Microwave-Assisted Synthesis of the Flexible Iron-Based MIL-88B Metal-Organic Framework for Advanced Energetic Systems

The 3D metal-organic framework (MOF), MIL-88B, built from the trivalent metal ions and the ditopic 1,4-Benzene dicarboxylic acid linker (H2BDC), distinguishes itself from the other MOFs for its flexibility and high thermal stability. MIL-88B was synthesized by a rapid microwave-assisted solvothermal method at high power (850 W). The iron-based MIL-88B [Fe3.O.Cl.(O2C-C6H4 -CO2)3] exposed oxygen and iron content of 29% and 24%, respectively, which offers unique properties as an oxygen-rich catalyst for energetic systems. Upon dispersion in an organic solvent and integration into ammonium perchlorate (AP) (the universal oxidizer for energetic systems), the dispersion of the MOF particles into the AP energetic matrix was uniform (investigated via elemental mapping using an EDX detector). Therefore, MIL-88B(Fe) could probe AP decomposition with the exclusive formation of mono-dispersed Fe2O3 nanocatalyst during the AP decomposition. The evolved nanocatalyst can offer superior combustion characteristics. XRD pattern for the MIL-88B(Fe) framework TGA residuals confirmed the formation of α-Fe2O3 nanocatalyst as a final product. The catalytic efficiency of MIL-88B(Fe) on AP thermal behavior was assessed via DSC and TGA. AP solely demonstrated a decomposition enthalpy of 733 J g-1 , while AP/MIL-88B(Fe) showed a 66% higher decomposition enthalpy of 1218 J g-1 ; the main exothermic decomposition temperature was decreased by 71 °C. Besides, MIL-88B(Fe) resulted in a decrease in AP decomposition activation energy by 23% and 25% using Kissinger and Kissinger–Akahira–Sunose (KAS) models, respectively.

Nitrocellulose Catalyzed With Manganese Oxide Nanoparticles: Advanced Energetic Nanocomposite With Superior Decomposition Kinetics

Nanostructured energetic materials can fit with advanced energetic first-fire, and electric bridges (microchips). Manganese oxide, with active surface sites (negatively charged surface oxygen, and hydroxyl groups) can experience superior catalytic activity. Manganese oxide could boost decomposition enthalpy, ignitability, and propagation rate. Furthermore manganese oxide could induce vigorous thermite reaction with aluminium particles. Hot solid or liquid particles are desirable for first-fire compositions. This study reports on the facile fabrication of MnO2 nanoparticles of 10 nm average particle size; aluminium nanoplates of 100 nm average particle size were employed. Nitrocellulose (NC) was adopted as energetic polymeric binder. MnO2/Al particles were integrated into NC matrix via co-precipitation technique. Nanothermite particles offered an increase in NC decomposition enthalpy by 150 % using DSC; ignition temperature was decreased by 8 0C. Nanothemrite particles offered enhanced propagation index by 261 %. Kinetic study demonstrated that nanothermite particles experienced drastic decrease in NC activation energy by - 42, and - 40 KJ mol-1 using Kissinger and KAS models respectively. This study shaded the light on novel nanostructured energetic composition, with superior combustion enthalpy, propagation rate, and activation energy.

An Experimental Study of the Decomposition and Carbonation of Magnesium Carbonate for Medium Temperature Thermochemical Energy Storage

To improve the energy efficiency of an industrial process thermochemical energy storage (TCES) can be used to store excess or typically wasted thermal energy for utilisation later. Magnesium carbonate (MgCO3) has a turning temperature of 396 °C, a theoretical potential to store 1387 J/g and is low cost (~GBP 400/1000 kg). Research studies that assess MgCO3 for use as a medium temperature TCES material are lacking, and, given its theoretical potential, research to address this is required. Decomposition (charging) tests and carbonation (discharging) tests at a range of different temperatures and pressures, with selected different gases used during the decomposition tests, were conducted to gain a better understanding of the real potential of MgCO3 for medium temperature TCES. The thermal decomposition (charging) of MgCO3 has been investigated using thermal analysis techniques including simultaneous thermogravimetric analysis and differential scanning calorimetry (TGA/DSC), TGA with attached residual gas analyser (RGA) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) (up to 650 °C). TGA, DSC and RGA data have been used to quantify the thermal decomposition enthalpy from each MgCO3.xH2O thermal decomposition step and separate the enthalpy from CO2 decomposition and H2O decomposition. Thermal analysis experiments were conducted at different temperatures and pressures (up to 40 bar) in a CO2 atmosphere to investigate the carbonation (discharging) and reversibility of the decarbonation–carbonation reactions for MgCO3. Experimental results have shown that MgCO3.xH2O has a three-step thermal decomposition, with a total decomposition enthalpy of ~1050 J/g under a nitrogen atmosphere. After normalisation the decomposition enthalpy due to CO2 loss equates to 1030–1054 J/g. A CO2 atmosphere is shown to change the thermal decomposition (charging) of MgCO3.xH2O, requiring a higher final temperature of ~630 °C to complete the decarbonation. The charging input power of MgCO3.xH2O was shown to vary from 4 to 8136 W/kg with different isothermal temperatures. The carbonation (discharging) of MgO was found to be problematic at pressures up to 40 bar in a pure CO2 atmosphere. The experimental results presented show MgCO3 has some characteristics that make it a candidate for thermochemical energy storage (high energy storage potential) and other characteristics that are problematic for its use (slow discharge) under the experimental test conditions. This study provides a comprehensive foundation for future research assessing the feasibility of using MgCO3 as a medium temperature TCES material. Future research to determine conditions that improve the carbonation (discharging) process of MgO is required.

Using Graphene Sulfonate Nanosheets to Improve the Properties of Siliceous Sacrificial Materials: An Experimental and Molecular Dynamics Study

The fabrication of high-performance cement-based materials has benefited greatly from the extensive use of graphene and its derivatives. This paper studies the effects of graphene sulfonate nanosheets (GSNSs) on sacrificial cement paste and mortar (the tested materials) and other siliceous sacrificial materials, especially their ablation behaviors and mechanical properties. Decomposition temperatures and differential scanning calorimetry were used to examine how different contents of GSNSs determines the corresponding decomposition enthalpy of the tested materials and their ablation behaviors. Molecular dynamics was also used to clarify the mechanism how the GSNSs work in the CSH (calcium silicate hydrated)/GSNSs composite to increase the resistance to high temperature. The experimental results show that: (1) the contents of GSNSs at 0.03 wt.%, 0.1 wt.%, and 0.3 wt.% brought an increase of 10.97%, 22.21%, and 17.56%, respectively, in the flexural strength of siliceous sacrificial mortar, and an increase of 1.92%, 9.16%, and 6.70% in its compressive strength; (2) the porosity of siliceous sacrificial mortar was decreased by 5.04%, 9.91%, and 7.13%, respectively, and the threshold pore diameter of siliceous sacrificial mortar was decreased by 13.06%, 35.39%, and 24.02%, when the contents of GSNSs were 0.03 wt.%, 0.1 wt.%, and 0.3 wt.%, respectively; (3) a decline of 11.16%, 28.50%, and 61.01% was found in the ablation velocity of siliceous sacrificial mortar, when the contents of GSNSs were 0.03 wt.%, 0.1 wt.%, and 0.3 wt.%, respectively; (4) when considering the ablation velocities and mechanical properties of siliceous sacrificial materials, 0.1 wt.% GSNSs was considered to be the optimal amount; (5) the GSNSs contribute to the reinforced effect of GSNSs on CSH gel through the grab of dissociated calcium and water molecules, and the chemical reaction with silicate tetrahedron to produce S–O–Si bonds. These results are expected to promoting the development of new kinds of siliceous sacrificial materials that contain GSNSs.

Significance of Theoretical Decomposition Enthalpies for Predicting Thermal Hazards

Much effort is currently put into the development of models for predicting decomposition enthalpies measured using differential scanning calorimetry (DSC). As an alternative to the purely empirical schemes reported so far, this work relies on theoretical values obtained on the basis of simple assumptions. For nitroaromatic compounds (NACs) studied in sealed sample cells, our approach proves clearly superior to previous ones. In contrast, it correlates poorly with data measured in pin-hole sample cells. Progress might be obtained through a combination of the present approach with the usual Quantitative Structure-Property Relationships (QSPR) methodologies. This work emphasizes the significance of the theoretical decomposition enthalpy as a fundamental descriptor for the prediction of DSC values. In fact, the theoretical value provides a valuable criterion to characterize thermal hazards, as a complement to experimental decomposition temperatures.