WO2006094512A2

WO2006094512A2 - Improving resistance against open fire and firing

Info

Publication number: WO2006094512A2
Application number: PCT/DK2006/000144
Authority: WO
Inventors: Christian Wille; Sten Nielsen; Inge Merete Lund
Original assignee: Stenca Trading A/S
Priority date: 2005-03-11
Filing date: 2006-03-13
Publication date: 2006-09-14
Also published as: WO2006094512A3

Abstract

Improving the resistance of polymeric organic materials to adverse actions of high temperatures, especially to fire, e.g. open fire, flames, e.g. flame spread, through methods and/or compositions in which, before solidification, the polymeric organic material is mixed with waste residues originating from desulphurisation of flue gasses and/or with mixtures of calcium hydroxide and calcium sulphite hemi hydrate, possibly added smaller amounts of other comminute inorganic materials comprising crystal water.

Description

Improving resistance against open fire and firing

The invention concerns a method for improving resistance against open fire and firing of organic materials, especially to organic polymeric materials, especially of porous organic polymeric materials, most especially of foamed polyurethane, using waste residue from the desulphurisation of flue gasses from incinerators, such as DDSW(Dry DeSulphurisation Waste Product) and/or a mixture of calcium hydroxide and calcium sulphite hemi hydrate, which method may be further improved through the application of a skin on specimens produced.

Furthermore, the invention concerns a composition of materials comprising waste residue from the desulphurisation of flue gasses from incinerators, such as DDSW (Dry DeSulphurisation Waste Product) and/or a mixture of calcium hydroxide and calcium sulphite hemi hydrate aiming at improving the resistance to open fire and firing of organic material, especially of polymeric organic material, especially of porous polymeric organic material, most especially of foamed polyurethane, the efficiency of which composition may be further improved through the application of a skin on specimens produced designing the composition to the use of such skin.

Organic polymeric materials are made from organic components being flammable or combustible materials. Though the size of the polymeric chains is increased during a polymerisation process, they will still be inflammable or combustible. Often such flammability or combustibility will be acceptable during the use of such materials. Often such flammability is directly desirable; i.e. in such cases where the materials are to be disposed of, as the calorific value of the materials may be utilised. In such cases the detour to the polymeric state may barely be considered a postponement of the use of the basic material for heating or other pyrolytic purposes.

However, in some cases the flammability of organic polymeric materials is undesired, e.g. in cases where the organic polymeric material during the period from polymerisation to disposing of by humans is intended to be used for technical or consumption purposes. In some unintended circumstances, temperatures exceeding the evaporation or decomposition temperature of the polymeric material may arise during the use of the organic polymeric material causing release of flammable gases. Releasing flammable gases, e.g. above the evaporation or decomposition temperature, the organic gases or fumes released may be set on fire or ignited through open fire or sufficiently high temperatures (exceeding the self ignition temperature of the released organic gases or fumes in question). It is characteristic of organic polymeric materials that their evaporation or decomposition temperature is low compared to that of most inorganic materials. From ancient time man has got used to handle inorganic materials and, therefore, has become used to employ open fire - presumably a prerequisite for the fact that man has differed from primates.

Organic polymeric materials have a number of advantages as to use; e.g. they are of the same nature as the building elements in the human body, they are light, flexible, are often highly able to insulate thermally against heat/cold and electrical currents, they are easy to produce and process, and they show a good workability, e.g. they posses a rather high tensile strength and a small hardness and brittleness.

However, the organic polymeric materials are most often characterised by their ability to add to a fire. In the service of man this will be desirable only at the stage of the planned disposal of the materials. However, in extreme cases, during use, the materials may be exposed to such temperatures that they will add to a fire. I order to control the behaviour of such organic polymeric materials under severe exposures man tries to reduce the ability of such organic polymeric materials to feed a fire during their application. Using known technology, this reduction in flammability is often achieved using flame retarders of organic nature, e.g. bromides, and/or pure inorganic materials comprising crystalline water or the like.

Using flame retarders of organic nature, e.g. in form of halogens, an undesired adverse effect is most often observed as these organic materials will be released through time and/or during a fire. Such released matter most often causes etching attacks on surroundings and/or causes health problems and/or causes adverse effects on the environment during its disposal.

Through the use of flame retarders of inorganic nature, such as pure inorganic materials comprising crystal water, most often the same adverse effects as observed in case of using the organic flame retarders are not observed, but most often the inorganic flame retarders are expensive, e.g. because they are produced solely for this use.

A special aspect of the present invention concerns a method, without the use of the customary flame retarders in the form of Halogens, e.g. Bromides, or the like and without the use of the customary inorganic flame retarders, to impart an improved resistance to organic polymeric materials against the influence from such temperatures that would otherwise expose such materials to suffer from thermally induced evaporation/degradation that would cause a risk of combustion/burning in case of open fire and/or increased temperatures, characterized in that during mixing of the organic material before solidification/polymerisation is added a waste residue from the desulphurisation of smoke/flue gasses, e.g. from power plants, from incineration plants for generating heat and/or electricity, e.g. plants incinerating household rubbish, from other combined heat- and electricity generating plants, e.g. incinerating coal, straw or wood, from other power plant like systems, or from domestically heating incinerators and the like. The special aspect of the invention is achieved through a method in which the organic material is intimately mixed with a waste residue from the desulphurisation of flue gasses from incinerators, such as DDSW (DeSulphurisation Waste Product) which is most often achieved from the spray drying of a watery slurry of Calcium hydroxide (lime), possibly comprising Calcium carbonate (chalk), into the flue gasses deriving from power plants and/or incinerators, the slurry being sprayed into the flue gasses from incinerating fossil and/or other organic solid or liquid fuels, whereby a reaction between Calcium hydroxide (Ca(OH)₂) and Sulphur dioxide (SO₂) in the flue gasses takes place resulting in the formation of Calcium sulphite hemi hydrate (CaSO₃^¹Z-H₂O)) and/or a mixture of Calcium hydroxide and calcium sulphite hemi hydrate. The possibility of using mixtures of Calcium hydroxide and Calcium sulphite hemi hydrate has not yet been proven, but according to the above it will be obvious that such a mixture should perform in the same manner as do DDSW. Probably, such artificially produced mixtures will not be of commercial interest - except from situations in which the amount of DDSW accessible is insufficient. The special aspect of the invention may be achieved through a method, in which the organic material during mixing before solidification in excess of a waste residue resulting from the desulphurisation of flue gasses from power plants and/or incinerators and/or a mixture of calcium hydroxide and calcium sulphite hemi hydrate possibly is added a smaller amount of another comminute inorganic material comprising crystal water or the like. The special aspect of the invention may be achieved through a method in which beforehand mixing of solidification is performed through an intimate combining process, where the term intimate combining process relative to a simple mixing process is characterised through mixing at relatively high shear strain rates in the material to be mixed, e.g. preferably using mixers with forced action compared to mixers with a free falling action (both types of mixers are known from the concrete industry), where mixing in a ball mill is preferred to mixing through simple tumbling of the material in an otherwise empty tumbling container, where mixing in a turbine is preferred to the simple and slower method of rotating a paddle in an open container, or where other high-intensity mixing is preferred to mixing using simple stirring by hand, e.g. using a spoon or the like. It should be a characteristic that by the intimate combining used will be obtained a material in which the inorganic particles are distributed in the organic material in a homogeneous way when observing units of volumes above 1 mm³. Observing units of volumes less than 1 mm³ will not be relevant as the preferred inorganic particles may have dimensions above 100 μm (0.1 mm). The special aspect of the invention may be achieved through a method, in which the intimate mixing is performed using one or more organic material(s), comprising an artificially produced plastic material, either in the form of a thermoplastic material, e.g. PE, PETP, PTFE, PP and others, or especially a thermoplastic material, e.g. epoxy, polyester, melamine, carbonate, acrylate and others, as well as silicones of all kinds, in which hardening is achieved through influence of chemicals, thermal action, or in another way, which plastic material may be mixed with bigger or smaller amounts of inorganic or organic 5 admixtures or additives, e.g. in the form of 1-, 2-, and/or 3-dimensional particles (fibres, flakes and/or spheres), e.g. in order to achieve changes in properties of the plastic material, e.g. with respect to rigidity and/or strength. Fibres, flakes, and/or spheres may often have a varied cross-sectional area. Another benefit from using waste residues according to the present invention is that the particles introduced will help in reinforcing 10 the organic polymeric material.

The special aspect of the invention may be achieved through a method in which the mixture of organic material comprising the waste residue (e.g. DDSW and/or the mixture of calcium hydroxide and calcium sulphite hemi hydrate or the like) is used for the production of a foamed end product.

15 The special aspect of the invention may be achieved through a method in which the mixture of organic material comprising the waste product is used for the production of a porous material from PUR (PolyURethane).

The special aspect of the invention may be achieved through a method in which, in addition to at least 25% by weight, preferably at least 50% by weight, more preferably at least

20 75% by weight, even more preferably at least 85% by weight, most preferably at least 95% by weight of a waste residue resulting from the desulphurisation of flue gasses from power plants and/or other incinerators, is used another finely comminute inorganic material, which material is achieved from natural deposits, such as gypsum, clay minerals, mica minerals, plagioclase minerals and the like, or which material is achieved from human

25 activities, such as gypsum (calcium sulphate dehydrate), calcium sulphate hemi hydrate, hydrated cement (of all types, such as Portland cement, aluminate cement and/or the like) and the like, or other inorganic materials comprising crystal water, or other inorganic materials, which during heating will absorb a high specific amount of energy in another way or in other ways.

30 The special aspect of the invention may be achieved through a method in which is used a comminute inorganic material comprising crystal water or the like, which comminute material is selected according to the type of organic material to which it is to be mixed. Preferably should be used comminute inorganic material comprising crystal water, which will be released from the inorganic material at temperatures below 800⁰C, preferably below

35 700⁰C, more preferably below 600⁰C, even more preferably below 500⁰C, most preferably below a temperature at which the organic polymeric material suffers from evaporation/ degradation, preferably below 90%, and more preferably below 80% of the temperature at which the organic polymeric material suffers from evaporation/degradation, the latter temperature being measured as absolute temperature, e.g. in K (degrees Kelvin).

The special aspect of the invention may be achieved through a method in which is used a comminute inorganic material selected after its ability to reduce the evaporation /degradation of PUR.

A further special aspect of the invention may be achieved through a method in which the surface or the surfaces, which during application/use in extreme cases may be expected to be exposed to temperatures at or above the temperature of evaporation/degradation of the organic polymeric material in use, is covered with a skin, preferably such a skin which can resist the temperatures to which the surface/surfaces are exposed, or such a skin which is made from a silicone or the like and inorganic fibres from a material, which may resist the temperatures, to which the surface is/the surfaces are exposed, more preferably such a skin which is made from a silicone and glass fibres, most preferably such a skin which is made from a silicone and a weave of glass fibres. It is assumed that the effect of this skin is legio, among others the effect of reducing the evaporation from the heated organic material, and the effect of holding the material mechanically together (reinforcing the material) in the area around an acting flame, in which area the flame will cause a certain non-insignificant shearing action on the organic material.

The further special aspect of the invention may be achieved through a method in which the skin itself has achieved an improved resistance to fire according to the invention, preferably in which the skin is made from silicone, preferably a two-component silicone, preferably in which the improved resistance to fire is achieved through the use of DDSWDDSW (Dry DeSulphurisation Waste Product DDSW).

Another special aspect of the invention may be achieved through the use of a composition, not using flame retarders of traditional kind, such as Halogens, e.g. Bromides, or the like, and not using traditional inorganic flame retarders, which composition will give organic polymeric materials an improved ability to resist influences from such temperatures, which would otherwise make such materials vulnerable to evaporation/degradation caused by temperature, resulting in a risk of flammability under the influence of open fire and/or increased temperatures, characterised by adding a waste residue to the organic material during mixing prior to solidification, which waste residue is achieved during desulphurisation of smoke/exhaust gasses, e.g. from power plants, from incineration plants for generating heat and/or electricity, e.g. plants incinerating household rubbish, from other combined heat and electricity generating plants, e.g. incinerating coal, straw or wood, from other power plant-like systems, or from domestically heating incinerators and the like. The special aspect of the invention may be achieved through the use of a composition which is made from intimately mixing the organic material with a waste residue from the desulphurisation of flue gasses from incinerators, such as DDSW (DeSulphurisation Waste Product) DDSW which most often derives from the spray drying a watery slurry of Calcium hydroxide (lime), possibly comprising Calcium carbonate (chalk) with flue gasses from power plants and/or incinerators, the slurry being sprayed into the flue gasses from incinerating fossil and/or other organic solid or liquid fuels, whereby a reaction between Calcium hydroxide (Ca(OH)₂) and Sulphur dioxide (SO₂) in the flue gasses takes place resulting in the formation of Calcium sulphite hemi hydrate (CaSO₃^¹Z-H₂O)) and/or a mixture of calcium hydroxide and calcium sulphite hemi hydrate. The possibility of using mixtures of Calcium hydroxide and Calcium sulphite hemi hydrate has not yet been proven, but according to the above-mentioned, it will be obvious that such a mixture should perform in the same manner as DDSW. Such artificially produced mixtures will probably not be of commercial interest - except from situations in which the amount of DDSW accessible is insufficient.

The special aspect of the invention may be achieved through the use of a composition in which a mixture of waste residue resulting from the desulphurisation of flue gasses, and/or a mixture of calcium hydroxide and calcium sulphite hemi hydrate, and possibly minor amounts of added comminute inorganic material comprising crystal water, or the like, is added to the organic material during mixing before solidification, and where the added mixture of waste residue, and/or the mixture of hydroxide and sulphite hemi hydrate, and possibly other comminute inorganic material comprising crystal water, may be pre-mixed or pre-treated with the purpose of adding each material separately.

The special aspect of the invention may be achieved through the use of a composition which is made through intimate combining of the added materials, where the term intimate combining process relative to a simple mixing process is characterised through mixing at relatively high shear strain rates in the material to be mixed, e.g. preferably using mixers with forced action compared to mixers with a free falling action (both types of mixers are known from the concrete industry), where mixing in a ball mill is preferred to mixing through simple tumbling of the material in an otherwise empty tumbling container, where mixing into a turbine is preferred to simple and slower rotating a paddle in an open container, or where other higher intensity mixing is preferred to mixing using simple stirring by hand, e.g. using a spoon or the like.

It should be a characteristic that by the employed intimate combining, a material will be obtained in which the inorganic particles are distributed in the organic material in a homogeneous way when observing units of volumes above 1 mm³. Observing units of volumes less than 1 mm³ will not be relevant as the preferred inorganic particles may have dimensions above 100 μm (0.1 mm). The special aspect of the invention may be achieved through the use of a composition comprising a mixture of a waste residue or the like and one or more organic material(s), comprising an artificially produced plastic material, either in the form of a thermoplastic material, e.g. PE, PETP, PTFE, PP, and others, or especially a thermoplastic material, e.g. epoxy, polyester, melamine, carbonate, acrylate and others, as well as silicones of all kinds, in which hardening is achieved through influence of chemicals, thermal action, or in another way, which plastic material may be mixed with bigger or smaller amounts of inorganic or organic admixtures or additives, e.g. in the form of 1-, 2-, and/or 3- dimensional particles (fibres, flakes and/or spheres), e.g. in order to achieve changes in properties of the plastic material, e.g. with respect to rigidity and/or strength. Fibres, flakes, and/or spheres may often have a varied cross-sectional area. Another benefit from using waste residues according to the present invention is that the particles introduced will help in reinforcing the organic polymeric material.

The special aspect of the invention may be achieved through the use of a composition in which the mixture of organic material comprising the waste residue (DDSW and/or the mixture of calcium hydroxide and calcium sulphite hemi hydrate, or the like) is used for the production of a foamed end product.

The special aspect of the invention may be achieved through the use of a composition in which the mixture of organic material comprising the waste product is used for the production of a porous material from PUR (PolyURethane).

The special aspect of the invention may be achieved through the use of a composition in which is used a waste residue resulting from the desulphurisation of exhaust gasses from power plants and/or other incinerators, in excess of at least 25% by weight, preferably at least 50% by weight, more preferably at least 75% by weight, even more preferably at least 85% by weight, most preferably at least 95% by weight, or in which is used another finely comminute inorganic material, which material is achieved from natural deposits, such as gypsum, clay minerals, mica minerals, plagioclase minerals and the like, or which material is achieved from human activities, such as gypsum (calcium sulphate dehydrate), calcium sulphate hemi hydrate, hydrated cement (of all types, such as Portland cement, aluminate cement and/or the like) and the like, or other inorganic materials comprising crystal water, or other inorganic materials, which during heating will absorb a high specific amount of energy in another way or in other ways.

The special aspect of the invention may be achieved through the use of a composition in which is used a comminute inorganic material comprising crystal water or the like, which comminute material is selected according to the type of organic material to which it is to be mixed. Preferably should be used comminute inorganic material comprising crystal water, which will be released from the inorganic material at temperatures below 800⁰C, preferably below 700⁰C, more preferably below 600⁰C, even more preferably below 500⁰C, most preferably below a temperature at which the organic polymeric material suffers from evaporation/degradation, preferably below 90%, and more preferably below 80% of the temperature at which the organic polymeric material suffers from evaporation/degradation, the latter temperature being measured as absolute temperature, e.g. in K (degrees Kelvin).

The special aspect of the invention may be achieved through the use of a composition in which is used a comminute inorganic material selected after its ability to reduce the evaporation/degradation of PUR. A further special aspect of the invention may be achieved through the use of a composition, characterised in that the surface or the surfaces, which during application/use in extreme cases may be expected to be exposed to temperatures at or above the temperature of evaporation/degradation of the organic polymeric material in use, is/are covered with a skin, preferably a skin which comprises a waste residue or the like, and which can resist the temperatures to which the surface or surfaces is/are exposed, or a skin which is made from a silicone, comprising a waste residue or the like, and inorganic fibres from a material, which may resist the temperatures to which the surface or surfaces is/are exposed, more preferably a skin which is made from a silicone and glass fibres, most preferably a skin which is made from a silicone, comprising a waste residue or the like, and a weave of glass fibres. It is assumed that the effect of this skin is legio, among others the effect of reducing the evaporation from the heated organic material, and the effect of holding the material mechanically together (reinforcing the material) in the area around an acting flame, in which area the flame will cause a certain significant shearing action on the organic material. A further special aspect of the invention may be achieved through the use of a composition, characterised in that the skin itself has achieved an improved resistance to fire according to the invention, preferably in which the skin is made from silicone, preferably a two-component silicone, preferably in which the improved resistance to fire is achieved through the use of a waste residue from the desulphurisation of flue gasses from incinerators, such as DDSWDDSW (Dry DeSulphurisation Waste Product DDSW).

Until now the achievement of improvements in resistance to thermally induced evaporation and degradation in organic polymeric materials has been obtained through addition of flame retarders in the form of Halogens, e.g. Bromides, or the like, which flame retarders have proven to possess the drawback that during ordinary use of the flame-retarded organic polymeric material they release such gasses that are hazardous to human activities. Furthermore, most of the flame retarders used so far often cause formation of so-called greenhouse gasses or lead to increased acidity to the atmosphere, e.g. through deposing of the material by means of burning processes. Thus, the use of such flame retarders must be worrying when considering effects to man and the environment. Recent interests in the media about the environmental effects from flame retarders on man and environment demonstrate this concern. Therefore, during the last couple of decades, alternative methods of achieving flame retardation have been devised, primarily through the use of comminute inorganic materials comprising crystal water. However, such technology has never been widely used, either because the efficiency is not very good, or because the technology is too expensive.

During use of the organic polymeric materials according to the present invention, a release to the environment will be only of such gasses that are characteristic to the organic polymeric material, which gasses may only be avoided if an alternative (organic polymeric) material is used, and possibly such gasses which are harmless to man, e.g. predominantly consisting of water vapour, as evaporations from waste residues from flue gasses, such as DDSWDDSW (Dry DeSulphurisation Waste Product DDSW), and/or mixtures of calcium hydroxide and calcium sulphite hemi hydrate, possibly added smaller amounts of comminute inorganic materials comprising crystal water, will take place through the release of the crystal water or water which is physically bound in the inorganic materials, which release will result in the formation of water vapour. It should however be admitted that some types of comminute inorganic materials, including the materials preferred according to this invention, will degrade thermally releasing also other gasses, e.g. carbon dioxide during the decomposing of chalk, or sulphuric dioxide during the decomposing of gypsum and/or calcium sulphite hemi hydrate. However, the temperatures at which such decomposing takes place will be well above the temperatures at which crystal water is released, and furthermore such decomposing gasses do not add to a fire (in some cases may even be used as fire extinguishers), and such decomposing gasses are not directly poisonous to man for short periods of exposure.

The special aspects achieved according to the invention are believed to be explainable in that a high absorption of energy of an inorganic material intimately incorporated into the organic polymeric material when heated unintentionally will reduce the heating rate of the combined/composite material; the higher the content of the inorganic material, the higher will be the reduction of the heating rate, and thereby the extent of the area damaged during the addition of a certain amount of heat will be reduced.

Specifically, when using inorganic materials having a high specific energy absorption, where the high energy absorption is achieved through the use of inorganic materials comprising crystal water, including the waste residues preferred in this invention, the special aspect, achieved according to this invention, may be explained by that the decomposition of crystal water most often takes place through an endothermic (heat consuming) process, whereby the amount of energy, which will be "available" for a thermal degradation of the organic polymeric material, will be reduced further.

In this context the term crystal water also comprises other sorts of water bound in the inorganic material, which water will not be released until heated, and then released through an endothermic process, e.g. the physically bound water in hydrated cement paste.

In this context the term organic polymeric material generally means an organic material of a specific composition as well as an organic material made through mixing more organic materials, each being of a specific composition, and co-polymeric materials. Such organic materials may or may not comprise inorganic components, e.g. extenders, reinforcing elements, such as particles, flakes, fibres, and other constituents.

A method for producing an organic polymeric material with improved resistance against thermal degradation according to the present invention can be described as follows: 500 cl Isocyanate (Make: Edulan, Type 99), 625 cl Polyol (Make: Edulan, Type C 1900-5), 500 g DDSW (DeSulphurisation Waste Product, Studstrupvaerket in Denmark), 150 g Portland cement and 150 cl dispersing agent are mixed by means of a high speed rotating whisk mounted in a drilling machine, after which, in a traditional way, the material is poured into a mould with adequate abutments in order to achieve a density as desired.

A composition for the production of an organic polymeric material with improved resistance against thermal degradation according to the present invention can be described as follows: 500 cl Isocyanate (Make: Edulan, Type 99), 625 cl Polyol (Make: Edulan, Type C 1900-5), 500 g DDSW (DeSulphurisation Waste Product, Studstrupvaerket in Denmark), 150 g Portland cement and 150 cl dispersing agent. This composition is mixed by means of a high speed rotating whisk mounted in a drilling machine. The material may, in a traditional way, be poured into a mould with adequate abutments in order to achieve a density as desired.

The invention is further explained in the following.

Figure 1 is a photo of a laboratory set-up for testing against fire of specimens from a plastic material or the like. The specimen is positioned against a L-shaped profile, made from aerated concrete, while a gas flame, originating at a distance of approximately 5 100 mm from the surface of the specimen, acts on the specimen. The gas is of a type having a flaming temperature of approximately 1750⁰C. During a testing sequence of 10 min., possible formations of flames and smoke are observed, and eventually damages are determined.

Figure 2 is a photo of the laboratory set-up during testing against fire of a plane specimen 0 of foamed PUR, produced in accordance with example 3 of the present invention.

Figure 3 is a photo of a plane specimen after testing against fire, the specimen being made from foamed PUR according to example 3 of the present invention.

Figure 4 is a photo of a laboratory set-up for testing against fire of tube-shaped specimens from a plastic material or the like. The specimen is positioned against an L-shaped profile, 5 made from aerated concrete, while a gas flame, originating at a distance of approximately 100 mm from the surface of the specimen, acts on the specimen. The gas is of a type having a flaming temperature of approximately 1750⁰C. During a testing sequence of 10 min., possible formations of flames and smoke are observed, and eventually damages are determined. 0 Figure 5 is a photo of a tube-shaped specimen after testing against fire, the specimen being made from foamed PUR according to example 4 of the present invention. Please observe that the tube has been cut through in the centre of flame action on the surface; this is further described in Figure 6.

Figure 6 is a photo of a tube-shaped specimen after testing against fire, the specimen 5 being made from foamed PUR according to example 4 of the present invention. The tube has been cut through in the centre of flame action on the surface; both halves are shown. Please observe that the area adversely heated did not penetrate the wall of the tube.

Figure 7. a is a photo of the two plates of glass-fibre reinforced polyester, ready to be tested in fire. In the photo, the specimen to the left is the material without DDSW, 0 mentioned in example 8, while the specimen to the right is the material with DDSW, mentioned in example 7.

Figure 7.b is a photo during start-up of firing action on the specimen without DDSW. Figure 7.c is a photo of the same specimen just after turning off the firing flame.

Figure 7.d is a photo of the specimen with DDSW taken during action on the specimen with 5 the gas flame. Figure 7.e is a photo of the specimen with DDSW taken shortly after turning off the gas flame.

Figure 7.f is a photo of both specimens taken shortly after taking the photo 7.e - that is shortly after turning off the flaming action on the sample with DDSW and at least 10 min. after turning off the flaming action on the sample without DDSW, still burning.

Figure 7.g is a photo of the specimen without DDSW after a renewed firing with the gas flame; it does not flame, while the specimen without DDSW still burns, even more intensely than before, which is further illustrated in figure 7.h.

In Figure 7.i both specimens are shown at a time when all polyester in the specimen without DDSW has been burned out. Still nothing more has happened to the specimen with DDSW, although a renewed firing using the gas flame was attempted, and although the specimen without DDSW continuously burned with an open flame at a distance of approximately 80 mm from the specimen with DDSW.

In Figure 7.j the back-sides of the two specimens tested are shown. It is observed that the gas flame has not penetrated the specimen with DDSW during the flaming action for 10 min., not even after the attempted renewed firing.

From notes made during the firing tests it was observed that DDSW quite effectively improves the resistance to open fire on specimens made from polyester: while a specimen not comprising DDSW burns completely on its own, an approximately 2 mm thick sheet of glass-fibre reinforced polyester comprising DDSW did not suffer from penetration after 10 minutes of action of a gas flame at a temperature of 1750°C, not even after a renewed short flaming action.

Figure 8 is a photo of a skin made from glass-fibre reinforced silicone comprising DDSW during influence from the gas flame, approximately 8 min. after initiating the flaming action. The skin lies close to the plate behind, which plate was made from calcium silicate from the company Skamol, type SuperPro 300.

Figure 9 is a photo of a skin made from glass-fibre reinforced silicone not comprising DDSW during influence from the gas flame, approximately 8 min. after initiating the flaming action. The skin is seen to be glowing much more than the skin comprising DDSW, cf. Figure 8. In this case, the skin lies closely against the plate behind.

Figure 10. a is a photo of two skins; the left without and the right with DDSW. The skin without DDSW was penetrated during the firing for 10 min. while the skin with DDSW was not penetrated. Casually the skin without DDSW was wrinkled slightly - causing a small distance between the skin and the plate behind - this small distance possibly allowing the material to be "blown away". Figure 10. b is a photo of a skin made form glass-fibre reinforced silicone comprising DDSW after a flaming action for 8 min. - the skin being supported so that there is a gap of approximately 20 mm between the skin and the thermally insulating plate of calcium silicate lying behind. It should be noticed that the centre of the area exposed to the flame was not "blown away".

Figures 11 to 15 show results from fire testing bars made from Edulan - being expanded PUR - covered with glass-fibre reinforced silicone. In the left photo is shown notes made during testing. In the middle photo is shown cross-sections after fire testing. In the photo to the right is shown one half of the bars after fire testing and cutting through. Fig 11 shows the results for specimen 1900-12-690.

Fig 12 shows the results for specimen 1900-12-660.

Fig 13 shows the results for specimen 1300-12-440.

Fig 14 shows the results for specimen 1900-13-645.

Fig 15 shows the results for specimen 1900-13-620.

EXAMPLES

Figure 1 shows a sketch of a laboratory set-up for thermal action on an organic polymeric foamed material, in which set-up a gas flame having a temperature of 175O⁰C is placed at a distance of 100 mm from a surface of the organic polymeric foamed material. The surface may be free, or it may be covered with a skin made from a weave of glass fibres, impregnated with silicone. Normal testing procedure for organic polymeric materials to be termed having a good resistance against open fire requires that the material can resist this action for at least 10 min. without bursting into self maintained fire.

Figure 4 shows a sketch of a set-up for similarly thermal action on a tube formed specimen. It should be observed that the set-up is a modified version of the set-up described in "IMO Resolution MSC 61 (67): Annex 1, Part 5", "Surface Flammability Test". IMO means International Maritime Organization.

Example 1.

If this set-up is used for testing resistance against open fire of a traditional foamed PUR, the PUR material will burn and continue to do so after the gas flame is removed.

Example 2.

Through high speed mixing of the materials added together, a foamed PUR is produced, comprising 500 cl Isocyanate (Make: Edulan, Type 99), 625 cl Polyol (Make: Edulan, Type C 1900-5), 500 g DDSW (Dry DeSulphurisation Waste Product, Studstrupvaerket in Denmark), 150 g Portland cement and 150 cl dispersing agent. The mixture is poured into a mould with abutments in order to achieve a density as desired (or almost). After curing, a test element in the form of a prism is cut out of the material. Dimensions of test prism: LxWxH = 1000x100x40 mm. The test prism is placed in accordance with the test specification in a steel holder in such a way that the surface having the width 100 mm is facing the gas burner.

Example 3.

Through high speed mixing of the materials added together, a foamed PUR is produced, comprising 500 cl Isocyanate (Make: Edulan, Type 99), 625 cl Polyol (Make: Edulan, Type C 1900-5), 500 g DDSW (Dry DeSulphurisation Waste Product, Studstrupvaerket in

Denmark), 150 g Portland cement and 150 cl dispersing agent. The mixture is poured into a mould with abutments in order to achieve a density as desired (or almost), in which mould one of the faces having a width of 100 mm is covered with a skin comprising a glass weave impregnated with silicone. After curing, a test element in the form of a prism is cut out of the material. Dimensions of test prism: LxWxH = 1000x100x40 mm. The test prism is placed in accordance with the test specification in a steel holder in such a way that the surface having a skin of glass weave impregnated with silicone is facing the gas burner. Figure 2 shows a sketch of a set-up for thermal action on a plane sheet of this material during testing. Figure 3 shows this plane sheet after foaming. Example 4.

Through high speed mixing of the materials added together, a foamed PUR is produced, comprising 500 cl Isocyanate (Make: Edulan, Type 99), 625 cl Polyol (Make: Edulan, Type C 1900-5), 500 g DDSW (Dry DeSulphurisation Waste Product, Studstrupvcerket in Denmark), 150 g Portland cement and 150 cl dispersing agent. The mixture is poured into a mould with abutments in order to achieve a density as desired (or almost), which mould forms a tube shape having its outer surface covered with a skin made from a glass weave impregnated with a silicone. After curing of the tube-shaped specimen, the specimen is placed according to testing specifications in a steel holder in such a way that the silicone- impregnated glass weave is facing the gas burner. Figures 4, 5 and 6 show the specimen produced during testing for thermal resistance. In Figure 4 the set-up is shown before thermal action. In Figures 5 and 6 the specimen is shown after testing and after cutting through the affected area. In Figure 5 the two halves are shown held together in position as during testing. In Figure 6 the tube-shaped specimen is shown in such a way that the cross-sectional area containing the thermally affected area appears. It should be observed that the inner surface of the tube has not been damaged at ali. Results after 10 min. action of gas flame at 1750⁰C:

Comparing examples 2 - 4 to example 1 shows that the use of DDSW in a foamed PUR is able to prevent the material to feed a fire. Through the use of a skin made from a silicone- impregnated glass weave, the gasses released during the firing action are prevented from getting into contact with the open gas flame thus causing a rather intense smoke development, which smoke finds its way out, typically through tunnels between the foamed PUR and the skin added. From example 2 it appears that the gasses released during contact with the acting gas flame will burn so that the gas residues are almost free from smoke (unburned gasses). In any case, the ability of the material to sustain a fire is prevented through the use of DDSW.

Through observation of the firing tests it was noted that in the vicinity of the point of acting gas flame a charring of the foamed PUR took place. For all materials comprising DDSW, during the 10 min. in which the gas flame was acting on the surface at a temperature of 1750⁰C, a charring of the foamed PUR took place. The charred material is blown away in the centre by the applied gas flame. Thus, after 10 min. an open wound results, the wound being approximately 20 mm in diameter and about 10 mm deep. The back side of the test specimen having a thickness of 40 mm never exceeds a temperature allowing touching by hand (evaluated to be below 40°C). Around the open wound of approximately 20 mm appears an area having a diameter of approximately 40 mm being quite white, the (surface) material in which area is easily removed when touching. Around this area is observed another area with a diameter being approximately twice as big (approximately 80 mm), which area is clearly darker than the original material.

The fact that the action of the gas flame can cause a discoloration of the material over an area with a diameter of approximately 80 mm while the temperature on the back side of the specimen, approximately 40 mm from the acting gas flame, does not rise significantly, indicates that the use of DDSW is able to improve the resistance against firing of the organic materials and even in such a way that the temperature is reduced. Example 5.

Through high speed mixing of the materials added together, a skin of a silicone- impregnated glass non-woven is produced, comprising 500 g component A (Make: Wacker Silicone, Type Kautschuk RTV-E, Component A), 50 g component B (Make: Wacker Silicone, Type Kautschuk RTV-E, Component B) and 500 g DDSW (Dry DeSulphurisation Waste Product, Studstrupvaerket in Denmark). 1/3 of the mixture is used to pour a thin layer on a plane surface, thereafter placing a non-woven of glass fibres (Make: PPG Fiber Glass, Type Chopped Strand Mat 79), after which the next 1/3 of the mixture is poured in a thin layer onto the placed non-woven of glass fibres. A next layer of non-woven glass fibres (same origin) is placed, and finally the last 1/3 part of the mixture is poured in a thin layer on the last layer of non-woven glass fibres. After curing the composite sheet, which will typically be used as a skin material, the sheet in accordance with the intensions in the testing specifications is placed in a v-shaped profile, produced from calcium silicate from Skamol (Make: Skamol, Type SuperPro 300 from Skamol A/S, østergade 58 - 60, 7900 Nykøbing M, Denmark), so that the surface faces the gas burner.

Example 6.

As example 5, but without the addition of DDSW.

Example 7.

Through high speed mixing of the materials added together, a skin of a glass fibre- reinforced polyester is produced, comprising 500 g component A (Make: Reichhold, Type Polylite® 413-M887), 10 g component B (Make: Reichhold, Type Katalysator # 1) and 500 g DDSW (Dry DeSulphurisation Waste Product, Studstrupvaarket in Denmark). 1/3 of the mixture is poured in a thin layer on a plane surface on which is placed a matt of non- woven glass fibres as described in example 5. The next 1/3 part of the mixture is poured in a thin layer onto the non-woven glass fibres, after which a next layer of non-woven glass fibres is placed. Finally, the last 1/3 part of the mixture is poured on top of the composite layer. After curing the composite sheet, which will typically be used as a skin material, the sheet in accordance with the intensions of the testing specifications is placed in a v-shaped profile, produced from calcium silicate as described in example 5, so that the surface faces the gas burner.

Example 8.

As example 7, but without the addition of DDSW.

Example 9.

Through high speed mixing of the materials added together, a skin of a silicone impregnated glass non-woven is produced, comprising 500 g component A (Make: Wacker Silicone, Type M 4642 from the company Viihelm Schertiger & Co. A/S, Køgevej 164, DK- 2630 Tastrup), 50 g component B (Make: Wacker Silicone, Type M 4642 from the company Vilhelm Schertiger & Co. A/S, Køgevej 164, DK-2630 Tastrup) and 500 g DDSW (Dry DeSulphurisation Waste Product, Studstrupvasrket in Denmark). 1/3 of the mixture is used to pour a thin layer on a plane surface, thereafter placing a non-woven of glass fibres, (Make: PPG Fiber Glass, Type Chopped Strand Mat 79) after which the next 1/3 of the mixture is poured in a thin layer onto the placed non-woven of glass fibres. A next layer of non-woven glass fibres (same origin) is placed, and finally the last 1/3 part of the mixture is poured in a thin layer onto the last layer of non-woven glass fibres. After curing the composite sheet, which will typically be used as a skin material, the sheet in accordance to the intensions of the testing specifications is placed in a v-shaped profile, produced from calcium silicate from Skamol (Make: Skamol, Type SuperPro 300 from Skamol A/S, østergade 58 - 60, 7900 Nykøbing M, Denmark), so that the surface faces the gas burner.

Example 10.

As example 9, but without the addition of DDSW.

Results after 10 min. action of gas flame at 1750⁰C:

Comparing examples 5 and 9 with examples 6 and 10 shows that the use of DDSW in a skin of glass fibre-reinforced silicone is able to prevent the material from feeding a fire. This positive effect is seen even better during the firing test at which time it was observed that residues of DDSW are left on the glass fibre non-woven and (subjectively evaluated - not objectively through e.g. measurements of dimensions) leaves a slightly less area disturbed by the fire, and that during the firing action it seems as if the flame, in case the skin comprises DDSW, tends to go out or be smothered, while such smothering is not observed if the skin does not comprise DDSW.

Comparing examples 7 and 8, cf. Figures 7. a - 7.j, it is obvious that in a sheet made from glass fibre-reinforced polyester, the use of DDSW prevents the material from burning completely.

During observing the test in progress it was observed that in the vicinity of the acting gas flame a charring takes place in the material acted upon, cf. Figures 7.c, 7.e - 7.g and 7.i.

Without DDSW the composite sheet made from polyester burns animatedly and accelerating, an illustration of which is attempted in Figure 7.h. From Figures 7.f - 7.h it becomes clear that even a neighbouring fire is not able to prevent the DDSW from acting as a fire retarder when the neighbouring fire is placed at a distance of approximately 80 mm.

The fact that the action of the gas flame can discolour the material over a bigger or smaller area, depending upon the type of the organic material, while the temperature on the back side of the material does not rise significantly, indicates that the use of DDSW is able to improve the resistance against fire of the organic materials, and even in such a way that the temperature is kept low. E.g. from Figure 7.j it becomes clear that without DDSW all polyester burns away, but that polyester comprising DDSW does not feed a fire, even in the case where the material is influenced by a neighbouring fire (at a distance of approximately 80 mm), and thus DDSW also acts as a retarder against flame spread.

For all materials comprising DDSW, during the 10 min. in which time interval the gas flame at 1750⁰C acts on the surface, a charring takes place on the surface of the composite sheet on which the gas flame acts. Charred material will gradually be blown away due to the acting gas flame, but the glass fibres tend to hold back charred material. Thus, after fire testing, an open wound is typically left, which is greater in skin made from glass fibre- reinforced polyester, cf. Figure 7.b and/or Figure 7.d, than in skin made from glass fibre- reinforced silicone, cf. Figure 8. The temperature on the back side of the approximately 2 mm thick glass fibre-reinforced composite sheet made from polyester comprising DDSW may exceed what is pleasant to the hand, but during the 10 min. time interval the sheet does not burn through, e.g. cf. Figure 7.j.

The composite sheet without DDSW burns slowly and controlled, an illustration of which is attempted in Figure 9. After firing action during the 10 min. time interval, the area disintegrated in the skin made from glass fibre-reinforced silicone without DDSW is greater than in skin made from glass fibre-reinforced silicone with DDSW. Furthermore, from Figure 9 it is observed that in both cases the skin is completely burned through in the centre of the acting gas flame, the skin in the test rig being laid close to the back sheet made from calcium silicate of the type SuperPro 300 from Skamol. From Figures 10. a and 10. b it is apparent that if the glass fibre-reinforced silicone composite sheet is placed at a distance of a couple of centimetres from this sheet of calcium silicate, the composite sheet does not burn through. Finally, a comparison of the areas disintegrated in the sheets made from glass fibre-reinforced silicone with and without DDSW (Figure 9 as well as Figure 10), silicone comprising DDSW shows a more homogeneous white area of damage than silicone not comprising DDSW. This means that residues from DDSW during the fire testing obviously remain on the glass fibre reinforcement. Further reasoning indicates that DDSW tends to make the gas flame less penetrating to deeper-laying material, which will furthermore promote the fire retarding action of DDSW. Example 11 - 15.

At the company Edulan A/S, Jens Olsens Vej 3, Skejby, 8200 Arhus N, Denmark, slabs are produced from expanded PUR comprising DDSW. The slabs are covered with a skin of glass fibre-reinforced silicone not comprising DDSW. Initially 5 slabs are produced in accordance with the present invention. The amount of DDSW added constitutes approximately 50% by weight of the amount of polyol used during the production. The make and type of polyol used is not known to the applicant. The DDSW is mixed with the polyol before the addition of water, which is used as a reactant and as the foaming agent. The proportion between polyol and water was varied slightly in order to achieve different densities. Two different batches of polyol were used: Batch 12 and batch 13. In 4 cases, polyol of the Type 1900 was used, while in one case polyol of the Type 1300 was used. Densities resulting were measured. Slabs produced were named MMM - NO - Density, where MMM identifies the type of polyol used, NO identifies the batch number, and Density identifies the density achieved in grams per slab (same dimensions for all 5 slabs: approximately 40 x 155 x 800 mm). After receiving the composite slabs produced by Edulan A/S, the slabs were placed in accordance with the intensions of the fire testing specifications in a V-shaped profile made from calcium silicate, of make and type as specified above, in such a way that the greater surface faced the gas burner.

Each single slab was then exposed to the action of a gas flame of approximately 1750⁰C for 10 min., the origin of which was placed at a distance from the surface of the slab of approximately 100 mm - as shown in Figure 1. In two cases, the time interval of the firing action was prolonged to 15 min. During the test period of 10 (15) min., formation of flames and smoke was recorded by eye and photo at start-up and after each 5 min., and after the firing test damages were recorded by photo, cf. Figures 11 - 15. The following were produced and observed:

n.o. = not observed

As is it remembered that similar slabs, produced from PUR not comprising DDSW (or other fire retarders), after having been affected by a fire, will burn on their own while developing smoke, the results show the positive effect from the use of DDSW - DDSW efficiently depresses flame spread, smoke development and self-sustained fire.

From the tests presented here it can not be disclosed that the few flames observed are related to the use of a skin of glass fibre reinforced silicone not comprising DDSW. After these tests, a skin from glass fibre-reinforced silicone comprising DDSW was produced. It has proven possible to produce a dense skin made from glass fibre-reinforced silicone containing up to 50% by weight of DDSW. According to examples 5 and 9, an addition of DDSW to glass fibre-reinforced silicone imparts such a fire retarding effect that the silicone will not itself sustain a fire. In the examples is described the use of DDSW (Dry DeSulphurisation Waste Product), produced during the desulphurisation of flue gasses at the electricity-generating power plant Studstrupvaerket in Denmark. The DDSW used was dried out of free water before use. The DDSW used was analysed, the results being as follows:

* 100 g DDSW was mixed with 100 ml of water. After some shaking, a little amount of water was filtered off, in which water the content of Na+, K+, and Ca++ was measured on AAS, and the content of Cl- was measured on IC.

** The samples were heated for 1 hour at 120⁰C with 10 ml 1: 1 HCI, thereafter measured on AAS.

DM = dry matter WM = wet (not dried) matter - = content below the detection limit stated.

Claims

1. Method of improving resistance of organic materials to open fire, firing, and/or flaming actions, characterised in that a waste residue deriving from desulphurisation of flue gasses is added to the organic material during mixing, and before solidification.

2. Method according to claim 1, characterised in that the added waste residue derives from desulphurisation of at least one of the following flue gasses: from oil and gas incinerators, from other fossil power plants or incinerators, from waste incinerators, or from straw incinerators, e.g. from oil and gas incinerators, from other fossil power plants or incinerators, from waste incinerators, e.g. incinerators for domestic waste and the like, from straw incinerators, or from other power plants, or the like.

3. Method according to claim 1 or claim 2, characterised in that the waste residue is so- called DDSW (Dry Desulphurisation Waste Product).

4. Method according to any of claims 1 to 3, characterised in that the waste residue is a mixture of calcium hydroxide and calcium sulphite hemi hydrate.

5. Method according to any of claims 1 to 4, characterised a waste product from the desulphurisation of flue gasses is added to the organic material during mixing, before solidification.

6. Method according to any of claims 1 to 5, characterised in that a mixture of calcium hydroxide and calcium sulphite hemi hydrate is added to the organic material during mixing, before solidification, and possibly minor amounts of another comminute inorganic material comprising crystal water or the like are added.

7. Method according to any of claims 1 to 6, characterised in that intimate mixing is performed of the organic material and the waste residue deriving from desulphurisation of flue gasses.

8. Method according to any of claims 1 to 7, characterised in that intimate mixing is performed of the organic material and a mixture of calcium hydroxide and calcium sulphite hemi hydrate, and possibly minor amounts of another comminute inorganic material comprising crystal water or the like are added.

9. Method according to any of claims 1 to 8, characterised in that at least one organic material is/are used in the intimate mixing, which at least one organic material is an artificially produced plastic material.

10. Method according to claim 9, characterised in that the artificially produced plastic material consists of at least one of the following materials: thermoplastic materials such as PE, PETP, PTFE, PP and others; preferably plastic materials obtained by thermosetting or setting by other means, such as epoxies, polyester, melamine, phenol, carbonate, acrylate

5 and the like; silicone of any type, in which setting is achieved through chemicals, thermal action, or by other means.

11. Method according to claim 9 or claim 10, characterised in that at least part of the plastic material is mixed with large or small amounts of inorganic or organic additions or admixtures in the form of one, two, or three-dimensional particles such as fibres, flakes or

10 spheres in order to achieve changes in properties of the plastic material with respect to stiffness and/or strength.

12. Method according to any of claims 1 to 11, characterised in that the mixture of organic material and the waste residue being DDSW and/or the mixture of calcium hydroxide and calcium sulphite hemi hydrate is used for a manufacturing a foamed final material.

15 13. Method according to any of claims 1 to 12, characterised in that the mixture of organic material and the waste residue is used for manufacturing a porous material from Polyurethane (PUR).

14. Method according to any of claims 5 to 13, characterised in that, in addition to at least 25%, possibly at least 50%, even possibly at least 75%, even also possibly at least 85%,

20 more even also possibly at least 95% by weight of a waste residue from the desulphurisation of flue gasses, is used another comminute inorganic material, originating from natural sources. ,

15. Method according to claim 14, characterised in that the waste residue consists of at least one of the following materials: gypsum, clay, mica, plagioclase and the like; waste

25 material from human activities, such as gypsum (calcium sulphate dihydrate), calcium sulphite hemi hydrate, calcium sulphate hemi hydrate, hydrated cement of any type, such as Portland Cement, Aluminate Cement and the like; or inorganic materials comprising crystal water; or inorganic materials which absorb a high specific amount of energy by other means during heating.

30 16. Method according to any of claims 5 to 15, characterised in that a comminute inorganic material is used, which comminute inorganic material is selected with respect to the type of the organic polymeric material with which it is to be mixed.

17. Method according to any of claims 5 to 16, characterised in that a comminute inorganic material is used, which comminute inorganic material is selected with respect to its ability 35 to reduce the evaporation/degradation of PUR.

18. Method according to any of claims 1 to 17, characterised in that the surfaces, which during use in extreme cases may be expected to be exposed to temperatures at or above the temperature of evaporation/degradation of the organic polymeric material in use, is covered by a skin, preferably a skin which can resist the temperatures to which the

5 surfaces are exposed, or preferably a skin comprising silicone or the like, and optionally comprising inorganic fibres from such material which may resist the temperatures to which the surfaces are exposed, more preferably a skin comprising silicone and glass fibres, most preferably a skin comprising silicone and a non-woven or a weave of glass fibres.

19. Method according to claim 18, characterised in that the skin itself has obtained an

10 improved resistance to fire and flammability according to the invention, preferably in which the skin comprises a silicone, more preferably in which the skin comprises a two- component silicone, preferably a skin in which the improved resistance to fire and flammability is achieved using DDSW.

20. Material for improving resistance of organic materials to open fire, firing and/or flaming 15 actions, characterised in that the material is a waste residue deriving from the desulphurisation of flue gasses.

21. Material according to claim 20, characterised in that the waste residue added derives from desulphurisation of at least one of the following flue gasses: from oil and gas incinerators, from other fossil power plants or incinerators, from waste incinerators, or

20 from straw incinerators, e.g. from oil and gas incinerators, from other fossil power plants or incinerators, from waste incinerators, e.g. incinerators for domestic waste and the like, from straw incinerators, or from other power plants, or the like.

22. Material according to any of claims 20 to 21, characterised in that the waste residue is a so-called DDSW (Dry Desulphurisation Waste ProductDDSW).

25 23. Material according to any of claims 20 to 22, characterised in that the waste residue is a mixture of calcium hydroxide and calcium sulphite hemi hydrate or a similar material.

24. Material according to any of claims 20 to 23, characterised in that minor amounts of another comminute inorganic material comprising crystal water or similar is added to the waste residue deriving from desulphurisation of flue gasses and/or the mixture of calcium

30 hydroxide and calcium sulphite hemi hydrate.

25. Material according to any of claims 20 to 24, characterised in that the waste residue deriving from desulphurisation of flue gasses and/or the mixture of calcium hydroxide and calcium sulphite hemi hydrate and possible minor amounts of another comminute inorganic material comprising crystal water or similar is intimately mixed prior to or at the latest

35 simultaneously with the mixing into the organic material.

26. Material according to any of claims 20 to 25, characterised in that at least one organic material is used in the intimate mixing, which at least one organic material is an artificially produced plastic material.

27. Material according to claim 26, characterised in that the artificially produced plastic

5 material consist of at least one of the following materials: thermoplastic materials, such as PE, PETP, PTFE, PP and others; plastic materials obtained by thermosetting or setting by other means, such as epoxies, polyester, melamine, phenol, carbonate, acrylate and the like; silicone of any type, in which setting is achieved through chemicals, thermal action, or by other means.

10 28. Material according to any of claims 26 to 27, characterised in that at least part of the plastic material is mixed with large or small amounts of inorganic or organic additions or admixtures in the form of one, two, or three-dimensional particles such as fibres, flakes or spheres in order to achieve changes in properties of the plastic material with respect to stiffness and/or strength.

15 29. Material according to any of claims 20 to 28, characterised in that the mixture of organic material and the waste residue (DDSW and/or the mixture of calcium hydroxide and calcium sulphite hemi hydrate) is used for manufacturing a foamed final material.

30. Material according to any of claims 20 to 29, characterised in that the mixture of organic material and the waste residue is used for manufacturing a porous material from

20 Polyurethane (PUR).

31. Material according to any of claims 24 and 25, characterised in that, in addition to at least 25%, possibly at least 50%, also possibly at least 75%, even also possibly at least 85%, more even also possibly at least 95% by weight of a waste residue deriving from the desulphurisation of flue gasses, is used another comminute inorganic material, originating

25 from natural sources.

32. Material according to claim 31, characterised in that the waste residue consists in at least one of the following materials: gypsum, clay, mica, plagioclase and the like; waste material from human activities, such as gypsum (calcium sulphate dihydrate), calcium sulphite hemi hydrate, calcium sulphate hemi hydrate, hydrated cement of any type, such

30 as Portland Cement, Aluminate Cement and the like; or inorganic materials comprising crystal water; or inorganic materials which absorb a high specific amount of energy by other means during heating.

33. Material according to any of claims 21 to 22 and any of claims 31 and 32, characterised in that a comminute inorganic material is used, which comminute inorganic material is

35 selected with respect to the type of the organic polymeric material with which it is to be mixed.

34. Material according to any of claims 24 to 27, characterised in that a comminute inorganic material is used, which comminute inorganic material is selected with respect to its ability to reduce the evaporation/degradation of PUR.

35. Material according to any of claims 20 to 34, characterised in that the surfaces, which during use in extreme cases may be expected to be exposed to temperatures at or above the temperature of evaporation/degradation of the polymeric organic material in use, is covered by a skin, preferably a skin which can resist the temperatures to which the surfaces are exposed, or preferably a skin comprising silicone or the like, and optionally comprising inorganic fibres from such material which may resist the temperatures to which the surfaces are exposed, more preferably a skin comprising silicone and glass fibres, most preferably a skin comprising silicone and a non-woven or a weave of glass fibres.

36. Material according to claim 35, characterised in that the skin in itself has obtained a resistance to fire and flammability according to the preceding claims, preferably with the proviso that the skin comprises a silicone, more preferably with the proviso that the skin comprises a two-component silicone, preferably a skin in which the improved resistance to fire and flammability is achieved using DDSW.