TPPO: A Replacement Candidate for Red Phosphorous

Joseph A. Domanico Chief, Pyrotechnics Team Building E3580 Beach Point Road AMSSB-REN-SP Edgewood Chemical Biological Center Aberdeen Proving Ground, MD 21010-5424 Voice: 410-436-2180 FAX: 410-436-4941 joseph.domanico@sbccom.apgea.army.mil ABSTRACT The Edgewood Chemical Biological Center has been actively pursuing a replacement for red phosphorous for use in military smoke producing ammunition. Both burning and bursting grenade designs using Triphenylphospine Oxide (TPPO) as the smoke material have shown the potential for nearly matching the amount of smoke produced from a similar sized device filled with red phosphorous. End burning hand grenade sized munitions provide a sizable smoke cloud for a substantial amount of time. Core burning devices provide a significant increase in smoke density and a reduced amount of time. TPPO is currently under evaluation for both its smoke producing capabilities, and also for its potential to reduce the environmental pollution caused by the use of red phosphorous in military ammunition. This paper will highlight the technical data, photographs, and videotape of the research and development efforts. Introduction The use of red phosphorous in military smoke ammunition gave an alternative to the hexachloroethane (HC) smoke system. HC smoke has been used for many years in general warfare to provide a visual screen which hides troop movements during battle. The zinc chloride based smoke cloud is quite toxic due to the formation of hydrochloric acid in the lungs when a sufficient quantity of smoke is inhaled. Additionally, the hexachloroethane used in the production of the grenade is now considered a carcinogen. Background Original formulations using red phosphorous were evaluated by the armed forces many years ago. Red phosphorous proved to be difficult to use in burning type grenades due to its low Tamman temperature. This characteristic of red phosphorous resulted in the original burning formulations to react during storage severely reducing their shelf life. Eventually, a formulation was devised using magnesium as the fuel and manganese dioxide as the oxidizer. The addition of zinc oxide as a curing catalyst and linseed oil as the binder allowed this formulation to be successfully used in a day/night marine marker. The large flame and copious smoke production allowed its use a a rescue signal. A starter composition consisting of lead dioxide, copper oxide, and silicon successfully passed the long term storage tests for compatibility.

Reformulation efforts using a boron and calcium sulfate mixture to replace the magnesium and manganese dioxide (fuel / oxidizer system) were successful at the Edgewood Chemical Biological Center and at other research and development facilities. The additional cost of the formulation was considered too high a price to pay for the hydrogen gas which was evolved from the magnesium during storage. This effort was subsequently dropped for financial considerations. An additional effort was successfully completed which used a binder which could prevent the pre-oxidation of the red phosphorous with the oxidizer during storage. The new composition used aluminum as the fuel and sodium nitrate as the oxidizer. This formulation was successfully used in burning wedges which were bare on all sides. There was no compatibility issues with the ignition composition as it was sealed inside the round and had no direct contact with the red phosphorous mix. Several of these types of formulations were fabricated in the traditional smoke grenade sized cans for use as a substitute for the HC smoke grenade by ground troops. The large flame produced by the red phosphorous grenades was a significant fire hazard and was considered the main reason preventing adoption of the system. Additionally, the red phosphorous based grenade could be accidentally ignited if the canister was impacted with sufficient pressure. It was possible that the level of impact required could be obtained by a soldier hitting the ground from a standing position. The subsequent flame and smoke would make him a dissatisfied customer as well as further highlighting his position to the enemy. If a substitute for HC smoke grenades was to be found, and phosphorous was to be used, simply designing burning grenades in a manner similar to air burst munitions would not be successful. The search for a substitute for HC, and subsequently RP, lead to the use of triphenylphospine oxide. Other materials are currently under evaluation, but sufficient data is not available at this time from publication. The use of triphenylphospine oxide as a successful substitute for red phosphorous in grenades and pellets may also allow its use as a substitute for HC smoke grenades. Materials and Equipment One of the goals of this effort was to only use techniques which could easily be scaled up into production level. Typical pyrotechnic handling procedures would be evaluated if they could be utilized with existing equipment or by slight modification of existing equipment. Special handling procedures such a the use of protective masks and respirators, and protective gloves would be used as simple precaution measures for the material handlers. Only a little is currently known on the toxicity of handling triphenylphospine oxide and its subsequent combustion and vaporization products. Dry blending of the components for manufacturing the smoke compositions was quite successful. The resulting mixtures burned well but the mixture contained excess amounts of trapped air. This resulted in a high degree of difficulty during the consolidation of the smoke blend. The excess trapped air makes the mixture fluffy. The direct result of pressing the loose powder into

a cake was extremely difficult as the mixture had a tendency to flow around the pressing ram and out of the can. The result was that a significant quantity of mixture could be found on the floor and not inside the canister. Blending the component chemicals with acetone and subsequently evaporating the acetone proved to greatly reduce the trapped air and increased the free flowing density of the smoke compositions. For mixtures with either a non-organic binder or a dry binder, this was the preferred mixing technique. The use of binders which were soluble in acetone followed the same mixing procedure. the binder was first dissolved in the acetone by directly adding the two components into the mixing bowl. After the binder went into solution, the dry powders were added. The oxidizer was always the final component to be added for safety reasons. (The mixture is not a pyrotechnic blend until AFTER the powdered oxidizer is added). This reduces the exposure time of the energetic composition to the handlers. Experimental Several fuel / oxidizer combinations were blended by one of the above mentioned techniques. The dry powders were pressed directly into standard grenade cans, both in end-burning configurations and core-burning configurations. The standard grenade can is approximately 4.5 inches in height and 2.3 inches in diameter. This is approximately the size of a 16 ounce soda (or beer) can. The end burning configuration is filled with smoke composition to a height of 4 inches, leaving an air space of 0.5 inches. The starter composition is pressed on the top surface. Loading pressure varied throughout the experiment but was maintained within the 1000 pounds per square inch and 10,000 pounds per square inch levels. The smoke exit ports for the end-burning configuration was 4 holes, each one 0.3 inches in diameter. The core-burning configuration is identical in external dimensions but use a lid without any holes and a 0.5 inch diameter hollow core in the axial center of the can. In the end-burning configuration the smoke exits from the top of the can which is the end containing the igniter. In the core-burning configuration the smoke exits from the single hole at the end opposite from the igniter. Electric igniters were used for all tests which replicate manually functioned mechanical grenade fuzes. Results and Discussion End-burning configurations using a high and low consolidation pressure were tested by an independent laboratory for particle size distribution and yield percentage. Subscale grenades consisting of 100 grams net weight of the TPPO based energetic smoke composition were fabricated with both small and large exit port diameters. Table 1 highlights the subscale grenade configurations.

Table 1 Subscale Grenade Configurations Loading Pressure Exit Port Diameter 1.3 cm 1.9 cm 1500 psi 1.3 cm 1.9 cm 3500 psi Average particle size determinations for the subscale grenades containing 40% TPPO by weight are shown in table 2. The average particle sizes usually followed the traditional bell shaped curve. Some exceptions were noted which will not be discussed here. Table 2 Average Particle Size Range for 40% TPPO Subscale Grenades Loading Pressure Exit Port Diameter Diameter (microns) 0.5 - 1.0 1.0 - 2.0 ~50% ~50% 3500 psi 1.3 cm ~30% ~70% 3500 psi 1.9 cm Mean aerosol yields of the smoke clouds were also determined to demonstrate the possible increase in smoke yield by the physical modification of the grenade. Table 3 shows the comparison in the smoke yield for both end-burning and core-burning grenades. By changing the end-burning configuration to a core-burning one, the smoke yield increased from 15% to 45% for the end burner to 42% to 58% for the core burner. Table 3 Mean Smoke Aerosol Yield (Core v.s. End Burning) Loading Pressure Physical Configuration Mean Aerosol Yield End burning 15% to 45% 1500 psi Core burning 42% to 58% 1500 psi Both internal and exit port burning temperatures were measure to determine the potential for the destruction of TPPO during its short life as a vapor inside the canister. Table 4 shows the differences between the exit port temperature and the internal burning temperature of the composition. Notice the wide difference in the temperature found inside the pressed composition in comparison with the temperature found at the exit port for the grenade pressed at the higher pressure. Table 4 Internal Temperature v.s. Exit Port Temperature Loading Pressure Internal Temperature Exit Port Temperature ~380 deg C ~390 deg C 1500 psi ~ 493 deg C ~345 deg C 3500 psi

Figure 1 shows a typical smoke cloud produced using 64% by weight of triphenylphospine oxide in a full scale smoke grenade. This configuration holds 250 grams of smoke mix with 6 grams of starter composition. The grenade burn time is 38 seconds. This configuration produces a thick smoke for a moderate duration. Figure 1 Smoke Production from a 64% TPPO Grenade

Conclusions Triphenylphospine oxide has shown its potential as a replacement for red phosphorous. It is currently a viable candidate based on its performance in making copious amounts of smoke. With loadings from 40 percent by weight to nearly 70 percent by weight, it has the potential to deliver copious smoke for short durations as well as high smoke production for extended smoke production times. The effort to increase the loading percent by weight, as well as the use of auxiliary fuels and oxidizers may allow either more smoke production within the size constraints.