WO2000046277A2 - Fireproofing material - Google Patents
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- WO2000046277A2 WO2000046277A2 PCT/UA2000/000006 UA0000006W WO0046277A2 WO 2000046277 A2 WO2000046277 A2 WO 2000046277A2 UA 0000006 W UA0000006 W UA 0000006W WO 0046277 A2 WO0046277 A2 WO 0046277A2
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- water
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- siliceous raw
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K21/00—Fireproofing materials
- C09K21/02—Inorganic materials
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Fireproofing Substances (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Abstract
A fireproofing material obtained on the basis of hydrosilicates of alkali metals as a product of mixing a crushed natural porous siliceous raw comprising at least 70 % (by weight) of amorphous silicon dioxide with aqueous solution of caustic alkali, heating the mixture to a temperature of generating a saturated water steam, and cooling the steamed mixture till it gains its viscoelastic state. This material is obtained from a siliceous raw which contains in its mass after crushing it up to 15 % of fragments over 10 mm in diameter, and from an aqueous solution of caustic alkali which is heated before mixing it with the said siliceous raw up to a temperature next to a water boiling point; with the mixture being instantly unloaded after its homogenization. The produced material has capability to change into a viscous-flow state in reheating it at a temperature of 45 to 250 °C.
Description
FIREPROOFING MATERIAL Field ofinvention This invention relates to materials based on complex mixtures of hydrosilicates of alkali metals, preferably hydrosilicates of natrium, the mixtures being obtained by treating natural raw materials containing amorphous silicon dioxide with caustic alkali. Such materials have common properties even though their final chemical formulations are hard to define precisely, viz under heating at a wide range of temperature they are capable to soften and expand thus creating an effective obstacle to flame. Therefore they can be utilized as fireproofing materials.
Prior art Usually fireproofing materials are: — to have their specific heat absorption as great as possible when in contact with a high-temperature heat source; to expand and increase in thickness when in contact with, predominantly, a naked flame, without evolving toxic or chemically aggressive gaseous matters, thus creating a barrier to separate the flame from a defended article surface; to have losses in weight as low as possible when heated long.
In view of mass demand for fire-shielding partitions and fireproofing coatings, such materials, in addition, are to be simple and cost-effective in production, suitable for long-term storage, stable in chemical formulation and thermal properties. There is no a critical deterrent to meet some of these requirements either apart or in combination. Really, there is plenty of known materials used to guard construction units (especially metallic and wooden ones), pipe lines, and cables against fire.
For example, to have a steelwork guarded for an hour against a naked flame there can be used a fiberglass-reinforced polymeric fireproofing composite (by SU 452224) comprising (by weight parts): up to 20.9 of a mixture composed of melamine-formaldehyde, urea-formaldehyde, and methylol- polyamide resins, which is used as a binder; up to 20.0 of butanol as a dispersing medium, removable in drying the applied coating; 15 to 16 of
diammonium phosphate as a gas developing agent; a number of other additives, like trace quantities of organosilicon resin, as a lubricant for fiberglass; and, cumulatively, up to 13.5 of dicyandiamide and triamino-S- heptazine. However, the practical use of this composite is quite problematic because of the composite complicacy, the expensiveness of its components, the toxicity of butanol and decomposing products of its binder, and rather a short fire- protection life.
Similar disadvantages limit the use of other fireproofing composites produced of components able to expand under heating and of binders like thermoreactive organic oligomers, such as epoxies with miscellaneous, sometimes highly exotic, hardeners (e.g., SU 447931 A1 , SU 709654 A1 , SU 730749 A1 , SU 749870 A1 , SU 709654 A1 , SU 749870 A1 ; DE 2227188, US 3372208). There are substantially cheaper and less dangerous in production and use fireproofing composite materials comprising preferably mineral ingredients, viz natural mineral fillers as vermiculite, and/or chrysotile-asbestos serpentine, andesite, kaolin, chalk, marl, phlogopite, and/or artificial mineraloid fillers as natrium polyphosphate, fly ash, silicofiuoric natrium, aluminium sulphate, expanded periite, etc., produced using preferably mineral binders (e.g., SU 850644 A1 , SU 952808 A1 , SU 1235138 A1 , SU 1652856 A1 , SU 1629277 A1 , SU 1701694 A1 ).
A well-known widely used mineral binder for fireproofing materials is so- called "water glass" (e.g., KPATKAA XH HMECKAA ΘHUUKJIOΠEΛHF!, Kratkaya Khimicheskaya Entsyklopediya, — M.: M3flaτeπbcτB0 "CoBeτcκaa SHMwαioπe Mfl", T. 4, 1965, cc. 1037-1038).
The basis of water glass is a hard "soluble glass" as a mixture of (oligo)silicates of alkali metals whose general formula is R20*mSi02 where R20 is a natrium oxide and/or a potassium oxide, and number m, called "siliceous module", is from 2.0 to 4.5. To produce soluble glass in an ordinary way, a mixture of quartz sand, soda, and/or natrium sulphate is fused at 1100 to 1400 °C. In fusing, crystalline SiO∑, the basis of quartz sand, changes into its amorphous phase which consolidates itself while the said silicates being formed. In sale, soluble glass arrives either as "silicate blocks" if its melt was
cooled by mass or as a "granular silicate" if its melt was cracked into grains while quickly cooled in running water. In any case, water glass can be obtained by crushing and dissolving the soluble glass in water.
Quartz sand is, however, refractory. So, power consumption per product weight unit is very large, hence pure soluble glass as a fireproofing material produced in such a way is too expensive for mass usage. Furthermore, it is known in the art that other than Si02 oxide admixtures in quartz sand sharply reduce the solubility of silicates of alkali metals. Admixtures of 1.0 to 1.35 % of AI203+Fe2θ3 or 0.4 to 0.6 % of CaO are considered being improper (e.g., the textbook for students of high schools XHMHH KPEMW H ΦM3HHECKA?I xwvina CHΠHKATOB, Khimiya Kremniya i Fizicheskaya Khimiya Silikatov by l~. B. KyKoπeB, — M.: H3flaτexibcτB0 "Bbicuiaa niKona", 1966, c. 164).
Thus in water glass production there regularly finds its utilization a raw with positive domination of amorphous Si02, the raw treated with solutions of caustic alkalis in autoclaves at a temperature of up to 200 °C, which results in a direct yield of natrium hydrosilicates solution (see the above Kratkaya Khimicheskaya Entsyklopediya). A reduction in process temperature, characteristic for this "wet" process, radically reduces energy consumption and prime product cost. Still in this case too, the prevailing trend to apply water glass only as a binder induces to provide for siliceous raw purity because the product of the raw reaction with solutions of caustic alkalis is difficultly soluble and ineffective in producing composite fire-resistant materials. So, the raw source is limited to siliceous raw deposits whose concentrations of amorphous Si02 are over 97.5 to 98.0 %. In addition, composite materials with binders solely of water glass (upon drying, soluble glass) are, firstly, hygroscopic and thus unstable in wet environment and, secondly, more tend to crack and fall off the surfaces of defended objects in a dry gas medium if the concentration of reinforcing fillers in the materials lessens. Finally, the water of water glass serves only as a dispersing medium, it can be readily removed in drying, hence it practically has no effect on the flame resistance of dry coatings.
Nevertheless, processing the siliceous raw whose concentration of amorphous Si02 less than 97.5 % is possible. According to UA Patent 3802 there is known a material based on hydrosilicates of alkali metals, the
hydrosilicates obtained by treating a dispersed siliceous raw containing less than 85 % of amorphous Si02 with an aqueous solution of caustic alkali during 20 to 60 min in a saturated water steam at a temperature of 80 to 100 °C. For 100 w.p. of amorphous Si02, the material contains 1 to 30 weight parts (w.p.) of an alkali metal hydroxide and 30 to 125 w.p. of water.
In comparison with the above materials, this material is the least power- consuming in production, and in the end of silica reaction with aqueous solution of caustic alkali it usually looks like a tenacious mass.
Unfortunately, the tenacity of this mass widely varies, so it is highly problematic to produce from it qualitatively stable fireproofing composites.
In technical essence, the nearest hydrosiiicate material compared by stability to the tendered one is the material by the international application PCT/UA96/00007 by the same applicant (publication WO 97/33843 of September 18, 1997). For the basis of this material there serve hydrosilicates of alkali metals obtained by — mixing a crushed (into medium-sized fragments of 1.0 to 2.5 mm) natural porous siliceous raw including not less than 70 % by weight of amorphous Si02 with a solution of caustic alkali, heating the mixture to a temperature of forming a saturated water steam, steaming the mixture and cooling it as long as it gains its viscoelastic state.
In reheating this viscoelastic material to a temperature above 100 °C it becomes viscous-flow, and it intensively expands and changes into its irreversible solid state if heated above 200 °C.
The specific production features of this hydrosiiicate material, which strongly affect the structural and the physicochemicai properties of it, are: — both reagents are mixed at an ambient temperature at which the exothermal effect of silica alkalization does not provide for steaming the reaction mixture, thus, despite of a rather thinly crushed siliceous raw and a make-up heating, the mixture usually homogenized at least 20 minutes; even with the reaction mixture intensively mixed, it is difficult to equalize the temperature field in the volume of high-viscous mixture either by additionally heating the mixture with saturated water steam if need be to add water to the
mixture or by externally heating it if there is enough water; the process is carried on as long as the introduced caustic alkali reacting with amorphous Si02 is practically used up; and the forced expansion of processed material is the indispensable condition for producing the known product as a heat-shielding material with low heat conduction.
So, this expandable hydrosiiicate material can be used for fireproofing the structures of fire-shielding partitions only, and it is quite unsuitable as a binder; also it is noncompetitive as a filler for rather thin coating composites if compared with the available fire-resistant fillers mentioned above.
Brief description of invention According to the aforesaid, in the invention ground there is an object to change the operation sequence and the production mode so that to get a fireproofing material capable to — retain water in its structure till its contact with a naked flame, provide by retaining water during fire-protection for a substantially greater specific heat absorption and for an exponentially ascending resistance to the flame as the fire-shielding layer thickness increases, possess essentially wider technological potentialities for processing this material into a composite fireproofing material and into articles of it.
This object is realized with a fireproofing material obtained on the basis of hydrosilicates of alkali metals as a product of — mixing a crushed natural porous siliceous raw comprising at least 70 % (by weight) of amorphous silicon dioxide with aqueous solution of caustic alkali, heating the mixture to a temperature of generating a saturated water steam, and cooling the steamed mixture till it gains its viscoelastic state; the material according to the invention is obtained from a siliceous raw which contains in its mass after crushing it up to 15 % of fragments over 10 mm in diameter, and from an aqueous solution of caustic alkali which is heated before mixing it with the said siliceous raw up to a temperature next to a water boiling point; with the mixture being instantly unloaded after its homogenization, and the produced material has its capability to change into a viscous-flow state
in reheating it at a temperature of 45 to 250 °C.
Such a product is a hydro(poly)silicate "thermosetting plastic" retaining in its mass efficiently bound water as a dispersion medium of solid gel and as hydrates. This product can be used as a fireproofing material either alone in the form of, preferably, reinforced and, if need be, guarded against moisture slabs and blocks or as a binder in the form of, for example, a tenacious water dispersion, or a "melt", or as a filler for composite materials for fireproofing coatings with arbitrary alkaliproof organic and mineral binders.
The first additional distinction of the invention is that in the fireproofing material mass there is present from 30 to 40 % of bound water and the second distinction additional to the first one is that the bound water is present in the form of a dispersion medium of solid gel, and the bound water is present in the structure of hydrates, the "dispersion" and the "hydrate" water being in the weight ratio of 5:3 to 4:1. So, according to the invention, at a flame contact with a fire-shielding article, or a coating, with the fireproofing material used, in the beginning there takes place the dispersion water evaporation, viz the medium water evaporation, thereupon at a temperature above 100 °C (usually 120 to 180 °C) there takes place the hydrates destruction, the material surface layer preliminarily expanding and melting thereupon finally expanding and forming a stable foam. As heating the foam continues, the processes of expanding, melting, and foaming in the material layers repeat and efficiently shield the article from the flame.
This effect can be explained as follows. In mixing, the reaction of hot aqueous solution of caustic alkali with a roughly crushed siliceous raw leads to heating the mixture due to the exothermicity of silica alkalization. With this occurring, nothing impedes equalizing the temperature field in the volume of the homogenized mixture, moreover the siliceous raw ballast admixtures, often making more than 20 % of the siliceous raw, by sorbing a part of natrium ions even promote homogenizing the stirred mixture. Thus, with the reaction mass being immediately unloaded after homogenizing, cooled, and changed into its viscoelastic state, the water present in this solid mass gets bound practically all, hence alkalizing the reaction mass gets "prolonged" till the first contact of the produced fireproofing material with a flame. Flame tests on this material show
that the bound water evaporation requires so much heat that the material surface holds its temperature around 100 °C during the whole evaporation (the thicker the layer of the fireproofing material according to the invention, the longer is the duration). The third additional distinction of the invention is that the fireproofing material additionally contains a dispersed mineral filler, viz periite, "sand", or fine "gravel", in the form of expanded fragments produced by crushing and heating the "thermosetting plastic" above 200 °C.
The fourth distinction, additional to the third one, is that the dispersed filler has spheroidal cavities which, unlike usual pores, not only provide for reducing the material heat conduction but also effectively impede the penetration of radiation heat into the body of fireproofing coating or article.
Brief description of drawings To explain the description there are drawings where: — fig. 1 is a diagram showing jointly in an equal time scale (t, min) the outcomes of differential-thermal (DTA), differential-thermogravimetric (DTG), and thermogravimetric (TG) analyses against the background of the curve (T, °C) of temperature rising with a speed of 7 °C per minute; fig. 2 is a diagram showing jointly in an equal time scale the outcomes of determining the time limits of the flame resistance of various fireproofing coatings against the curve background of a temperature rising in a fire.
Best mode for invention carrvinq-out The invention essence is further illustrated by: — a description of a method of producing the fireproofing material as a hydropolysilicate thermosetting plastic, the outcomes of the fireproofing material research with references to the appended drawings, a description of methods for using this thermosetting plastic in fire- shielding structures with directions for producing particular fireproofing materials.
The needed siliceous raw, viz tripoli, diatomite, opoka, spongiolite, radiolarite, etc., is practically available to all (e.g., CTPOHTEJibHbiε MATEPHAJibi M n3flEJik U3 KPE HHCTbix πopofl, Stroitelniye Materialy i Izdeliya is Kremnistykh Porod, by HβaHβHKO B. H., Knee, "EYfliBEJibHUK", 1978, p. 5).
Since the above sedimentary rocks, usable as a raw, are similar by chemical formulation, there are data only for one experimentally used to check the invention for its embodiment efficiency, viz a tripoli from Konoplyanske deposit (Ukraine); the tripoli containing in its initial phase up to 38.0 % (by weight) of a free and a hydrate water. Tables 1 and 2 respectively show the average chemical formulation of the tripoli dry residue (in % by weight) and the average granulometric composition and the bulk weight of the crushed tripoli fractions.
Table 1 Average chemical formulation of tripoli
Table 2 Average granulometric composition and bulk weight of crushed tripoli
To alkalize the raw and simultaneously to have it at least partially water- impregnated there can be used either a caustic soda, viz a 42 to 46 % solution of water-dissolved caustic soda, or a solid technical caustic soda previously dissolved in piped domestic water before introducing it into the raw mixture. A dissolving water quantity is determined regarding the natural moisture content of a particular siliceous raw batch, the caustic soda consumption usually making 300 to 400 kg per 1000 kg of tripoli.
A method for producing the fireproofing material as a hydropoiysilicate thermosetting plastic includes: —
crushing a siliceous raw to obtain its fragments with average sizes predominantly limited to 1.0 to 10.0 mm, the crushed mass containing up to 15 % of fragments with >10 mm in diameter; proportioning the crushed siliceous raw and an aqueous solution of alkali metal hydroxide; preheating the said hydroxide solution up to a temperature next to a water boiling point; water-impregnating and alkalizing the siliceous raw by mixing it with the hot aqueous solution of alkali metal hydroxide till the mixed mass is homogeneous; immediately unloading and cooling the mass to a room temperature (18 to 25 °C) or lower, the material produced being the necessary thermosetting plastic as a solid gel.
It is known in the art that heating an aqueous solution of alkali metal hydroxide can precede proportioning it, and cooling a homogeneous mass can be carried out upon pouring it into moulds.
The produced fireproofing material appears as a dark breakable mass capable at a room temperature to flow very slowly under the action of gravity. This material was investigated by well-known methods for differential-thermal (DTA), differential-thermogravimetric (DTG), and thermogravimetric (TG) analyses. As a result of the investigation, in fig. 1 there is given a diagram, one of many assembled ones.
This diagram shows the "dispersion" water evaporation starting at a temperature about 30 °C and ending at a temperature about 110 °C, the water loss peak arriving at a notably narrow temperature range of 100 to 105 °C. The weight loss peak resulting from the "hydrate" water evaporation takes place at a temperature range of 120 to 200 °C, this peak being smoother and limited by a temperature range of 150 to 165 °C, the mass visco-fluidity lasting up to a temperature of 250 °C. With other speeds of heating present, the curves DTA, DTG, and TG are essentially similar to ones of fig. 1. Accordingly, the above temperature ranges practically remain the same.
In fig. 1 , these data visually demonstrate that in the fireproofing material according to the invention water is present in its two different forms. Just by these two forms of water presence explain an essential enlargement in the
temperature range of the material effective heat absorption while in contact with a high-temperature heat, a naked flame contact inclusive.
By conventional physicochemical methods for testing the material samples taken from different batches of the fireproofing material produced at different time from different siliceous raw portions differentiating by its chemical formulation, it was established that the total quantity of the bound water makes from 30 to 40 % of the solid gel mass total, and the ratio of "dispersion" and "hydrate" water makes from 5:3 to 4:1 by weight.
The bound water affect on the material fire-resistance and the water behavior difference in both the "dispersion" and the "hydrate" water were additionally confirmed by comparative flame tests on the material specimens with their carriers as steel plates of 250 by 250 mm in dimensions and 4 mm thick, the steel plates coatings of: — the material according to the invention (MAI) 15 mm thick; the material according to the invention 20 mm thick; a mixture in the weight ratio of 1 :1 of the material according to the invention and a common periite (MAI + CP) 25 mm thick; a vermiculite 20 mm thick.
The vermiculite was used because of its capability to expand in heating like the material according to the invention.
These samples were installed into the embrasures of a refractory firing chamber equipped with a kerosene burner with flow regulators to adjust fuel and oxidant in programmatically increasing the heat load for the coatings, the sample carriers having thermocouples connected to their backs. Fig. 2 shows a "shelf in the heating curve of a fireproofing material, which moves this curve to the right from the ordinate axis, the "shelf being characteristic for all the coatings with the fireproofing material according to the invention because of the heat consumption in heating and evaporating the "dispersion" water. This "shelf is notably expressed in specimens with coatings of the pure material according to the invention, it is flattened in specimens with a mixture of the same material with periite, but misses in specimens with vermiculite coatings. What is more, a minor enlargement (for 5 mm) in coating thickness of the pure material according to the invention distinctly prolongs (almost twice as much) the duration of holding the carrier temperature at about
100 °C. Also fig. 2 shows that the heat consumption for removing the "hydrate" water surely lessen the curve inclination of the carrier temperature rise comparing to the curve inclination of the firing chamber temperature rise (viz "a fire temperature"). In simple cases, to protect articles against a naked flame affect of short duration, surfaces of defended articles can be coated with at least one layer of a creamy water dispersion of the material according to the invention, thereupon the layers dried up thus forming rather thin (some millimeters thick) fireproofing coatings. Regarding other practical applications, the material according to the invention is to be expediently reinforced: — outside (mostly with facing tiles produced from an appropriate alkaiiproof material, e.g., rigid mats made of a basalt fabric, to prevent the layers of pure fireproofing material to flow from the surfaces of defended articles) and/or inside (e.g., with a wire fabric, preferably with fire-resistant dispersed mineral fillers, and, most preferably, with mineral fillers having spheroidal cavities).
In accordance with the earlier international application of the same applicant (op. cit. WO 97/33843), in the capacity of a dispersed mineral filler there can be used either a periite or an expanded heat-insulating material as a
"sand" or a fine "gravel". Mixtures of such fillers with the material according to the invention are not capable to flow even under external pressure.
It is necessary to underline that the dispersed mineral fillers can be added both into a melt of the material according to the invention and into such a produced material as a tenacious homogenized mass described above.
Irrespective of the order of introducing the fillers composed of the produced composites in which the material according to the invention serves as a binder, by conventional methods, viz by either pouring the material into moulds with following cooling or packing it into forms and premoulding with following cooling it, there can be produced a lot of miscellaneous fireproofed articles, viz flat or shaped plates, blocks, boxes, etc.
Similarly, either producing the material according to the invention as a tenacious homogenized mass or pouring a melt of the material into arbitrary moulds, with the blanks of "lower" carriers laid before pouring and the blanks of
"upper" carriers laid after pouring, there can be produced fireproofed articles with external reinforcement.
Composites for fireproofing coatings with the material according to the invention can also be produced by way of other methods known in the art. Particularly, the above-described hydropolysilicate thermosetting plastic can be crushed and: — either dispersed in water, with the aim to get a colloidal solution of acceptable viscosity, and in such a form mixed with a suitable alkali- and fire- resistant filler, or, as a fire-resistant filler in the form of powder or granules, introduced into a suitable alkali-resistant mineral or organic binder.
For damp environment, to lend perfect stability to coatings made either of the pure material according to the invention or of composites with this material, the coatings, or at least one side of material-reinforced plates or blocks, can be additionally waterproofed with suitable coatings available in the market of hydrophobic materials.
Industrial applicability
The material according to the invention can be produced from widely available siliceous raw, and when applied in structures and articles it can afford an effective fire-protection for random constructions, particularly wood and metallic ones, like frameworks, specific parts of buildings, facilities, pipe lines, etc., without regards to its specific application form.
Claims
1. A fireproofing material obtained on the basis of hydrosilicates of alkali metals as a product of — mixing a crushed natural porous siliceous raw comprising at least 70 % (by weight) of amorphous silicon dioxide with aqueous solution of caustic alkali, heating the mixture to a temperature of generating a saturated water steam, and cooling the steamed mixture till it gains its viscoelastic state; characterized in that it is obtained from a siliceous raw which contains in its mass after crushing it up to 15 % of fragments over 10 mm in diameter, and from an aqueous solution of caustic alkali which is heated before mixing it with the said siliceous raw up to a temperature next to a water boiling point; with the mixture being instantly unloaded after its homogenization, and the produced material has its capability to change into a viscous-flow state in reheating it at a temperature of 45 to 250 °C.
2. A fireproofing material according to Claim 1 characterized in that it holds from 30 to 40 % of a bound water.
3. A fireproofing material according to Claim 2 characterized in that the said bound water is present as a dispersion medium of a solid gel and as a component of hydrates, the ratio of the "dispersion" and the "hydrate" water being from 5:3 to 4:1.
4. A fireproofing material according to Claim 1 characterized in that it additionally contains a dispersed mineral filler.
5. A fireproofing material according to Claim 1 characterized in that the said filler has spheroidal cavities.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCT/UA2000/000006 WO2000046277A2 (en) | 1999-02-05 | 2000-02-03 | Fireproofing material |
| AU2000236906A AU2000236906A1 (en) | 1999-02-05 | 2000-02-03 | Fireproofing material |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| UA99020649A UA62932C2 (en) | 1999-02-05 | 1999-02-05 | A fire-proof material |
| UA99020649 | 1999-02-05 | ||
| PCT/UA2000/000006 WO2000046277A2 (en) | 1999-02-05 | 2000-02-03 | Fireproofing material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| WO2000046277A2 true WO2000046277A2 (en) | 2000-08-10 |
| WO2000046277A3 WO2000046277A3 (en) | 2002-05-10 |
Family
ID=26667094
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/UA2000/000006 WO2000046277A2 (en) | 1999-02-05 | 2000-02-03 | Fireproofing material |
Country Status (1)
| Country | Link |
|---|---|
| WO (1) | WO2000046277A2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009105051A1 (en) * | 2008-02-22 | 2009-08-27 | Illarion Eine | Method for preparation of hard hydrosilicate gel |
| CN112724840A (en) * | 2020-12-25 | 2021-04-30 | 中国建筑材料科学研究总院有限公司 | Fireproof adhesive, preparation method thereof and composite fireproof glass containing fireproof adhesive |
| WO2021248173A2 (en) | 2020-06-10 | 2021-12-16 | Illarion Eine | Fire protection system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1518772A (en) * | 1977-02-01 | 1978-07-26 | Skamol Skarrehage Molerverk As | Method of producing an aqueous solution of water glass |
| SU919992A1 (en) * | 1980-04-02 | 1982-04-15 | Минский научно-исследовательский институт строительных материалов | Method of producing water glass |
| DE3515233A1 (en) * | 1985-01-10 | 1986-10-30 | Mittex Ag, Vaduz | Process for preparing water glass solutions |
| RU2085489C1 (en) * | 1995-06-06 | 1997-07-27 | Братский Индустриальный Институт | Method of liquid glass production |
-
2000
- 2000-02-03 WO PCT/UA2000/000006 patent/WO2000046277A2/en active Search and Examination
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1518772A (en) * | 1977-02-01 | 1978-07-26 | Skamol Skarrehage Molerverk As | Method of producing an aqueous solution of water glass |
| SU919992A1 (en) * | 1980-04-02 | 1982-04-15 | Минский научно-исследовательский институт строительных материалов | Method of producing water glass |
| DE3515233A1 (en) * | 1985-01-10 | 1986-10-30 | Mittex Ag, Vaduz | Process for preparing water glass solutions |
| RU2085489C1 (en) * | 1995-06-06 | 1997-07-27 | Братский Индустриальный Институт | Method of liquid glass production |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009105051A1 (en) * | 2008-02-22 | 2009-08-27 | Illarion Eine | Method for preparation of hard hydrosilicate gel |
| WO2021248173A2 (en) | 2020-06-10 | 2021-12-16 | Illarion Eine | Fire protection system |
| CN112724840A (en) * | 2020-12-25 | 2021-04-30 | 中国建筑材料科学研究总院有限公司 | Fireproof adhesive, preparation method thereof and composite fireproof glass containing fireproof adhesive |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2000046277A3 (en) | 2002-05-10 |
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