What Have We Learned From Decades of CRT, And Where Do We Go From Here?
2006
The Chemical Reactivity Test, or CRT, has been the workhorse for determining short-to-medium term compatibility and thermal stability for energetic materials since the mid 1960s. The concept behind the CRT is quite simple. 0.25 g of material is heated in a 17 cm{sup 3} vessel for 22 hours at 80, 100, or 120 C, and the yield of gaseous products are analyzed by gas chromatography to determine its thermal stability. The instrumentation is shown in Figure 1, and the vessel configuration is shown in Figure 2. For compatibility purposes, two materials, normally 0.25 g of each, are analyzed as a mixture. Recently, data from the past 4 decades have been compiled in an Excel spreadsheet and inspected for reliability and internal consistency. The resulting processed data will be added this year to the LLNL HE Reference Guide. Also recently, we have begun to assess the suitability of the CRT to answer new compatibility issues, especially in view of more modern instrumentation now available commercially. One issue that needs to be addressed is the definition of thermal stability and compatibility from the CRT. Prokosch and Garcia (and the associated MIL-STD-1751A) state that the criterion for thermal stability is a gas yield of less than 4 cm{sup 3}/g for a single material for 22 hours at 120 C. The gases from energetic materials of interest ordinarily have an average molecular weight of about 36 g/mol, so this represents decomposition of 0.5-1.0% of the sample. This is a reasonable value, and a relatively unstable energetic material such as PETN has no problem passing. PBX 9404, which yields 1.5 to 2.0 cm{sup 3}/g historically, is used as a periodic check standard. This is interesting in itself, since the nitrocellulose in the 9404 is unstable and probably has partially decomposed over the decades. However, it is not clear whether this aging of the standard would lead to more or less gas, since the initial gaseous degradation products are captured by the DPA stabilizer. Clearly this is an issue that needs reconsideration. The criterion for compatibility is less clearly correct. Although some LLNL reports say that generation of gas in excess of the materials by themselves is an indication of incompatibility, LLNL reports invariably say that materials are compatible if they generate less than 1 cm{sup 3}/g of gas. There are two problems with this criterion. First, it is not stated whether the gas yield is per gram of energetic material or mixture. Second, a material that generates >2 cm{sup 3}/g by itself could never pass the compatibility tests as stated, because even a mixture of equal masses of that material with a completely inert material would generate >1 cm{sup 3}/g of gas per mixture. Furthermore, Prokosch states that a yield equal to or less than from the materials individually means that no reaction has occurred. Clearly, less gas can not be generated unless some type of interaction has occurred. An obvious example would be mixing CaO with a CO{sub 2}-generating energetic material. In the absence of any direct action of the CaO on the energetic material, the CO{sub 2} product would be captured by the CaO, thereby decreasing the gas yield and liberating considerable heat. In a large, closed volume, this could tip the balance to thermal runaway.
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