Simultaneous Differential Scanning Calorimetry Research Articles

Pyrolysis of folic acid: Identification of gaseous/volatile products and structural evolution of N-doped graphitic carbon

Folic acid (FA) is a low-cost and suitable source for producing different N-doped carbon materials by pyrolysis. However, the pyrolytic steps of FA are not entirely understood, particularly above 350 °C, which hampers the intelligent design of tailor-made carbon materials by a one-pot route. In this work, the pyrolytic decomposition steps of FA were investigated by simultaneous thermogravimetric analysis (TGA) and differential scanning calorimetry (TGA-DSC). The released gaseous/volatile products were probed by coupling TGA to infrared spectroscopy and mass spectrometry (TGA-FTIR-MS). Considering the thermal analysis data, FA was pyrolysed in a furnace at 350, 430, 570, 800, and 1000 °C, and the products were analysed by X-ray diffractometry (XRD), vibrational spectroscopy, and X-ray photoelectron spectroscopy. In situ high-temperature X-ray diffractometry (HT-XRD) experiments were also conducted under the nitrogen atmosphere. According to the data set, insights about FA decomposition steps could be proposed, including gaseous/volatile products released during the process and the structural evolution of N-doped graphitic carbon. The formation of carbonaceous material initiated between 200 and 350 °C through polymerisation/condensation reactions, and this step was marked by the release of 2-pyrrolidone and aniline. The graphitisation was enhanced above 350 °C, increasing graphitic nitrogen while the amide groups vanished. The process was accompanied by deoxygenation (i.e., CO and CO2 release) and denitrogenation (e.g., NH3, HNCO, and HCN) reactions. In the 570–800 °C range, the N-enrichment of carbon material (N-pyridine, N-pyrrole/Csp2-N in 5,7-membered rings, and nitrile) could occur by the reaction of released NH3 over the char surface. Graphitic-like structures containing mainly N-graphite and N-pyridine were obtained above 800 °C. The original data about the thermal decomposition steps of FA allow for optimising the synthesis of N-doped carbon materials suitable for applications in adsorption, sensing, catalysis, and energy storage.

Bimetallic Ba(II)-Cr(III) and trimetallic Ba(II)-Ln(III)-Cr(III) (Ln(III) = Gd, Tb, Dy, Ho, Er, Yb, Y) coordination polymers formed by Cr(III)-containing building blocks with cyclopropane-1,1-dicarboxylate anions

The reaction of chromium(III) nitrate with Ba(cpdc) (H2cpdc = cyclopropane-1,1-dicarboxylic acid) in a ratio of 1:3 yielded a 1D coordination polymer {[Ba2Cr2(OH)2(cpdc)4(H2O)8]·5H2O}n (1) formed by binuclear units [Cr2(OH)2(cpdc)4]4− and a 3D polymer [Ba2Cr(cpdc)3(NO3)(H2O)6]n (2) constructed from tris-chelate blocks [Cr(cpdc)3]3−. The addition of rare-earth metal nitrates (Cr:Ln = 1:2) in this reaction led to the formation of a series of trimetallic 3D coordination polymers {[Ba3Ln2Cr4(cpdc)12(H2O)24]·8H2O}n (3Ln, Ln = Gd, Tb, Dy, Ho, Er, Yb, Y), in whose structures tris-chelate fragments [Cr(cpdc)3]3− are bound in layers by Ln3+ ions and, further, in a framework due to the coordination of Ba2+ ions. The crystal structures of 1, 2, and 3Gd were determined by single-crystal X-ray diffraction (XRD), and isostructurality of all the compounds in the series 3Ln was proved by powder X-ray diffraction (PXRD). DC-magnetic susceptibility measurements revealed weak ferromagnetic exchange interactions between Cr3+ ions in compound 1 (J = +0.74 cm−1). According to ac-magnetic susceptibility measurements, complexes 3Er and 3Y exhibit field-induced slow relaxation of magnetization. According to the data of simultaneous thermal analysis (STA) and differential scanning calorimetry (DSC) performed under Ar atmosphere, dehydration of the compounds obtained takes place in one (for 1 and 3Gd) or three stages (for 2). The initial temperature of the organic part degradation process decreases when moving from compound 1 containing dimerized bis-chelate fragments [Cr2(OH)2(cpdc)4]4− (330 °C) to compounds 2 (276 °C) and 3Gd (261 °C) based on tris-chelate units [Cr(cpdc)3]3−.

ZnSnO3 - SnO2 nanocomposite as a catalyst for efficient hydrogen production through sodium borohydride methanolysis

In this work, we describe a straightforward modified sol gel approach for producing zinc stannate-tin oxide (ZnSnO3-SnO2) nanocomposite particles by combining tin chloride and zinc acetate using EDTA ammonium salt as an electrosteric inhibition agent. The acquired samples were characterized using simultaneous thermal gravimetric and differential scanning calorimetry (TGA/DSC), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), UV-Vis spectroscopy and scanning electron microscopy (SEM). The catalyst activity of ZnSnO3-SnO2 particles in hydrogen production was determined by the methanolysis reaction from NaBH4. The hydrogen generation rate TOF (Turnover Frequency) The hydrogen generation rate, activation energy (Ea), enthalpy (ΔH) and entropy (ΔS) values of the hydrogen production reaction were calculated as 374.11 ml min−1.g−1 (832.38 h−1), 43.19 kJ mol−1, 40.65 kJ mol−1 and -178.96 J/mol.K, respectively. The prepared ZnSnO3-SnO2 composite can be recycled and used without obvious loss of activity; This makes the procedure economical and environmentally friendly.

Simultaneous Thermogravimetry-Differential Scanning Calorimetry (TG-DSC) in Nanoporous Materials: Examples of Data for Zeolites, Metal–Organic Frameworks (MOFs), Clay Based and Mesostructured Solids

AbstractThis article presents and discusses the results of a compilation of experimental results of thermogravimetry with simultaneous differential scanning calorimetry (TG-DSC), obtained in the same apparatus and under similar experimental conditions, for a selection of nanoporous materials with interesting properties as adsorbents and catalysts, namely clays and clay-based materials (such as pillared-clays and porous clays heterostructures), zeolites and related materials (such as titanosilicates), mesostructured silicas and MOFs. Materials functionalized with a relatively common silane, the (3-aminopropyl)triethoxysilane (APTES) were also analyzed and discussed.

PH-Triggered Controlled Release of Chlorhexidine Using Chitosan-Coated Titanium Silica Composite for Dental Infection Prevention.

Peri-implantitis is a growing pathological concern for dental implants which aggravates the occurrence of revision surgeries. This increases the burden on both hospitals and the patients themselves. Research is now focused on the development of materials and accompanying implants designed to resist biofilm formation. To enhance this endeavor, a smart method of biofilm inhibition coupled with limiting toxicity to the host cells is crucial. Therefore, this research aims to establish a proof-of-concept for the pH-triggered release of chlorhexidine (CHX), an antiseptic commonly used in mouth rinses, from a titanium (Ti) substrate to inhibit biofilm formation on its surface. To this end, a macroporous Ti matrix is filled with mesoporous silica (together referred to as Ti/SiO2), which acts as a diffusion barrier for CHX from the CHX feed side to the release side. To limit release to acidic conditions, the release side of Ti/SiO2 is coated with crosslinked chitosan (CS), a pH-responsive and antimicrobial natural polymer. Scanning electron microscopy coupled with energy dispersive X-ray spectroscopy (SEM/EDX) and Fourier transform infrared (FTIR) spectroscopy confirmed successful CS film formation and crosslinking on the Ti/SiO2 disks. The presence of the CS coating reduced CHX release by 33% as compared to non-coated Ti/SiO2 disks, thus reducing the antiseptic exposure to the environment in normal conditions. Simultaneous differential scanning calorimetry and thermogravimetric analyzer (SDT) results highlighted the thermal stability of the crosslinked CS films. Quartz crystal microbalance with dissipation monitoring (QCM-D) indicated a clear pH response for crosslinked CS coatings in an acidic medium. This pH response also influenced CHX release through a Ti/SiO2/CS disk where the CHX release was higher than the average trend in the neutral medium. Finally, the antimicrobial study revealed a significant reduction in biofilm formation for the CS-coated samples compared to the control sample using viability quantitative polymerase chain reaction (v-qPCR) measurements, which were also corroborated using SEM imaging. Overall, this study investigates the smart triggered release of pharmaceutical agents aimed at inhibiting biofilm formation, with potential applicability to implant-like structures.

Characterization of enalapril maleate: An approach using thermoanalytical, thermokinetic and spectroscopic techniques

Enalapril maleate is a widely used drug for the treatment of cardiovascular diseases. Its mechanism of action is to inhibit the angiotensin-converting enzyme selectively. Therefore, it is metabolized to enalaprilat by liver cells. The thermal behavior of enalapril maleate was investigated by simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC), and evolved gas analysis by simultaneous thermogravimetry and differential scanning calorimetry coupled infrared spectroscopy (TG-DSC-FTIR). The results provided information on thermal stability, purity, thermal decomposition steps, and the main products formed in the heating. The enalapril maleate was found to be stable up to 148 ?C. Above this temperature causes thermal degradation of the substance, which occurs in two stages in an inert atmosphere (N2) and three stages in an oxidizing atmosphere (air). Through the TG-DSC-FTIR the released gases were identified as maleic anhydride as a thermal decomposition intermediate. DSC analysis showed that the material obtained 99.5% purity, which indicates high purity. Employing both the Kissinger and Friedman equations, alongside Model Fitting methods, the study reveals key insights. The Kissinger method unveils an apparent activation energy of 47.07?15.45 kJ mol?? for the complete thermal breakdown, a finding corroborated by the Friedman method. Model Fitting methods, the article applies them, yielding an apparent activation energy of 55.70?3.4 kJ mol?? with a three-dimensional diffusion thermal degradation model.

Optimising thermochemical energy storage: a comprehensive analysis of CaCO3 composites with CaSiO3, CaTiO3, and CaZrO3.

With the increasing amount of renewable energy produced, many governments and industries are pushing for the installation of battery energy storage system (BESS) solutions. Thermal batteries are systems that store heat made from various energy sources, and can be used to produce electricity upon demand. These systems are easily scalable and can be installed in cities, homes and remote locations. Thermochemical energy storage (TCES) uses the enthalpy of a chemical reaction to store and release heat through endothermic and exothermic processes, respectively. CaCO3 has been identified as an ideal TCES material as it is cheap and abundant, but maximising long-term cyclability is key to ensure battery longevity. This article investigates the addition of CaSiO3, CaTiO3 and CaZrO3 to CaCO3 in a 1 : 1 ratio to ascertain the reaction properties and cyclic capacity over time. Cycling longevity and thermodynamic properties were determined using simultaneous differential scanning calorimetry and thermogravimetric analysis (DSC-TGA) along with the Sieverts technique, and their reaction pathway studied by powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). The low cost of the CaCO3-CaSiO3 material of $1.8 USD per kW hth suggests that if a suitable particle refinement agent were to be employed to ensure cycling longevity this material would be an excellent TCES material. Despite the CO2 cycling capacity of the CaCO3-CaZrO3 system only reducing by 16 wt% over 100 cycles, the cost of ZrO2 brings the materials cost to $30.9 USD per kW hth, making this material currently unsuitable for application. The CaCO3-CaTiO3 system showed only a 17% drop in total CO2 uptake over 100 cycles, although the cost was $11.1 USD per kW hth.

Green Synthesis, Characterization and Thermal Investigation of Ni(II) and Cu(II) Complexes Constructed by Pyridine-2,6-Dicarboxylic Acid

Two complexes [Ni(pda)(H2pda)]·3H2O (1) and [Cu(pda)(H2pda)] (2) containing pyridine-2,6-dicarboxylic acid (H2pda) were synthesized by room-temperature solid state reaction and characterized by elemental analyses, powder X-ray diffraction (PXRD), single crystal X-ray diffraction and infrared spectroscopy. The powder complexes were confirmed as single phase with their PXRD. The thermal property was studied using simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC) techniques. The complexes were decomposed in several stages and the final products of their thermal decomposition were NiO and CuO, respectively. In order to explore application of the complexes, the nano-NiO and nano-CuO particles were produced by using the powder complexes as precursors at different temperatures. The particles were characterized and observed by PXRD and scanning electron microscope (SEM), and their average diameters of the pyrolysis products at 500 and#176;C were about 12 and 30 nm, respectively.

EFFECT OF STEEL’S THERMAL CONDITION ON THE TRANSFORMATION TEMPERATURES OF TWO HOT-WORK TOOL STEELS WITH INCREASED THERMAL CONDUCTIVITY

The aim of our study was to investigate how different thermal conditions affect the transformation temperatures of two hot-work steels with high thermal conductivity. We focused on two conditions: soft annealing, and quenching and tempering. Soft annealing results in a ferritic steel matrix with spherical carbides, while quenching and tempering result in a fully hardened and tempered martensitic matrix with secondary and tempering carbides. We analysed samples using a simultaneous thermal analysis (STA) and differential scanning calorimetry (DSC) to determine the transformation temperatures. Controlled heating and cooling allowed us to observe the energy changes associated with the phase transformations. The equilibrium temperatures were calculated using the CALPHAD method. Our study investigated the influence of thermal conditions on different transformation temperatures, including solidus/liquidus temperatures, austenite solid transformation temperatures (A1 and A3), austenite solidification temperatures and bainite and/or martensite transformation temperatures. A DSC analysis was used to quantitatively measure the transformation temperatures and energy absorption during the endothermic processes (austenite solid transformation and melting) and to study the energy release during the exothermic processes (solidification and transformation). The results showed that soft annealing reduced the solidification interval and the solidus temperature, while energy absorption increased during melting. Conversely, quenching and tempering reduced the austenite solid transformation temperatures and energy release during solidification, including δ-ferrite solidification.

Disentangle the drivers of soil organic carbon mineralization and their temperature sensitivity in both topsoil and subsoil: Implication of thermal stability and chemical composition

Information about the temperature dependence of soil organic carbon (SOC) mineralization is important to predict the possible carbon (C) release from the terrestrial ecosystem facing global warming. However, the way in which SOC quality and mineral protection of SOC affects mineralization rates and their response to increasing temperature remains poorly understood. Here, we focused on investigating thermal stability and chemical composition of soils which differed greatly with the type and extent of organo-mineral associations, and revealing their implications for SOC mineralization. Chemical composition and thermal stability of SOC were analyzed with 13C nuclear magnetic resonance spectroscopy (13C NMR) and simultaneous thermogravimeteric analysis and differential scanning calorimetry (TG-DSC), respectively. Soil mineralization and its temperature sensitivity (Q10) were assessed by incubating soils at 15 and 25 °C for 90 days.Our results showed that SOC of subsoil was more biologically stable, but exhibited higher temperature sensitivity than those of topsoil. Significant differences in chemical composition and thermal stability of SOC were detected across soils developed from four parent materials but not between two soil layers, and indicators obtained from the two techniques showed apparent associations with depth-specific SOC mineralization rates. Increase in SOC mineralization rates at two incubation temperatures and two soil layers were observed when the soils were characterized by higher percentage of labile SOC fractions (i.e., O-alkyl C and organic carbon oxidized during exothermic reactions). The Q10 values of topsoil were positively and mostly related to the percentage of Alkyl C. In addition to notable relationships with chemical composition, the Q10 values of subsoil were positively correlated with Exo1/Exo2 ratios and Energy density values, and negatively correlated with TG-50. It was interesting to note that thermal stability was possibly as a function of soil texture and total oxides. Results from VPA analysis further revealed that SOC mineralization rates at two soil layers and Q10 of topsoil were mainly driven by SOC quality, while it was related to both SOC quality and chemical protection for subsoil, implying that factors controlling the temperature sensitivity of SOC mineralization were depth-specific. Altogether, substrate accessibility as a function of chemical composition and chemical protection would play vital role in determining the feedbacks of the subsoil SOC pool to the future climate warming.

Thermal decomposition of fluorinated polymers used in plasticized explosives and munitions

AbstractA number of military explosives and munitions employ fluorinated polymers as binders or components, e. g., PBXN‐5. To determine potential environmental releases during disposal operations, the thermal decomposition of the fluorinated polymers Viton A, Kel‐F, and Teflon were examined alone and in combination with the explosive HMX. Although PBXN‐5 only contains 5 % by weight Viton A, laboratory prepared analogs were made with 5 % polymer as well as with 50 % polymer to ensure polymer decomposition products could be detected. Under air and under nitrogen decomposition was examined by SDT [simultaneous differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA)], TGA‐infrared (IR) spectrometry, and pyrolysis gas chromatography with mass spectrometric analysis (GC‐MS). All three techniques, SDT, TGA‐IR, and pyrolysis GC‐MS, suggest that decomposition of HMX could be completed at low temperature before polymer decomposition ensues. To confirm this observation, pyrolysis GC‐MS was performed at temperatures below 350 °C since above this temperature all three polymers exhibited some fluorinated decomposition products.

Laboratory evaluation of different bio-oil recycled aged asphalts: Conventional performances and microscopic characteristics

The performance of diverse types of bio-oils varies greatly from each other, which makes it arduous to apply different bio-oils directly in engineering practice. This study is based on physical and microscopic properties, studying different types of bio-oil recycled asphalt and analyzing their differences. Five bio-oils (castor oil, straw oil, soybean oil, gutter oil, and vegetable oil) were used to regenerate asphalts after short-term and long-term aging to prepare recycled asphalts. The physical performances of recycled asphalts with different bio-oils were assessed, including penetration, softening point, and ductility tests. In addition, scanning electron microscopy was utilized to investigate the microscopic morphologies of recycled asphalts. Simultaneous thermogravimetry and differential scanning calorimetry were applied to determine the thermal stabilities of recycled asphalts. Finally, Gel permeation chromatography was employed to analyze the asphalt's relative molecular masses. The results revealed that vegetable and gutter oil have apparent adverse effects on temperature sensitivity and high-temperature performance of aged asphalt. In contrast, they have positive effects on low-temperature performance. All five bio-oils can repair cracks on the surface of aged asphalt. However, the surface wrinkles of vegetable oil-recycled asphalt and castor oil-recycled asphalt are relatively less and have an outstanding recycling effect. The slight thermal weight loss of recycled asphalts corresponding to castor oil, straw oil, and soybean oil at high temperatures positively impacted the high-temperature stability of aged asphalt. The castor oil and soybean oil recycled asphalts have significantly larger relative molecular masses and have advantages in high-temperature performance. This paper reveals the impact of different bio-oils on asphalt regeneration, which contributes a theoretical basis for promoting the practical implementation of bio-oil in road projects, with obvious economic and social benefits.

Occurrence and transformation behaviour of silicon-bearing minerals during high silicon coal combustion from Yunnan Province, China

To understand the mineralogical characteristics and transformation behaviours of silicon-bearing minerals during coal combustion, seven typical high silicon (high-Si) coals and two high-Si fly ashes generated from high-Si coal-fired power plants were chosen. The coals were first treated by a method of low temperature ashing and the float-sink test for heavy minerals separation. Subsequently, low temperature ashes (LTA), light mineral fractions (LM), heavy mineral fractions (HM), and fly ashes from coal-fired power plants were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) combined with energy spectrum analysis (EDX), X-ray fluorescence spectrometry (XRF), and simultaneous thermogravimetry and differential scanning calorimetry (TG-DSC).The results show that The mineral compositions in the LTA and LM are almost the same and majorly composed of quartz, kaolinite, calcite, dolomite, daphnite, chlorite-serpentine, pyrite, and anatase. The mineral compositions identified in the HM are clearly different from those in the LTA and LM. Pyrite, fluorapatite, anatase, siderite, dolomite and a plenty of silicate minerals including quartz, clinochlore, daphnite, chlorite, and chamosite are found in the HM. Chlorite is a quite common mineral in the HM with different shapes, including schistose, long tetragonal prism, cylindrical, block-shaped, and near-spherical, can be identified. The minerals identified in the fly ashes from the high-Si coal-fired power plants include quartz, mullite, and hematite. The mullite in the fly ashes is derived from the transformations of quartz, kaolinite, and chlorite in the coals. The quartz in the fly ash is mainly derived from the unchanged quartz in coal and a secondary origin from the SiO2-Al2O3 phase transformation. The high-Si fly ash with the size fraction of 38.5–74 μm contains the highest SiO2 content.

Towards a heat‐ and mass‐balanced kinetic model of TATB decomposition

AbstractTATB (1,3,5‐triamino‐2,4,6‐trinitrobenzene) was thermally degraded by two small‐scale analytical methods – simultaneous differential scanning calorimetry and thermogravimetric analysis (SDT) and a hot‐stage microscope with Fourier Transform Infrared (FTIR) analysis capabilities. SDT used ramped heating, isothermal soaking, and thermal pretreatment at various conditions. The heat flow and mass loss were monitored during various treatment conditions to derive chemical decomposition kinetics and Arrhenius parameters. FTIR experiments used isothermal heating, and changes were monitored spectroscopically. Solid samples generated at specific conditions were collected from both methods and were analyzed by DMSO extraction followed by chemical speciation by optical and mass spectrometric methods. Characterization provided the following reaction insights:1. TATB decreases in a sigmoidal pattern in isothermally heated samples. Other soluble products gradually increase in concentration and then abruptly decline in concentration during the second exotherm, such as diamino‐dinitro‐benzofurazan and amino‐nitro‐benzodifurazan.2. FTIR showed gradual changes in the amino and nitro functionality, shifting positions and decreasing intensity for the first 40 min. Then the solid gradually appeared more like an amorphous C with N incorporated, similar to previous studies on thermally degraded TATB‐type materials.3. Extracted residues (DMSO‐soluble components removed) examined by FTIR showed an abrupt change in chemical composition between 40‐ and 45‐min isothermal treatment, indicating early forming solids are different than later forming residues.4. A reliable mass‐ and energy‐balanced global reaction network must include at least two autocatalytic reactions, either in parallel or series, and at least one must have an explicit initiation reaction having a low activation energy.

Comparison of two enthalpic models for the thermodynamic characterization of the soil organic matter in beech and oak forests

The thermodynamic characterization of the soil organic matter could be achieved by different enthalpic models little explored for soil. This paper compares two of them for calculating the enthalpy change, the Gibbs energy change and the entropy change of the soil organic matter combustion reaction, by simultaneous differential scanning calorimetry and thermogravimetry. Soil samples were collected in beech and oak forests from different geographical areas, and at different depths to represent the L/F horizon and the mineral soil, at each sampling site. The thermodynamic state variables were calculated using two different enthalpic models, to examine how they differed in relation to different types of SOM and different forest ecosystems. Both models yielded thermodynamic variables, which although closely and significantly correlated, were statistically significantly different. All the thermodynamic variables depended on the different forest types and the different nature of the soil organic matter under study. Results allowed to discern which of the models applied better to the SOM combustion reaction designed.

Thermokinetic and Ballistic Property Studies of Azide‐Based Airbag Gas Generants with Dual Oxidizers (Sr(NO3)2 and KNO3)

Thermokinetic degradation studies of an airbag gas generant ternary mixture comprising NaN3, KNO3, and SrNO3 are carried out for the first time using simultaneous differential scanning calorimetry–thermogravimetric analysis. The results point toward the fact that the use of dual oxidizers has improved the reactivity of the azide‐based airbag gas generant mixture and reduced the amount of residual masses remaining after degradation to a minimal value of 2%. The activation energy of the mixture is also found to be increased to a maximum value of 249 kJ mol−1 which is better than the conventional airbag mixtures. The ballistic property studies done on the ternary mixture show that it can activate the airbag within 43.3 ms of crash which is very much an improved timeframe compared to the existing airbag mixtures. The study indicates that stoichiometric mixture containing NaN3/Sr(NO3)2/KNO3:75/12/13 by weight can be used as a potential airbag gas generant for automotive airbags. The blended mode methodology used in this research work combining the thermokinetic and ballistic property measurement can be effectively used to evaluate the performance parameters of airbag gas generants.

Polymorphic transitions in flufenamic acid-trehalose composites

The combination of poorly-soluble drugs with small molecule co-formers to generate amorphous solid dispersions (ASDs) has great potential to improve dissolution rate and kinetic solubility, and thus increase the bioavailability of these active ingredients. However, such ASDs are known to be unstable and to crystallise upon storage or heating. In this work, we explore the crystallisation of flufenamic acid (FFA) from ASDs prepared with trehalose. FFA-trehalose mixtures were prepared at a range of w/w composition ratios, heated to melting and crash cooled to form ASDs. They were then subject to a further heat/cool cycle, which was monitored by simultaneous differential scanning calorimetry – X-ray diffraction to observe the phase changes occurring. These varied with the composition of the blend. Upon short-term storage, formulations with low trehalose contents (FFA:trehalose 5:1 w/w) recrystallised into form I FFA, while higher trehalose contents crystallised to FFA form IV. When heated, all FFA trehalose combinations ultimately recrystallised into form I before melting. Upon a second cooling cycle, systems with low trehalose content (FFA:trehalose 5:1 w/w) recrystallised into form IV, while higher trehalose contents led to FFA form I. It is thus clear that even with a single excipient it is possible to control the crystallisation pathway through judicious choice of the formulation parameters.

Processing, Phase Stability, and Conductivity of Multication-Doped Ceria

Multicomponent doping of ceria with four cations is used as a preliminary investigation into the ionic conductivity of high-entropy-doped ceria systems. Different compositions of Ce1-x(Ndx/4Prx/4Smx/4Gdx/4)O2-δ (x = 0.05, 0.10, 0.15, and 0.20) are synthesized using the oxalate co-precipitation method yielding single-phase oxalate precursors. X-ray diffraction, Raman spectroscopy, and Fourier-transform infrared spectroscopy are used to characterize the precipitated oxalates. Simultaneous thermal gravimetric analysis and differential scanning calorimetry reveal a two-step decomposition of the oxalates into the doped oxide. The ionic conductivity of the samples is measured from 250 °C to 600 °C using electrochemical impedance spectroscopy. All samples exhibit similar grain conductivity values at 600 °C, comparable to singly doped samples. However, an increase in total conductivity is observed with an increase in doping concentration up to 15% followed by a decrease beyond this concentration. These findings suggest that multicomponent doping may not significantly enhance the grain conductivity of doped ceria beyond conventional single and co-doped compositions but can modulate the grain boundary conductivity and thus the total conductivity of ceria ceramics.

Preparation of Mesoporous Si Nanoparticles by Magnesiothermic Reduction for the Enhanced Reactivity.

In this study, mesoporous silicon nanoparticles (M-Si) were successfully prepared by a magnesiothermic reduction of mesoporous silica nanoparticles, which were synthesized by a templated sol-gel method and used as the precursors. M-Si exhibited a uniform size distribution with an average diameter of about 160 nm. The measured BET surface area was 93.0 m2 g-1, and the average pore size calculated by the BJH method was 16 nm. The large internal surface area provides rich reaction sites, resulting in unique interfacial properties and reduced mass diffusion limitations. The mechanism of the magnesiothermic reduction process was discussed. The reactivity of prepared M-Si was compared with that of commercially available non-porous Si nanopowder (with the average diameter of about 30 nm) by performing simultaneous thermogravimetry and differential scanning calorimetry in the air. The results showed that the reaction onset temperature indicated by weight gain was advanced from 772 °C to 468 °C, indicating the promising potential of M-Si as fuel for metastable intermolecular composites.

Preparation of Si@PVDF composite microspheres by electrostatic spraying for enhanced energetic characteristics

In this study, Si@PVDF composite microspheres are prepared by the electrostatic spraying method. The spheres are with average diameter of around 2 μm (when at ideal stoichiometry), within which Si nanopowder is uniformly distributed. The exothermic properties of samples are studied through simultaneous thermogravimetry and differential scanning calorimetry. Benefiting from the improved interfacial contact quality, Si@PVDF shows increased chemical reactivity in terms of reduced reaction onset temperature, peak temperature and apparent activation energy than those of physically mixed Si/PVDF counterpart. Si/PVDF cannot be ignited through Joule heating, either in the powder of pellet form, while self-sustained combustion propagation is observed for Si@PVDF pellets. The combustion behaviors of Si@PVDF pellets are systematically studied in open-air (where light signal is analyzed) and constant-volume (where pressure signal is analyzed) conditions. The results show that the combustion process is influenced by the equivalence ratio, porosity of the pellet and the accessibility of O2 gas in the environment. Overall, the encapsulation of Si nanopowder into PVDF microspheres using electrostatic spraying shortens the mass and heat transfer distance and thus realizes enhanced energetic characteristics.