Thermochemical Analysis of Improvised Energetic Materials by Laser-Heating Calorimetry.

Thermochemical analysis of six improvised energetic materials was carried out using laser-heating calorimetry to demonstrate the feasibility of this methodology to provide distinctive thermal signatures and information on the material shelf life. The chemicals evaluated were erythritol tetranitrate, hexamethylene triperoxide diamine (HMTD), poor-man's C-4 (blend of potassium chlorate and petroleum jelly), R-salt (represented by 1,3,5-trinitroso-1,3,5-triazinane), triacetone triperoxide (TATP), and urea nitrate. The measurement technique records the temperature rise with time, from which one can estimate the material endothermic/exothermic behavior, energy release rate, and total specific energy release (heating value, enthalpy of explosion), as well as the sample mass rate of change. Measurements were carried out in an inert nitrogen environment at laser heating rates up to 60 K/s with steady-state temperatures reaching about 933 K. Sample initial mass was between 1.0 mg and 4.0 mg. Experiments were carried out with freshly prepared samples, as well as refrigerated samples and those stored at room (laboratory) temperature for three years. Results indicated that the samples reacted rapidly between 0.50 s and 0.75 s, being initiated near the material decomposition temperature. The total specific energy release, using two different thermal-analysis models, was calculated and compared to values available in the literature. One model represents sample reaction and decomposition within the spherical reactor volume, while the second represents reactions emanating from sample in a pan centrally positioned within the sphere; the former model was found to be the more appropriate approach for these faster-reacting energetic materials. The thermal signatures (temperature-time derivatives with temperature) were different for each chemical, a feature that may be important for energetic material identification. The initiation and peak reaction temperatures were found to decrease with increasing initial sample mass. Also, the shelf life for TATP and HMTD was found not to degrade under nonideal conditions after three years.

Simultaneous Transmission/Absorption Photometry of Particle-Laden Filters from Wildland Fires during the Biomass Burning Observation Project (BBOP) Field Campaign.

Transmissivity and absorptivity measurements were carried out simultaneously in the visible (wavelength of 532 nm) at laboratory conditions using particle-laden filters obtained from a three-wavelength particle/soot absorption photometer (PSAP). The particles were collected on filters from wildland fires over the Pacific Northwest during the Department of Energy Biomass Burning Observation Project (BBOP) field campaign in 2013. The objective of this investigation was to apply this measurement approach, referred to as simultaneous transmission/absorption photometry (STAP), to estimate the aerosol extinction coefficient from actual field-campaign filter aerosol, and compare results with the PSAP. The STAP approach offers several advantages over the PSAP, including estimation of the extinction coefficient from temperature measurements (avoiding the complexities associated with filter reflectivity/scattering measurements), as well as determination of the filter optical properties and filter effects on particle absorption (resulting in particle absorption enhancement). The experimental arrangement included a laser probe beam impinging normal to the particle-coated surface of a vertically mounted filter, and a thermocouple placed flush in the middle of (and in thermal contact with) the filter uncoated back surface. With this simple arrangement, the transmissivity and absorptivity were determined simultaneously at a given laser beam wavelength. The measurement repeatability was better than 0.3 K (95 % confidence level) for temperature and 0.4 mW for laser power. The limit of detection for the extinction coefficient was estimated to be (8 to 12) Mm-1 (95 % confidence level) at about 1.9 mW laser power. The extinction coefficient was determined through measurement of both PSAP blank and exposed filters. Filters were obtained from nine different aircraft flights conducted during the BBOP campaign, representing different flight patterns, days, stages of burning, landscapes, and wildland fires. The STAP extinction coefficient matched the darkness of the filter coating, however the PSAP-filter results did not follow the same order. Although there were differences in transmissivity between the two techniques, the estimated values for absorption coefficient were in good agreement.

Laser-Driven Calorimetry and Chemometric Quantification of Standard Reference Material Diesel/Biodiesel Fuel Blends.

Requirements for blends of drop-in petroleum/bio-derived fuels with specific thermophysical and thermochemical properties highlights the need for chemometric models that can predict these properties. Multivariate calibration methods were evaluated using the measured thermograms (i.e., change in temperature with time) of 11 diesel/biodiesel fuel blends (including four repeated runs for each fuel blend). Two National Institute of Standards and Technology Standard Reference Material® (SRM®) pure fuels were blended by serial dilution to produce fuels having diesel/biodiesel volumetric fractions between (0 to 100) %. The fuels were evaluated for the prepared fuel-blend volume fraction and total specific energy release (heating value), using a laser-driven calorimetry technique, termed 'laser-driven thermal reactor'. The experimental apparatus consists of a copper sphere-shaped reactor (mounted at the center of a stainless-steel chamber) that is heated by a high-power continuous wave Nd:YAG laser. Prior to heating by the laser, liquid sample is injected onto a copper pan substrate that rests near the center of the reactor and is in contact with a fine-wire thermocouple. A second thermocouple is in contact with the sphere-reactor inner surface. The thermograms are then used to evaluate for the thermochemical characteristic of interest. Partial least squares (PLS) and support vector machine (SVM) models were constructed and evaluated for SRM-fuel-blend quantification, and determination of prepared fuel-blend volume fraction and heating value. Quantification of the fuel-blend thermograms by the SVM method was found to better correlate with the experimental results than PLS. The combination of laser-driven calorimetry and multivariate calibration methods has demonstrated the potential application of using thermograms for fuels quantification and analysis of fuel-blend properties.

Simultaneous transmission and absorption photometry of carbon-black absorption from drop-cast particle-laden filters.

Simultaneous transmissivity and absorptivity measurements were carried out in the visible at a laser wavelength of 532 nm on drop-cast, carbon-black-laden filters under ambient (laboratory) conditions. The focus of this investigation was to establish the feasibility of this approach to estimate the mass absorption coefficient of the isolated particles and compare results to earlier work with the same carbon-black source. Transmissivity measurements were carried out with a laser probe beam positioned normal to the particle-laden filter surface. Absorptivity measurements were carried out using a laser-heating approach to record in time the sample temperature rise to steady-state and decay back to the ambient temperature. The sample temperature was recorded using a fine-wire thermocouple that was integrated into the transmission arrangement by placing the thermocouple flush with the filter back surface. The advantage of this approach is that the sample absorptivity can be determined directly (using laser heating) instead of resolving the difference between reflectivity (filter surface scattering) and transmissivity. The current approach also provides the filter optical characteristics, as well as an estimate of filter effects on the absorption coefficient due to particle absorption enhancement or shadowing. The approach may also be incorporated into other filter-based techniques, like the particle/soot absorption photometer, with the simple addition of a thermocouple to the commercial instrument. For this investigation, measurements were carried out with several blank uncoated quartz filters. A range of solution concentrations was prepared with a well-characterized carbon black in deionized water (i.e., a water-soluble carbonaceous material referred to as a surrogate black carbon or 'carbon black'). The solution was then drop cast using a calibrated syringe onto blank filters to vary particle loading. After evaporation of the water, the measurements were repeated with the coated filters. The measurement repeatability (95% confidence level) was better than 0.3 K for temperature and 3 × 10-5 mW for laser power. From the measurements with both the blank and coated filters, the absorption coefficient was determined for the isolated particles. The results were then compared with an earlier investigation by You et al. and Zangmeister and Radney, who used the same carbon-black material. The measurements were also compared with Lorenz-Mie computations for a polydispersion of spherical particles dispersed throughout a volume representative of the actual particles. The mass absorption coefficient for the polydispersion of carbon-black particles was estimated to be about 7.7 ± 1.4m2 g-1, which was consistent with the results expected for these carbon black particles.

Laser-Driven Calorimetry Measurements of Petroleum and Biodiesel Fuels.

Thermochemical characteristics were determined for several National Institute of Standards and Technology standard-reference-material petroleum and biodiesel fuels, using a novel laser-heating calorimetry technique. Measurements focused on the sample thermal behavior, specific heat release rate, and total specific heat release. The experimental apparatus consists of a copper sphere-shaped reactor mounted within a chamber, along with laser-beam-steering optical components, gas-supply manifold, and a computer-controlled data-acquisition system. At the center of the reactor, liquid sample is injected onto a copper pan substrate that rests and is in contact with a fine-wire thermocouple. A second thermocouple is in contact with the inner reactor sphere surface. The reactor is heated from opposing sides by a continuous-wave, near-infrared laser to achieve nearly uniform sample temperature. The change in temperature with time (thermogram) is recorded for both thermocouples, and compared to a baseline thermogram (without liquid in the pan). The thermograms are then processed (using an equation for thermal energy conservation) for the thermochemical information of interest. The results indicated that the energy reaching the pan is dominated by radiative heat transfer processes, while the dominant thermal process for the reactor sphere is the stored (internal) thermal energy within the sphere material. Sufficient laser power is necessary to detect the fuel thermal-related characteristics, and the required power can differ from one fuel to another. With sufficient laser power, one can detect the preferential vaporization of the lighter and heavier fuel fractions. The total specific heat release obtained for the different conventional and biodiesel fuels used in this investigation were similar to the expected values available in the literature.

Laser-Driven Calorimetry of Single-Component Liquid Hydrocarbons.

A novel laser-heating technique, referred to as the laser-driven thermal reactor (LDTR), was used to determine sample thermal (exothermic/endothermic) behavior, specific heat release rate, and total specific heat release of three volatile single-component liquid hydrocarbons, i.e., n-decane, n-butylcyclohexane and n-butylbenzene. The objective was to demonstrate measurement repeatability and extend the LDTR model from earlier investigations. The experimental apparatus consists of a copper sphere-shaped reactor mounted within a vacuum chamber, with sample and substrate supported on a thermocouple near the center of the reactor. The reactor is heated from opposing sides by a near-infrared laser to achieve nearly uniform sample temperature. The change in temperature with time (i.e., thermogram) is compared to a previously recorded baseline (no liquid sample) thermogram. A model, based on thermal energy conservation, is used to evaluate the thermograms for the thermochemical characteristics of interest. This study represents a step toward applying this technique to more complex volatile multi-component fuels of unspecified composition. Results for the LDTR were compared with a differential scanning calorimetry/thermal gravimetric analysis (DSC/TGA) instrument. The model analysis was extended to include an estimation of the hydrocarbon mass change with increasing temperature, based on the temporal change in the specific heat release rate. An estimate of the total specific heat release was obtained for these three liquid hydrocarbons and found to be consistent with the literature values when the measurements were carried out under suitable operating conditions.

Absorption/Transmission Measurements of PSAP Particle-Laden Filters from the Biomass Burning Observation Project (BBOP) Field Campaign.

Absorptivity measurements with a laser-heating approach, referred to as the laser-driven thermal reactor (LDTR), were carried out in the infrared and applied at ambient (laboratory) non-reacting conditions to particle-laden filters from a three-wavelength (visible) particle/soot absorption photometer (PSAP). The particles were obtained during the Biomass Burning Observation Project (BBOP) field campaign. The focus of this study was to determine the particle absorption coefficient from field-campaign filter samples using the LDTR approach, and compare results with other commercially available instrumentation (in this case with the PSAP, which has been compared with numerous other optical techniques). Advantages of the LDTR approach include 1) direct estimation of material absorption from temperature measurements (as opposed to resolving the difference between the measured reflection/scattering and transmission), 2) information on the filter optical properties, and 3) identification of the filter material effects on particle absorption (e.g., leading to particle absorption enhancement or shadowing). For measurements carried out under ambient conditions, the particle absorptivity is obtained with a thermocouple placed flush with the filter back surface and the laser probe beam impinging normal to the filter particle-laden surface. Thus, in principle one can employ a simple experimental arrangement to measure simultaneously both the transmissivity and absorptivity (at different discrete wavelengths) and ascertain the particle absorption coefficient. For this investigation, LDTR measurements were carried out with PSAP filters (pairs with both blank and exposed filters) from eight different days during the campaign, having relatively light but different particle loadings. The observed particles coating the filters were found to be carbonaceous (having broadband absorption characteristics). The LDTR absorption coefficient compared well with results from the PSAP. The analysis was also expanded to account for the filter fiber scattering on particle absorption in assessing particle absorption enhancement and shadowing effects. The results indicated that absorption enhancement effects were significant, and diminished with increased filter particle loading.

Thermal Signature Measurements for Ammonium Nitrate/Fuel Mixtures by Laser Heating.

Measurements were carried out to obtain thermal signatures of several ammonium nitrate/fuel (ANF) mixtures, using a laser-heating technique referred to as the laser-driven thermal reactor (LDTR). The mixtures were ammonium nitrate (AN)/kerosene, AN/ethylene glycol, AN/paraffin wax, AN/petroleum jelly, AN/confectioner's sugar, AN/cellulose (tissue paper), nitromethane/cellulose, nitrobenzene/cellulose, AN/cellulose/nitromethane, AN/cellulose/nitrobenzene. These mixtures were also compared with AN/nitromethane and AN/diesel fuel oil, obtained from an earlier investigation. Thermograms for the mixtures, as well as individual constituents, were compared to better understand how the sample thermal signature changes with mixture composition. This is the first step in development of a thermal-signature database, to be used along with other signature databases, to improve identification of energetic substances of unknown composition. The results indicated that each individual thermal signature was associated unambiguously with a particular mixture composition. The signature features of a particular mixture were shaped by the individual constituent signatures. It was also uncovered that the baseline signature was modified after an experiment due to coating of unreacted residue on the substrate surface and a change in the reactor sphere oxide layer. Thus, care was required to pre-oxidize the sphere prior to an experiment. A minimum sample mass (which was dependent on composition) was required to detect the signature characteristics. Increased laser power served to magnify signal strength while preserving the signature features. For the mixtures examined, the thermal response of each ANF mixture was found to be different, which was based on the mixture composition and the thermal behavior of each mixture constituent.