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AU664254B2 - Fire extinguishing composition - Google Patents

Fire extinguishing composition Download PDF

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Publication number
AU664254B2
AU664254B2 AU36516/93A AU3651693A AU664254B2 AU 664254 B2 AU664254 B2 AU 664254B2 AU 36516/93 A AU36516/93 A AU 36516/93A AU 3651693 A AU3651693 A AU 3651693A AU 664254 B2 AU664254 B2 AU 664254B2
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Australia
Prior art keywords
composition
mixture
group
thermally
document
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AU664254C (en
AU3651693A (en
Inventor
Pavel Petrovich Anashkin
Elena Lvovna Andreeva
Vyacheslav Vladimirovich Belokon
Vladimir Ivanovich Belyakov
Vyacheslav Ivanovich Deruzhinsky
Maria Viktorovna Dikova
Anatoly Dmitrievich Golubev
Tatyana Pavlovna Korobenina
Nikolai Alexeevich Krivosheev
Robert Alexandrovich Kuznetsov
Anatoly Vasilievich Marchenko
Zinovy Petrovich Pak
Boris Petrovich Perepechenko
Dmitry Leonidovich Rusin
Galina Grigorievna Shakhrai
Vladimir Nikolaevich Vershinin
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LJUBERETSKOE NAUCHNO-PROIZVODSTVENNOE OBIEDINENIE "SOJUZ"
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LJUBERETSKOE N PROIZV OB SOJUZ
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    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/06Fire-extinguishing compositions; Use of chemical substances in extinguishing fires containing gas-producing, chemically-reactive components
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0007Solid extinguishing substances
    • AHUMAN NECESSITIES
    • A62LIFE-SAVING; FIRE-FIGHTING
    • A62DCHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0007Solid extinguishing substances
    • A62D1/0014Powders; Granules

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)
  • Fire-Extinguishing Compositions (AREA)
  • Fireproofing Substances (AREA)

Description

,OPI DATE 01/09/93 AOJP DATE 28/10/93 APPLN. ID 36516/93 N~ 1111~~I PCT NUMBER PCT/RU93/00025 iII111 AU366) (51) MeacpyuapoAua! IJaccH4)HKBIIHH (11) Homep meacpyuaPopuo0f ny6afEaqiHH: WO 93/14820 Hiao6peTemflI 5: Al (43) Aa'ra memcpynaPOpliOft A62D 1/00 ny6Jawgn: 6 a.Brycra 1993 (05.08,93) (21) Homep meac~yuapopnofi 3aanKi: PCTIRU93/00025 RoBc1~afl o6ji., ya. CHOPTHBHan1, A. 10, He. 97 (RU) [PAK, Zinovy Petrovich, Dzerzhinsky KPH- (22) Aara meapyIHapoxuofi Hopa'ql: BOIHEEB Himxoniaf AjiexceeBpi [RU/RU]; A[aepHCHH- 28 allnapfl 1993 (28.01.93) ciwil 140056, Mocx~oacxan o6ji., yjz. OoeTC~ai, g. 2, KB, 37 (RU) [KRIVOSHEEV, Nikolai Alexeevich, AIauHie 0 UPHOPUrere: Dzerzhinsky AIEPY)KHHCKIHk BHleciiaB 5034846 30 misaps 1992 (30.01.92) RU Hsa.Hoa~ri [RU/RU]; Alaepj=Hiciwii 140056, MOCICOBcicas o6a., yn., CIIopTHHafl, A. 19, im, 3 (RU) [DERU- (71) 3alUH a JIIOBEPELIKOE HAY'IHO-HIPOI'3- ZHINSKY, Vyacheslav Ivanovich, Dzerzhinsky BOAC~TBEHHOE OB'bEAgHHEHI4E COIO3- [RU/ BEJIOKOHb BqecjiaB BAPHPOBH'I [RU/RU]; RU]; gI~epatmicidi 140056, MocRwsciaui o6i,, yq. Co- MocKwa 115470, yn. HoHammdi, A. 15, 1dB. 10 (RU) [BE- BecnaA 6(R)[L.JUBERETSKOE NAUCHNO- LOKON, Vyacheslav Viadimirovich, Moscow BeRcIZVDa TENO OBEDN.I 6 (RU) KY3HE1jOB Po6epT AneltcaiAPpoBauq [RU/RU]; PzROhiZVSTVENO OBIEDNENI OUZaHKT-rleTep6ypr 193230, yqx. TejiamaHa, g, 28, KB.
Dzerhinsy (R)].441 (RU) [KUZNETSOV, Robert Alexandrovich, (72) Hao6peraTeau: HIEPEHIELIEHKO Bop:uc fleTpoaIH Sankt-Peterburg BEJISIKOB B~anaimHp Ilea- [RU/RU]; Aa~ep~tiadi 140056, Mocxoacxasi o6, ya HiOaii [RU/RU]; Mra 187300, JIeiurpacxas o6ji., yji, JlepMrnrroa, A. 12-a, 1dB, 10 (RU) [PEREPECHENKO XKeneaHOMPpOdla3, A. 167, im. 1 (RU) [BELYAKOVI Boris Petrovich, Dzerzhinsky ROPOBEHI4HA Vladimir Ivanovich, Niga rojiYBEB AaTrnu Tammi~a rlaunoDHa Moexna 109443, Bonro- AImHrpiiemiq' [RU/RU]; Oamm-flerp6ypr 192242, yji.
rpagciarii UP., A. 84, itopi. 1, KH. 46 (RU) [KOROBE- Bygane=ncicaH, A. 9, :copn 1, imn. 288 (RU) [GO- NINA, Tatyana Pavlovna, Moscow UIIAXPAh LUBEV, Anatoly Dmitrievich, Sankt-Peterburg r~ama Ppmropbewia [RU/RU]; ,Taepmciii 140056, PY0I4H Amurpilii JReoI.oBIM [RU/RU]; Mac- Mocldoacxas o6ji., yni. J~epMoHToBa, A. 24, KB 83 (RU) Idna 562, AA'rydlnescicoe mocce, A. 18-B, ICB. 445 (RU) [SHAKHRAI, Galina Grigorievna, Dzerzhinsky [RUSIN, Dmitry Leonidovich, Moscow BEP- AHAILIKHH flaaen fleTpasnq1 [RU/RU]; Mocidna IIIHHHH BJnapMimip Hmtoniaemml [RU/RU]; Aa~ep- 113556, tIoHrapcKufi 6ynaaaRP, p. 1/3, KB. 301 (RU) wancii 140056, Mocicosccan o6j,, yji, JleCixaq, g, [ANASHKIN, Pavel Petrovich, Moscow AH-- HB. 92 (RU) [VERSHININ, Vladimir Nikolaevich, ALPEEBA EJneHa Jhnouula [RU/RU]; ,iAepH1HHCK11fi Dzerzhinsky 140056, MOCidonClanR o~ii., yqi TomHniHI, p. 13, KB.
53 (RU) [ANDREEVA, Elena Lvovna, Dzerzhinsky (74) Areur.-C OOIO3flATEHT-; Mocxsa 103735, ya, Hnlb- ,LHKOBA Mapiin Bmmrpoinia [RU/RU]; Xiim- mmxa, p. 5/2 (RU) [-SOJUZPATENT., Moscow xs-6 141400, Mocitoac:xas o6n,, yji, Buijare'naa A- 29, im. 17 (RU) [DIKOVA, Maria Viktorovna, Khim- (81) Yicaaauue rocYpapcTna: AU, CA, JP, euporieiicxiiii ki-6 MAP t IEHRO AiiaTOJIiit Badainbentiz narewrr (AT, BE, CH, DE, DK, ES, FR, GB, GR, IT, [RU/RU]; AIaepmmidc~dii 140056, Monciesa o~iyi LU, MC, NL, PT, SE).
TomunHicxafl, A. 25, im. 52 (RU) [MAROHENKO, Anatoly Vasilievich, Dzerzhinsky flAK 3 HiIa- Oliy6JIHRoBauia W&i IIerpawIn [RU/RU]; Aepaicmi 140056, Moc- C om -temoAt o Atcow~yILapoaom flouiceL.
(54) Title: FIRE EXTINGUISHING COMPOSITION 66425 4 (54) Haausauuie H3o6pCTeuuh: Komnowign4S JAJI5H TYIIIEHI-Iqno)I{APA (57) Abstract A fire extinguishing composition containing a thermally dispersible component, an oxidizer, an oxygen-containing binder and an additive, where the thermally dispersib m component is a non-organic compound chosen from a group containing a chloride, sulphate, sulphide or phosphate of 'kaline or alkaline-earth metals, an ammonium salt or their mixture, at the following ratio of said components in per cent by weight: thermally dispersible component 1,0-36.0, oxidizer 60.0-94.0, oxygen-containing binder 3,0-25,0, additive 1,0-25,0.
(57) Pe)e paT KUAOvMo3 I a nAJa TyllelIwA Ho'apa, coxiepxMcAuta Tepmirec- Km4 paccelifaemu ROMIOHOHT, oRXCJ1TeJIL, xxcOJopogoco~epxcawiee caffayoulee x4 godaBicy, O~m iuaiS TeM, 1TO'B RaqeCT- Be TepMn~eCK4 pace14Baemoro Ko0vrnOieHTa npImeieHO Heopra- Hw~eCice coe~lTHeH14e, Budpa-Hoe x3 rpynnu, coIep2,Kaute~i xJiopi, cyjih(laT, cyu 14,, toctaT I~eJIItHLX MAX1' uteJIOHO-3e- MeAIBHbIX MeTaIJzoB, alvmOHIeBytO COMI, 14511 I'X CMeCL, X TeM, MqTO YKa3aHHLIe IOMflOHGHTU cogepmaTCSIH X ripi GOJI M~etM 'XX COOTHO~eHITH, Bec./o: TepMTqecXXI pacce1xi~aemUr KOMTIOHeHT 1,0 -35,0, OICT AT3T 50,0 -94,0, 1c1cJmpoJgocogepmiaUee oBSMYIOU~ee 3,0 25,0, godaBica 1,0 25,0.
HC1IJIoqITEJIbHO WJIf LJEJTEft HHOOPMAgH Koghir, itenowbayehime gan o6omma'emuin erpai-metioD PCT HU Tirry?UuWhX Jniiciax 6pomtop, B KOTOPb1X uiy6rnucyorca mext~ytapo~1nde aanuiau n coome'rim c POT AT AacTp~a Fit CIpaH1ua MW Maniami AU Ancrpanun GA Pa60H NI, Hiz~epniani,.
BB1 Bap~naoc GBl Bcmuto~p1uT1aluu NO Hopuern BE Beau" GN Paiuien NZ Honan 3eiaiimzuu BF Byp1muia cl)aco 6,Ri rpcLtw pi, n~LwUma BG Boju'apun IIU Em'upun PT Flopiyramii 11. Betum I E H4pniBAiW RO Pymhi.HiI B R Bpaaniuuui IT' H1TLUUW. R U Poccuiicxan (IDe~cpaw'lul CA HaHaAa 3J) sInoiuui SD Py~zaH CF 14eirpaAHOa(lpwIcaiiexaH Kil Hopeficim HapOgHo-Aehio- SE wneuwun Pecy~niiwKpawwcwRPgl6mmIa SK Caouauxa.R Pecny6anw CG Houro KR Kopeficitan Pecny6 uixa SN Ceiierai CH IInhihapi KZ KaIBXCTaH SU Coneccif 'oIl CI HOT A'1Th'YaP LI JTneiuumiin TD 4Aj CM KamepyH LK lllpn JRaia TG Toro CS t ICxocJIoi3aXIw LU JbiOccm6ypr UA Yxpainia CZ t Iemucxal Pecny6niixa MC monialt US COe~rutfie WTaThI DE repmamin MG MaAarac~ap Amepiuni DK Ilami ML, Mi VN Bbenaam ES II cnamin MN Mourommu Fl (PIiImHA119 MR MaBpilTamuHl r FIRE EXTINGUISHING COMPOSITION Technical field The present invent,'n relates to fire-fighting means, more specifically, to a fire-suppression composition.
Most effectively the present invention can be used for volumetrically suppressing fires of burning solids, such as wood, coal, textile, polymeric material articles; liquid substances, such as benzine, diesel fuel, alcohols, ethers, glycols;.gaseous substances, such as hydrogen, methane:, propane or mixtures thereof;, metals such as light-weight metals: AI, Mg or their alloys, alkali metals, K, Na metal-containing compounds: metal hydrides, metallo-organic, materials.
By "volumetric" fire-suppression we understand creating in a limited space, say, in a room, hold, shop, etc., called a protected space, a medium that does not maintain combustion, which is achieved by feeding gaseous substances or aerosols to the protected space by evenly distributing same in this space in an amount that assures a concentration thereof, which makes combustion and explosion impossible.
Prior art By now, in view of a sharp increase in and growth of industrial potential, the number of fires is increased propertionally, with the chemical and gas-petroleum refining industries suffering in particular, where there can occur emergency ejections of easily inflammable liquids and gas fuels etc, which are dangerously explosive, as well as the wood and coal industries. For ages fires remain one of the most serious accidents on ships. Up to 30% of all disasters on vessels a year come of a destructive action of fires. The efficient extinguishing of fires is an urgent problem of safety of navigation.
One of the most popular compositions is a halogencontaining gaseous composition to be fed to the combustion zone ("Halon"), for instance, Halon 13BT- based on Strifluorobromomethane,Halon. 114B2- based on tetrafluoro- 2 dibromomethane, which is distinguished by high fire-fighting and operation properties, but belongs to the class of ozone-destructive'compositions.
(Review of T 3 NIITESTROIMASH, construction, road-building and municipal engineering, Series 6, "Fire equipment", Issue 3, "State-of-the-art automatic gas fire-suppresion installations", 1983, Moscow, pp. 3-40) In accordance with the protocol of Montreal (1987) concerning international measures toward protection of the ozone layer of the Earth, they will be fully prohibited by 2000 year.
Another wide-spread fire-fighting medium is a composition,based on carbondioxide, which on getting into the seat of fire lowersthe temperature of the combustion zone, thanks to the evaporation of the composition flakes and reduces the amount of oxygen, contained in the combustion S zone.
I!
However, CO 2 based compositions are toxic and tend to affect respiratory tracts of the people finding themselves in the combustion zone, caused by suffocation, resulting in death.
A Halon-based composition likewise exerts a toxic effect on the human body, while I-Ialn thermal decomposition products are distinguished for high corrosion activity.
Moreover, a variety of application has been found in the world by a powder of the type, used for fire-suppresion, which substantially is a mechanical mixture on the basis of, say, sodium bicarbonate or phosphoric-ammonium salts up to 95-97 wt.% with Aerosil or graphite (M.E.
Krasnyanskii "Firefighting and explosion-suppressing powders", 1990, "Donbass", Donetsk, pp. 16-25). Said powder is conveyed to the combustion zone by a gas under pressure. The powder, ejected under pressure forms an air-gas mixture, which blankets flames and suppresses them by isolating same from air oxygen. However, the known powder displays lowered operation properties becau-
I
43T FIAQ7~-itl e 6~7 ao' WV, I 3 se of tendency to caking and lumping, a factor that hampers its feed from equipment to the combustion zone. The said powder is in the main applicable only for fighting local fires.
Known in the art is a fire-suppression composition as shown and described in USP No.3972820. The prior art composition is in reality a solid mixture including 25-85 wt.% of a thermally dispersed halogen-containing organic component, demonstrating a fire-fighting property and selected from a group consisting of hexachlorobenzene, hexabromobenzene, perchloropentacyclodecane;, c- dibromotoluene, 1,2,3,4-tetrachlorodibromobutane, decabromodiphenyl oxide, tribromopentyl alcohol, tetetrabromo-x-diethyl benzene, c(-tetrabromo-o-xylene, octachloronahpthalene, 1,2,4,5-tetrabromobenzene, 1,2,4,5tetrachlorobenzene, polybromonaphthalenes, dibromotetrafluoroctane, 1,2-dibromo-l,1-dichloroethane, 1,2-dibromo- 3-chloropropane, o6-dibromoethyl benzene; 15-45 wt.% of the oxide selected from a group consisting of sodium chlorate, potassium chlorate, sodium perchlorate and perchlorate of potassium; 3-50% wt.% of a binder assuring the binding of a composition, its processibility and combustion in the presence of an oxidant; about 2 wt.% of a catalytic addition to accelerate solidification of the composition.
The distinction of the known composition is its capability, when being burnt, to sublimate a crystalline, thermally dispersed organic component, which brings about a reduction of the specific consumption of the composi.'.on to 128 g/m 3 Due to interaction of the oxidant with the binding agent the heat is liberated for subliming a crystalline, organic, thermally dispersed component, or in other words, a halogen-containing gaseous phase is formed, which inhibits a chemical reaction of combustion in the fire zone, and a solid phase in the form of black that is neutral Sto the chemical reactions, proceeding in the fire zone.
r i I The gas phase of the composition has a harmful effect on the human body and destroys the Earth's ozone layer.
Then, the known composition is toxic because of volatility of the organic compounds, used as a thermally dispersed component; besides said composition is distinguished by lowered vital activity because of a high rate of growth of its mass viscosity, explained by the employment of a catalytic addition, represented by tertiary amines, Lewis acid, metal oxides. In utilizing said known composition under an elevated pressure, say, over 2 atmospheres, one can observe its unstable combustion, entailing its attenuation.
Disclosure of the Invention The basis of the present invention is to create a composition for fire-suppression with improved operating qualities, an expanded range of its application under a reduced specific consumption thereof by means of changing the nature of a thermally dispersed components and by varying the weight percentage of an oxidant, oxygen-containing binder and addition agents and the combustion products of which would be ecologically pure and contribute to protecting the Earth's ozone layer.
There is disclosed herein a fire-fighting composition comprising 1.0 to 35.0 wt% of a thermally dispersible component, 50.0 to 94.0 wt% of an oxidant, 3.0 to 25.0 wt% of 0 an oxygen-containing binder and 1.0 to 25.0 wt% of an addition agent as hereinbefore 20 described, wherein said thermally dispersible component is an inorganic compound selected from the group consisting of chloride, sulfate, sulfide, alkali or earth alkaline °metal phosphate, ammonium salt and a mixture thereof.
0 t o a 0 0 0*0000 0 0 INALI3AAI4931 SAK ;ic The nature of the thermally dispersed component in the above-indicated composition is such that it is selected from a series of salts of inorganic acids,which explains non-volatility of the composition and its ecologic purity. The utilization of the composition according to the invention shows improved operating properties obtained due to an increased share of a finely divided solid phase down to 2 ,4m in aerosol, formed during burning of the composition.
The increased share of the finely divided solid phase in aerosol permits expanding the range of application of said composition, say, in extinguishing "smoldering" fires and burning metals, which is explained by the fact that the finely divided solid phase descends on the burning surface and isolates it from access of the atmospheric oxygen. The selection of an inorganic, thermally dispersed component makes it possible to produce a protective coating in the form of a viscous polymeric film, formed through crystallization'of said finely divided solid phase melt at a temperature of the burning surface.
In addition, the composition according to the invontion exhibits improved operating qualities owing to the fact that the increased share of the finely divided pha- 1 se in aerosol eases the inhibition of chemical reactions of combustion, increasing the likelihood of destruction of the "active" burning centers over the surface of the finely divided phase.
The content of a thermally dispersed component of Jless than 1% by weight in the composition resu: s in that the product of combustion thereof do not coiitribute to continuity of the formed protective coating, which hampers extinguishing "smoldering" fires. Given the contained thermally dispersed component in the composition being over 35 there is observed unstable combustion of the composition because of an insufficient quantity of oxygen therein.
c4 With an oxidant content in the composition amounting r I 6 6 to less than 50 one can observe a lack of oxygen, as a result of which after inflammation the composition does not burn independently. In case the amount of oxidant exceeds 94% by weight, it is impossible to produce said composition and to form a fire-suppression charge therefrom.
With an oxygen-containing binder being present in the composition in the amount of Less than 3 a fire-suppression charge cannot be formed, whereas with its content exceeding 25 the complete burning of the charge is not attained and the burning is accompanied by a great amount of carbon production in the form of black.
If the amount of an addition agent in the composition exceeds 25 the latter does not burn because of the deficit of oxygen therein, whereas if its content in said composition makes less than 1 one cannot achieve homogeneity of the chemical composition of a fire-suppression charge, and, consequently, its even layer after layer burning.
It is recommended to include an oxidant in the composition in the form of potassium perchlorate, or sodium perchlorate, or ammonium perchlorate, or potassium nitrate, or sodium nitrate, or ammonium nitrate, or a mixture thereof.
The choice of the above-indicated oxidants depends on a high content of oxygen therein and the formation in the combustion product of the composition of an additional amount of a finely dispersed solid phase, such as Na 2 0, K 2 0, KOH, K 2
CO
3 Na 2
CO
3 KCl, which inhibits the course of chemical reactions of combustion, a factor that enhances the efficiency of said fire-fighting composition eventually causing a reduction of its specific consumption.
The employment in a composition of a mixture of said oxidizing agents makes it possible to control the burning rate thereof within a wide range of.values, say, from about 0.3 mm/s to about 5.0 mm/s under an atmospheric r I i I- r -7
I"
7 pressure.
j; It is advisable,to include an oxygen-containing binder into the composition in the form of a cellulose ester: ethyl cellulose, acetate cellulose, nitro cellulose or a mixture thereof; or rubber: butadiene nitrile, butyl rubber, urethane, natural, divinyl styrene, divinyl nitrile or a mixture thereof; or a polymer: chlorinated polyvinyl chloride, polyvinyl chloride,polyvinyl butyral, polyvinyl acetate or a mixture thereof: or a resin: epoxy, unsaturated polyester, phenol formaldehyde or a mixture thereof; or their mixture.
The use of the indicated oxygen-containing binders in the composition enables one not only to form a firesuppression charge, but also to decrease the specific consumption of the composition in putting fires out.
When using said esters of cellulose, or their mixture as an oxygen-containing binder in the composition, the latter can be formed into a fire-suppression charge according to the forming process of thermo-setting materials.
According to the same technology there can be formed a charge from a composition, containing as oxygen-containing binding agents the indicated above rubbers, polymers or a mixture thereof.
When usinq said resins or their mixtures as oxygencontaining binders in the composition, the latter are formed according to the technology of "free" moulding or injection moulding to shape a fire-suppression charge.
i- The use of said resins and said cellulose esters in 30 the composition permits expanding the temperature range of said charge application, up to 600C by improving the physico-mechanical properties of the composition, based on an increase in density of polymeric nets in the composition structure.
Besides, the presence of oxygen in the binder contributes to better composition burning and allows a re- ©,gy duction of the oxidant content with a simultaneous inftk4 S. 8 8 crease in the portion of an inorganic thermally dispersable component, which results in a reduced specific consumption of composition for fighting fires.
It is desirable to use potassium chloride as athermally dispersable component in the amount of from 1 to wt. The use of said potassium chloride is motivated by its enhanced ability to bind "active" centers, responsible for the development of combustion in the seat of fire, a factor that has caused a reduction of its content in the composition to 25% by weight. Also, this leads to a reduction of the specific consumption of said composition for fighting fires.
The composition may contain potassium nitrate and potassium perchlorate as an oxidant in the amount of from about 50 to about 85 wt.%.
It is common knowledge that these substances are lowhygroscopic and therefore their nitroduction into the composition eliminates a need in sealing the fire-suppression charges, mounted on river and sea-going vessels. A combination of potassium nitrate and potassium perchlorate explains a high oxygen balance of the composition, which makes it possible to lower the upper limit of their content down to 85 wt.%.
SuCA as The composition must contain -a an addition agent 4 a plasticizer, a combustion modifier, a process admixture, or a mixture thereof.
To form a fire-suppression charge according to the technology of producing thermosetting materials, a plasticizer is needed. With the content of the oxygen-containing binder in the composition being from 3.0 to 10 wt.% according to the invention, a process admixture is added thereto to form a charge by the method of injection moulding.
With the content of an inorganic, thermally dispersable component in the composition from 10 to 35 wt.% and I providing its combustion under a pressure exceeding the
MMMMMMP
atmospheric one, it is necessary to introduce a combustion modifier thereinto.
It is advisable to include a plasticizer into the composition, represented by esters and polyesters from a series of dibutyl-phtalate, dibutyl-sebacinate, tributyl phosphate, glycerol triacetate, tricresyl phosphate or a mixture thereof; organic nitrates: nitroglycerin, dinitratediethylene glycol, dinitratetriethylene glycol or a mixture thereof;,organic azide, including S-triazine series: 2,4-diazido-6-amino-S-triazine, 2,4-diazido-6-azidoethoxy-S-triazine; 2-axido-4,6-diazidoethoxy-S-triazine or a mixture thereof; or their mixture.
The application of said esters and polyesters as well as of organic nitrates is conditioned by utilization in the composition of cellulose esters, rubbers or polymers, or a mixture thereof as an oxygen-containing binder. Besides, organic nitrates increase the oxygen balance of said composition, while their mixture permits expanding the temperature range of application for the fire-suppression charge, say, up to 260 0
C
by lowering the cristallization temperature of the mixture. When used in the composition, organic azides increase the rate of the composition combustion, which makes it possible to increase the content of a thermally dispersable components in the.composition from 25 to 35 which results in an improved efficienty of fire-suppression.
One would desire to include a combustion modifier in- Sto the addition agent in the amount from 1.0 to 15.0 wt.%.
i 5 With the modifier content amounting to about 1 wt.%, the composition does not burn at an environmental pressure exceeding the atmospheric one and it resiststo ignition because of the use of thermally stable oxidants therein.
The content of the combustion modifier in the addition agent in excess of 15 increases the consumption of said composition in fire fighting.
R Depending on the nature of the selected oxidants and I I r .i i U ~I_ inorganic thermally dispersable component, the composition may contain a combustion modifier, represented by a group including carbon, silica, aluminium, alumina, ferrum, ferrum oxide and a mixture thereof.
Carbon may be represented by black, graphite, diamond, and the dispersity of silica, aluminium and alumina, ferrum and ferrum oxide may be varied.
The process admixture contained in the composition, should amount to from 0.5 to 6.0 per cent by weight.
Its optimal content in the composition is associated with the nature of the indicated above oxygen-containing binder and the technology selected to form a firesuppression charge. When moulding procedure is used to form said charge, the optimal content of the process admixture is equal from 3 to 6 whereas when forming it according to the technology of thermosetting materials and "free" moulding and also injection moulding the content of process admixture is from 0.5 to 3.5 per cent by weight.
Embodiments of the Invention Given below are specific examples, illustrating production of the composition for fire-suppression in accordance with the present invention.
EXAMPLE 1 A fire-fighting composition according to the invention comprises a thermally dispersable component, an oxidant, an oxygen-containing binder and an addition agents with the following content thereof in wt.%.
thermally dispersable component inorganic compounds,potassium chloride KC1 oxidant: r; r 1 potassium nitrate, potassium perchlorate oxygen-containing binder:
KNO
3 KC10 38.5 39.5 -11 po,. vinyl acetate pheno.J maldehide resin 8.8 addition agent plasticizer dibuty phtalate process admixture 3.7 The composition is prepared as follows.
The mixing apparatus is fed with an oxygen-containing binder polyvinyl acetate in the amount of 8.8 g either in the form of powder with 10% of water added per the powder mass, or in the form of 30-50% aqueous dispersion, and a phenolformaldehyde resin in the amount of g; thereafter the binder mixture is agitated for minutes to achieve its homogenization. Then the obtained homogenized mixture of the binder is added with the crystalline powder of a thermally dispersable component of potassium chloride KC1 in the amount of 1.0 g, the matter being agitated for 3-5 minutes to yield a mechanical mixture of said binder and said thermally dispersable component. The thus prepared mechanical mixture is added with an oxidant, being substantially a crystalline powder, potassium nitrate KNO 3 and potassium perchlorate 4 in the amount of 78.0 g, followed by agitation for minutes to obtain a mechanical mixture of water, a binder, a thermally dispersable co:mponent, and an oxidant.
25 Said mechanical mixture is added with an addition agent in the amount of 7.2 g. Said'addition agent comprises a viscous-liquid plasticizer dibutylphthalate in the amount of 3.5 g to impart plasticity to the oxygen-containing binder polyvinyl acetate, polymer which facilitates further treatment of the composition at the foiming stage; and the process admixtures in the amount of 3.7 g, which comprise viscous petroleum jelly in the amount of 1 g, to enhance the effect of plastification of the binder -polyvinyl acetate polymer; carbon in the form of black in the amount of 0.2 g, used to reduce friction between crystals of the thermally dispersahle component i
I
iI i, "ia~4 a r- S- 1.2 and the oxidant; a tetrafluoroethylene polymer powder in the amount of 1.5 g and a sodium stearate crystalline powder in the amount of 1 g to facilitate treatment of the composition at the forming stage. The mechanical mixture with additional agents is agitated for 60 minutes and the mixture obtained is transferred to the rolling stage to produce a web therefrom. A repeated rolling operation results in additionally plasticized polymers: polyvinyl acetate and tetrafluoroethylene polymer and also in removing water due to elevation of roll temperature up to 70-90°C. Usually the number of rolling steps is 12 to 20. Then a roll is formed from the resulting web, which is subjected to mou3ding conducted at a temperature from 60 to 90 0 C and at a pressure above 1000 kgf/cm 2 to obtain an intermediate product of the fire-suppression charge having a diameter of 70 mm with and/or without a central channel. The resulting hot blank intermediate product is cut into charges of the required length.
EXAMPLE 2 A fire-fighting composition according to the invention comprises a thermally dispersable component, an oxidant, an oxygen-containing binder and ari addition agent having the following ratio: thermally dispersable' component: inorganic compounds potassium chlorate KC1 oxidant: potassium nitrate KNO 3 16.0 potassium perchlorate KC10 4 34.5 oxygen-containing binder: nitrocellulose containing 12.8% of nitrogen 25.0 addition agent: plasticizer-nitroglycerol 18.4 process admixture 1.1 The composition is prepared as follows.
A reaction vessel with water is added under constant
F,
13 stirring. An oxygen-cbntaining binder-fibrous nitrocellulose in the amount of 25.0 g is added to a reaction vessel with water under continuous stirring; the mixture is agitated for 15-20 minutes to prepare a stable suspended matter of nitrocellulose fibers in water. The quantity of water in the reaction is 125.0 g. The resulting suspended matter is added with an addition agent. Then under constant stirring, the addition agent which is a viscous-liquid plasticizer nitroglycerol in the amount of 18.4 g is added to the resulting suspended matter to impart plasticity to the oxygen-containing binder nitrocellulose fibers, a factor that facilitates a further treatment of the composition. The addition of nitroglycerol is carried out in small portions. Upon completion of feed of said nitroglycerol into said suspended matter, the latter being still agitated for 20 to 30 min to obtain a suspension containing water and partially plasticized nitrocellulose. The resulting suspension is then added with process admixtures in the amount of 1.1 g, which include viscous petroleum jelly in the amount of 0.5 g, carbon in the form of black in the amoint of 0.2 g and a crystalline powder of calcium stearate in the amount of 0.4 g, facilitating the further treatment of the composition. The suspension is then agitated together with the addition agents for 60 min, whereupon it is freed of water by squeenzing out with the resultant mechanical mixture being exposed to air for 24 hours for further removal of water and "maturing" of the mixture. There is obtained a mechanical mixture with a humidity of 10 to to be supplied to the mixing apparatus. The mixture obtained is then added with a crystalline powder of a thermally dispersable component- potassium chloride KC1 in the amount of 50 g, agitated for 3 to 5 min to obtain a mechanical mixture consisting of a partially plasticized binder, process admixtures and thermally dispersable component. The resulting mechanical mixture is added with an oxidant in the form of a crystalline powder of potassip Nt t-p 14 um nitrate KNO 3 and potassium perchlorate KC10 4 in the amount of 50.5 g, agitated for 60 min to produce a mechanical mixture of said thermally dispersable component, oxidants, partially plasticized binder and process admixtures. Said mixture is transferred to the rolling stage to obtain a web therefrom. A repeated rolling operation results in the final plasticization of nitrocellulose and in the removal of water due to increased temperature of rolls up to 70-90 9 C. Generally the number of rolling steps is 15 to 20. Thereafter a roll is formed from the web obtained, which is subjected to moulding. The further process of the moulding and forming of-an intermediate product of the fire-suppression charge.is carried out in a way similar to Example 1.
EXAMPLE 3 A fire-fighting composition according to the invention comprises a thermally dispersable component, an oxidant, an oxygen-containing binder with a ratio thereof as follows, wt.%: thermally dispersable component: inorganic compoundpotassium chloride KC1 15.0 oxidant: potassium nitrate KNO 3 64.0 oxygen-containing binder: divinylnitrile rubber 4.4 polyvinylbutyral 4.4 addition agent: plasticizer-glycerol triacetate combustion modifier carbon process admixtures, 1.7 The composition is prepared as follows.
An oxygen-containing, binder, being substantially a mixture of polyvinylbutyral in the amount of 4.4 g in the form of a powder with the addition of about 100 of water per the powder mass and divinyl-nitrile rubber are fed to the mixing apparatus in the amount of 4.5 g in the I I form of a latex to improve the physico-mechanical properties of the composition. Said mixture is agitated for min to obtain a stable suspen'ed matter and to uniformly distribute said binder components therebetween. The resultant suspended matter is added with a crystalline powder of said thermally' dispersable component potassium chloride KC1, 15.0 g, and the whole mixture is agitated for 3 to 5 min to produce the suspension of the binder and the thermally dispersable component. This suspension is added with an oxidant in the form of a crystalline powder potassium nitrate KNO 3 in the amount of 64.0 g and agitated for 20 minAn addition agent in the amount of 12.2 g is introduced into the suspension comprising water, a binder, a thermally dispersable component and an oxidant, and the whole matter is agitated for 60 min.
Said addition agents include: a viscous-liquid plasticizer-glycerol triacetate, 3.5 g, to impart plasticity to polyvinylbutyral polymer and divinylnitrile rubber, which facilitates further treatment of the composition; a combustion modifier carbon in the form of black, in the amount of 7.0 g, to provide stable burning of the composition, a.id process admixtures in the amount of 7.7 g which include a tetrafluoroethylene polymer powder, g, and a sodium stearate crystalline powder in the amount of 0.7 g, which ease further treatment of the composition.
SAs a result of agitation, obtained is a suspended i ,matter, comprised of water, a binder, a thermally dis- 2 persable component, an oxidant and &n addition agent, which undergoes further treatment according to the run of Example 1.
EXAMPLE 4 A fire-fighting composition according to the invention comprises a thermally dispersable component, an oxidant, an oxygen-containing binder and an addition agent with the following ratio thereof, wt.%.
16 thermally dispersable component: inorganic compound: potassium chloride KC1 9.7 oxidant: potassium nitrate KNO 3 54.0 potassium perchlorate 4 10.0 4 oxygen-containing binder: unsaturated polyester resin 23.8 addition agent plasticizer-dibutylphtalate combustion modifier-carbon and process admixtures The composition is prepared as follows.
A viscous unsaturated polyester resin, viscous-liquid dibutylphthalate, carbon in the form of black and viscous-liquid sulforicinate as a process admixture are fed to the mixing apparatus successively, the introduced components are agitated for 15 to 20 min at 25 0 C. The resultant mixture is added with a crystalline powder of a thermally dispersable component-potassium chloride KCl and the whole matter is agitated for 10 to 15 min. The mechanical mixture obtained is added with a crystalline powder of potassium nitrate KNO 3 and potassium perchlorate KC10 4 the components being agitated for 60 min with the simultaneous vacuum evaporation of the mechanical mixture. Then the resulting mixture is vacuum cast into moulds, which are subjected to thermostatic treatment at 80 to 90 0 C for days to get mixture solidified. The resultant intermediate products of fire-suppression charges are subjected to machining. The diameter of the charges obtained is 280 mm.
The specific consumption of the compositions according to the invention in given in Tables 1 to 4.
I ~_UI1L 17 Table 1 Component and parameter under check Content of component in composition, and value of parameter under check 1 2. 3 4 5 6 7 8 9 10 11 12 Thermally dispersable component: potassium chloride' 15 1 12 sodium chloride 13 ammonium chloride 2 sodium sulfide 15 25 10 potassium sulfide 15 sodium sulfate 5 calcium sulfate 10 monoammonium phosphate- 5 dipotasium phosphate 10 disodium phosphate 10 magnesium chloride 12 calcium phosphate 10 Oxidant Oxygen-containing binder Addition agent Specific consumption, g/cm 3 64 55 65 50 78 94 55 60 69 65 8.8 20 5 25 13.8 3 18 10 3 10 3 12.2 3 10 10 7.2 1 2 5 3 5 2 63 65 62 70 38 42 54 59 48 39 49 I 1 18 Table 2 Component and parameter Content of component in compounder check sition, and value of parameter under check Thermally dispersable component: potassium chloride 5 2 1 1 4 9.7 2 potassium sulfate 1 1 Oxidant: potassium perchlorate 34.5 50 50 40 80 60 10 sodium perchlorate 44 ammonium perchlorate 15 potassium nitrate 16 40 54 sodium nitrate 35 ammonium nitrate 5
I
Oxygen-containing binder Addition agent Specific consumption, g/m 3 25 3 8 10 18 15 23.8 15 19.5 9 1 5 1 1 2.5 3 70 50 52 60 46 59 68 55 F_ :19 Table 3 Component and parameter Content of component under check tion, wt.l.,and value ter under check in composiof parame- Nr~~ 12 3 6tS 7 8 9 10 11 Thermally dispersable component: potassium chloride 6 1 1 2. 1 2 4 20 10 Oxidant: potassium nitrate 10 35 53 55 55 59 30 27 40 potassium perchlorate 60 50 16 16 16 10 30 38 16 Oxygen.-containing binder: ethyl cellulose 10 acetate cellulose 12 nitro cellulose 3 butadiene nitrile rubber 1 butyl rubber 6 urethane rubber 6 6 natural rubber 2 divinyl styrene rubber 7 '7 rubber 0.5 2.3 chlorinated pol.yvinyl chloride -4 polyvinyl. chloride-, polyvinyl, butyral 2.5 6 polyvinyl acetate 7 epoxy resin -3 4 unsaturated polyester rosin F- 20 Table 3 (cont.) 2 3 4 5 6 82 9 10 1.1 phenol formaldehyde Additional agent: Plasticizer: dibutyl phthalate 7 2 3 dibutyl sebacinate 3 tributyl phthalate 3 glycerol. triacetate tricresyl. phosphate nitroglycerol 4 din it rate di ethylene glycol 2 dinitratetriethylene glycol
I
2, 4-diazida-G-amino- S-triazine 4 2, 4-diazido-6-azidoethoxy-S-triazine 2-azido-4m6-dliazidoethoxy-S-triazine--------3 Combustion modifier 3 1.5 5 6 6 6 15 2 15 6 Process admixture 3 0.5 5 6 6 3 1 2 6 2 Specific consumption, 21~ 9/M3 50 23 21 30 110 42 75 60 52 43 21 Table 4 Component and parameter Content of component in comnunder check position, wt. and value of parameter under ckeck Thermally dispersable component: potassium chloride 25 15 5 2 1 8 amnmonium chloride 5 3 Oxidant: potassium nitrate 3 19 30 42 34 20 16 pot-assium porchlorate 47 35 30 30 30 65 oxygen containing binder: epoxy resin 1L9.9 23 17 10 24 divinyl nitrile rubber 2 20 Addition agent: Pl.asticizer: dibutyl phthalate 1.6 1 5 3 3 1 Combustion modifier carbon 9 1- 9-1- 3 silica 1 aluminium (ferrum) 1 6 alumina (ferrum oxide)- I 10 Process admix-Lure 0.5 1 2 6 1 1 Specific consumption, g/m 3 48 70 63 53 61 33 43 j -22 INDUSTRIAL APPLICABILITY In accordance with the invention, Lhe employment of said composition for fire-fighting provides an effective quenching of power cables, fire-supression in oil and gas wells, quenching of fires of gases, liquids and solids in any premises, e.g. offices, garages, warehouses of practically any shape, elevator wells, mines, metro and railway tunnels, etc. Provision is made for blocking the spreading of fires and preventing gas explosions in production premises, in any type of processing equipment.
The compositions according to the invention can be used in the form of charges with a weight from 10 g to t and more, depending on the design of generators on their basis and concrete volumes of the objects to be protected.
ir

Claims (6)

1. A fire-fighting composition comprising 1.0 to 35.0 wt% of a thermally dispersible component, 50.0 to 94.0 wt% of an oxidant, 3.0 to 25.0 wt% of an oxygen-containing binder and 1.0 to 25.0 wt% of an addition agent as hereinbefore 59 described, wherein said thermally dispersible component is an inorganic compound selected from the group comprising chloride, sulfate, sulfide, alkali or earth alkaline metal phosphate, ammonium salt and a mixture thereof.
2. The composition as claimed in claim 1 wherein said oxidant is selected from the group comprising potassium perchlorate, sodium perchlorate, ammonium perchlorate, potassium nitrate, sodium nitrate, ammonium nitrate and a mixture thereof.
3. The composition as claimed in claim 1 or claim 2 wherein said oxygen containing binder is selected from the group comprising a cellulose ester, a rubber, a polymer, a resin and a mixture thereof.
4. The composition as claimed in claim 3 wherein said cellulose ester is selected from the group comprising ethyl cellulose, acetate cellulose, nitro cellulose and a mixture thereof. The composition as claimed in claim 3 or claim 4 wherein said rubber is selected from the group comprising butadiene nitrile, butyl rubber, urethane, natural .divinyl styrene, divinyl nitrile and a mixture thereof. S 20 o 6. The composition as claimed in any one of claims 3 to 5 wherein said polymer is selected from the group comprising chlorinated polyvinyl chloride, polyvinyl chloride, polyvinyl butyral, polyvinyl acetate and a mixture thereof. 7, The composition as claimed in any one of claims 3 to 6 wherein said resin is 0 selected from the group comprising epoxy, unsaturated polyester, phenol formealdehyde and a mixture thereof. i; 8. The composition as claimed in any one of the preceding claims wherein said t thermally dispersable component is potassium chloride in the amount of from 1,0 to
25.0 wt%. 9. The composition as claimed in any one of the preceding claims wherein said oxidant is potassium nitrate or potassium perchlorate in the amount of from 50.0 to wt%. The composition as claimed in any one of the preceding claims wherein said addition agent is selected from the group comprising a plasticizer, a combustion modifier, a process admixture and a mixture thereof. 11, The composition as claimed in claim 10 wherein said plasticizer is selected from the group comprising an ester or polyester of any one or more of dibutyl phthalate, dibutyl sebacinate, tributyl phosphate, glycerol triacetate, tricresyl or phosphate; an organic nitrate; an organic azide and a mixture thereof. c LN:\LIfAA1493i SAK 24 12. The composition as claimed in claim 11 wherein said organic nitrate is selected from the group comprising nitroglycerine, dinitratediethylene .glycol, dinitratetriethylene glycol and a mixture thereof. 13. The composition as claimed in claim 11 or claim. 12 wherein said organic azide is selected from the group comprising S-triazine series-2,4-diazido-6-amino- S-triaxine, 2,4-diazido-6-azidoethoxy-S-triazine, 2-azido-4,6-diazidoethoxy-S-traizine and a mixture thereof. 14. The composition as claimed in any one of claims 10 to 13 wherein said combustion modifier is selected from the group comprising carbon, silica, aluminium, alumina, ferrum, ferrum oxide and a mixture thereof. The composition as claimed in any one of claims 10 to 14 comprising 1.0 to 15.0 wt% of said combustion modifier. 16. A composition as claimed in any one of claims 10 to 15 comprising from about 0.5 to about 6.0 wt% of said process admixture. 17. A fire-fighting composition substantially as hereinbefore described with reference to the Examples excluding any comparative examples. Dated 8 September, 1995 Ljuberetskoe Nauchno-Proizvodstvennoe Obiedinenie "Sojuz" Patent Attorneys for the Applicant/Nominated Person o 20 SPRUSON FERGUSON S0 9 4 o0 o 0 4 o o 4' 00 0 4. J Fire-fighting composition SAbstract A fire-fighting composition comprises a thermally dispersable component, an oxidant, an oxygen-containing binder and an addition agent. For a thermally dispersable Scomponent use is made of an inorganic compound, selected from a group comprising chlbride, sulfate, sulfide, alka- li and/or earth alkaline metal phosphate, ammonium salt or a mixture thereof. Said components have the following ratio, wt.%: thermally dispersable component 1.0 35.0 oxidant 50.0 94.0 oxygen-containing binder 3.0 25.0 addition agent 1.0 25.0 1 LI~-i~YI)PII" INTERNATIONAL SEARCH REPORT International application No. PCOr/RU 93/00025 A CLASSIFICATION OF SUBJECT MATTER Int. C1- 5 A62D 1/00 According t. ,nternatio nal Patent Classification (11C0 or to bath national classificaiion and IPC' B, FIELDS SEARCHED Minimum oocumentation searched iclassification system tollowed classificaion svnhol.; A62D 1/00 Documentation searched other than minimum documentation i0 theC eXtent that sucn documents are included in tne fields searcried Electronic data tiase consulted during tic international search name of data nase and. wnere practicable. search terms usedI C. DOCUMENTS CONSIDERED TO BE RELEVANT Category' Citation of document, with indication, where appropriate. of the relevani passages Rue-3vant to claim No. A GB,A,l 106 603 (THE DOW CHEMICAL COMPANY) 3,4 March 1968 (20.03.68), page 1 1,3,4, A Gi?.A,1 410 469 (JOHN KERR AND COMPANY 1,3,4,11 (MANCHESTER) LIMITED), 15 October 1975 (15.10.75), page 1 A GB,A,1 315 822 (UNITED KINGDOM ATOMIC 1,3,4,11 ENERGY AUTHORITY) 2 May 1973 (02.05.73), page 1 A GB,A,l 218 384 (WEINSTOCK SIEBERT 1,11 6 January 1971 (06.01.71), page 1 A DE,A,1 ?19 331 (NEB FEUERL OSCHGERATEWERK), 1,3 16 January 1966 (16.01.66), page 1 A DEA,1 206 729 (UNITED KINGDOM ATOMIC 1 ENERGY AUTHORITY), 9 Decemfber 1965 (09.12.65), page 1 Further documents are listed in the continuation of Box C. See patent famhilyannex. Special categonie of cited documents: T7 later document pulblished at ter the internitinnal filig ate or nontv document defining the general state of ihe art which is nni considered date and not in conflidi wth the application but C11i'a to understand to bie at particular relevance the pninciple or theory underlying the invention c ''earlier document but published on or alter the international filing date "NX" document of narticular relevance: the claimed inveniton cannot be consioered novel or cannot the considered to involve an inventive document which may throw doubts on rinorii claintisi or which is ste Ihntedcmnti ie tn cited to establish the oublicatton daie at another citation or other se nh oueti ae ln SDCC121 reason Itas specified I document at pazrticular relevance: the claimed inventkion cannot he Cocument retemrng to an oral disclosure, tise, exhibition or other considered io involve an inventive step wnen ine ocument is means conimined wit none or more otner such documents. sucn comnoinalton T' document aublished aoor to ihe international filinti dale but later than hetng onviou.q to a ierson skilled in tne art the oflonlY date claimed document memher at the same tiatent lamil'. Date ot the actual completion of tne international search Date ot mattne ot the international searcn report 1 April 1993 (01.04.93) 14 April 1993 (14.04.93) Name and mattin[e address ot the ISA I Authorized ottict- /RU L!acat m IlIe Nio Teletmnone No' i'orm I 1 CT'1SAnilutseconcj ,necti (July 19:
11111116- INTERNATIONAL SEARCH REPORT International application No. PCT/RU 93/00025 C (Continuation). DOCUMNTS CONSIDERED TO BE RELEVANT Category' Citation of document, with indication, where appropriate, of the relevant passages Relevant to claim No. US,A,3 830 738 (ARNOLD GEORGE CO~TRELL), August 1974 (20.08.74), paige 1 GBA,l 588 876 (C E C A S. 29 April 1981 (29.04.81), page 1 FR,Al, 2 632 866 (AEROSPATIALE SOCIETE NATIONALE INDUSTRIELLE), 22 December 1989 (22.12.89), the abstract Form PCTIISA/21O (cononuation of second shect) (July 1992) IOT'-ET 0 MEJIAYIAP0JtHOM UQUGJKE Me-yyiapoAHa1 azBKa No. POT/RU 93/00025 A. IUAOCM0IIX TJPE7WMTA V13OBPETEH4.9F A62D 1/00 CoriiacHo MelZiyHapoAHof4 raTelITTIOA 1lacWa LU4I4 (MRVI- BS. Oi3JIACTJ4 RIRHN'I MIHI'MYM AD~KYMeHiTaiI'id (OWOTeMa cl KHLT5 u,14Mz m4 ZH-- A62D 1/00 gag 0 8~1 1 l~1~ B TOf4 Mepe, B KIiKOJi 011' Bli,.IlO-- gK6RRAfi Ro~lH8R 8Ejqpp R n~Hlfo Hcle (HasBa- C. "UIORYMERHh, ClIJ4TAIallJ4CF PEJIEBAHTHNIM rCV(r Ceu]J K 8KY a T i FJgC STC) __TCO A GB, A, 1106603 (THE DOW CHEMICAL COMPANY)) 3.,4 MaIpT@ 1958 (20. 03. 68), c. I A GB, A, 1410469 (JOHN KERR AND COMPANY 1,3,4,Ii _____(MANCHESTER) LIMITED:), 15 OKT26p.) 1975 *Ocobue 1KaTerop14 CCblIOtflIbIX 9Q}(YWMB: "All YM~ P 1 O HTe T"B N "L jVeHT a CO Ph i ge o8- za xe. m HB la Bc O.J 4-3- 7,TJ~~a~ 1488fl~AI (lopma PCT/ISA/210 (BTop09 JIWOT) (Mo~b 1992) OTqE T 0 ME)IUYIAPO1UIM ITOMCKE M :ap I-Ii a; 1Nc C BKoILTm e 0 4KYME-HTH, CI4AO~VE? 1 K a~ er Cc L I- I d y H b 1,0aa TaH1 1 Pii ~JEBAI' HbiIff rj~- EVTC; A A A A A LJ. i I C~i, A 1I~o~.(UNITED KINGDOM ATOMIC" ENERG' AUTHORITY'. 2 maF 10-73: (02.05.73) c. GB, 12-18384 (WE71OCK S IEB E;-T LGj C: J9HBaDY1 19"71 (06. 01, 71) C D E' 1219211 (VEB EUE .ICGRTEE1 16 ZHDELpF 1966 (16.01.66), c.1 DE, A, 1206729 (UNITED KINGDOM ATOMIC ENERGY AUTHORITY), 9 ze~zabnz 1955 (09.12.55), c.1 US, A. 282)30728 ARNOLD GEORGE COTTPELL). 2C, aDrYCT& 1974 (20. 08. 74), c. GB, A, '1588876 (C E C A S. A. 29 aripeain 1981 (29.04.81)., c.1 Al. 262,2866 (AEROSPATIALE SOCIETE NA-T IOCNALS: INDUSTRIELLE).2 Epei 1989 *pecp~paT HOCI4TC7 i: fl~H1~TY W, 1,3.4,11 L~11 1,2 1 1*1 12 I I N- -A- D~VP. -A r1Do~oJI2je!-1w: .1IIACT~ IAKXIiI- I JC~
AU36516/93A 1992-01-30 1993-01-28 Fire extinguishing composition Ceased AU664254C (en)

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RO5034846 1992-01-30
SU5034846 RU2005517C1 (en) 1992-01-30 1992-01-30 Extinguishant
PCT/RU1993/000025 WO1993014820A1 (en) 1992-01-30 1993-01-28 Fire extinguishing composition

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EP4094810A4 (en) * 2020-01-22 2024-02-28 Yamato Protec Corporation FIRE EXTINGUISHING SHEET

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EP4094810A4 (en) * 2020-01-22 2024-02-28 Yamato Protec Corporation FIRE EXTINGUISHING SHEET
EP4094809A4 (en) * 2020-01-22 2024-02-28 Yamato Protec Corporation FIRE EXTINGUISHING SHEET

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AU3651693A (en) 1993-09-01

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