blown vermiculite (from KramerProgetha Deutschland) with a particle size of 3 mm to 15 mm, a bulk density of 100 g / liter and an experimentally determined void volume of about 60% by volume.

Coating composition: The coating composition used is a 50% strength by weight sodium waterglass solution (Henkel) (viscosity: 500-830 mPa.s), in which finely ground sodium perborate and the waterglass hardener Fabutit 277 (Chemische Fabrik Budenheim, Germany) are mixed.

• Procedure: Due to the large specific surface area of the expanded vermiculite, it is possible to work directly with the unfilled 50% by weight solution of waterglass to which only foaming agents and hardeners are added. Hardening and foaming are carried out with a waterglass hardener slow at room temperature and rapid microwave heating with sodium perborate. This gives a filling of the void volume of about 50 volume percent. Although only a volume reduction of about 12% over the original bulk volume of the expanded vermiculite and despite the low density of 0.27 g / cm ³ obtained compared to the waterglass bound vermiculite fireplates (0.35-0.50 g / cm ³ ), due to the foam structure of the silicate and quartz framework obtained very solid moldings.

Example 4.

Styrofoam particles and polyurethane foam

In the following, the bonding of coarse-grained polystyrene particles with a foaming polyurethane composition as a coating composition.

Experimental procedure:

3 g of polystyrene particles are mixed with a mixture of 3 g of component 1 (polyester) and 4.2 g of component 2 (isocyanate) for 30 seconds and cured under slight pressure.

Remarks:

• Particles: The polystyrene beads have a size of 3 mm to 5 mm, a bulk volume of 100 cm ³ / g and a void volume of 72 volume percent.

Coating composition: The coating composition used was the unfoamed polyurethane composition obtained by premixing components 1 ((EWIDUR PU foam h 1716, Ing.E.Wildschek & Co., Austria) and component 2 (diphenylmethane diisocyanate) in the mixing ratio of component 1 : Component 2 = 100: 140 was prepared and which produces a foam with a density of free foamed of 0.05 kg / m ³ at a starting time of about 60 seconds and a rise time of about 2.5 minutes used.

• Procedure: The entire foaming process was completed in about 5 minutes.

The volume of the shaped body is essentially given by the bulk volume of the polystyrene particles. The void volume is about 2/3 full. The density of the shaped body is 0.04 g / cm ³ .

Claims

Claims 1

Foamable, mouldable and hardening composition containing inorganic particles whose surfaces are at least partially coated with a foamable and curable coating composition.

Claim 2

Foamable, mouldable and hardening composition containing organic particles whose surfaces are at least partially coated with a foamable and curable coating composition.

Claim 3

Foamable, mouldable and hardening composition containing mixtures of inorganic and organic particles whose surfaces are at least partially coated with a foamable and curable coating composition.

Claim 4

Composition according to claims 1 and / or 3, characterized in that the mass contains inorganic dense particles, for example consisting of gravel, gypsum stone or other rocks, or mixtures thereof.

Claim 5

A composition according to claims 1 and / or 3 and 4, characterized in that the mass inorganic low-density particles, such as porous particles or hollow spheres, such as expanded clay, expanded glass, expanded, Perlite, inflated mica, distended vermiculite, volcanic rocks , Tuff, pumice, or corundum, chamotte, molochite, or glass balls, corundum hollow balls or mixtures thereof.

Claim 6

A composition according to claims 2 and / or 3 and 4 and 5, characterized in that the mass contains organic particles from the group of organic polymers, for example polystyrene, cork, wood chips, foam particles, Styrofoam particles or mixtures thereof. Claim 7

Composition according to claims 2 and / or 3, characterized in that the mass contains organic particles of various recycled materials belonging to the group of organic polymers, for example Styrofoam particles.

Claim 8

A composition according to claims 1 and / or 3, characterized in that the composition comprises as particles inorganic microspheres, for example of aluminum oxide, quartz, hafnium oxide, zirconium oxide or glass or organic microspheres, e.g. of polystyrene, PMMA, preferably with the particle size of from 0.2 to 0.6 mm, or mixtures thereof.

Claim 9

A composition according to claims 2 and / or 3, characterized in that the composition comprises inorganic nanospheres, for example of alumina, quartz, hafnia, zirconia or organic nanospheres, e.g. of polystyrene, PMMA, or mixtures thereof.

Claim 10

Composition according to claims 1 to 9, characterized in that the particles are preferably the grain sizes of 1 mm to 24 mm, to 50 mm or to a maximum of 100 mm, in particular grain size ranges, such as those between 4 mm and 12 mm, or preferably from 2 mm to 4 mm, 4 mm to 8 mm, 8 mm to 16 mm or 12 mm to 20 mm, as well as their mixtures or any other grain size ranges or selected in these ranges Einkornzusammensetzungen or that they are less than 1 mm in diameter, for example, diameter of 0, 2 mm to 0.6 mm or diameter in the nano or micro range.

Claim 11

Composition according to Claims 1 to 10, characterized in that the coating composition is predominantly inorganic, and a) a binder, such as phosphate-based, preferably aluminum monophosphate or magnesium phosphate, water-based, cement-based, gypsum-based, sorrel cement-based, etc. or optionally mixtures thereof and b) a hardening substance for inorganic binders, for example for aluminum monophosphate-soluble polyvalent metal oxides, their carbonates, for water glass, especially acid-removing hydrolyzers, for cement and gypsum water serves as a hardening substance, in sorrel cement magnesium oxide is hardened by magnesium salts, such as their chloride or sulfate, and c) a gas-evolving substance such as ammonium carbonates or alkali carbonates, polyvalent metal carbonates, aluminum powder, organic or inorganic peroxides, sodium perborate, hydrogen peroxide, etc. and d) optionally inorganic milled fillers such as kaolin, chalk, slate, mica, quartz and / or also optionally fine to coarse-grained hydrates, such as gypsum, gypsum, magnesium sulfate hydrate, aluminum sulfate hydrate, etc or organic fillers, such as starch, sugar, etc., and e) optionally flame retardants, such as hydrates of salts , preferably sulfates, phosphates or pyrophosphates or hydroxides of aluminum, magnesium, calcium, and f) optionally reinforcing fillers, such as inorganic or organic fibers, for example glass fibers, wood fibers, pulp fibers, plastic fibers, or rod-shaped fillers, such as wollastonite and g) optionally thixotropic acting substances, such as hydrophilic or hydrophobic colloidal or fumed silica, synthetic polymers having ionic and / or other associating groups, such as homopolymers and Copoplymere of acrylic acid, their alkali and ammonium salts, smectites, organically modified bentonites, montmorillonites, carboxymethyl cellulose and water-soluble melamine-formaldehyde resins or urea derivative resins, gelatin, hydroxypropylmethyl cellulose, ethylene oxides and propylene oxide copolymers, and h) optionally various additives, such as wetting agents, flow aids, curing retarders and i) optionally washing binding substances, preferably when using aqueous binders, such as calcium sulfate, magnesium sulfate, aluminum sulfate, various phosphates or pyrophosphates of alkali metals, magnesium and calcium, which form hydrates or contains water-reactive substances. Claim 12

A composition according to claim 1 to 10, characterized in that the coating composition is predominantly organic, and a) a binder, such as polyester, polyurethane, acrylates, epoxy resins, bituminous compounds, and b) a hardening substance, for example isocyanates, peroxides, epoxides, etc and c) a gas-evolving substance such as water in polyisocyanates, aluminum powder, organic or inorganic peroxides, sodium perborate, hydrogen peroxide, etc., and d) optionally inorganic ground fillers such as kaolin, chalk, slate, mica, quartz, etc. and / or also optionally fine to coarse-grained hydrates, such as gypsum, gypsum, magnesium sulphate hydrate, aluminum sulphate, etc. or also organic fillers, such as starch, sugar, etc. and e) optionally flame retardants, such as, for example, hydrates of salts or hydroxides of aluminum, magnesium, Calcium, etc. both finely ground or used as coarse-grained fillers, and f) optionally verst curative fillers, such as inorganic or organic fibers, for example glass fibers, wood fibers, cellulose fibers, plastic fibers, or rod-shaped fillers, such as wollastonite and g) optionally thixotropic substances, such as hydrophilic or hydrophobic colloidal or fumed silica, synthetic polymers with ionic and / or other their associating groups, such as homopolymers and copolymers of acrylic acid, their alkali and ammonium salts, smectites, organically modified bentonites, montmorillonites, carboxymethylcellulose and water-soluble melamine-formaldehyde resins or urea derivative resins, gelatin, hydroxypropylmethylcellulose, ethylene oxides and propylene oxide copolymers, and h) optionally Various additives, such as wetting agents, flow aids, Auscärtungsverzögerer and i) optionally water-binding substances such as calcium sulfate, magnesium sulfate, aluminum sulfate, various phosphates or pyrophosphates of alkali metal s, magnesium and calcium, which form hydrates or contain water-reactive substances. Claim 13

Hardened and foamed composition according to claims 1 to 12, characterized in that the void volume between the particles is substantially completely filled by the foamed mass.

Claim 14

Hardened and foamed composition according to claims 1 to 12, characterized in that the void volume between the particles is filled by the foamed mass in an adjustable percentage, for example 10%, 20%, 50%, 75% or 90% of the void volume ,

Claim 15

A cured and foamed composition obtainable by foaming and hardening the composition according to any one of claims 1 to 12, wherein the particles are in mechanical contact with each other substantially.

Claim 16

Process for producing a cured, foamed mass, characterized in that the composition according to one of Claims 1 to 12 is hardened and foamed.

Claim 17

A process for producing a cured, foamed mass, characterized in that the composition according to any one of claims 1 to 12 applied to a surface or filled in cavities or is used to fill composite elements and occasionally a compaction is connected with shaking.

Claim 18

A process for producing a cured, foamed mass, characterized in that organic or inorganic particles or mixtures thereof are at least partially coated with a foamable and curable coating composition, wherein in the foamable and curable composition an empty volume between the particles is maintained and the coating composition is a binder , a hardening substance, a gas-evolving substance and optionally fillers, flame retardants, reinforcing substances, thixotropic substances, various additives and water-binding substances, and in the first process step - the preparation of the coating composition and the coating of the particles with it - the coating composition is either prepared in advance in a separate vessel and as such is added to the particles in a mixer or by stepwise applying the individual components on the particle surfaces in one Mixer is prepared, wherein the dosage of the coating composition is such that after the curing and foaming process, the void volume between the particles is filled to a determinable extent, and used in the mixing process fast or slow running mixer in continuous or discontinuous mixing processes and in the second process step a shaping process, which immediately follows the mixing process or takes place at a later time, this mass containing the coating composition coated particles, preferably with shaking, in a mold, in a cavity or in composite elements te with, for example, metallic outer layers, such as panels or fire doors, is filled, or brought to a surface where it foams and cures in a third step - a foaming and curing process at rest to a predetermined extent or is brought to foaming and curing , and in a case by case fourth process step - a drying process - either by means of the mass-added water-binding substances or by sucking air through the molding or by standing in air, is subjected to drying and then the molded body is either removed from the mold or in remains in the cavity, in the mold, in the composite element or on the surface.

Claim 19

A process for producing a cured, foamed mass, characterized in that organic or inorganic particles or mixtures thereof are at least partially coated with a foamable and curable phosphate-based coating composition, wherein in the foamable and curable composition an empty volume between the particles is maintained and the mass according to the method is prepared so that it consists of at least two components, wherein one component contains the binder, preferably as a binder polyvalent Metal phosphate solutions, preferably Aluminiummonophosphatlösungen be used, and after the distribution of the binder component on the particle surfaces another component containing the hardening substance, in the form of reactive salts of polyvalent cations, such as magnesium oxide, and preferably also the gas-releasing substance, such as carbonates or hydrogen peroxide, is added in the mixing process in liquid or solid form, wherein the components according to the method are coordinated so that the curing of the coating composition by the almost complete neutralization of the secondary hydrogen atoms of the phosphoric acid groups, and as the next step, this curable and foamable composition , after its preparation, is filled into molds, cavities or composite elements, where it foams and hardens, preferably a subsequent drying of the hardened and foamed mass by in de R added water-binding substances or by sucking air through the molding or by standing in the air, and that occasionally subsequent demolding takes place, or the resulting molding remains in the cavity, in the mold, in the composite element or on the surface.

Claim 20

A method according to claims 16 to 19, characterized in that the foaming and curing either automatically takes place at room temperature or is started and carried out by heating, for example with thermal energy with heaters or with microwave or high frequency energy and that this process occasionally by a simultaneously or subsequently running drying process, either by hydrate formation either at room temperature or at elevated temperature, wherein a temperature range of 30 ⁰ C to 90 ⁰ C, preferably at 40 ⁰ C to 75 ⁰ C, is maintained, or by air suction through the molding or by standing at the Air slowly running automatically, is supplemented.

Claim 21

Use of the composition according to claims 1 to 12 and the cured and foamed composition according to claims 13 to 15 and the hardened compositions produced according to the processes described in claims 16 to 20 for the production of insulating material or fire protection material in the form of plates or any other shape Moldings or as filler in cavities. Claim 22

Use of the composition according to Claims 1 to 12 and the cured and foamed composition according to Claims 13 to 15 and the cured and foamed compositions produced according to the processes described in Claims 16 to 20, using inorganic particles, such as expanded glass, expanded clay, Expanded slate, expanded vermiculite and inorganic binder, preferably phosphate-based or silicate-based, occasionally using water-binding substances, preferably by hydrate formation, or with the addition of hydrates to increase fire resistance, for example gypsum or epsom salt, as molded parts and as casting compounds for filling composite elements, such as fire doors and panels, as well as backfill material for frames.

Claim 23

Use of the composition according to claims 1 to 12 and the cured and foamed composition according to claims 13 to 15 and the cured and foamed compositions produced according to the methods described in claims 16 to 20, using correspondingly light inorganic or organic particles, such as on the basis of expanded glass, expanded vermiculite or based on organic polymers, for example polystyrene particles, and binders, preferably based on phosphate or silicate or based on organic polymers, for example polyurethane base, as masses and as moldings for the insulation sector in the form of plates or other moldings and as filling material in cavities, for example in the construction industry for wall and ceiling components or for the filling of composite elements, such as in panels and doors.

Claim 24

Use of the composition according to claims 1 to 12 and the cured and foamed composition according to claims 13 to 15 and the cured and foamed compositions produced according to the processes described in claims 16 to 20, using light inorganic or organic particles such as expanded glass or styrene particles and inorganic or organic binders, for example based on polyurethane or aluminum phosphate, as masses and as shaped articles in household appliances. Claim 25

Use of the composition according to claims 1 to 12 and the cured and foamed composition according to claims 13 to 15 and the cured and foamed compositions produced according to the methods described in claims 16 to 20, using correspondingly high temperature solid particles such as corundum particles, hollow spherical corundum or Aluminiumoxidmicrospheres and high temperature resistant binder, preferably based on aluminum phosphate, as a mass and as a shaped body for the high temperature range from 600 ⁰ C to 2200 ⁰ C, preferably in the range of 900 ⁰ C to 1450 ⁰ C and 1450 ⁰ C to 1750 ⁰ C used, for example in ovens and heating systems for industry, commerce and household.

Claim 26

Use of the composition according to claims 1 to 12 and the cured and foamed composition according to claims 13 to 15 and of the cured and foamed compositions produced according to the processes described in claims 16 to 20 as packaging material.