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EP1154821B1 - Formulation de mousse decontaminante et anti-dispersante - Google Patents

Formulation de mousse decontaminante et anti-dispersante Download PDF

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Publication number
EP1154821B1
EP1154821B1 EP00906112A EP00906112A EP1154821B1 EP 1154821 B1 EP1154821 B1 EP 1154821B1 EP 00906112 A EP00906112 A EP 00906112A EP 00906112 A EP00906112 A EP 00906112A EP 1154821 B1 EP1154821 B1 EP 1154821B1
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EP
European Patent Office
Prior art keywords
foam
formulation
weight
decontamination
surfactant
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP00906112A
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German (de)
English (en)
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EP1154821A1 (fr
Inventor
John G. Bureaux
George R. Cowan
N. Edward Cundasawmy
J. Garfield Purdon
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Hm Queen In Right Of Canada As Repr By
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Royal Canadian Mounted Police
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    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
    • A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
    • A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42B—EXPLOSIVE CHARGES, e.g. FOR BLASTING, FIREWORKS, AMMUNITION
    • F42B33/00—Manufacture of ammunition; Dismantling of ammunition; Apparatus therefor
    • F42B33/06—Dismantling fuzes, cartridges, projectiles, missiles, rockets or bombs
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F42—AMMUNITION; BLASTING
    • F42D—BLASTING
    • F42D5/00—Safety arrangements
    • F42D5/04—Rendering explosive charges harmless, e.g. destroying ammunition; Rendering detonation of explosive charges harmless
    • F42D5/045—Detonation-wave absorbing or damping means
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/02—Chemical warfare substances, e.g. cholinesterase inhibitors
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
    • A62D2101/06—Explosives, propellants or pyrotechnics, e.g. rocket fuel or napalm

Definitions

  • This invention relates to foam formulations having both blast-suppressant and decontamination capabilities.
  • Improvised explosive devices represent an increasingly dangerous threat to society, particularly when they contain a toxic chemical/biological (CB) agent. It is vital that both the blast effects (a compression or pressure wave, heat and shrapnel) and the CB agent and aerosols, released from the initiation of such devices, are contained. Once released, CB agents also present a decontamination problem when deposited on the surfaces of various equipment and vehicles, or spilled on the ground.
  • CB chemical/biological
  • US Patent 4,964,329 assigned to Broken Hill Ltd. describes a foam composition consisting of a mixture of foamable liquid and a particulate additive to be supported as a dispersion in the foam.
  • the dispersion is claimed to be effective in sound attenuation and shock wave attenuation.
  • US Patent 4, 442,018 to P. Rand describes a foaming composition which has decreased solution viscosity for high expansion foam capability and decreased liquid drainage.
  • a foaming composition comprises a combination of a water soluble polymer of the polyacrylic acid type, a foam stabilizer of dodecyl alcohol, a surfactant, and a solvent.
  • a key is the combination of the stabilizer and polymer used.
  • a very interesting US Patent No. 5,434,192 to Thach et al. describes a composition of surfactants and stabilizers consisting of a mixture of modified natural and synthetic polymer and solvents capable of producing foam viable for 12 hours to several days at 75 -105 degrees F. Such foam is used to suppress the emission of volatile gases and vapors.
  • a blast may be suppressed using foam contained in a barrier.
  • Applicants initially conducted blast tests with a foam product known as aqueous film forming foam (AFFF) - initially designed for knocking down fire.
  • AFFF aqueous film forming foam
  • the blast suppression results were very inconsistent; the foam would break down very quickly and varied from a watery form to very light and airy.
  • the lessons learned during this phase included the realization that the physical form of the foam could be varied considerably by the foam-dispensing rate, the percentage of surfactant in the composition and the foam-dispensing nozzle characteristics. This work led to the development of a containment system described in Applicant's co-pending US application Serial No.
  • That system includes a tent-like enclosure that is deployed over an IED and is filled with an air-aspirated aqueous foam material deemed a Dispersal Suppressant Foam (DSF).
  • DSF Dispersal Suppressant Foam
  • the foam material used comprised a product sold under the trademark of SILVEX as described by US Patent no. 4,770,794 to Cundasawmy, which issued on 13 September 1988.
  • CB agents chemical and biological (BW) warfare agents
  • decontamination of radioactive particles is not possible due to their nuclear origin, however, removal by encapsulation significantly reduces aerosolization potential.
  • Decontamination of chemical and biological agents usually occurs by oxidation, reduction or hydrolysis.
  • a broad spectrum decontaminant which does not produce toxic by-products in its mode of action on any of the likely contaminants, is of greatest use when the nature of the warfare agent is unknown.
  • the blast suppression and decontamination should be a result of a single process, increasing the efficiency of the operation and allowing access to the site as quickly as possible. Further, vital evidence contained within the suppression zone should not be damaged by either the suppressant foam or by the decontaminating agent.
  • decontaminant In order to provide a single step suppression/decontamination foam, decontaminant must be included as a part of the foam formulation. While foam for blast suppression is currently available, as are decontaminants, it is not merely an obvious step to mix them together for the combined purpose of blast suppression and decontamination.
  • German Emulsion (C8) was designed to be of low corrosivity, dissolve thickeners and penetrate paint to react with embedded agents in a emulsion formulation. It was discovered however, that the emulsion or foam was somewhat unreliable and sometimes did not form at all. Such decontaminant foams would not be suitable for blast suppression for a period of time after generation.
  • any inclusion of ingredients into a foam formulation must be carefully assessed to determine their effect on the bubble size and uniformity within the foam. Further, the new formulation must possess sufficient stability, as indicated by low liquid drainage rates and an acceptable expansion ratio, to continue to provide optimum blast suppression.
  • blast suppression and decontamination foam that combines optimum blast suppression characteristics, such as uniform bubble size, slow drainage, vertical cling, vapor suppression and low toxicity and corrosivity, with optimum broad spectrum decontamination characteristics such as solubilization and emulsification of contaminants, rapid and complete degradation of chemical and biological warfare agents to non-toxic products and low toxicity and corrosivity.
  • the present invention discloses the discovery that a foam formulation exists which is suitable for both blast suppressing and decontamination, particularly desirable when faced with an explosive device which has been rigged with a contaminant for destructive dissemination.
  • a contaminant can be shown to be substantially contained by a foam, but the used foam becomes heavily contaminated.
  • a serendipitous foam formulation is provided, combining both the advantages of blast suppression and chemical and biological agent decontamination.
  • the present invention provides process for neutralizing an explosive CB contamination device comprising:
  • the process further comprises surrounding the explosive CB contamination device with a containment structure and filling the structure with the aerated foam.
  • the chloroisocyanuric acid salt is preferably selected from the group consisting of an alkali metal salt of monochloroisocyanuric acid, dichloroisocyanuric acid, and a combination thereof with cyanuric acid.
  • the invention also provides a system for dispersal suppression of an explosive CB contamination device comprising:
  • the foam formulation may comprise:
  • the present invention further provides a decontaminating and dispersion suppressing foam formulation in water comprising:
  • a system for dispersal suppression of an explosive CB contamination device comprising:
  • the foam formulation in water comprises about 0.4 - 4 weight % of a surfactant; about 0.03 - 0.5 weight % of a foam stabilizer; and about 0.10 - 9.5 weight % of a co-solvent; about 3 - 6% of the chloroisocyanuric acid salts; the buffer and the balance being water.
  • a blast suppressing decontamination foam formulation and means for its use are provided for incorporating the known active decontamination ingredient, hypochlorite, in a uniquely buffered solution designed to be incorporated into a blast suppressing foam to be used to suppress the blast shock wave, contain shrapnel and toxic vapors following detonation of IED's and decontaminate chemical and warfare agents contained therein.
  • incorporation of solvents and particulates into foam formulations may adversely effect those characteristics required for blast suppression, those characteristics being slow liquid drainage rates, high expansion ratios and optimum bubble size.
  • foam agents and solvents into decontaminant solutions should not alter the effective pH ranges of the active ingredients and stabilizers, nor should it result in the production of toxic by-products or cause false positive or negative readings on monitoring equipment.
  • a suitable foamer concentrate comprising (a) a surfactants 40-80%/w; (b) a foam stabilizer 3-7 %/w; (c) a polyalkyleneglycol solvent 10-30%/w; and (d) water balance to 100%.
  • the surfactants was a mixture of two surfactants.
  • the use of the term surfactant herein is defined as individual or a mixture of surfactants as set forth in the context.
  • a foam formulation generally comprises a surfactant, a co-solvent and a stabilizer.
  • the surfactant is capable of acting as an emulsifier and forms a foam, over a wide range of pH, when aerated. Ideally the surfactant should be soluble in fresh or seawater and is chosen to be compatible with other ingredients in the foam formulation.
  • the surfactant may be a single ingredient or a mixture of two or more surfactants such as Cedepal® TD-407, a sodium alkyl ether sulfate, and Bioterge® AS-90, an alpha olefin sulphonate.
  • the co-solvent acts as a coupling agent for solubilizing the surfactant and as solubilizer for chemical warfare agents that are not water soluble.
  • the term co-solvent is used herein to define organic-based chemicals that solubilize CB agents, e.g. from alkyd-coated (painted) surfaces.
  • One such co-solvent is polypropylene glycol (PPG426).
  • PPG425 still permits good foaming characteristics over a wide range of pH in both fresh and seawater.
  • the stabilizer acts to increase foam stability.
  • One such stabilizer is dodecanol :Lorol®) 70:30 which is a blend of C12-14 aliphatic alcohols in the ratio of 70:30.
  • Another is Alfol® 1412, a mixture of 1-dodecanol and 1-tetradecanol.
  • the foamer consists of a surfactant, a co-colvent and a foam stabilizer.
  • corrosion inhibitors can be added in very small quantities.
  • suitable surfactants include a composition of either the formula [R(OCH 2 CH 2 ) n X] a M b where R is an alkyl group having from eight to eighteen carbon atoms, n is an integer from 1 to 10; X is selected from the group of SO 3 2- , SO 4 2- .
  • a suitable foam stabilizer is an alkyl alcohol, R-OH, where R is an alkyl group having from eight to sixteeen carbons.
  • the Silv-Ex formulation consists of a surfactant comprising: 20% by weight of a surfactant C 10 H 21 (OCH 2 CH 2 ) 2.3 SO 4 - Na + and 20% by weight of C 14 H 29 (OCH 2 CH 2 ) 3 SO 4 - NH4 + ; a co-solvent of 20% by weight of diethylene glycol monobutyl ether; and a stabilizer ot 5% by weight of C 12 H 25 OH, The balance is water.
  • the formulation contains a further 0.5% of corrosion inhibitors.
  • foamers which do not contain diethylene glycol monobutyl ether as the co-solvent are preferable, as residuals of this low molecular weight constituent can be detected by some conventional decontamination monitoring equipment (such as Graseby lonicsTM Chemical Agent Monitor or CAM) and are thus interpreted falsely as positive detection of residual contaminant.
  • some conventional decontamination monitoring equipment such as Graseby lonicsTM Chemical Agent Monitor or CAM
  • a suitable non-residual foamer (or NR-foamer) consists of a composition of alkyl ether sulphate salt, an alpha olefin sulfonate, a co-solvent, an alkyl alcohol, and water. More specifically the surfactant, co-solvent and foam stabilizer are in mixture in water, the component formulas being:
  • one preferred composition of the NR-foam formulation consists of
  • this NR-foamer is capable of generating foam of uniform bubble size, is capable of coating vertical surfaces, is compatible with water, gray water and seawater as the main solvent, and is readily removed following decontamination by rinsing with water.
  • This particular NR-foamer is subject to soft thixotropic gelling at temperatures below about 10°C, which could be troublesome if shipped or used in adverse weather at this concentration.
  • NR-foamer consists of:
  • the decontamination formulation comprises an active decontamination agent in a buffer system designed to optimize the initial reaction pH above 8.5 and more preferably in the range of 10 to 11 for favoring hydrolysis of G-agents, and oxidation of VX and HD agents.
  • the decontamination formulation of the present invention contains as an active ingredient, sodium dichloroisocyanurate.
  • Other chloroisocyanuric acids, their alkali metal salts or a combination of acids including trichloroisocyanuric acid are also suitable for use as the active ingredient.
  • alkali metal salts of monochloroisocyanuric or dichloroisocyanuric acid or a combination of any of the above salts with cyanuric acid may be used.
  • the decontamination formulation contains from about 1% to about 15%, and preferably from about 3% to about 9%, by weight, of the hydrated dichloroisocyanuric acid salt when used for decontamination alone.
  • the formulation contains from about 1% to about 6% by weight, of the hydrated dichloroisocyanuric acid salt and preferably from about 3% to about 6% by weight, of the hydrated dichloroisocyanuric acid salt.
  • the formulation may additionally comprise lithium hypochlorite to enhance the activity of the dichloroisocyanuric acid salt.
  • the decontamination formulation of the present invention further comprises a buffer that temporarily maintains an initial pH in the range of 10 to 11, sufficient to enable hydrolysis of G-agents and favor oxidation of the V and mustard agents so as to produce non-toxic products.
  • An initial pH in the range of 10 to 11 is sufficient to provide adequate hypochlorite ions for decontamination.
  • hypochlorous acid becomes more prevalent as hypochlorite ions react with available hydrogen ions. Hypochlorous acid is the more active species with respect to the destruction of BW agents as neutral species are able to enter the BX agent cell more easily. Should a BW agent survive the initial decontamination, the BW agent and decontamination formulation may continue to co-reside over time, perhaps after rinsing, and, as the pH falls, BW agent decontamination continues at an even more effective pH. Further, from an environmental standpoint, a more neutral final pH of the decontamination formulation is less hazardous.
  • the buffer must be capable of buffering the release of HCl due to hydrolysis of the chloroisocyanuric salts by water. Most preferably, the pH is maintained above 8.5 during the duration available for decontamination.
  • the most suitable buffering system is an inorganic buffering system, adjusted to an initial pH in the range of 10 to 11.
  • Sodium salts such as a mixture of sodium tetraborate decahydrate and anydrous sodium carbonate, are preferable since quaternary ammonium compounds result in depletion of hypochlorite through reaction with the hydrolysis product of hypochlorite, chloride ion.
  • the decontamination formulation may further optionally include lithium hypochlorite to augment the active hypochlorite content of the solution over a short term, thus providing a higher level of active species in the initial stages after the addition of water.
  • lithium hypochlorite is present in amounts in the range of from about 5 to about 10% by weight of the active ingredient dichloroisocyanuric acid salt and taking into account that commercially available lithium hypochlorite is normally only available as 30% pure.
  • small amounts of Super Tropical Bleach (STB) or High Test Hypochlorite (HTH), below their solubilisation limits so that no solid or slurry results, could serve the same function as the addition of lithium hypochlorite.
  • the decontamination formulation of the present invention may further optionally include inorganic/organic bromide to increase the reactivity of the chloroisocyanuric acid and generate low levels of hypobromite and bromine chloride.
  • a foamer compatible decontamination formulation is mixed with foamer to provide a preferred foam formulation capable of simultaneous blast suppression and decontamination comprising;
  • a decontaminant with minimal or no blast suppression capability.
  • a 6% active ingredient formulation can be used.
  • additional co-solvent can added to raise the total co-solvent (foamer and added co-solvent) to about 8% for more effectively solubilizing penetrated CB agents from surfaces.
  • the combined foamer and decontamination formulation can now be applied to IED's which contain a contaminant which would require both blast suppression and decontamination capabilities.
  • an explosive device including explosive contamination device is surrounded by an encapsulating foam containment structure.
  • the foamer and decontamination formulation are mixed in water and foamed to fill the containment structure, thereby surrounding the IED.
  • formulation #3 being the preferred formulation. All subsequent testing and field tests were performed using formulation #3.
  • the decontaminating solution was then prepared by combining two solutions as follows:
  • foaming solution and the buffer/oxidizing agent solution were directly mixed and foam characteristics were measured as a function of time. It was found that there was no drop in expansion ratio nor increase in drainage rate after the mixture had been standing for over 30 minutes.
  • Example 2 The first series of tests, Example 2, were performed using non-fragmenting explosive dissemination models designed to project CB simulants. SILVEX foam formulation was used and the results extrapolated to other foam formulations based on blast tests conducted using the formulation of this invention.
  • the second series, example 3 studied the performance of the preferred foam formulation, when challenged by non-explosive dispersal models as well as by high energy devices.
  • the high energy explosive dispersal models provided an indication of the upper device limits that were containable.
  • Example 2 During the development stage the nylon tent, used in Example 2, was reinforced by adding a layer of ballistic material over the foamed enclosure. Two ballistic materials were tested; DYNEEMA and KEVLAR. Each fabric was tested alone and in combinations with the other. DYNEEMA was selected as the fabric to be used in the containment structure because it demonstrated superior qualities in capturing high velocity bomb fragments.
  • the dome tent shaped design evolved to a base unit being fabricated from 3 layers of DYNEEMA and an outer and inner layer of rip stop nylon. Two containment structure sizes were produced, one approximately 2.75 meters in diameter and the second approximately 2 meters in diameter (used in Example 3).
  • the contaminant system is the subject of co-pending US application serial no. 60/069,533, filed December 12, 1997, and replaced by a regular application.
  • the Chemical Agent Device Model used was a simple device that included a 1 liter high density polyethylene laboratory bottle and a center burster of approximately 125 grams of C-4 explosive, initiated by an electric blasting cap.
  • the bottle was filled with approximately 950 milliliters (mL) of methyl salicylate, a chemical agent simulant for mustard agent.
  • the Biological Agent Device Model used was essentially the same design as was used in the chemical simulant test, except that the methyl salicylate was replaced by a biological agent simulant, calcium hydroxide.
  • the tests were conducted in a cylindrical shaped blast test chamber, 32 feet in diameter and 20 feet high.
  • a four person, dome shaped nylon tent, 2 meters in diameter was used to contain the foam formulation.
  • the foam formulation used was SILVEX foam concentrate diluted to 1.7 %/w in water. It will be appreciated by those skilled in the art that these results can be extrapolated to other foam formulations according to the invention based on the evaluation of various physical properties of the foam produced with these formulations as compared to SILVEX foams, and a blast test with a preferred formulations against an actual improvised chemical dispersant device containing weapons grade material. Similar blast mitigation properties were observed.
  • MIRANTM miniature infra-red gas analyzer
  • Fig. 2 illustrates the concentration gradient of simulant in the test chamber, over 30 minutes, for the three tests performed in Example 1.
  • Fig. 3 illustrates the comparison between unmitigated baseline tests and biological tests.
  • the biological simulant formed a fine aerosol that behaved like that of a biological agent.
  • the biological simulant was contained in the order of 95%.
  • Fig. 4 illustrates the readings obtained by the pressure transducer, placed at 1.5 meters.
  • the foam suppressed simulant tests showed negligible pressure in PSI compared to that observed for the baseline tests.
  • Example 2 In contrast to the dispersal device used in Example 1, a more energetic fragmenting device was used to disperse agent as well as a selection of less energetic dispersal systems such as high pressure aerosol formation.
  • the dispersal devices used were as follows:
  • the tests were conducted on an open range and in a test chamber measuring 20 ft. x 30 ft. x 10 ft. or 6.10 m x 9.15 m x 3.05 m (170 m 3 )
  • a dome shaped DYNEEMA tent was used as the enclosure structure which was subsequently filled with SILVEX foam (approx. 570 cubic ft. or 16 m 3 ) to suppress the blasts of the various dispersal devices.
  • MIRANTM miniature infra-red gas analyzer
  • DAAMS Depot Area Air Monitoring System
  • Blast overpressures were determined using ENDEVCOTM piezoresistive pressure transducer and Anderson blast gauges.
  • Fig. 5 depicts the concentrations of simulant in the test chamber after an unmitigated baseline test and a contained test. The lethal level of Sarin after a one minute exposure is shown for reference. A high level of simulant capture was observed.
  • Fig. 6 illustrates the over pressure measurement at the noted distances from the device for both unmitigated and contained tests. Over pressure containment was observed in the order of 90% for contained tests.
  • Fig. 7 illustrates the air concentrations of simulant as measured by DAAMS tube samplers in an outdoor trial, their locations further illustrated in Fig. 8.
  • Fig. 9 illustrates the over pressures recorded on two tests, one unmitigated and the other contained. The readings recorded for the contained test were barely measurable i.e. ⁇ 1 PSI.
  • Fig. 10 depicts a baseline unmitigated test and three contained tests, each performed using different explosive amounts. Samplers were located as illustrated in Fig. 8. Containment was realized in excess of 95%.
  • Fig. 11 illustrates the over pressure readings measured at 1.5 meters from the test device for one unmitigated baseline test and three contained tests, each with different explosive loads, as noted. Over pressure readings were diminished by greater than 90% in the contained tests.
  • G-agent simulant and mustard agent was determined using conventional decontamination monitoring equipment such as Graseby lonicsTM Chemical Agent Monitor or CAM and Chemical Agent Detection Systems Mark II (CADS II) stations, each comprising two CAMs. Further, confirmation of the presence or absence of these agents in air samples was determined using HapsiteTM, a portable gas chromatograph/mass spectrometer (GC/MS).
  • Graseby lonicsTM Chemical Agent Monitor or CAM and Chemical Agent Detection Systems Mark II (CADS II) stations each comprising two CAMs.
  • confirmation of the presence or absence of these agents in air samples was determined using HapsiteTM, a portable gas chromatograph/mass spectrometer (GC/MS).
  • Hapsite was adapted for measurement of chemical agents under ambient test conditions by equipping it with an M213 membrane system capable of more rapid permeation of chemical agents, substituting the standard DB-1 GC capillary column by a DB-5 capillary column, adjusting operating temperature to 80°C rather than the usual 60°C used for volatile organic chemicals, and operating the probe inlet line at 45°C rather than the usual 35°C.
  • the air samples were subjected to a mass spectral analysis alone, as the agents used in the trials were known. This type of analysis does not require any prior chromatographic separation and allows for longer air sampling times. Typically 5 minute samplings were used for the staged testing.
  • Hapsite was also used for full chromatographic separation and mass spectral analysis in the event that the samples demonstrated unexpected results using mass spectral analysis alone.
  • a first stage the ability of the CAMS and Hapsite to measure dispersion of the agent simulant, diethyl malonate, was determined.
  • a second stage the ability of the blast suppressing decontamination foam formulation to decontaminate mustard painted onto a vehicle surface was tested.
  • the dispersal devices were activated (functioned). As soon as the site was declared safe from explosive hazard, the witness cards were examined and the site monitored by personnel carrying CAMs. Hapsite was brought to the site to acquire and test air samples at locations near the ring stands, vehicle surfaces, open ground and witness cards.
  • CAMs produced G-mode readings in the range of 2 to 6 bars indicating mild to heavy contamination with simulant (DEM registers as a G-agent on a CAM).
  • Fig. 13 shows the results of the mass spectral data analysis indicating that the chemical is indeed diethyl malonate with a probability of 97.5%.
  • the foam formulation was tested to determine its ability to act as a decontaminant in Stage 2.
  • CARC chemical agent resistant coating
  • Fig. 14 shows the Hapsite readings prior to application of the foam formulation and Fig. 15 shows the identification of the sample, containing a predominant mass 109 fragment, as being mustard (bis (2-chloroethyl) sulphide), verifying live agent was used for the trials.
  • mustard bis (2-chloroethyl) sulphide
  • the foam formulation was capable of decontaminating the mustard agent, therefore the remaining stage 3 trials were directed towards the foam formulations ability to simultaneously decontaminate and suppress an explosive blast wave.
  • a dispersal device was loaded with 250 ml of simulant or agent and secured to a ring stand approximately 50 cm off the ground.
  • Four CADS II monitoring stations were deployed near the site, three in the downwind direction. The stations were activated and allowed to collect and provide data to a remote CPU and computer system.
  • the dispersal device was placed inside a commercial tent and then the tent was filled with foamed formulation.
  • a special tent with an opening in the bottom, but of the same shape and size as the commercial tent, was placed over the dispersal device and then filled with the foamed formulation.
  • the device was armed and then functioned. As soon as the area was declared safe from explosive hazard, a survey of the site around the tent was performed by personnel carrying CAMs. Hapsite was used to acquire air samples from around the tent and, in the case of the agent trial, was inserted through an opening in the top of the tent to sample the head space above the foam to detect any mustard contamination. CAM readings of the tent head space were also taken.
  • a second staged trial was performed. Two formulations of blast suppressing/decontamination foam were used.
  • a first CB-decontaminating blast suppressant foam formulation contained 3% active decontaminating ingredient and a second surface decontaminating foam formulation, contained 6% active decontaminating ingredient.
  • a 250mL Nalgene bottle filled with DEM was fastened to a ring stand at approximately 0.3 m above the ground and 4 m from a small metal building.
  • Witness cards were set out near the device and affixed to the facing surfaces of the building to indicate dispersed liquid spray.
  • the witness cards were examined and showed a heavy spray of small droplets for at least 20m downwind of the device location.
  • the blast produced a loud noise readily heard at least 200m away.
  • CAMs used to survey the area showed strong G-mode responses 10 minutes after dispersal of the simulant.
  • An air sample acquired by Hapsite showed the sample to contain a high concentration of a single component, subsequently identified as DEM, as shown in the total ion chromatogram of Fig. 20.
  • the dispersal equipment used was capable of dispersing simulant over the test site and the instrumentation used to measure the contamination, capable of measuring the G-simulant, DEM.
  • a CARC painted armored personnel carrier was placed within a plastic-lined containment pit and four CADS stations were deployed in a circular pattern around the pit at a standoff distance of approximately 5 m.
  • Hapsite was used to measure a head-space air sample above a bottle of mustard agent producing a total ion and mass 109 reconstructed ion chromatogram as shown in Fig. 21. This was subsequent verified to be that of mustard, with very few impurities.
  • One side of the APC was painted with approximately 75mL mustard. All CADS II stations, especially those in the downwind direction, showed an immediate, strong response in the H-mode, indicative of mustard vapor. Surface decontaminating foam (6%) was applied to the vehicle, the vehicle was then scrubbed with long handled brushes and allowed to sit for 15 minutes.
  • the CADS stations responses returned to baseline, indicating the absence of mustard vapor.
  • CAMs were used to survey the air around the vehicle 10 minutes following foam application and showed no H-mode response. An air sample acquired by Hapsite during the scrubbing process did not show the presence of mustard vapor. After 30 minutes, the vehicle was washed down with water and further CAM surveys were conducted, which verified the absence of mustard vapor.
  • Two stage 3 trials were performed, one using G-agent simulant (DEM) and one using mustard agent.
  • a 250 mL Nalgene bottle equipped with detonation equipment and filled with simulant or agent was placed on the floor of a steel containment tray, placed inside a 12 ft. x 12 ft. x 10 ft. or 3.66 m x 3.66 m x 3.05 m wood frame enclosure sealed with polyethylene vapor barrier.
  • Two CAMs and components of a CADS station were located within the enclosure. Further, four CADS stations were deployed around the enclosure at a distance of approximately 5 m. All CAMs were set in G-mode for the simulant trial and in H-mode for the mustard trial.
  • a ballistic tent was placed over the bottle, the tent was filled with CB-decontaminating blast suppressant foam and the bottle was remotely detonated.
  • Hapsite GC/MS analysis as shown in Fig. 22 showed a small amount of DEM and dichloroethyl acetate, most likely produced by a reaction between DEM and the chlorinated oxidant in the decontaminant, to be present in the head-space air of the simulant trial.
  • CAM surveys of the released foam materials after 30 minutes showed no evidence of DEM.
  • CAM surveys in the head space air of the agent trial showed a strong H-mode response which was subsequently proven by Hapsite GC/MS analysis, as shown in Fig. 12, not to be mustard, but to be 1,2-dichloroethane instead. It is thought this compound may be a reaction product of the mustard with the chlorinated oxidant in the decontaminant. Again CAM readings taken over the released foam after 30 minutes show no evidence of mustard vapor.
  • the foam formulation is capable of suppressing a blast and decontaminating the CB agents released as a result.
  • Examples 6 through 9 are directed solely at various foam formulation's ability to decontaminate various types of contamination. These include, chemical warfare agents of the G and V classes, mustard agent, biological spore-forming warfare agents and radioactive particulates.
  • CB agents and simulant DFP were provided by the Canadian Single Small Scale Facility at the Canadian Defense Research Establishment Suffield (DRES) in southern Alberta, Canada and Aldrich Chemical Company, respectively.
  • GB stock calibration solution was prepared by weight in acetonitrile (AcCN) and several dilutions were prepared ranging from 25 to 900 ng/ ⁇ L for calibration of the FPD, UV, and MSD responses.
  • Stock solutions of the other CW agents were prepared volumetrically in AcCN and similarly diluted for calibration.
  • samples were prepared in 2.0mL autosampler vials.
  • the first addition was a water solution containing the foamer and, if necessary, the co-solvent.
  • buffer concentrate which had been separately prepared by adding the active ingredient, anhydrous sodium dichloroisocyanuric acid (SD), to water and heating to 29°C with stirring for 15-30 minutes.
  • SD sodium dichloroisocyanuric acid
  • the CB agent was added defining time zero, and aliquots, at noted elapsed times, were directly injected into the LC.
  • the temperature of the vial holder was maintained at 25.0°C and a mini stirbar in the vial mixed the components.
  • Fresh samples were prepared for each FPD analysis to obtain residual agent concentration profiles over time and these same solutions were subsequently analyzed by LC-MS.
  • Fig. 24 the effectiveness of several decontaminant formulations against selected G-type nerve gases GB, GA and GD and mustard gas, HD, was determined.
  • the formulations tested consisted of an active ingredient, a foamer, an inorganic buffer mixture and, optionally, co-solvent, in excess of that already present in the foamer mixture.
  • the co-solvent values in Fig. 24 represent added co-solvent and that contained in the foamer.
  • Three decontamination formulations were assessed for effectiveness against typical G-nerve agents; the mildest formulation, using 3% w/w SD, a 2/3 strength buffer, and 1.3% w/w foamer, an intermediate strength formulation with 6% w/w SD, full strength buffer, 4.6% w/w foamer and an additional 6.9% w/w to 7.8% w/w co-solvent, and a full strength formulation with 9% w/w SD, full strength buffer, 4.8% w/w foamer and 6.9% w/w additional co-solvent.
  • anhydrous SD was used in preparation of the solution, percentages are quoted in terms of the equivalent amount of dihydrate. Percentages (w/w) quoted for foamer represent undiluted double-strength foamer which has 45.5% surfactant.
  • the intermediate formulation also tested for effectiveness against HD and demonstrated no residual HD after 2.47, 5.27, or 53.3 minutes. Verification by LC-MS could not be performed as HD cannot be detected using positive API-ES under these conditions.
  • Example 6 Samples were prepared as described in Example 6. Two decontaminant formulations were assessed for effectiveness against VX-nerve agent: the mildest formulation (MILD) with 3% w/w SD, 2/3 strength buffer, and 1.3% w/w foamer, and the full strength formulation (FS*) with 9% w/w SD, full strength buffer, 4.8% w/w foamer and 6.9% w/w additional co-solvent. As with Example 6, percentages quoted for foamer represent undiluted double-strength foamer.
  • MILD mildest formulation
  • FS* full strength formulation
  • Control formulations were also examined. These included a formulation containing only full strength buffer and foamer (Buffer/Surf) and a formulation containing all ingredients of the full strength decontaminant but without active ingredient (FS*wo/SD).
  • Buffer/Surf full strength buffer and foamer
  • FS*wo/SD active ingredient
  • the control formulation of buffer and foamer (Buffer/Surf) was tested at a low concentration of VX (4 ⁇ L/ml). After six days, 42% of the VX remained and toxic product in significant quantity was detected.
  • the control formulation of full strength formulation without active ingredient (FS*wo/SD) was tested against a concentration of 12 ⁇ L/ml of VX. Again, significant quantities of VX and toxic product were found at 125 minutes and 6 days. Additionally, there was evidence of VX droplets in the solution at 125 minutes indicating that saturation levels of VX were present in solution and that removal of VX from the system was slow. When full strength formulation with SD was employed in excess (18.2:1 active speciesNX), all VX was destroyed in less than 7 minutes with no evidence of toxic product.
  • Trial 1 and Trial 2 indicate, respectively, that, on average, only 0.0108% and 0.00109% of the original material on the decontamination foam-treated coupons remained viable, translating into a 99.989% and 99.999% kill for simple contact with the decontamination foam for a period of 30 minutes.
  • Data from Anthrax Spore Decontamination Trials Experiment Colony Counts Plate 1 Plate 2 Plate 3 Plate 4 Trial 1 - Decon foam 33 26 28 21 Trial 1 - Control foam 22 ⁇ 10 4 22 ⁇ 10 4 29 ⁇ 10 4 28 ⁇ 10 4 Trial 2 - Decon foam 13 10 5 3 Trial 2 - Control foam 66 ⁇ 10 4 72 ⁇ 10 4 68 ⁇ 10 4 78 ⁇ 10 4
  • Fig. 26 the effectiveness of the one variant of the foaming agent by itself to effect decontamination of radioactive dusts from the exterior surface of an armored vehicle was demonstrated.
  • the vehicle a French AMX-10 Armored Personnel Carrier, was contaminated by spraying the exterior with 140 La particles (100-200 ⁇ m) to simulate surface contamination as might be caused by driving across contaminated dusty terrain.
  • Decontamination formulation using Silv-Ex foamer was sprayed over the surface of the vehicle using a powered pressure washer fixed with an air induction foam nozzle of the type normally used in applying fire-fighting foams. Subsequent to the application of decontaminant, the vehicle was towed to a sensing frame where radiation measurements on the exterior could be made.
  • the radiation level measured inside the vehicle in the first trial was observed to be in the order of 30 mRem/hr.
  • the radiation level was observed to drop significantly (to approximately 11 mRem/hr) presumably due to foam layers dropping off the sides of the vehicle during the application stage.
  • the radiation level flattened off over the course of the decontamination probably due to residual particles remaining on the vehicle in areas where the foam could not drop off (top, crevices) readily.
  • the radiation level dropped even further (to approx. 6 mRem/hr) presumably due to flushing off some of the remaining radioactive particles.
  • a map of the radiation emitted from the exterior surface of the vehicle as sampled by a frame of 80 probes confirmed that the radiation had been significantly reduced by decontamination using Silv-Ex-based decontamination foam.

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Claims (23)

  1. Méthode de neutralisation d'engin explosif de contamination CB consistant à :
    (a) Produire une mousse aérée composée d'une formulation aqueuse comportant un surfactant, un co-solvant choisi dans le groupe du polypropylèneglycol, du polyéthylèneglycol, de leurs dérivés et mélanges, d'un stabilisateur de mousse, d'un sel de l'acide chloroisocyanurique et d'un tampon servant à maintenir ladite formulation à un pH d'à peu près 11 à environ 8,5
    (b) Entourer l'engin de contamination CB de ladite mousse
  2. La méthode de la revendication 1, à laquelle s'ajoute l'enveloppement de l'engin de contamination CB par une structure de confinement et le remplissage de la structure avec la mousse aérée.
  3. La méthode de la revendication 1 ou 2, dans laquelle ledit sel d'acide chloroisocyanurique est sélectionné dans le groupe composé d'un sel de métal alcalin de l'acide monochloroisocyanurique, d'acide dicholorisocyanurique et d'une combinaison de ceux-ci avec l'acide cyanurique.
  4. La méthode de la revendication 3, dans laquelle ledit sel de métal alcalin de l'acide dichloroisocyanurique est le dichloroisocyanurate de sodium.
  5. La méthode de l'une ou l'autre des revendications 1 à 4, dans laquelle ledit tampon se dégrade avec le temps, permettant de ramener le pH d'une valeur initiale d'environ 11 à environ 8,5.
  6. La méthode de la revendication 5, dans laquelle le tampon maintient le pH de la formulation à plus de 8,5 pendant au moins 30 minutes.
  7. La méthode de l'une ou l'autre des revendications 1 à 6, dans laquelle le co-solvant est le polypropylèneglycol de formule chimique R1-(OCH(CH3)CH2)n-OR2, où R1 et R2 sont indépendamment H, un alkyle ou un groupe ester et n>1.
  8. La méthode de la revendication 7, dans laquelle ledit groupe alkyle représentant R1 ou R2 est un groupe méthyle, éthyle ou butyle ou un mélange de ceux-ci.
  9. La méthode de la revendication 6, dans laquelle au moins un desdits R1 ou R2 est l'hydrogène.
  10. La méthode de la revendication 7, dans laquelle, R1 et R2 sont tous deux l'hydrogène.
  11. La méthode de l'une ou l'autre des revendications là 6, dans laquelle ledit co-solvant est un polypropylèneglycol partiellement éthérifié.
  12. La méthode de la revendication 11, dans laquelle ledit polypropylèneglycol partiellement éthérifié est de formule R1-(OCH(CH3)CH2)n-OR2, où l'un des deux, R1 ou R2, est indépendamment H ou un groupe alkyle et n ≥ 1.
  13. La méthode de la revendication 12, dans laquelle ledit alkyle représentant R1-ou R2 est un groupe méthyle, éthyle, propyle, butyle ou un mélange de ceux-ci.
  14. La méthode de la revendication 12, dans laquelle au moins un desdits R1-ou R2 est l'hydrogène
  15. La méthode de l'une ou l'autre des revendications là 14, dans laquelle l'hypochlorite de lithium est inclus dans la formulation décontaminante en quantités allant d'environ 5 à environ 10 % en poids du sel de l'acide chloroisocyanurique.
  16. Système anti-dispersion d'engin explosif de contamination CB comportant:
    (a) Une structure de confinement servant à entourer l'engin de contamination explosif
    (b) Une mousse aérée contenue dans la structure formée d'une formulation de mousse dans l'eau comportant un surfactant, un stabilisateur de mousse, un co-solvant sélectionné dans un groupe comprenant le polypropylèneglycol, le polyéthylèneglycol, des dérivés et mélanges de ceux-ci, un sel de l'acide chloroisocyanurique et un tampon servant à maintenir le pH de ladite formulation à une valeur d'à peu près 11 à environ 8,5
  17. Le système de la revendication 16, dans lequel la formulation de mousse comprend :
    (a) Un agent moussant comportant un surfactant, un co-solvant choisi dans le groupe composé du polypropylèneglycol, du polyéthylèneglycol, de leurs dérivés et mélanges et d'un stabilisateur de mousse ;
    (b) Une formulation de décontamination comportant un sel de l'acide chloroisocyanurique et un tampon servant à maintenir le pH de ladite formulation à une valeur d'à peu près 11 à environ 8,5
  18. Le système de la revendication 17, dans lequel la formulation de mousse comporte :
    (a) Environ 0,4 à 4 % de surfactant en poids, environ 0,03 à 0,5 % de stabilisateur de mousse en poids et environ 0,1 à 9,5 % de co-solvant en poids
    (b) Environ 3 à 6 % de sel d'acide chloroisocyanurique en poids
    (c) De l'eau pour le reste
  19. Le système de la revendication 18, dans lequel la formulation de mousse comporte :
    (a) Environ 3 % d'un sel de l'acide chloroisocyanurique en poids
    (b) Environ 0,6 % de surfactant en poids
    (c) Environ 0,03 % de stabilisateur de mousse en poids
    (d) Environ 0,75 % en poids du co-solvant choisi dans le groupe composé du polypropylèneglycol, du polyéthylèneglycol ainsi que de leurs dérivés et mélanges
    (e) Un tampon servant à maintenir le pH de ladite formulation à une valeur d'à peu près 11 à environ 8,5
    (f) D'eau pour le reste
  20. Formulation décontaminante et anti-dispersante aqueuse comportant:
    Un surfactant
    Un stabilisateur de mousse
    Un co-solvant choisi dans le groupe constitué du polypropylèneglycol, du polyéthylèneglycol, de leurs dérivés et mélanges
    Un sel de l'acide chloroisocyanurique
    Un tampon servant à maintenir le pH de ladite formulation entre à peu près 11 et environ 8,5
  21. La formulation décontaminante et anti-dispersante de la revendication 20, dans laquelle la formulation de mousse comporte:
    (a) Environ 0,4 à 4 % de surfactant en poids, environ 0,03 à 0,5 % de stabilisateur de mousse en poids et environ 0,1 à 9,5 % de co-solvant en poids
    (b) Environ 3 à 6 % de sel de l'acide chloroisocyanurique en poids
    (c) De l'eau pour la différence
  22. La formulation de mousse décontaminante et anti-dispersante de la revendication 20, comportant :
    (a) Environ 3 % de sel de l'acide chloroisocyanurique en poids
    (b) Environ 0,6 % de surfactant en poids
    (c) Environ 0,03 % de stabilisateur de mousse en poids
    (d) Environ 0,75 % en poids du co-solvant sélectionné dans le groupe composé du polypropylèneglycol, du polyéthylèneglycol, de leurs dérivés et mélanges
    (e) Un tampon servant à maintenir le pH de ladite formulation à une valeur d'à peu près 11 à environ 8,5
    (f) De l'eau pour la différence
  23. La formulation de mousse décontaminante et anti-dispersante de la revendication 22, à laquelle s'ajoute de l'hypochlorite de lithium en quantités comprises entre à peu près 5 et environ 10% de sel de l'acide chloroisocyanurique en poids.
EP00906112A 1999-02-26 2000-02-25 Formulation de mousse decontaminante et anti-dispersante Expired - Lifetime EP1154821B1 (fr)

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PCT/CA2000/000199 WO2000051687A1 (fr) 1999-02-26 2000-02-25 Formulation de mousse decontaminante et anti-dispersante

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Cited By (1)

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Publication number Priority date Publication date Assignee Title
FR3103549A1 (fr) * 2019-11-25 2021-05-28 Arianegroup Sas Dispositif mobile de neutralisation d'arme chimique ou biologique

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WO2004052918A2 (fr) 2002-12-09 2004-06-24 The Trustees Of Columbia University In The City Of New York Peptides et methodes de desactivation d'insecticides et d'agents neurotoxiques a base
FR2931687B1 (fr) * 2008-05-27 2017-11-24 Commissariat Energie Atomique Solution aqueuse decontaminante et moussante.

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JPS5271592A (en) * 1975-12-12 1977-06-15 Mitsubishi Chem Ind Ltd Production of regenerared nylon resin
ZA775615B (en) * 1976-10-26 1978-08-30 Stauffer Chemical Co Hard surface cleaning composition
JPS56143300A (en) * 1980-04-09 1981-11-07 Kao Corp Foamable composition
JPS5953314B2 (ja) * 1980-04-09 1984-12-24 花王株式会社 発泡性組成物
KR930009035B1 (ko) * 1990-03-19 1993-09-22 국방과학연구소 수용성 제독제 조성물
FR2679458A1 (fr) * 1991-07-23 1993-01-29 Commissariat Energie Atomique Mousse de decontamination a duree de vie controlee et installation de decontamination d'objets utilisant une telle mousse.
AU6646798A (en) * 1997-01-10 1998-08-03 Loizeaux Group Int'l Ltd Method and apparatus for the destruction of articles

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3103549A1 (fr) * 2019-11-25 2021-05-28 Arianegroup Sas Dispositif mobile de neutralisation d'arme chimique ou biologique
WO2021105584A1 (fr) * 2019-11-25 2021-06-03 Arianegroup Sas Dispositif mobile de neutralisation d'arme chimique ou biologique
US11781848B2 (en) 2019-11-25 2023-10-10 Arianegroup Sas Mobile device for neutralizing a chemical or biological weapon

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DE60011050D1 (de) 2004-07-01
EP1154821A1 (fr) 2001-11-21
IL145033A (en) 2006-07-05
WO2000051687A1 (fr) 2000-09-08
AU766865B2 (en) 2003-10-23
DE60011050T2 (de) 2005-11-03
ATE267630T1 (de) 2004-06-15
WO2000051687B1 (fr) 2000-11-23
CA2299259A1 (fr) 2000-08-26
IL145033A0 (en) 2002-06-30
CA2299259C (fr) 2007-12-04
AU2789800A (en) 2000-09-21

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