EP1154821A1 - Decontaminating and dispersion suppressing foam formulation - Google Patents
Decontaminating and dispersion suppressing foam formulationInfo
- Publication number
- EP1154821A1 EP1154821A1 EP00906112A EP00906112A EP1154821A1 EP 1154821 A1 EP1154821 A1 EP 1154821A1 EP 00906112 A EP00906112 A EP 00906112A EP 00906112 A EP00906112 A EP 00906112A EP 1154821 A1 EP1154821 A1 EP 1154821A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formulation
- foam
- decontamination
- foamer
- explosive
- 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.)
- Granted
Links
Classifications
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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
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- 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
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- 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
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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
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/02—Chemical warfare substances, e.g. cholinesterase inhibitors
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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
- 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 long term
- 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.
- Such a 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
- 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 AFFF was contained in nylon dome tents that were deployed around the blast threat. 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.
- 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.
- a prior art decontaminant, 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.
- 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.
- the choice of solvent in a foam formulation can have dramatic effects on the solution viscosity and liquid drainage from the foam.
- solvents and co-solvents present in decontamination formulations can act effectively as de-foamers if incompatible with the foam formulation.
- Particulates or oxidizing components present in decontamination formulations may also have significant detrimental effects on foam characteristics.
- 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. Accordingly, a serendipitous foam formulation is provided, combining both the advantages of blast suppression and chemical and biological agent decontamination.
- a foam formulation which is compatible with a decontaminant includes the following compositions:
- n 5-49 and most preferably 7;
- the decontamination components compatible with the above foamer include hydrated chloroisocyanuric acid salts, prefereably chloroisocyanuric acid is selected from the group consisting of an alkali metal of monochloroisocyanuric acid, dichloroisocyanuric acid, and a combination thereof with cyanuric acid.
- chloroisocyanuric acid is selected from the group consisting of an alkali metal of monochloroisocyanuric acid, dichloroisocyanuric acid, and a combination thereof with cyanuric acid.
- a preferred alkali metal of dichloroisocyanuric acid is sodium dichloroisocyanurate.
- a preferred decontamination formulation suitable also for blast suppression comprises:
- a buffer system to initially maintain said formulation at a pH from about 8.5 to about 11 for a minimum of 30 minutes and preferably initially, from about 10 to about 11 ;
- the foamer components have a preferred composition of
- a novel method of handling explosive devices comprises the steps of:
- a foamer is prepared from a surfactant, a co-solvent selected from the group consisting of polypropylene glycol, polyethylene glycol, and derivatives and mixtures thereof, and a foam stabilizer;
- a decontamination formulation is prepared from a chloroisocyanuric acid salts, and a buffer to maintain said formulation at a pH from about 11 to about 8.5; mixing the foamer and decontamination formulation in water; and foaming the mixture.
- 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.
- Figures 1 - 4 relate to Example 2.
- Figure 1 illustrates the concentration values of methyl salicylate (mustard simulant) in the test chambers, after two baseline shots (no enclosure) and three test device shots (enclosure with foam + placement of a tent over the device followed by the injection of DSF). The percentage of agent capture and containment exceeded 90 %;
- Figure 2 illustrates the concentration gradient that was measured in the test chamber over a thirty minute duration - NOTE: These are the same shots as in Figure 1 , Baseline shots not shown as the scale was too large. This is still within acceptable limits but has prompted an effort to make further improvements to the foam mitigating capacity;
- Figure 3 illustrates the comparison between unmitigated Baseline shots and Test shots of Example 2.
- Figure 6 illustrates the over pressure measurements at the noted distances from the device for both an unmitigated and a contained shot.
- Figure 7 represents the air concentrations of simulant as measured by DAAMS Tube Samplers in an outdoor trial as noted in Fig. 8. This simulated a device being initiated outside of a structure. The data recorded during the Test Device shot indicated containment greater than 95%;
- Figure 8 illustrates the Range DAAMS Tube Sampler Setup;
- Figure 9 illustrates the over pressures recorded on two tests, an unmitigated test and a contained test. The readings recorded on the contained
- Figure 10 depicts one baseline unmitigated shot, and three contained test shots with different explosive amounts as noted. Samplers set as noted in Fig. 8. Containment realized in excess of 95%; and Figure 11 shows the over pressure values measured at 1.5 meters from the test device unmitigated and three contained shots, each with different explosive loads as noted. Over pressure values were diminished by greater than 95%.
- Figures 12 - 19d relate to Example 4.
- Figure 12 represents a total ion chromatogram created from Hapsite data after simulant dispersal showing a single organic chemical with a predominant mass 115 fragment, consistent with diethyl malonate;
- Figure 13 shows the results of the mass spectral data analysis indicating that the chemical in Fig. 12 is indeed diethyl malonate with a probability of 97.5%;
- Figure 14 shows total ion chromatograms of HapsiteTM readings following vehicle contamination with mustard, prior to application of the foam formulation;
- Figure 15 shows mass spectral identification of the sample in Fig. 14, containing a predominant mass 109 fragment, as being mustard (bis (2-chloroethyl) sulphide);
- Figure 16 shows total ion chromatograms of Hapsite data from air samples acquired after vehicle decontamination showing the absence of mustard vapor;
- Figure 17 shows total ion chromatograms of two separate air samples of tent head-space air, taken at 20 seconds and at one minute during the 5 minute sampling period, following activation of the device;
- Figure 18a shows the total ion chromatogram of the mustard sample, sampled by Hapsite, from the head-space air of the bottle containing mustard, used for vehicle contamination trials;
- Figure 18b shows the total ion chromatograms from the mustard head- space air sample of Fig.
- Figure 20 shows a total ion chromatogram of an air sample acquired by Hapsite during the Example 5 simulant dispersal trial showing the sample to contain a high concentration of a single component, subsequently identified as DEM;
- Figure 21 shows a total ion chromatogram of a head-space air sample above a bottle of mustard agent acquired by Hapsite showing a total ion and mass 109 reconstructed ion chromatogram identifying the substance as mustard;
- Figure 22 shows a total ion chromatogram of the tent head-space air sample acquired by Hapsite 10 minutes after detonation in the simulant trial showing a small amount of simulant and dichloroethyl acetate;
- Figure 23 shows a total ion chromatogram of the tent-head-space air sample acquired by Hapsite after
- FIG. 25 is a table illustrating the effectiveness of a foam formulation containing 9% active ingredient (FS) and one containing 3% active ingredient (Mild) against the nerve agent VX; and
- Figure 26 is a graph illustrating the effectiveness of the foaming agent by itself to effect decontamination of radioactive dusts from the exterior surface of an armored vehicle.
- 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 lED's and decontaminate chemical and warfare agents contained therein.
- Formulations which are suitable for the suppression of blasts are discussed in co-pending US provisional patent application 60/120,874, filed 19 February 1999, and replaced by a regular application filed on or about 18 February 2000, which is incorporated herein by reference in its entirety.
- a suitable foamer concentrate comprising (a) a surfactants 40-80%/w; (b) a foam stabilizer 3-7 %/w; (c) a polyalkylenegiycol 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.
- 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 (PPG425).
- PPG425 still permits good foaming characteristics over a wide range of pH in both fresh and seawater.
- the stabilizer acts to increase foam stability. Long chain, often water insoluble, polar compounds with straight chain hydrocarbon groups of approximately the same length as the hydrophobic group of the surfactant, such as long chain fatty acids, act as foam stabilizers.
- the foamer consists of a surfactant, a co-solvent 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 Mb, 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
- M is an alkali metal, alkaline earth metal, ammonium or amine derivative
- a is the valence of M
- R is an alkyl group having from eight to eighteen carbon atoms
- m is an integer from 0 to 3
- X is selected from the group of S0 3 2" , SO 4 2" , C0 3 2” and P0 4 3"
- M is an alkali metal, alkaline earth metal, ammonium or amine derivative
- a is the valence of M
- a suitable foam stabilizer is an alkyl alcohol, R-OH, where R is an alkyl group having from eight to sixteen carbons.
- R-OH alkyl alcohol
- one such suitable foamer is Silv-ExTM made by Ansul Fire Protection described in US Patent 4,770,794 issued to Cundasawmy et al. September 13, 1988.
- the Silv-Ex formulation consists of a surfactant comprising: 20% by weight of a surfactant Ci 0 H 2 i(OCH 2 CH 2 ) 2 3 SO ⁇ 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 of 5% by weight of d 2 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 IonicsTM 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:
- optional corrosion inhibitors such as sodium tolyltriazole, ammonium dimolybdate and sodium pentahydrate silicate; and
- 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. It has been determined that to lower the thixotropic gelling point of the surfactant, to be useful in a wider range of environments, one approach is to provide an alcohol stabilizer component which comprises more C- ⁇ 2 than d 4 . It has been found that, even more significantly, diluting the surfactant 1 :1 with water for storage and transport further lowers the gelling point. Accordingly, a more dilute 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 When used simultaneously as a blast suppressant, 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.
- Buffer 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.
- the buffer fail, allowing the pH to decrease eventually to a more neutral pH to enable more efficient destruction of the BW agents.
- 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.
- 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.
- a more neutral final pH of the decontamination formulation is less hazardous. It is important to maintain the initial moderately high pH over a prescribed duration (such as a NATO designated duration of 30 minutes for a military decontamination), to provide sufficient hypochlorite ions to effect decontamination - favoring hydrolysis of G-agents, favoring oxidation of VX agent which avoids the formation of toxic hydrolysis byproducts, and favoring oxidation of HD agents and avoiding HD reformation. Accordingly, the buffer must be capable of buffering the release of HCI 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 buffer system to initially maintain said formulation at a pH from about 8.5 to about 11 for a minimum of 30 minutes and preferably initially, from about 10 to about 11 ;
- Example 1 DECONTAMINATION EFFECTIVENESS EVALUATIONS In the process of foam formulation optimization, the three most promising formulations, # 1 , #3 and #4 in Table 1 , incorporating the PPG425 co-solvent, were prepared and evaluated for their agent simulant solubilisation capabilities (ability to dissolve and solubilize compounds simulating real agents)
- 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: 1) A buffer solution consisting of: a) sodium tetraborate decahydrate, used at a concentration in the decontamination solution so as to produce 0.004167 mol/L after being mixed with the surfactant solution; and
- anhydrous sodium carbonate used at a concentration in the decontamination solution so as to produce a molar concentration of 0.0333 mol/L after dilution with the surfactant solution.
- An oxidizing/decontaminating agent sodium dichloro-s- triazinetrione (more commonly known as sodium dichloroisocyanuric acid), with a chlorine content of 62% w/w. This material was used at a concentration so as to produce a concentration of 3% w/w in the final solution. It must be pointed out that the oxidizing agent displays signs of precipitation on standing at concentrations above 2%.
- Example 2 and 3 Two test series were conducted to determine the mitigation capacities of foam formulations to contain CB agents.
- 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.
- 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.
- 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, both of which are incorporated herein in their entirety.
- Example 2 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. Effectiveness of chemical containment was measured using a miniature infra-red gas analyzer (MIRANTM).
- MIRANTM miniature infra-red gas analyzer
- Biological containment was determined using an airborne aerosol mass concentration determination wherein simulant is collected on a filter pad in a Gillian Personnel Sampler pump and airborne aerosol mass concentration is extrapolated given known flow rates and chamber volume. Blast overpressures were determined using ENDEVCOTM piezoresistive pressure transducer and Anderson blast gauges. Two baseline tests were performed without an enclosure or foam formulation to determine the dispersal of the methyl salicylate, mustard simulant. Three tests were performed using the containment tent and the foam formulation. The results, as shown in Fig. 1 , show that compared to the baseline test, the tent and foam formulation were able to contain the mustard simulant in excess of 90%. Fig.
- 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 3 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. Tests were performed using mustard agent simulant, methyl salicylate only. It was felt that chemical contamination represented the worst case scenario and that biological testing would be an unnecessary duplication.
- the dispersal devices used were as follows:
- Device 4 - a commercial garden sprayer containing 1 liter MS The tests were conducted on an open range and in a test chamber measuring 20 ft. x 30 ft. x 10 ft. (169 m 3 ) A dome shaped DYNEEMA tent was used as the enclosure structure which was subsequently filled with SILVEX foam (approx. 570 cubic ft.) to suppress the blasts of the various dispersal devices. Effectiveness of chemical containment was measured using a miniature infra-red gas analyzer (MIRANTM). Further, chemical concentration ranges were determined by collecting simulant aerosols on a Depot Area Air Monitoring System (DAAMS) tube followed by thermal desorption into an HP5890 gas chromatography system equipped with a flame ionization detector.
- MIRANTM miniature infra-red gas analyzer
- 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.
- 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. Examples 4 and 5 In Examples 4 and 5, staged field tests were conducted to determine the blast suppression decontamination foam formulation's ability to both decontaminate and to suppress a blast. The presence of G-agent simulant and mustard agent was determined using conventional decontamination monitoring equipment such as Graseby IonicsTM Chemical Agent Monitor or CAM and Chemical Agent Detection
- HapsiteTM a portable gas chromatograph/mass spectrometer
- 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.
- Example 4 In a first stage, the ability of the CAMS and Hapsite to measure dispersion of the agent simulant, diethyl malonate, was determined. In a second stage, the ability of the blast suppressing decontamination foam formulation to decontaminate mustard painted onto a vehicle surface was tested. In a third and last stage, the ability of the blast suppressing decontamination foam formulation to suppress blasts while containing G-agent simulant and mustard vapor and simultaneously decontaminating the mustard agent, were tested.
- Stage 1 - Simulant Dispersion Tests Two dispersal devices, each containing 250 ml of a diethyl malonate (DEM)(propanedioic acid, diethyl ester)/water (50/50 v/v) mixture, were secured to ring stands located in the proximity of target vehicles. One was placed 50 cm above the ground and the other at 75 cm above the ground.
- Witness cards containing dyed paper for detecting liquid drops were placed on the ground near the dispersal devices, on the nearby vehicles and on the ground 20 meters downwind of the dispersal devices. 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. All witness cards showed evidence of impact from liquid drops.
- the 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).
- An MS-only survey method, employed on Hapsite provided data for a total ion chromatogram as shown in Fig. 1 , having a single organic chemical with a predominant mass 115 fragment, consistent with diethyl malonate.
- 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%. Having determined that the detection equipment was capable of monitoring simulant, the foam formulation was tested to determine its ability to act as a decontaminant in Stage 2.
- Stage 2 - Vehicle Decontamination Trial An armored personnel carrier painted with chemical agent resistant coating (CARC) was painted, on one side, with 150mL mustard.
- CARC chemical agent resistant coating
- Four CADS II monitoring stations were deployed near the vehicle, three placed downwind.
- a sample of head-space air was taken from the bottle from which the mustard was taken, using Hapsite and CAM readings were taken near the vehicle prior to the application of the foam formulation.
- Blast suppressant decontaminating foam was applied to the surface of the vehicle using a hose and spray head assembly, followed by manual scrubbing of the surface with long handled brushes. After a 30 minute waiting period, the foam was washed away with water and the vehicle surface re-surveyed with CAMs.
- Hapsite was used to take air samples around and downwind the vehicle.
- 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.
- the CADS II and CAM H-mode readings dropped to a zero response.
- Hapsite air samples acquired around the vehicle did not show any mustard content as shown in Fig. 16.
- 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.
- Stage 3 - Blast suppression/decontamination Tent Trials Two separate stage 3 trials were performed, the first using G-agent simulant, diethyl malonate and the second using mustard chemical agent. The ambient temperature during the trials was 6°C.
- 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.
- the CADS II and CAM readings taken in close proximity to the tent found no G- mode readings. No evidence of diethyl malonate was found on in the Hapsite reading over a 5 minute period.
- CADS II and CAM readings, taken in the proximity of the tent also showed no H-mode response. No mustard was found in the tent head space air.
- the CAM surveys did show a significant H-mode response coupled with a response indicative of a low reference ion peak. This response was exhaustively determined, through both chromatograph and mass spectral analysis (Figs.
- Example 5 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.
- Stage 1 - Open Dispersion trial 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. Following detonation, 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.
- Stage 2 - Vehicle Decontamination A CARC painted armored personnel carrier (APC) 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 subsequently 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.
- APC CARC painted armored personnel carrier
- a 250mL 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. x12 ft. x 10 ft. 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 5m. 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. In both trials, the tent remained intact and containing all materials.
- Examples 6-9 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. Further, in each of Examples 6 - 8, quantitative analyses for residual agents were performed on a high pressure liquid chromatography (HPLC) system for separation of the reaction components, equipped either with a HPLC-UV detector in series with a commercially available dual flame gas chromatographic flame photometric detector (FPD) from Varian Associates, or, where possible, on a Hewlett-Packard 1100 LC-MS system equipped with a diode-array UV-VIS spectrophotometer and mass selective detector (MSD). The water used in the reactions, prepared solutions, and in the HPLC was distilled and deionized.
- HPLC high pressure liquid chromatography
- FPD flame photometric detector
- MSD mass selective detector
- formulation for the surfactant foam was first warmed to 32°C to ensure
- 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
- Example 6 Having reference also to 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.
- 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. In order to standardize concentrations between experiments, the effectiveness was calculated as a percentage of residual agent. Using 0.29% w/w GB, there was no evidence of residual agent in any of the LC-FPD or LC-MS analyses for the mildest and intermediate strength formulations (3% w/w and 6% w/w SD). GB was destroyed in each case before the first sample could be taken (0.43 and 1.13 minutes respectively). For the most potent formulation (9% w/w SD), only LC-FPD analysis was performed at 1.78 minutes elapsed time and no agent was detected indicating complete destruction of the agent within 1.78 minutes.
- Example 7 Having reference also to Fig. 25, the effectiveness of several formulations against the nerve agent VX was determined. 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. Control formulations were also examined.
- MILD mildest formulation
- FS* full strength formulation
- Example 8 The effectiveness of foam phase-detoxification of anthrax spores was determined.
- a suspension of Bacillus anthracis (Ames strain) was heat shocked to kill the vegetative cells, leaving only the viable spores.
- Small metal coupons, painted as per in-service military vehicles, were cleaned with ethanol wipes and
- each coupon was removed from the petri dish using forceps, rinsed with sterile PBS, then swabbed twice over its entire surface with a sterile sampling swab.
- the swab was placed in 5 ml of Heart Infusion broth and vortexed.
- control foam-treated coupon were plated onto each of four Blood Agar plates. The plates were incubated overnight at 37° C and the Colony Forming Units (CFU) observed the following day, are given in Table II. The Control foam results are shown multiplied by 10 4 to adjust for the 10 "4 dilution.
- 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.
- 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.
- the same vehicle was contaminated to a level of approximately 45 mRem/hr. During movement of the contaminated vehicle to the site of decontamination, significant loss in the level of radioactivity was observed. The loss was such that the trial was terminated. It was apparent that the exterior surface, having been previously cleaned in an earlier trial, did not retain radioactive particles sprayed onto it. In other words the surface had been degreased and dust adherence had been significantly decreased, suggesting an additional benefit to the use of the formulation.
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Abstract
Description
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Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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US12209199P | 1999-02-26 | 1999-02-26 | |
US122091P | 1999-02-26 | ||
PCT/CA2000/000199 WO2000051687A1 (en) | 1999-02-26 | 2000-02-25 | Decontaminating and dispersion suppressing foam formulation |
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EP1154821A1 true EP1154821A1 (en) | 2001-11-21 |
EP1154821B1 EP1154821B1 (en) | 2004-05-26 |
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EP00906112A Expired - Lifetime EP1154821B1 (en) | 1999-02-26 | 2000-02-25 | Decontaminating and dispersion suppressing foam formulation |
Country Status (7)
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EP (1) | EP1154821B1 (en) |
AT (1) | ATE267630T1 (en) |
AU (1) | AU766865B2 (en) |
CA (1) | CA2299259C (en) |
DE (1) | DE60011050T2 (en) |
IL (2) | IL145033A0 (en) |
WO (1) | WO2000051687A1 (en) |
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WO2004052918A2 (en) | 2002-12-09 | 2004-06-24 | The Trustees Of Columbia University In The City Of New York | Peptides and methods for deactivation of organophosphorus-based nerve agents and insecticides |
FR2931687B1 (en) * | 2008-05-27 | 2017-11-24 | Commissariat A L'energie Atomique | AQUEOUS DECONTAMINANT AND FOAMING SOLUTION. |
FR3103549B1 (en) * | 2019-11-25 | 2021-12-03 | Arianegroup Sas | MOBILE DEVICE FOR NEUTRALIZING CHEMICAL OR BIOLOGICAL WEAPONS |
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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 (en) * | 1980-04-09 | 1984-12-24 | 花王株式会社 | foamable composition |
KR930009035B1 (en) * | 1990-03-19 | 1993-09-22 | 국방과학연구소 | Aqueous antidote composition |
FR2679458A1 (en) * | 1991-07-23 | 1993-01-29 | Commissariat Energie Atomique | DECONTAMINATION FOAM WITH CONTROLLED LIFETIME AND DECONTAMINATION INSTALLATION OF OBJECTS USING SUCH FOAM. |
AU6646798A (en) * | 1997-01-10 | 1998-08-03 | Loizeaux Group Int'l Ltd | Method and apparatus for the destruction of articles |
-
2000
- 2000-02-25 CA CA002299259A patent/CA2299259C/en not_active Expired - Fee Related
- 2000-02-25 IL IL14503300A patent/IL145033A0/en active IP Right Grant
- 2000-02-25 AU AU27898/00A patent/AU766865B2/en not_active Ceased
- 2000-02-25 EP EP00906112A patent/EP1154821B1/en not_active Expired - Lifetime
- 2000-02-25 AT AT00906112T patent/ATE267630T1/en not_active IP Right Cessation
- 2000-02-25 DE DE60011050T patent/DE60011050T2/en not_active Expired - Lifetime
- 2000-02-25 WO PCT/CA2000/000199 patent/WO2000051687A1/en active IP Right Grant
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2001
- 2001-08-21 IL IL145033A patent/IL145033A/en not_active IP Right Cessation
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See references of WO0051687A1 * |
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Publication number | Publication date |
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ATE267630T1 (en) | 2004-06-15 |
WO2000051687B1 (en) | 2000-11-23 |
DE60011050T2 (en) | 2005-11-03 |
IL145033A0 (en) | 2002-06-30 |
IL145033A (en) | 2006-07-05 |
CA2299259C (en) | 2007-12-04 |
AU766865B2 (en) | 2003-10-23 |
AU2789800A (en) | 2000-09-21 |
DE60011050D1 (en) | 2004-07-01 |
EP1154821B1 (en) | 2004-05-26 |
WO2000051687A1 (en) | 2000-09-08 |
CA2299259A1 (en) | 2000-08-26 |
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