FR2458294A1 - PORTABLE EXTINGUISHER, EXTINGUISHING METHOD AND PRODUCTS USED IN THIS EXTINGUISHER - Google Patents

Abstract

THE INVENTION RELATES TO A PORTABLE FIRE EXTINGUISHER. PORTABLE FIRE EXTINGUISHER INCLUDING A TANK 1 CONTAINING PRESSURIZED WATER, A VALVE, A DUCT 7 CONNECTING THIS VALVE TO A NOZZLE 9, AS WELL AS A CARTRIDGE HOLDER 8 INTERPOSED IN THIS DUCT, THIS CARTRIDGE INCLUDING A MASS SHAPED BY A CONSTITUT SOLID AND AGGLOMERATED MIXTURE OF A FLUORALIPHATIC TENSIO-ACTIVE AGENT, SOLUBLE IN WATER, AND OF A FLUOR-FREE TENSIO-ACTIVE AGENT, SOLUBLE IN WATER, THIS MASS RECEIVING CONTACT WITH THE WATER CIRCULATING IN THE CARTRIDGE TO ADJUSTMENT 9 FOR THE FORMATION OF AN AQUEOUS FILM-GENERATING FOAM SOLUTION. THIS EXTINGUISHER MAKES A FILM-FORMING SOLUTION OF RELATIVELY CONSTANT COMPOSITION THROUGHOUT THE DISCHARGE PERIOD.

Description

The present invention relates to a portable fire extinguisher

  to discharge an aqueous film-forming foam. It also relates to a mixture of a water-soluble fluoro-phatic surfactant and a water-soluble, fluorine-free surfactant as well as to articles shaped into such a mixture. According to yet another of its aspects, the invention relates to a process for extinguishing fires created by flammable liquids or for preventing such fires, by applying to the surface such a liquid. a foam of an aqueous film-forming solution by means of a portable fire extinguisher. One of the most effective agents in the form of foams for extinguishing fires created by flammable liquids, for example, fires by liquid fuels, is an aqueous film-forming solution which it is applied to a fire in the form of a foam (these agents are commonly known by the acronym "AFFF"), a commercial extinguishing agent of this type being sold in the form of a concentrate. aqueous liquid under the brand name "Light Water". This agent has been successfully used by diluting it with water to extinguish a series of fires created for testing as well as real fires, including a fire at a petrochemical storage facility, a fire an oil tanker that had been burning for three days, aircraft fires, and numerous industrial fires involving widespread fuels and solvents. Suitable surfactant compositions for use in, or in the form of, agents for the control of fires, including agents of the AFFF type, have been described in particular in US patents. of America 3.258.423 2458294 2 (Tuve et al.), 3.562.156 (Francen), 3.661.776 (Fletcher et al.), 3.772.195 (Francen), 3.957.658 (Chiesa et al.), 4,090,967 (Falk) and 4,149,599 (Chiesa). These compositions consist of solutions of a water-soluble fluor-aliphatic surfactant, a water-soluble, fluorine-free surfactant, and water. When applying these compositions by employing, for example, a foam or water mist blasting apparatus, a foam is formed which spreads or floats on the surface of the burning liquid. for example gasoline, forming a vapor-tight film which extinguishes the fire. This film also protects non-inflamed areas and prevents them from igniting. These compositions are usually provided and stored as aqueous concentrates which are diluted with water in use, or they can also be stored in the diluted form. AFFF extinguishing systems are used to prevent and control fires in the case of flammable, relatively large, hazardous or potentially dangerous liquid masses, and require a specially designed dosing and flow facility, which acts by mixing the required amount of concentrate with water to create the foam. Since recently, AFFF portable fire extinguishers have been available on the market, such as the Spoiler brand extender of the applicant company, which was described in this company's bulletin Y-FEBIR (1062). MP, which can be used to combat fires due to relatively small masses of flammable liquids, as might be found in garages, paint shops, etc. These fire extinguishers are specially designed and contain about 9.5 liters of a pre-mixed AFFF agent and prat to use, such fire extinguishers being useful for combating small so-called "Class B" fires, as well as fires called "Class A". In summary, according to one embodiment of the present invention, there is provided a portable extinguisher comprising a tank charged with pressurized water, a valve and pressure lever assembly, surmounting the tank and preferably provided with a pin of and a manometer, a flow conduit connected to the valve assembly and terminating in a nozzle, and a cartridge holder connected to the upstream side of the nozzle and containing a cartridge having a shaped solid mass having at least an exposed surface consisting of a water-soluble, solid, agglomerated mixture of a water-soluble fluoro-phatic surfactant and a fluorine-free surfactant; in the water, compatible with the preceding, this extinguisher, when operated, operating by discharging water from the reservoir through the cartridge holder for this water to come into contact with the aforesaid surface e of the cartridge to dissolve the surfactants and to provide, via the addition, a foam of an aqueous film-forming solution (type

  "AFFF") of a relatively constant composition which can be applied to a flammable liquid mass to suppress a fire (ie a so-called "Class B" fire) or to prevent such a fire by the formation of an aqueous film, forming and spreading rapidly, durably and reliably on the surface of the flammable liquid, and in a manner generally described in US Pat. earlier. The fire extinguisher according to the invention can also be used to combat a fire of solid combustible material, such as paper and wool (ie fire of the type of fire). Class A "), more efficiently than a traditional 9.5 liter water-cooled portable fire extinguisher. Such a traditional extinguisher can easily be converted, as will be described later, into an extinguisher according to the invention for the purpose of combating the two aforementioned classes of fires. The cartridges used in the extinguishing systems according to the invention may consist of a single shaped mass comprising the solid mixture of surfactants. By way of example, in one form of construction of such a cartridge, the solid surfactant mixture is in the form of a sheet, with or without a reinforcing matrix (e.g. machine needle felt) deposited on water-insoluble, non-woven, water-permeable fabric, the whole being wound to form a reel or roll and loaded as a cartridge into a sleeve, the loaded sleeve being introduced into a cartridge holder. More particularly, the solid mixture of surfactants can be heated and compressed into a sheet, then cut to size, placed in exact alignment on a piece of nonwoven fabric, heated to soften, rolled up and fed into a sleeve as a cartridge for it. In another example, the shaped mass comprising the solid mixture of surfactants is in the form of a single solid cylinder having a star-shaped axial channel for the passage of water. In another embodiment, the cartridge is constituted by an agglomeration of a series (for example from 50 to 20,000) shaped masses (constituted by the solid mixture of surfactants) permeable to water, in the form of discrete pellets, pearls, sticks, etc. of relatively uniform size and shape, the water permeability of such agglomeration being due to to the interstitial spaces existing between the various shaped pellets, etc., which create channels for the passage of water through the cartridge. These types of cartridges, consisting of one or more shaped masses of the solid mixture of surfactants, provide an aqueous film-forming solution of relatively constant composition when the surfactant mixture dissolves into the stream. water supplied from the tank. The total area of the one or more shaped masses of the surfactant mixture is a predetermined area which is sufficient to provide the AFFF type solution having the relatively constant composition required at a given discharge rate. This predetermined area will vary depending on the particular solid mixture of surfactants, the manufacture and composition of the one or more shaped masses, the number, shape and dimensions of the one or more shaped masses, and the volume, flow rate discharge and the temperature of the water in the tank. By the term "relatively constant composition" it is meant that the minimum concentration of surfactants in the resulting solution, during the extinguishant discharge period, is at least about 50%, preferably at least 55% of the maximum concentration. To achieve this required composition, the amount of the shaped mass (s) of the cartridge is such that there will generally be a residual amount of mass or shaped masses left in the cartridge carrier after the discharge of all the water out of the tank. The invention will be further described further with reference to the accompanying non-limiting drawings. Figure 1 is an elevational view of an extinguisher embodiment according to the invention, with a loaded cartridge holder. Figure 2 is a partial cross-sectional longitudinal view of the charged cartridge nozzle and support assembly of Figure 1. Figure 3 is an isometric view of a preform embodiment. or cartridge stock, which can be wound up and loaded into the cartridge holder of Fig. 2. Fig. 4 is an isometric view of a cartridge made from the preform of Fig. 3. In Figure 1, the reference number 1 de-

  generally sign an embodiment of a portable extinguisher according to the invention, this extinguisher 20 having a tank 2 surmounted by an assembly comprising a pressure lever 3, a pressure gauge 4, a valve (not visible) and a locking pin 6, which assembly is connected to a flow conduit 7 whose other end is attached to a cartridge holder 8 which is itself connected to an air suction nozzle 9. Class A traditional portable water extinguisher (normally containing approximately 9.5 liters of water and approximately 2.8 liters of compressed gas, eg air or nitrogen) may be modified in a simple manner, for the purposes of the present invention, by removing its single nozzle and replacing it with the combined nozzle and cartridge holder assembly, illustrated in FIGS. 1 and 2. Alternatively, a fire extinguisher 2458294 7 traditional type A class can be changed to c Orpant its conventional flow conduit, by interpolating a cartridge holder according to the invention, by attaching this cartridge holder to the cut ends of the conduit by means of clips or other suitable devices, and replacing the traditional nozzle with an air intake adjustment. FIG. 2 illustrates an embodiment of a loaded cartridge holder according to the invention, this support being constituted by a cylinder formed of the two parts 10 and which are screwed to one another, for example by virtue of a spiral trapezoidal screw thread or a straight thread, as described in NASA Tech Brief 71-10336 (September 1971), this cylinder 15 forming an internal chamber 12 for a cartridge (of a volume of about 250 cm3, for example), this chamber being intended to contain, inside a sleeve 20, a cartridge 13 according to the invention, the upstream end of the cylinder portion 11 comprising an adapter 5 des- 20 receiving the downstream end of the conduit 7, while the downstream end of the cylinder portion 10 is intended to connect to an air intake nozzle 9, the upstream end of which comprises air openings 15 and a check valve 16 to prevent the circulation of a fluid, for example moist air or water, to the cartridge holder via the nozzle. The outside of the cartridge holder may have splines to allow the operator to securely grip the nozzle and holder assembly during discharge of the extinguisher. 3 shows a preform or cartridge reserve 13 'constituted by a porous, rectangular and flat support 21, on which is disposed a shaped mass 22 of surfactants of the fluoriphatic type and of the type without chlorine, in the form of a slightly smaller rectangular flat sheet, set back from the sides and with respect to an end of the support 21, while the other end of this sheet 22 coincides with the Another end of the support 21. When the preform 13 'of FIG. 3 is wrapped on itself, it takes the form of a roll 13 as illustrated in FIG. support 21 forming the outer wall of this roll. In this wound state, the cartridge 13 can be introduced into a sleeve 20 (which may be considered as part of the cartridge), made of plastic, metal, cardboard, paper impregnated with a phenolic resin, etc., and the assembly can then be placed in the cartridge chamber 13 of the support 8 of FIG. 2, the porous support 21 serving both to separate the surface portions of the mass 22 and to create channels for the passage of air in contact with these surface portions as this water flows from the reservoir to the nozzle. Optionally, as illustrated in Figures 3 and 4, a second short porous support 23 may be placed on one end of the shaped mass 22 to create a central channel 25 when the preform 13 'is wound on itself. In operation, fire control is achieved by removing the locking pin 6 by pressing the control lever 3 to open the valve and allow pressurized water to flow through the conduit 7 to the cartridge holder 8 for the discharge, through the nozzle 9, a foam of a solution "AFFF" of a relatively constant composition, that is to say a foam formed of a film-forming solution. aqueous gene generally containing from 0.05 to 1% by weight of a fluoro-phatic surfactant, the weight ratio of which to the fluorine-free surfactant is 10: 1 to 1 / 25. The water, as it flows through the cartridge holder, traverses the channels formed by the porous support 21, 23 thereby contacting the surface of the shaped mass 22 to dissolve the mixture. tensioactive agents. The area of the conformed mass 22 and the speed

  Each component is relatively constant during the discharge period. The contents of 9.5 liters of water will be discharged over a period of 45 to 2 90 seconds at an initial pressure of approximately 7 kgf / cm. The extinguisher can be refilled using approximately 9.5 liters of water and approximately 2.8 liters of compressed gas and providing a new cartridge after drying the cartridge holder. When the cartridge used is formed by a single shaped mass, it can be manufactured in a variety of other forms as long as the area of the shaped mass of surfactants, exposed to the flow of water from the reservoir, does not vary significantly during the dissolution of these surfactants. By way of example, the shaped mass may consist of a solid cylinder comprising an axial channel having a star shape in cross-section, the walls of this channel being exposed to the water discharged from the reservoir. In such an embodiment, a porous support will usually not be needed. Instead of charging the carrier with a cartridge made of a single shaped mass of the surfactant mixture, a carrier formed by agglomeration permeable to the carrier can be provided in the carrier. water of a series of shaped masses, for example pellets, whose area decreases during dissolution. Referring to FIG. 2, the cartridge 13 can be replaced by an agglomeration of a series of shaped masses of this kind. The sleeve 20 may be provided, at least at its downstream end, with a suitable, porous or liquid-permeable cap formed, for example, by one or more disks made of a non-woven, open-mesh, low density web. of the type described for example in US Patent Nos. 2,958,593 and 3,537,121, and sold under the trademark "Scotch-Brite". Such discs can be fixed in place, if desired, by their periphery to the sleeve, particularly by friction fitting or by employing an insoluble adhesive in the water, especially a temperature vulcanizable silicone rubber. ambient (of the type known as "RTV"). Such caps will retain agglomeration of shaped masses within the sleeve during handling and during dissolution during operation of the extinguisher. The series of shaped masses may be prepared by shaping the solid surfactant mixture into the shape and dimensions required by extruding the mixture or forming it into pellets. To maintain channels for the passage of water through a cartridge formed of such shaped masses, these are preferably made to be spherical or flattened so that masses having mainly round or curved surfaces. The shaped surfactant mass (s) used according to the invention, for example foil 22 of FIGS. 3 and 4, comprises an agglomerated solid admixture of one or more surfactants. - 5 fluoraliphatic fins, soluble in water, and one or more surfactants without fluorine, soluble in water and compatible with the above. The mixture is normally solid at ambient temperatures and does not become liquid below about 50 ° C. The fluriphatic surfactant contains one or more fluorinated aliphatic radicals (Rf) and one or more polar water solubilization groups (Z) which are usually joined by appropriate linking moieties (Q). Particularly useful fluoraliphatic surfactants are those described in US Pat. No. 3,562,156. The particular structure of the fluoro-phatic surfactant is not critical; on the other hand, it is the balance of the physical properties of the compound which determines its interest for the envisaged needs. It is necessary that the combination of the fluoroiphatic radical and the water solubilization group be balanced to give the surfactant a solubility in water at 250C of at least 0.01% by weight. It is preferred that the solubility in water be at least about 0.25% by weight. The surfactant should be of sufficient surfactant activity to give a surface tension of less than about 28 dynes / cm, preferably less than 23 dynes / cm, in aqueous solution at a concentration of about 0.25% or less. If the fluoro-lipid surfactant is too soluble in hydrocarbon liquids, it will be extracted too rapidly from the aqueous film to provide a sufficiently durable coating. In general, this requires the presence of at least about 20% by weight of fluorine, i.e., carbon-bonded fluorine, in the surfactant. For present

  In view of these properties, the fluorinated aliphatic radical can be broadly defined as a non-aromatic, monovalent, saturated, fluorinated radical of at least 3 carbon atoms. The aliphatic chain may be straight, branched or, if sufficiently large, cyclic, and may include trivalent oxygen or nitrogen atoms, which are only bound to carbon atoms. A totally fluorinated radical is preferred, but there may be hydrogen or chlorine atoms as substituents, provided that there is not more than one hydrogen or chlorine atom for each group of 2 carbon atoms, and preferably also provided that the radical contains at least one terminal perfluoromethyl group. Although radicals having a larger number of carbon atoms act suitably, compounds having not more than about 20 carbon atoms are preferred since larger radicals usually represent less efficient use of fluorine. only in the case of shorter chains. Fluoriphatic radicals containing about 5 to 12 carbon atoms are particularly preferred. The polar group for solubilization in water may be an anionic, cationic, nonionic or ampholytic moiety, or any combination thereof. Examples of anionic groups are: CO 2, CO 2 M, SO 2 M, SO 3 H, SO 3 M, OP (PH) 2 and OP (OM) where M is a metal ion, such as sodium, potassium, potassium, and the like. Examples of cationic groups are NH 2, NHR, where R is a lower alkyl group, such as a methyl, ethyl or butyl group, NR'3A ', R' is a lower alkyl group or hydrogen and A is an anion, such as anion chloride, sulfate, phosphate, hydroxyl, etc. Examples of nonionic groups are -NR2-40 and groups derived from polyethylene oxide and mixed polyols of polyethylene oxide and polypropylene oxide. Examples of mixed or ampholytic groups are: -N (C 2 H 4 OH) 2, -NHC H NHC H NH -N (CH) C 4 CO-, 2 4 2 4 2 '+ 3 2 24' [N + (CH) CH COONa] OH-, -N (CH) (C H4CO2H) -> O, etc. The linking group is a polyvalent, generally divalent group, for example an alkylene, arylene, sulphonamidoalkylene, carbonyl midalkylene, etc. group. In some cases, more than one fluoroaliphatic group may be bonded to a single linking group, whereas in other cases only one fluoroaliphatic radical may be bound to more than one linkage group or may be bound by a single linking moiety to more than one polar solubilization moiety. A particularly valuable class of fluoro-phatic surfactants which may be employed in the present invention include the compounds of the formula (Rf) n (Q) m Z, where Rf is the above-mentioned fluriphatic radical. , n is 1 or 2, Q is the previous linking group, M is 0 to 2, and Z is the above-mentioned water solubilization group. Examples of fluorodynamic surfactants of interest in this invention are: 2C2i4OH C7F15CONHC3I6N (CHi3) 2C2H4COO- C8F17C2H4SC2il4CONHC (Cli 3) 2Ci2SO3Na C8F17SO2N (C2H5) C2H4 P (O) (OH) 2 C6F13SO2NHC3H6N (CH3) 3C1 10 C8F17SO2NHC3H6N (CH3) 303SOC2H5 (CF3) 2CF (CF2) 6COOH H2NC2H5 C7F15COOH'H2NC3H6N ( CH3) 2C2H4COO C7F15CONHC3H6N (CH3) 2 -O C8F17SO2N (C2H5) CH2CO2K CFC HSO NC cHN + (H) CHCl3 C6F 13C2H4S 2N (CH3) C2H4N (CH3) 2C2H4CC6F13SO2N (CH2CHOHCH2SO3Na) C3H6N (CH3) 2C8F17C2H4SCH (CH2COONa) COONa C8F 17C2H4SC2H4CONHC2H4N + (CH3) 3C1 CF HOC H4SO Na 10 20 6 4 3 (CF3) 2CF (CF2) 4CONHC2H4SO3Na [C6F13SO2NHIC2H6N (CH3) 2C2H4OH] OH [C6F13SO2N (CH2CH2OH) C3H6N + (CH3) C2H4OH] OH C6F13SO2N (CH2CH2OH) C3H6N (CH3) 2 and mixtures thereof. The water-soluble, fluorine-free surface-active agents used in the present invention are agents which are water-soluble, rot-proof and synthetic organic compounds which are soluble in water. at least about 0.02% by weight at 25 ° C and are capable of promoting the film-forming ability of an aqueous fluorocarbon tensioactive solution, which is not normally film-forming. Such surfactants substantially completely emulsify at least one phase of a mixture of equal volumes of cyclohexane and water at a concentration of about 0.1 to 10% by weight of the water. In addition, the fluorine-free surfactants used according to the present invention must be compatible with the fluoro-iphatic surfactants. Compatibility means in this case that the two types of surfactants do not react together to create an inactive product. Fluoride-free surfactants, which are

  Of particular interest to the present invention are the agents described in the patents mentioned earlier and can be selected on the basis of the tests described in U.S. Patent No. 3,772,195. Examples of fluorine-free surfactants of interest in the practice of the present invention are: C8H17 OSO3Na C10H2 1OSO3Na C12H25 OSO3iNa 20 C10H21SO 3K XCH2 CH1 + CH2CH2OCH2COONa 8 17 NCH2COONa 25 OH-2 C12H25N (CH2CH2COONa) ) C8H17C6H40 (C2Hi40) 30HCl2ClN (CHI3) 2C2H4SO3O8H 1702CCH2CHII (CO2C8H17) SO3NaCl2H2ON (CH3) 3Cl (C8H17O) 2PO2Na HO (C2H4O) a (C3H60) b (C21H40) H, MW 6500 12H2O2 (C2H4O) 4C2H4OSO3NH4 C8H17SC2H4CONHIC (CH3) 2CH2SO3Na C12H25SO2N (CH2COO-) C36N + (CH3) C12H25N (CH3) 2O0, and mixtures thereof. It is known that certain fluorine-free silicone surfactants are useful in forming AFFF-type solutions and can therefore be used as well. In general, the ratio by weight between the fluorine-free surfactant and the fluoro-iphatic surfactant is of the order of 1/25 to 10/1. The composition of the shaped mass (s) may contain, in addition to the two types of surfactants, various auxiliaries which assist in the preparation. or the formulation of the one or more shaped masses (e.g. solid polyethylene glycols or methoxy polyethylene glycols, having a number average molecular weight of 1000 to 20,000, preferably 1000 to 6000), foam stabilizers (eg polysaccharide stabilizers) which stabilize the foam when applied to lower alcohols, ketones and other flammable polar liquids, auxiliaries which modify the softening temperature of the mass or masses (e.g., sorbitol), effervescent agents which assist in dissolving (e.g., citric acid with sodium bicarbonate), auxiliaries traditionally used in the preparation of AFFF-type solutions. (Provided that these auxiliaries are compatible with the particular combination of surfactants used and do not unduly lower the point of softening of the mass. Desired below 50 ° C), and antioxidants and biocides, such as fungicides, which improve the stability and shelf life of the one or more shaped masses. In some instances, a single fluoro-lipid surfactant and a single fluorine-free surfactant may form the desired AFFF-type solutions, but more frequently mixtures of two or more of each of these types of agents. Surfactants are more readily available and can be used to provide more preferred AFFF solutions. A particularly useful composition for the shaped mass comprises the following:% by weight C6 F13SO2N (CH2CHOHCH SO) CH CH CH N (CH) CH CH OH 10-20 CF3 2 3 2 2 2 3 222 C8F1 SO3K 5-20 8 C10 H21 OSO3Na 40-80 HO (CH2CH2O) H (average molecular weight 0-202 m 3000 to 4000) HOCH2 (CHOH) 4CH2OH (sorbitol) 0-20 Solid mixtures of agents can be prepared surfactants by spraying an aqueous solution containing the fluoro-phatic surfactant and the fluorine-free surfactant (in the ratios mentioned above) in a spray dryer, such as that manufactured by Niro Atomizer, Inc. and sold under the trademark "Niro", this dryer having a diameter of 1.26 m. The spray dryer can be operated at an air flow rate of about 7.5 cc / min using an air intake temperature of about 800 ° C and an air outlet temperature of - viron 401C. The solution can be fed to a rotating, high speed (eg 24,000 rpm) split disk provided at the top of the unit which sprays the solution into very small droplets. The droplets are dehydrated by the circulating air and the resulting solid particles are harvested by means of a cyclone separator. The particles may be formed into the shaped mass (s) required by various means, for example by extrusion, calendering, molding, etc. When the cartridge consists of a single shaped mass, it is preferably in the form of a sheet (which may be corrugated, embossed, etc., depending on one or both surfaces to increase its area. ), which is wound with a water-insoluble, water-insoluble, three-dimensional, open mesh web as shown in the drawings. A particularly interesting support for this purpose is constituted by a three-dimensional non-woven, low-density, open mesh web formed of numerous interwoven, randomly arranged, flexible, durable organic fibers which are firmly bonded together at the points where they occur. intersect and are in contact with each other through blood cells

  an organic binder, for example a fibrous material described in United States Patent Nos. 2,958,593 (Hoover) and 3,537,121 (McAvoy). Articles of fibrous materials of this type, having a void volume of about 70 to 95% and made of thermoplastic fibers, are sold on the market under the trademark "Scotch-Brite", for example the product "Scotch-Brite", Brite "25 type A, made of nylon 66 with a denier of 12 to 15 (12-15 g / 9000 meters). Alternatively, the single molded mass can be prepared by saturation of a water-insoluble, water-permeable, reinforcing matrix, for example a fibrous and porous web, particularly of felt, wool, etc., by a solution of the mixture of surfactants followed by removal of the solvent. The impregnated web or matrix can then be rolled ~~. ~ 2458294 19 with a porous support, such as the product mentioned above "Scotch-Brite". Other objects and advantages of the invention will become apparent from the following examples, in which the amounts are given in parts by weight and the water used is deionized water unless otherwise indicated. The controls used are solutions, in tap water, of the particular compositions described, the concentrations of these solutions being shown in the Tables. When film velocities are reported, these are velocities obtained by placing 2 drops of the AFFF-type solution on the cyclobexane surface at room temperature (ca. Petri with a diameter of 5 cm and measuring the time required for the film to cover the surface. Example 1 The following ingredients are combined, stirred and heated (85 ° C) for about 30 minutes to obtain a homogeneous solution. Table I Parts + a. 5.88 C6F13SO2N (CH2CHOHCH2SO3) CH2CH2CH2N (CH3) 2CH2CH2OH 2.95 C8F17 SO3K 0.5 C12H25 OSO3Na 0.5 ~ 12 25 3 11.4 C10H210SO3Na 22.1 b 22.1 HO (CH2CH2O) nHb 22.1 CH3O ( CH2CH2O)) nHc 35.0 water a. Prepared according to the method of Example 7 of Australian Patent No. 38028/72, by reacting C6F13 SO2N (Na) (CH2) 3N (CH3) 2CH2CH2OH with sodium 2-hydroxy-3-chloro-propanesulfonate instead of 2458294. Propanesultone. b. Polyethylene glycol "Carbowax" 4000 (average molecular weight about 3000-3700) c. Methoxy polyethylene glycol "carbowax" 2000 (average molecular weight of about 1900). The hot solution (211 g) was used to saturate a 24 cm x 14 cm piece of needle-shaped felt (polyester / viscose rayon 65/35, density 0.088 g / cm, thickness 0.32 cm) . The resulting impregnated felt is dried at about 1000C for 6 hours to remove most of the water. The dried felt having the agglomerated mixture is cut to about 22 cm x 14 cm and placed on a 15 cm x 24 cm x 0.5 cm piece of "Scotch-Brite" type A fabric, and the combined layers are tightly wrapped, the "Scotch-Brite" fabric lying outside, thereby forming a cartridge 15 cm long and about 4 cm in diameter. The cartridge is mounted in a galvanized steel pipe (diameter 4 cm x 20 length 15 cm) threaded at both ends. Pipe adapters are placed on each end of the pipe. The loaded conduit, or cartridge holder, is introduced into the conduit of a conventional 9.5 liter portable water extinguisher, the nozzle of this extinguisher being replaced by a nozzle. foam and air suction having a flow rate of about 20 liters / minute at a pressure of 7 kgf / cm. The extinguisher is charged with about 9.5 liters of pressurized city water at about 7 kgf / cm. This extinguisher is unloaded to give an AFFF solution having, as shown hereinafter, an almost uniform concentration of dissolved product over the entire discharge period, which is determined from measurements of the refractive index of samples taken at intervals of 10 seconds. Table II Time, Dissolved product, film speed, conc. dry. g / l sec. The following ingredients are combined, stirred and heated (85 ° C.) for about 30 minutes. to form a homogeneous solution. Table III Parts 8.6 C6F13SO2N (CH2CHOHCH2SO3) CH2CH2CH2N (CH3) 2CH2CH2OH 4.3 C8F17 SO3K 8 17 3 25.7 Clo H21 OSO3Na 0.8 C12H250SO3Na 12.8 HO (CH2CH2O) nH 12.8 HOCH2 (CHOH) 4CH2OHb 35.0 water a. "Carbowax" 4000 30 b. Sorbitol The aqueous solution (1600 g) is spray-dried in a "Niro" type dryer, using the conditions described above, and 2458294 22 1% by weight of fumed silica ("Cabosil" MS-7) is added. obtain an incoherent powder (8 to 65 microns). A sample of 150 g is pressed. pulverulent product obtained in a platen press at a pressure of 70 kgf / cm to form a flat sheet,

  solid, agglomerated, having an average thickness of about 0.34 cm. This sheet is cut to the dimensions of about 13 cm x 19 cm and, at these dimensions, it weighs 118 g. This sheet is placed on a piece of 15 cm x 10 24 cm of a sheet of "Scotch-Brite" type A, centered on the narrow dimension and the sheet is placed so that an end (A) coincides with the end of the web, a second 2.5 cm × 15 cm piece of the web being placed over the solid sheet at the end (A) so as to form a layered construction. After heating this assembly for one hour at 66.degree. C. to soften the solid sheet, a narrow winding is carried out from the end (A) (the largest piece of web lying outside), then the assembly is introduced into a 4 cm x 15 cm steel pipe. This conduit is connected to a 9.5 liter water extinguisher as described in Example 1. This extinguisher is charged with about 9.5 liters of pressurized city water at a rate of about 7 kgf / cm 2 of compressed nitrogen, this extinguisher discharging completely over a period of 68 seconds. A good quality AFFF solution of relatively uniform concentration is produced, as demonstrated by the following results obtained from samples collected during the discharge. 2458294 23 Table IV Index of Product Time Velocity, Refraction, Dissolved, Film, Dry n20 conc. dry. nD ~ ~ ~ ~ / sec. D ~~~~~~ g / 1 5 2 1.3338 7 10 10 1.3338 7 9 20 i, 3337 6 11 30 1.3337 6 10 40 1.3337 6 15 10 50 1.3337 6 15 60 1 , 3337 6 23 68 1.3339 8 6 Eau de ville 1.3330 0 - Witness 1.3339 8 6 ____________________ 15 The cartridge is then removed and the sheet is unrolled. The remaining solid compound weighs 55 g, demonstrating that 63 g of the solid composition was apparently dissolved uniformly, resulting in an average concentration of 6.6 g / liter. Example 3 The following ingredients are combined, stirred and heated at about 80 ° C for about 30 minutes to form a homogeneous solution. Table V Parts 88.4 CF 1SO N CHOHCH SOQ CH CH N + (CH3) 2-6 13 2 2 2 3 22 22 3 2 CH2CH20H 5 44.2 C8F17S03K 172 C10H21SO3Na 7.5 C12H 25OSO3Na 12 25 3,331.5 HO (CH CH 0) Ha. 2 2 n b. 331.5 CH3O (CH2CH2O) nH 10 524.9 water a. "Carbowax" 4000 b. "Carbowax" 2000 About 210 grams of the foregoing composition (65% solution) were poured onto a 24 cm × 14 cm piece of a needle machine felt (same as Example 1). in a glass plate 15 cm x 25 cm. This tray is placed in a forced air oven at a temperature of 110 ° C. and the water is allowed to evaporate from the composition over a period of 6.5 hours. The solid compound is inverted and heated in a vacuum oven at 50 ° C. for 2 hours, then cut to 22 cm × 14 cm, placed on a 24 cm × 15 cm piece of a Scotch-Brite cloth. A-type, the combined layers then being closely wound, the web outside, the assembly then being introduced into a 15 cm piece of a 4 cm diameter steel threaded conduit. . This duct is connected to the ducting of a 9.5 liter water extinguisher, as envisaged in Example 2, this extinguisher being loaded with about 9.5 liters of tap water. and pressurized to about 7 kgf / cm 2 with nitrogen. A layer of about 2.5 cm of heptane (lying on a layer of water) is ignited in a 4.65 m2 square steel pan and allowed to burn for 30 seconds, followed by stirring. quenching in a period of 71 seconds using substantially all of the contents of the fire extinguisher described above. The details of the events are presented below. Table VI Time mn: sec Events 0:00 inflammation 10 0:30 start of extinction 0:40 15% of extinction 0:50 40% "0:60 90%" 1:10 97% "15 1:20 99% "1:30 98%" 1:40 99% "1:41 100%" 10:56 flameback test for torch hepstane, observation of a small passing flame but no sustained fire A weighing of the contents of the duct (cartridge) after drying showed that 18 g of solid material remained in the felt support and that 110 g of material had therefore been used to extinguish the fire. A solution is prepared from the following ingredients: TABLE VII Parts 6 13 2 2 2 FSO (3) CH 2 CH 2 CH 2 N + (CH) CH CH OH 2.5 C 8 F 17 SO 3 K 8 17 3 9.75 mixture of 42 parts of C8H170 OSO3Na and 57 parts of C H2O SO3Na 10 21 3 0.4 C12H 25OSO3Na 12 25 3 b 24.5 HO (CH2CH2O) nH '24.5 CH O30 (CH2CH2O) nHC 3 2 2 No. 33,35 water ______________________a Blend sold under the brand name "Stepan" 670-15 b. "Carbowax" 4000 c. "C arbowax 2000 The pH of the solution is adjusted to 9.0 with 10% aqueous sodium hydroxide solution. Foam and surfactant properties, measured according to MIL specification F-24385B, modification 1,

  May 16, 1969, on a solution containing 100 g of solids in 9.5 liters of water are as shown below. Table VIII Dilatation Sewage-Tensio-activation Interfacial (b), dynes / cial tension between cymouss (a) 25% cm to 22 C clohexane and 25 meau, dynes / cm to 22 C 8.3 4.8 15.8 4.2 (a) Ratio of foam volume to volume of solution (b) Time required for 25% of liquid to drain from bulk foam. The foregoing composition is applied to a needle machine felt (same as that used in Example 1) at a rate which gives 0.39 g of agglomerated solids per cm after drying. A piece of 10 cm x 25 cm of the dried impregnated fabric is placed on a piece of 10 cm x 27 cm of a 5 "Scotch-Brite" type A and rolled up and placed in a cartridge holder formed by a conduit of a diameter of 4 cm over a length of 10 cm, and this as in the case of Example 1. It attaches the cartridge holder to a water extinguisher with a capacity of 10 9.5 liters, this extinguisher was charged with water, pressurized and discharged as described in Example 1. Samples were collected during the discharge and the concentration of dissolved product was determined. and that the film-forming properties are as presented below. Table IX Time, Index of Dissolved Product Speed of sec. refraction, filmstrip, 20 g / l sec. 20 12 1.3342 10 5 20 1.3341 9 5 30 1.3339 8 5 45 1.3339 8 5 60 1.3338 7 5 25 City water 1.3330 0 Indicator 1.3346 13 5 A fire test with 9.5 liters of the aforementioned control solution discharged over a period of 65 seconds from a 9.5 liter fire extinguisher having an air intake nozzle makes it possible to malfunction a test fire in 35 seconds. seconds and reach a total extinction in 63 seconds. The fire is a 4.6 foot heptane fire, which is obtained by the method described in the Underwriters Laboratories Standard 711. Example 5 The following ingredients are combined, stirred and heated to about 50 ° C to form a homogeneous solution with a pH of 4.2. Table X Parts 10 42.1 CF SO NHC HN (CH) Cl- 6 13 2 3 + 6 + 3 3 21.05 C 8 F 17 SO NHC 3 H 6 N (CH 3) 3 C 8.3 CF 15 COO H 3 N C 3 H 6 N (CH 3) 2 C 2 H 4 COO 7 15 3 3624 145.8 HO (C 2 H 4 O) (CHO) (CH 2 O) Ha. 24a 36b 2 4c 70.9 H0 (CH 2 CH 2 O) 70.9 HOCH 2 (CHOH) 4 CH 2 OHc 5.9 CH 3 COOH 3.55 CH 3 COONa 530.5 water a. "PLURONIC" F-77, molecular weight 6500 20b. "Carbowax" 4000 c. Sorbitol This solution (366.2 g) was used to saturate a piece of needle-tip felt (same as that used in Example 1) placed in a glass pan. The dimensions, the drying and the preparation of the cartridge are the same as in the case of Example 3. The weight of the solid mixture of the surfactants agglomerated in the cartridge is 117.5 g or 0.42 g / cm2 of the impregnated felt. The cartridge is attached to a 9.5 liter water extinguisher, charged thereon, pressurized and discharged as in Example 1. A solution of the type is produced. AFFF having an effective and nearly uniform concentration of dissolved product over the entire discharge period, which is determined from the concentration of dissolved product in samples taken at intervals of about 10 seconds. Table XI Time, Refractive index Dissolved product, 20 conc. dry. not. g / l 2 1.3333 3 10 10 1.3333 3 20 1.3333 3 30 1.3333 3 40 1.3333 3 50 1.3333 3 15 60 1.3333 3 70 1.3333 3 76 1.3335 4 City water 1.3330 - indicator 1.3339 8 The foam expansion and the 25% drip time are measured between the 2 and 10 second intervals and found to be respectively 2.4 and 3.5 minutes. An analysis of the contents of the cartridge after the test showed that 25.2 grams of the 117.5 grams of solids were used during the unloading. Calculations show that there should be 2.7 g of dissolved product per liter in the discharged solution, which is very close to the value obtained. Although the AFFF solution is very dilute, it is suitable for retarding the vaporization of volatile solvents. Example 6 The following ingredients are combined with agitation and heating. Table XII Parts 11.2 C8F17 SO3K 22.4 CF SO N (CH) CHOHCH 0) CHCHCHN (CH) CH CH OH 6 13 22 2 32 22 3 22 2 5 350,8 sodium alkyl sulfates ("Polystep") B-25, 38.6% aqueous solution of C8H17 OSO3Na, CHOH21 3 C12H25 OSO3Na in a weight ratio of 2/75/23) The water is evaporated to give 305.3 g of solution. About 270 grams of this was poured into a 15 cm × 25 cm glass pan containing a 24 cm × 14 cm piece of needle-machine felt (identical to that used in the Example). 1). The tank and its contents are heated at 1080C for 13 hours to

  remove substantially all of the remaining water (within 2 g of the expected dry weight, ie about 1.5% water). The dried felt is compressed in a 250 C tabletting press, cut to 13 cm x 19 cm, and then placed on a 15 cm x 24 cm piece of nonwoven fabric, heated to soften the materials. Agglomerated solids, then the combined materials are coiled and introduced into a 4 cm x 15 cm steel threaded conduit, which is fitted with pipe adapters. The resulting cartridge is connected to a conventional 9.5-liter water extinguisher charged with about 9.5 liters of tap water, pressurized to 7 kgf / cm2 and discharged completely onto the water. a period of 64 sec. An effective AFFF solution of fairly uniform composition is obtained, as demon- strated by the following results obtained on samples collected during the discharge. TABLE XIII Fast Voltage Interfacial Voltage Cross-section between Refraction Film Product, Cyclohexane Time, Dissolved, Cell, Dynes / cm and Water, 5 sec. nDconc. 5 sec.nD cng / l sec. at 22 C dynes / cm _ _ _ _ _ _ _ _ _ _ _ at 220C 2 10 20 10 30 40 50 60 64 15 Control 1.3341 1.3337 1.3336 1.3337 1.3336 1.3336 1, 3336 1.3337 1.3339 City water 1.3330 __________________ (a) 60-second covering (b) 60-second covering 10 60 (a) 17.6 4.0 6 60 (b) - - 5 21 18.0 3.3 6 45 - _ 5 14 18.0 3.3 5 18 - - 5 55 18.0 3.2 6 35 - _ 8 8 17.6 4.2 O - - 25% of the surface of cyclohexane in 90% of the surface of cyclohexane Example 7 The following solid ingredients are sieved individually and then mixed together. 11.3 g C8F17 SO3K 22.7 g C6F13SO2N (CH2CHOHCH2SO3) CH2CH2CH2N (CH) 2 CHCH2OH 135.0 g sodium alkyl sulphates ("Polystep" B-25, dried solids) This mixture is heated to 100 ° C and it is compressed several times in a platen press to obtain a solid, waxy, pale amber, agglomerated sheet having an average thickness of 0.34 cm. After cutting, the solid sheet is 13 cm x 19 cm in size and weighs 114.5 g. It is heated to 110 ° C to soften it, placed on a piece of 15 cm × 24 cm of a sheet of "Scotch-Brite" type A, then the combined layers are wound and introduced into the assembly forming led, described previously. The final cartridge is connected to a conventional water extinguisher, which is charged with 9.5 liters of tap water, then pressurized to 7 kgf / cm and discharged completely onto the water. a period of 57 seconds. An effective AFFF solution of a completely uniform composition is obtained, as demonstrated by the following results obtained on samples collected during the discharge. Table XIV Fast Voltage Interfacial Voltage Super-refractive index between film, cyclohexane Time, dissolved, water, dynes / cm and water, dry. D conc. dry. at 220 C dynes / cm g / l at 22 C 20 2 1.3338 8 11 - -1.3338 8 17 16.4 3.5 20 1.3338 8 16 - - 30 1.3337 7 12 16 5 3,4 40 1,3337 7 10 - - 25 50 1,3337 7 9 16,7 3,4 57 1,3339 8 1l - - Control 1,3339 8 5 16,2 3,9 City water 1.3330 0 - - - 30 The weight of the solid sheet of agglomerated material, remaining after the discharge, is 53.3 g, which indicates that there has been a dissolution of 61.2 g- of material, corresponding to an average concentration of 6.5 g of dissolved product per liter. EXAMPLE 8 190 g of the powdery surfactant described in Example 2 are combined and mixed with 19 g of a powdery polysaccharide gum (K 8A13, product sold by Kelco Division of Merck & Co. ), and the resultant mixture was compressed in a platen press at 70 kgf / cm 2 to form a flat, solid, and agglomerated sheet. Two sheets of a thickness of 0.25 cm were prepared and sized to 13.3 cm x 14.0 cm x 128 g weights. Using a mold with a sawtooth pattern (hollow 0.18 cm deep, 0.35 cm between the tips), grooves are created in both leaf surfaces at right angles compared to the longest dimension. These sheets are placed end to end by matching their short dimensions on a piece of "Scotch-Brite" fabric, heated to soften, and wrapped in a direction perpendicular to that of the leaf grooves. to create a cartridge as described in Example 2. This cartridge is introduced into a polyvinyl chloride tube 15.2 cm in length, with an outside diameter of 4.48 cm and with an internal diameter of 4.25 cm. This is placed in a nozzle and cartridge holder made of acrylonitrile / butadiene / styrene plastic (ABS), similar to that illustrated in FIG. 2 (the cartridge holder has a cavity 15 , 2 cm and an internal diameter of 4.50 cm). This set is connected to a portable water extinguisher that is charged

  About 9.5 liters of tap water at 210 ° C., then pressurized to about 7 kgf / cm 2 with nitrogen and totally discharged over a period of 66 ° C., 5 seconds. Table XV Time Voltage Voltage Speed Product Index Dilatation of sewage-superfluor of peel- Time, dissolved refraction, of 25% foam, thin, facial, pale, dry. 20 conc. m dynes / cm dynes / cm g / 1 22oC 220C se 5 1.337 40 1.33355 Indicator 1.3338 City water 6.1 4.8 7.0 8.6 7.6 5.3 2.2 16.8 16.8 16.7 3.3 3.3 3.3 8 13 3.5 1.3330 (D% 0 rt cnd CD rh (D'PJ (% çt 1 - CD 'r H CD nD Pi' D 0 CD HO rP 0 cn (D y çt 0 M) From To) r ~ (0 (i0 1 ~, n cn J> CDw (n O (0 Ca. CD çt o 'r (oD \ (D` D mn 0 ## EQU1 ## The Weight of Solid Waste Material in the Cartridge Holder was 71 g, demonstrating that 57 g of material (44%) was dissolved in another example, which is similar to that described above (except that the polysaccharide is dried to remove the the ratio of the powdery polysaccharide powdery active agent to 188 g / 12 g), there is a higher percentage of dissolution of the solid composition, namely 74 g on 128 g (58%) Example 9 The following ingredients are combined It is heated and heated at 85 ° C for about 30 minutes to form a homogeneous solution. Table XVI Parts 7t9 C6F13SO2N (CH2CHOHCH2SO7) CH2CH2CH2N (CH3) 2CH2CH2OH 4.0 C8F17SO3K 234a C10H21OSO3Nab '0.6 C17H35OSO3Na' 12 HO (CH2CH2O) nH. ~ ~ E 12 HOCH2 (CHOH) 4CH2OH 0.06 C6H5 ~~~~ ~~~~~~ 25 25 9 ONa 4H2Of '0.06 CH30 c OH 40 Water _____________________ a. on the basis of the solid material b. "Richonol" 7227 30 c. "Niaproof" Anionic 7 d. "Carbowax" 4000 e. Sorbitol f. The aqueous solution (about 10 kg) is spray-dried in a "Niro" dryer using the conditions described above and 1% by weight of fumed silica ("Cabosil" MS-1) is added. 7) to obtain an incoherent powder with a residual water content of about 1%. About 2.3 kg of this powder are processed into pellets at room temperature in a California-type CL-type pelletizing machine using a matrix having apertures with a diameter of 0.48 cm. small cylinders (pellets) having the following dimensions: diameter of about 0.46 cm, length of 0.33 to 0.9 cm (average of about 0.6 cm) and density of 1.28 g 120 g of the pellets (having a total area of about 1150 cm 2) are placed in a cardboard sleeve impregnated with a phenolic resin (outer diameter of 4.48 cm -1 internal diameter of 4.25 cm 2). cm, length 15.2 cm). In order to retain the pellets in the sleeve 20 in the form of an agglomerate, each end of this sleeve is provided with a 4.3 cm diameter disc made of "Scotch-Brite" fabric, the outer surface of the disc being positioned about 0.5 cm from the end of the sleeve and an RTV silicone rubber bead being used to seal each disc at its juncture with the sleeve. The loaded sleeve is introduced into the nozzle and cartridge holder assembly of Example 8 - (Figure 3) and connected to a 9.5 liter portable water extinguisher. This extinguisher is charged with about 9.5 liters of tap water at 210 ° C., then pressurized with nitrogen to about 7 kgf / cm 2 and the extinguisher discharged over a period 61 seconds. An AFFF solution of good quality and a fairly uniform concentration is obtained, as demonstrated by the following results obtained on foam samples collected at intervals during the discharge. Table XVII Index of Product Time Velocity, Refraction, Dissolved, Film, Conc. dry. nD g / l sec. 10 2 1.3348 14.4 1.5 10 1.3346 12.8 1.5 20 1.3343 10.4 2 30 1.3340 8.0 3 40 1.3338 6.4 6 15 50 1.3338 6.4 4 60 1.3338 6.4 5 City water 1.3330 O - indicator 1.3340 8.0 4 After the discharge, the cartridge is removed and the remaining pellets are dried in a circulating oven. at 110 ° C. for about 6 hours. The weight of the dried solids was 20.7 g, demonstrating that 99.3 g of material had been dissolved. EXAMPLE 10 The following ingredients are separately sprayed and combined. Table XVIII Parts 13.3 C6F13SO2N (CH2CHOHCH2SO3) CH2CH2CH2N + (CH3) CH2CH2OH 6 232 2 3232 22 3 2 2 6.7 C8F17SO3K 80 sodium alkyl sulfates. at. Solids obtained by evaporation of water from "Polystep" B-25 2458294 38 Using a small plastic laboratory extruder, the above pulverulent mixture of surfactants is converted into a rod. continuous under heating (56-75oC) and pressure. The pale amber rod (diameter 0.39 cm, density 1.41 g / cm) is cut into lengths of about 12.7 cm and 81 rods of this type (total weight 172.3 g; area

  total of about 1275 cm) are packaged as an agglomerate in a cartridge sleeve of the same type and size as in Example 9. The ends of the loaded sleeve are filled with discs made of "Scotch-Brite" fabric and they are closed by an RTV silicone adhesive as in the case of Example 9.

The loaded sleeve is introduced into the nozzle and cartridge holder assembly of Example 8 and connected to a 9.5 liter portable water extinguisher. This fire extinguisher is charged with about 9.5 liters of tap water, pressurized to 7 kgf / cm 2 with nitrogen, and the fire extinguisher is fully discharged over a period of time. 58.5 seconds. An effective AFFF solution with a very uniform composition is obtained as demonstrated by the following results obtained on foam samples collected at intervals during the discharge.

Table XIX Index of Product Time Velocity, Refraction, Dissolved, Film, Conc. dry. nD g / l sec. 2 1.3334 3.2 24 10 1.3335 4.0 14 20 1.3335 4.0 12 30 1.3335 4.0 12 40 1.3335 4.0 13 50 1.3335 4.0 8 Water from City Control 1.3330 1.3340 8.0 7.0 Example 11 After drying in a vacuum oven (75.degree. C., 18 hours), 557 g of the surfactant powdery product were combined and mixed together. Example 2 and 45.9 g of a powdery polysaccharide gum (K8A13). This mixture is converted into a rod by employing a small laboratory extruder at an extruder barrel temperature of about 50 C and a matrix temperature of about 65 C. The pale amber color rod (diameter 0 , 38 cm, density about 1.38 g / cm3) is cut into lengths of about 1.3 cm and 120 of these rods (representing a total area of about 1050 cm 2) are placed in the form of Agglomerate in a sleeve of the same type and dimensions as in Example 9. The ends of the loaded sleeve are lined with Scotch-Brite cloth discs and sealed. as described in Example 9. The filled sleeve is inserted into the nozzle and cartridge support assembly of Example 8 and connected to a portable water extinguisher of one embodiment. capacity of 9.5 liters. This extractor is charged with about 9.5 liters of water (210 ° C), pressurized to 7 kgf / cm2 with nitrogen and the total discharge of this extinguisher is carried out over a period of 68 hours. seconds. An effective AFFF solution of very uniform composition and properties is obtained, as demonstrated by the following results obtained on foam samples collected at intervals during the discharge. Table XX Product Index Time Rate, Refraction, Dissolved, Film, Conc. 15 sec. g / l sec. 2_ __ __ _ _ 33_ _ __8 _ __ _ __ _4 _ 8 ------------ 2 1,3338 6,4 8 10 1,3338 6,4 7 20 1,33375 6.0 10 30 1.3337 5.6 12 20 40 1.3337 5.6 12 50 1.3337 5.6 l 60 1.3337 5.6 13 City water 1.3330 0 - 25 Control 1.3340 8, The undissolved pellets of the cartridge weigh 57.7 g (after drying), indicating that 62.3 g of material had dissolved. The invention is obviously in no way limited to the details given above because many modifications and variants can obviously be envisaged without departing from the scope of this patent. 2458294 41

Claims (12)

  1. A portable fire extinguisher (1), comprising a tank (2) for holding water under pressure. A valve surmounting the tank, a pipe (7) connected thereto and a nozzle air suction (9) connected to this pipe, characterized in that a cartridge holder (8) is interposed in this pipe and is connected to the nozzle (9), this support being loaded with a cartridge (13) comprising a shaped mass consisting of a solid and agglomerated mixture of a water-soluble fluoro-lipid surfactant and a water-soluble, fluorine-free surfactant; shaped mass having at least one exposed surface for receiving water flowing through the cartridge holder (8) for dissolution of said shaped mass and for forming a solution film-forming foam of a relatively constant composition during the discharge period of water out of the tank. 20   2. Fire extinguisher (R) according to claim 1, characterized in that the cartridge (13) is constituted by a single shaped mass (22) comprising the mixture of surfactants.   3. Fire extinguisher according to claim 1, characterized in that the cartridge (13) comprises a series of shaped masses (22) in the form of a water-permeable agglomerate.   4. Fire extinguisher according to any one of claims 1 to 3, characterized in that the aforesaid exposed surface is adjacent to a water-insoluble, water-insoluble medium, so that the cartridge (13) comprises at least one channel (23) for passing water through the cartridge in centact with this surface. 2458294 42   5. Fire extinguisher according to claim 1, characterized in that the cartridge consists of an assembly comprising two types of sheets in the form of a roll (13), one of these types of sheet comprising the solid mixture of surfactants, while the other type of sheet (22) consists of a three-dimensional, elastic, open mesh, water permeable, insoluble in water.   6. Fire extinguisher according to claim 1, characterized in that the shaped mass (22) consists of a composite system consisting of the solid mixture of surfactants, distributed throughout a permeable reinforcing matrix. water, insoluble in water. 15   7. Fire extinguisher according to any one of claims 1 to 7, characterized in that the fluoroiphatic surfactant has the formula (R f) n (Q) MZ wherein Rf is a monovalent, saturated organic radical, fluorine containing a perfluoromethyl terminal group containing from 3 to 20 carbon atoms, in which the carbon atoms of the chain are substituted only by fluorine, chlorine or hydrogen atoms, a hydrogen atom or maximum chlorine being provided for each group of two carbon atoms, the chalne may comprise a divalent oxygen atom or a trivalent hydrogen atom, which is only bound to carbon atoms , n is 1 or 2, Q is a polyvalent linking group, ma is 0, 1 or 2, and Z is a polar group for solubilization in water, while the surfactant without fluorine is composed of an organic agent, of hydrocarbon type, rot-proof, synthetic, soluble less than about 0.02% by weight at 250C, which agent substantially completely emulsifies at least one phase of a mixture of equal volumes of cyclohexane and water at a concentration of from about 0.1 to about 10% by weight of the water, the weight ratio of the fluoro-aliphatic surfactant and the fluorine-free surfactant of the mass being 10: 1 to 1:25 .   8. Fire extinguisher according to any one of claims 1 to 7, characterized in that the solid mixture of surfactants additionally comprises a polyethylene glycol or a methoxy polyethylene glycol, normally solid, having a number average molecular weight of order of about 1000 to 20,000.   9. Method of extinguishing fires of Class A or Class B, consisting in applying to the fire a foam of a film-forming aqueous solution of a relatively constant composition, formed of a fluoro-lipid surfactant. , soluble in water and a water-soluble, water-soluble surfactant, characterized in that this solution is produced by circulating a predetermined amount of pressurized water in contact with the surface of the water. at least one shaped mass comprising a solid and agglomerated mixture of the above surfactants. 25   10. Shaped mass (22). characterized in that it consists of a solid and agglomerated mixture of a water-soluble fluoro-phatic surfactant and a water-soluble, fluorine-free surfactant, said shaped mass (22). The invention provides an exposed surface which upon contact with a predetermined amount of circulating water is dissolved and forms an aqueous film-forming foam solution of relatively constant composition. 2458294 44   11. Water-permeable agglomerate formed from a series of shaped masses (22) having an exposed surface, characterized in that each of these masses consists of a solid and agglomerated mixture of a tenside agent. a water-soluble, water-soluble fluoro-active agent, and a water-soluble, fluorine-free surfactant, said agglomerate having a predetermined area which, upon receiving contact with a predetermined amount of circulating water at a given rate, dissolves and forms an aqueous film-forming foam solution of a relatively constant composition.   12. A mixture of a water-soluble fluorodynamic surfactant and a water-soluble, fluorine-free surfactant, characterized in that it consists of a mixture of The mixture is a solid and agglomerated surfactant which when in contact with a predetermined amount of water circulating at a given rate of dissolution dissolves to form an aqueous film-forming foam solution of relatively constant composition.