Composite powders combining boron with BiF3 and Bi in different amounts were prepared by high energy milling. Thermal analysis in an argon-oxygen mixture showed significant oxidation starting about ...200 K lower than for pure boron. Selective oxidation of metallic Bi at low temperatures was observed. Composites containing either Bi or BiF3 ignited more readily than pure boron when heated by a CO2 laser beam. The composites containing BiF3 ignited more readily than boron when in contact with a hot wire. Burn times of particles aerosolized in air and ignited using the CO2 laser were measured as durations of the recorded emission pulses produced by burning particles. Statistical distributions of the measured burn times were correlated with the respective powder's particle size distributions. Compared to elemental boron, burn times of all prepared composites were shorter, including those containing only 10 wt.% of BiF3 or ca. 8 wt.% of Bi, and for most composites combustion temperatures were higher.
This paper critically analyzes the traditional method of kinetic determination of activation energy by sectioning the recorded differential thermal analysis peak area. This procedure is incorrect ...because it misses the impact of thermal inertia, which changes the shape of the peak's base line from straight to s‐shape. This effect has been known since the Newton cooling law, but the resulting errors persist to be interwoven into all the kinetic methods based on nonisothermal thermoanalytical measurements. Relating to calorimetry, it is necessary here because heat inertia has become a standard part of heat determination via using the Tian historical equation. The role and impact of heat inertia is discussed and analyzed in detail.
Paraffin wax (PW) coatings are widely used in the military as the most effective way to reduce the sensitivity of energetic materials, but their inert nature is not conducive to energy release. In ...this work, paraffin-like fluorine-containing molecules (FPW) which are highly anticipated on a large scale were synthesized by combining crystalline units with fluorine units via a simple method. Core-shell Al@FPW was prepared for further characterization. FPW exhibits better lubrication and greater density (1.14 g/cm3 vs. 0.81 g/cm3) than PW, which can provide favorable guarantees for reduced friction sensitivity and increased energy density. The similar melting temperatures and crystallization enthalpies (168 J/g vs. 201 J/g) of FPW and PW are advantageous for mitigating the temperature sensitivity of nano-Al. Furthermore, the improved hydrophobicity of Al@FPW prevents further oxidation of the active metal, thereby enhancing the preservation of nano-Al. Moreover, the reaction process of Al@FPW was characterized by DSC-Tg. Notably, the combustion pressure, pressurization rate and calorific value of Al@FPW are significantly increased compared to Al@PW. Meanwhile, the ignition delay time is reduced by 83 % and the combustion rate is increased by 330 %, which is attributed to the action of fluorine during the reaction. The exceptional performance of FPW holds great potential for replacing PW in various applications.
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•Fluorine-containing materials (FPW) can be simply synthesis.•The unique properties of FPW in lubrication, hydrophobicity and thermal management enhance the safety performance of energetic materials.•The FPW coating effectively improves the reactive properties of the active nano-Al.•FPW can significantly shorten the ignition delay time and greatly increase the combustion rate of nano-Al.
The Kissinger method is an overwhelmingly popular way of estimating the activation energy of thermally stimulated processes studied by differential scanning calorimetry (DSC), differential thermal ...analysis (DTA), and derivative thermogravimetry (DTG). The simplicity of its use is offset considerably by the number of problems that result from underlying assumptions. The assumption of a first-order reaction introduces a certain evaluation error that may become very large when applying temperature programs other than linear heating. The assumption of heating is embedded in the final equation that makes the method inapplicable to any data obtained on cooling. The method yields a single activation energy in agreement with the assumption of single-step kinetics that creates a problem with the majority of applications. This is illustrated by applying the Kissinger method to some chemical reactions, crystallization, glass transition, and melting. In the cases when the isoconversional activation energy varies significantly, the Kissinger plots tend to be almost perfectly linear that means the method fails to detect the inherent complexity of the processes. It is stressed that the Kissinger method is never the best choice when one is looking for insights into the processes kinetics. Comparably simple isoconversional methods offer an insightful alternative.
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•An optimized manufacturing strategy with PVP addition allowed to obtain micro/nano structured carbon-phenolic ablators.•FTIR analysis enlightens hydrogen bonds between PVP and ...phenolic resin.•Oxyacetylene flame torch exposure shows that the PVP-enriched ablators have superior performances than the standard ones.•Microstructures and porosities were analyzed with SEM and XRM analysis.•Compression tests enlighten superior mechanical properties for charred PVP-enriched ablators.
Carbon-phenolic ablators can efficiently protect space vehicles from the extreme temperatures typical of the reentry phase in a planet’s atmosphere. Their performances are attributed to the low thermal conductivity and to the decomposition of the phenolic resin. These phenomena are strongly influenced by the materials microstructure. In the present work, standard and polyvinylpyrrolidone (PVP)-modified carbon-phenolic ablators were manufactured and characterized: the influence of PVP on the final microstructure and chemistry of the ablators was studied through SEM-EDS, X-ray Microscopy (XRM) analysis and FTIR technique; the mechanical properties were evaluated through compression tests on virgin and charred samples while ablative performance of the ablators were evaluated with an oxyacetylene flame exposure test. Weak bonds between phenolic resin chains and PVP were observed. The microstructure of the ablators, both before and after the exposure to the oxyacetylene flame, is strongly influenced by the PVP addition, furthermore the addition of 10 and 20 %wt of PVP can guarantee a reduction of about 30 % of the back temperature during the oxyacetylene flame test with respect to the standard carbon-phenolic ablator. Compression tests on the manufactured ablators enlighten also an improvement in the mechanical properties for PVP-enriched ablators, in particular considering their charred state.
Pultrusion is a rapid and cost-effective manufacturing technology for continuous fibre reinforced thermoplastic composite profiles. As the cross-sections of pultruded profiles grow to meet increasing ...performance requirements, manufacturing challenges concerning heat transfer are encountered. In this study, a two-dimensional finite element model was used to simulate the heat transfer and fluid flow physics of the pultrusion process for increasing diameters from Ø 5–Ø 40 mm. To facilitate the experimental validation, a novel batch-wise pultrusion concept is introduced in which the impregnation process is observed in-situ using a transparent die. The pultrusion studies, conducted on glass-fibre/amorphous polyethylene terephthalate (GF/PET) commingled yarns, show that – with proper design – pultrusion is able to deliver consistent, high quality (void content < 2%) profiles up to at least Ø 40 mm.
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•Pultrusion of solid thermoplastic composite rods from commingled yarns with diameters up to Ø 40 mm.•Multi-physics FE model simulating the temperature distribution and evolution during pultrusion.•In-situ observation of novel batch-pultrusion process via a transparent die.
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► Higher extractives content in wood promote ignitability at lower temperatures. ► Wood cellulose crystallinity influences on wood thermal stability. ► Cellulose crystallite size ...affects the thermal degradation temperature of wood.
The influence of wood components and cellulose crystallinity on the thermal degradation behavior of different wood species has been investigated using thermogravimetry, chemical analysis and X-ray diffraction. Four wood samples, Pinus elliottii (PIE), Eucalyptus grandis (EUG), Mezilaurus itauba (ITA) and Dipteryx odorata (DIP) were used in this study. The results showed that higher extractives contents associated with lower crystallinity and lower cellulose crystallite size can accelerate the degradation process and reduce the wood thermal stability. On the other hand, the thermal decomposition of wood shifted to higher temperatures with increasing wood cellulose crystallinity and crystallite size. These results indicated that the cellulose crystallite size affects the thermal degradation temperature of wood species.
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