Simultaneous Thermal Analysis Research Articles

A Binary Salt Mixture LiCl–LiOH for Thermal Energy Storage

For thermal energy storage, the most promising method that has been considered is latent heat storage associated with molten salt mixtures as phase-change material (PCM). The binary salt mixture lithium chloride-lithium hydroxide (LiCl-LiOH) with a specific composition can store thermal energy. However, to the best of our knowledge, there is no information on their thermal stability in previous literature. The key objectives of this article were to investigate the thermophysical properties, thermal repeatability, and thermal decomposition behavior of the chosen binary salt mixture. FactSage software was used to determine the composition of the binary salt mixture. Thermophysical properties were investigated with a simultaneous thermal analyzer (STA). The thermal results show that the binary salt 32 mol% LiCl-68 mol% LiOH melts within the range of 269 °C to 292 °C and its heat of fusion is 379 J/g. Thermal repeatability was tested with a thermogravimetric analyzer (TGA) for 30 heating and cooling cycles, which resulted in little change to the melting temperature and heat of fusion. Thermal decomposition analysis indicated negligible weight loss until 500 °C and showed good thermal stability. Chemical and structural instability was verified by X-ray diffraction (XRD) by analysing the binary salt system before and after thermal treatment. A minor peak corresponding to lithium oxide was observed in the sample decomposed at 700 °C which resulted from the decomposition of LiOH at high temperature. The morphology and elemental distribution examinations of the binary salt mixture were carried out via scanning electron microscopy (SEM) coupled with energy dispersive spectroscopy (EDS). X-ray photoelectron spectroscopy was conducted for surface analysis, and their elemental composition verified the chemical stability of the binary salt mixture. Overall, the results confirmed that the binary salt mixture is a potential candidate to be used as thermal energy storage material in energy storage applications of up to 500 °C.

A2Zr2O7 (A=La/Gd/Yb): Grain growth effect on phase stability properties at 1300°C

The present study aims to investigate the influence of grain growth during heat treatment on the phase stability of AZO: A2Zr2O7 compounds at 1300°C. To this end, three cations of La3+, Gd3+, and Yb3+ (corresponding to large, medium and small cations, respectively) were placed in the A-site of the AZO compounds through co-precipitation–calcination technique at 1000°C for 3 h to achieve LaZO: La2Zr2O7, GdZO: Gd2Zr2O7, and YbZO: Yb2Zr2O7, respectively. The phase stability of LaZO, GdZO, and YbZO was assessed under 50 h of heat treatment at 1300°C. Characterization techniques such as conventional and high-temperature XRD, Raman and Fourier transform infrared (FTIR) spectroscopies, simultaneous thermal analysis (DTA/TG), and field-emission scanning electron microscopy (FESEM) were employed to assess the synthesized compounds. FESEM results of LaZO, GdZO and YbZO calcinated powders indicated orderly particles, uniform in shape and size, with a relative tendency of agglomeration and with an average particle size of less than ∼100 nm. XRD results of LaZO and YbZO powders after calcination indicated the formation of pyrochlore and defect fluorite structures, respectively. The placement of Gd3+ (GdZO) led to the formation of a dual pyrochlore-defect fluorite structure. The current research also indicated an enhancement in the tendency to form pyrochlore structure in GdZO and YbZO compounds along with the growth of the grains after 20 (mean grain size of ∼250 nm) and 50 h (mean grain size of ∼800 nm) of exposure to the temperature of 1300°C, respectively.

Thermally treated coal mining waste as a supplementary cementitious material – Case study from Bogdanka mine, Poland

The presented study deals with the comprehensive analysis of coal gangue from the Bogdanka mine (Lubelski Węgiel „Bogdanka" S.A.) in terms of its properties in both raw and activated states, and with the evaluation of the functional parameters of blended cement pastes containing 10 wt%, 15 wt%, and 20 wt% of thermally treated mining waste. The assessment of the raw material included chemical, physical, mineralogical, and morphological characterization, thermogravimetry, and pozzolanic activity tests. The motivation for the research was the intention to utilize a significant amount of waste from the Bogdanka mine with low additional energy consumption for processing. For this purpose, the temperature of 600 °C was chosen for its thermal activation based on the simultaneous thermal analysis (STA) measurement. The activated coal gangue was tested in the same way as the raw materials and then applied in the blended cement pastes as a partial cement substitute. The cement pastes were evaluated in the fresh state (flow table test), and also at the age of 7, 28, and 90 days. The structural, microstructural, mechanical, and hygric parameters were investigated and compared with the plain cement paste. Furthermore, the development and rate of the pozzolanic reaction were studied using simultaneous thermal analysis with mass spectrometry (STA-MS), X-Ray diffraction (XRD), isothermal calorimetry, and assessment of strength activity index (SAI). The performed analyses gave evidence of the pozzolanic activity of thermally activated coal mining waste (ACMW) from the Bogdanka mine and its effectiveness in cement blends. The slightly dropped hydration degree was later compensated by prolonged curing time and progress in the pozzolanic reaction. The blending of Portland cement with the examined ACMW did not negatively affect the rheology and setting time of fresh blended pastes. Considering the hardened cement blends' structural, microstructural, and mechanical parameters, ACMW can be safely used as a part of a PC-based blended binder for up to 20% replacement of cement mass.

Double Pseudopolymeric [Au{S2CN(CH2)5}2]2[Ag2Cl4]·CH2Cl2 Complex: Preparation, Principles of Supramolecular Self-Assembly, Thermal Behavior, and Biological Activity against Mycolicibacterium smegmatis Strain

The double Au(III)–Ag(I) complex crystallizing as the solvated form of [Au{S2CN(CH2)5}2]2[Ag2Cl4]· CH2Cl2 (I) was obtained by the reaction of silver(I) N,N-pentamethylenedithiocarbamate with a solution of Na[AuCl4]/5.15 M NaCl. According to X-ray diffraction data (CIF file CCDC no. 2062810), the structural units of the compound are nonequivalent [Au{S2CN(CH2)5}2]+ cations (noncentrosymmetric A and centrosymmetric B and C in a ratio of 2 : 1 : 1), cyclic tetrachlorodiargentate(I) anions, [Ag2Cl4]2–, and solvating CH2Cl2 molecule. The latter is retained in the structure due to two nonequivalent C–H···Cl hydrogen bonds formed with the cyclic [Ag2Cl4]2– anion involving its terminal Cl(1) and bridging Cl(2) chlorine atoms. The supramolecular self-organization of I is based on a system of multiple Ag···S and Cl···S secondary interactions that сombine the ionic structural units of the complex into an intricate two-dimensional pseudopolymer layer. A study of the thermal behavior of I by simultaneous thermal analysis established the conditions for quantitative reduction of bound gold(III) and silver(I). The studied Au(III)–Ag(I) compound exhibits a high level of biological activity against the nonpathogenic M. smegmatis strain.

Analysis of thermal and electrochemical properties of electrical double-layer capacitors by using an in-situ simultaneous thermal analysis cell

In this work, the impact of temperature and voltage on aging of electrical double-layer capacitors (EDLCs) made with a model silica-templated carbon has been investigated by using an in-situ simultaneous thermal analysis (STA) cell. We show that the use of such a cell allows the electrochemical performance of EDLCs and the heat generation occurring within these devices to be simultaneously measured. In EDLCs containing adiponitrile (ADN) based electrolytes, the combination of high voltage (≥ 3.5 V) and elevated temperature of 60 °C leads not only to a fast decrease in capacitance retention, but also to important degradation processes causing a significant increase of heat flow within the system. For a temperature of 60 °C, the heat flow at 3.75 V is about 6.5 times higher than in an EDLC operating at 3.0 V. The correlation of the heat flow and electrochemical properties provides a helpful insight into the stability of EDLCs, and thus the in-situ STA cell appears as an interesting and novel tool for the investigation of these systems.

The structure, antioxidant activity, and stability of fish gelatin/chitooligosaccharide nanoparticles loaded with apple polyphenols.

Apple polyphenols (APs) with multiple biological effects have attracted extensive attention due to their broad opportunities for application. However, the use of APs is hampered by their instability in the face of environmental changes. Designing efficient carriers to improve the bioavailability of APs is the key to solving these problems. In this study, gelatin-chitooligosaccharide nanoparticles produced by the Maillard reaction (GCM) were fabricated to encapsulate AP, and the structure, antioxidant activity, and stability of the GMM-AP nanoparticle system were evaluated. The results of endogenous fluorescence spectrum, Fourier-transform infrared (FTIR) spectroscopy, X-ray diffraction, and simultaneous thermal analysis confirmed structural changes and interactions between GCM and AP. Combination with GCM did not adversely affect the antioxidant properties of AP, and the GCM-AP nanoparticles possessed superior temperature and storage stability. In comparison with fish gelatin-apple polyphenol nanoparticles, the GCM-AP nanoparticles were more stable at a wider pH range, and were more resistant to the electrostatic shielding effect of NaCl. After simulating gastric digestion, the particle size and polydispersity index (PDI) of GCM-AP nanoparticles were almost unchanged. The findings suggest that GCM nanoparticles loaded with AP could be used as good carriers with good antioxidant activity and stability. This study therefore provides a theoretical foundation for the development and industrial application of food functional factors. © 2023 Society of Chemical Industry.

Experimental and numerical simulation study on thermal decomposition model of ammonium nitrate

High heating rates is one typical character under fire scenario and thermal decomposition behavior of ammonium nitrate (AN) under high heating rates is still unclear. In the current study, a thermal decomposition model of AN was developed to predict thermal decomposition process under high heating rates by a numerical simulation solver Thermakin2Ds based on experimental results. To be more specific, average apparent activation energy and pre-exponential factor were calculated as 75.16 kJ/mol and 3.6×103 s−1 respectively according to simultaneous thermal analyzer (STA) experimental results. Thermal decomposition products were determined as H2O, N2O, NO2, and HNO3 by thermogravimetric-Fourier transform infrared spectrometer (TG-FTIR) experiments. The obtained information was utilized for modelling and determining the most reliable thermal decomposition numerical model of AN. The simulated mass loss and mass loss rate at 10 K/min by the model were accordance with experimental data. The prediction ability was verified at heating rates of 5, 16, 25 K/min. Finally, thermal decomposition processes at higher heating rates of 100, 125, 150, and 200 K/min were predicted. This work is significantly meaningful for the storage safety of AN, providing theoretical guidance for preventing the occurrence of AN explosion from the early fire stage.

Creep Properties of Cylinder Metal Rubber under Static Compression at Elevated Temperatures

In this study, the creep properties of cylindrical metal rubber (MR) specimen under static compression at elevated temperatures were investigated by a series of creep experiments. The cylindrical MR specimen has a good symmetrical property, and the mechanical properties are consistent in its different axial section. The failure determination parameters of MR under the coupling of thermal and mechanical static load of the forming direction were proposed in four aspects: the overall height, the average stiffness, the energy dissipation, and the variation of the loss factor. The variation patterns of the properties of the MR specimens were investigated with a static load at different temperatures for 324 h. The analytical equipment, including the simultaneous thermal analyzer (TGA/DSC), X-ray diffractometer (XRD), and scanning electron microscope (SEM), were used for material characterization and failure analysis. Based on the results, it is found that there are significant differences in the MR property variations subjected to creep tests at different elevated temperatures. The results indicated that an appropriate heat treatment for MR specimens would improve the creep resistance at elevated temperatures. In addition, the overall height and energy dissipation of the MR specimens were increased, and the average stiffness and the loss factor were decreased under the creep tests at 200 °C and 250 °C. However, under the creep tests at 25 °C, 300 °C, 350 °C, and 400 °C, the overall height, the energy dissipation and the loss factor were decreased, but the average stiffness was increased.

Mass spectrometric study and modeling of the thermodynamic properties of SrO-Al2 O3 melts at high temperatures.

The SrO-Al2 O3 system holds promise as a base for a wide spectrum of advanced materials, which may be synthesized or applied at high temperatures. Therefore, studying vaporization and high-temperature thermodynamic properties of this system is of great practical importance. Samples of the SrO-Al2 O3 system were obtained by solid-state synthesis and identified by X-ray fluorescence analysis, X-ray phase analysis, scanning electron microscopy, electron probe microanalysis, simultaneous thermal analysis, and thermogravimetric analysis. The thermodynamic properties of the SrO-Al2 O3 system were studied by the Knudsen effusion mass spectrometric (KEMS) method and were fitted by the Redlich-Kister and Wilson polynomials. The thermodynamic values obtained were also optimized within the generalized lattice theory of associated solutions (GLTAS). The vapor composition, temperature, and concentration dependences of the partial vapor pressures over the samples under study as well as the SrO activities in melts of the SrO-Al2 O3 system were determined by the KEMS method. Usage of the Redlich-Kister and Wilson polynomials allowed calculation of the excess Gibbs energies, enthalpies of mixing, and excess entropies in the concentration range 0-33 mol% of SrO at temperatures of 2450 and 2550 K. Significant negative deviations from the ideality were observed in the melts of the SrO-Al2 O3 system at 2450, 2550, and 2650 K. The Wilson polynomial was found to be the optimal approach to describe the thermodynamic properties in the system studied. Optimization of the experimental data using the GLTAS approach allowed the characteristic features of the thermodynamic description of the SrO-Al2 O3 system to be elucidated and explained.

Shear-induced distortion of clay minerals aids in dynamic weakening of shallow faults during earthquakes

Coseismic faulting may activate complicated physicochemical processes in the fault zone through both mechanical deformation and frictional heating. While plenty of work emphasizes the great importance of thermal effects on dynamic fault weakening, less attention has been paid to the mechanochemical effects. We study the effects of mechanochemical changes of chlorite on its dynamic weakening process via low- and high-velocity friction experiments, simultaneous thermal analysis, X-ray diffraction, microstructural observation, and numerical modeling in this work. With higher degrees of deformation, the experimentally sheared chlorite samples generally show more pronounced reductions in the onset temperature of thermal decomposition (Td0; from 561°C to 189°C in the extreme case) and more striking increases in the reaction rate. The exponential-decay formula can well describe the relation between Td0 and the mechanical work (integral of shear stress with respect to displacement) in the shear deformation. Moreover, the presence of pore water and the variation in chlorite content could significantly affect the mechanochemical changes of the sheared chlorite-bearing samples. Taking the markedly lowered Td0 as the characteristic temperature leading to thermal softening of asperity contacts, numerical modeling shows that flash weakening of chlorite-rich samples can be significantly promoted, dwarfing the thermochemical pressurization that is also enhanced by mechanochemical effects though. This is largely supported by high-velocity experiments (∼m/s) performed on the pre-deformed chlorite samples, which show both lower peak friction and fracture energy, and earlier activation of dynamic weakening. Clearly, shear deformation plays a key role in aiding thermally-activated mechanisms in weakening faults and facilitating rupture propagation during earthquakes.

Comprehensive research method for explosive coal dust

The article briefly analyses the explosion and fire hazard properties of coal dust of different dispersions. It is emphasised that many experts working in the field of explosion protection and industrial safety pay insufficient attention to changes in the properties of the dust when reducing its dispersity. It is suggested to develop a new, complex methodology based on the dispersed composition of coal dust. The authors suggest to put methods of special sample preparation and dispersing of samples in two stages as a basis of the complex methodology. To do research with the help of thermal synchronous analysis of the smaller fractions, the authors propose to regrind the coal fraction obtained after the cone crusher in an analytical mill. To exclude adhesion of particles due to the process of static charges accumulation it is suggested to use impactless sieving machine of Retsch company which allows to take out the accumulated charges of static electricity. The coal dust fractions obtained after sieving were sent for granulometric analysis by a dynamic image processing method in CAMSIRE and by an optical microscopic method using a LEICA DM 4000 with image scope colour processing. A simultaneous thermal analysis was performed selectively for fractions smaller than 1000 μm. This was carried out with an STA 449 F3 and NETZSCH Proteus termal analysis application software. The authors consider that the obtained results allow to conclude that it is further expedient to carry out research work in this direction and will make it possible to develop recommendations aimed at prevention of coal dust aerosol explosions.

Superprotonic conductivity in RbH2-3y(PO4)1-y: a phosphate deficient analog to cubic CsH2PO4 in the (1 - x)RbH2PO4 - xRb2HPO4 system.

In contrast to CsH2PO4 (cesium dihydrogen phosphate, CDP), a material with a well-established superprotonic transition to a high conductivity state at 228 °C, RbH2PO4 (rubidium dihydrogen phosphate, RDP) decomposes upon heating under ambient pressure conditions. Here we find, from study of the (1 - x)RbH2PO4 - xRb2HPO4 system, the remarkable occurrence of cubic, off-stoichiometric RbH2-3y(PO4)1-y, or α-RDP, with a variable Rb : PO4 ratio. Materials were characterized by simultaneous thermal analysis and in situ X-ray powder diffraction performed under high steam partial pressure, from which the phase diagram between RbH2PO4 (x = 0) and Rb5H7(PO4)4 (x = 1/4) was established. The system displays eutectoid behavior, with a eutectoid transition temperature of 242.0 ± 0.5 °C and eutectoid composition of x = 0.190 ± 0.004. Even the end-member Rb5H7(PO4)4 appears to transform to α-RDP, implying y in the chemical formula of 0.2 and a phosphate site vacancy concentration as high as 20%. Charge balance is attained by a decrease in the average number of protons on the remaining phosphate groups. The cubic lattice parameter at x = 0.180, near the eutectoid composition, and at a temperature of 249 °C is 4.7138(2) Å. This value is substantially smaller than the estimated ambient-pressure lattice parameter of stoichiometric RbH2PO4 of 4.837(12) Å, consistent with the proposal of phosphate site vacancies in the former. The superprotonic conductivity of the x = 0.180 material is 6 × 10-3 S cm-1 at 244 °C, a factor of three lower than that of CDP at the same temperature. While the engineering properties of α-RDP do not suggest immediate technological relevance, the discovery of a superprotonic solid acid with a high concentration of phosphate site vacancies opens new avenues for developing proton conducting electrolytes, and in particular, for controlling their transition behavior.

Green synthesis of copper oxide nanoparticles using Ficus elastica extract for the electrochemical simultaneous detection of Cd2+, Pb2+, and Hg2.

In this paper, for the first time, we report the use of a new carbon paste electrode based on a low-cost pencil graphite powder modified with polyaniline (PANI) and green synthesized copper oxide nanoparticles using Ficus elastica extract as a sensor for Cd2+, Pb2+, and Hg2+. The elaborated electrode was characterized by FT-IR spectroscopy, field-emission gun scanning electron microscopy (FEG-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and simultaneous thermal analysis (TGA/DSC). The electrochemical behavior of the sensor was evaluated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy techniques. According to CV, as well as square wave voltammetry (SWV) results, it was found that the CuONPs/PANI-CPE sensor was able to determine very low concentrations of Cd2+, Pb2+, and Hg2+ in HCl (0.01 M) either in single metal or in multi-metal solutions with a high sensitivity. Furthermore, Cd2+, Pb2+, and Hg2+ simultaneous detection on CuONPs/PANI-CPE achieved very low limits of detection (0.11, 0.16, and 0.07 μg L-1, respectively). Besides, the designed sensor displayed a good selectivity, reproducibility, and stability. Moreover, CuONPs/PANI-CPE enabled us to determine with high accuracy Cd2+, Pb2+, and Hg2+ traces in environmental matrices.

Species of Gold(III) Binding by Binuclear Zinc Dipropyldithiocarbamate: Supramolecular Self-Organization and Thermal Behavior of Ionic Complexes [Au(S2CNPr2)2]2[ZnCl4] and [Au(S2CNPr2)2]2[AuCl4][AuCl2

The reaction of binuclear zinc dipropyldithiocarbamate [Zn2{S2CN(C3H7)2}4] with an AuCl3/2 М HCl solution is studied. The double ionic complex [Au{S2CN(C3H7)2}2]2[ZnCl4] (I) is identified as the main species of gold(III) binding in the heterogeneous system under study and is characterized by 13С and 15N CP-MAS NMR spectroscopy. Single crystals of heterovalent compound [Au{S2CN(C3H7)2}2]2[AuCl4][AuCl2] (II) are sampled as a by-product. The crystal and supramolecular structures of complexes I and II are determined by the direct XRD method (CIF files CCDC nos. 2159171 and 2159170, respectively). The self-organization of the complex pseudopolymeric structures of compounds I and II are shown to be due to the binding of ionic structural units by secondary nonvalent interactions Au⋅⋅⋅S and S⋅⋅⋅Cl and hydrogen bonds C–H⋅⋅⋅Cl. The thermal behavior of the complexes is studied by simultaneous thermal analysis (STA), and the quantitative regeneration of bound gold (I and II) with the partial transformation of released ZnCl2 to ZnS (I) is found.

Investigating the kinetics of the thermolysis of 3-nitro-2,4-dihydro-3H-1,2,4-triazol-5-one (NTO) and reduced size NTO in the presence of cobalt ferrite additive

The co-precipitation technique was used to successfully produce nanometer cobalt ferrite (CoF). Utilizing the solvent-antisolvent approach, the reduction in the size of sensitive HEM 3-nitro-2,4-dihydro-3H-1,2,4-triazol-5-one (NTO) was effectively achieved. Using simultaneous thermal analysis, the effect of 5% by mass CoF on the thermolysis of NTO and nanosize NTO (r-NTO) was investigated. The kinetic parameter of NTO and r-NTO in the presence of CoF additive was assessed using three isoconversional methods: Flynn–Ozawa–Wall, Kissinger–Akahira–Sunose and Starink. It was found that lowering NTO’s size and adding CoF may both lower the material’s thermal breakdown temperature, with the former dropping it more significantly than the latter. The activation energy of both NTO and r-NTO was raised in the presence of CoF additive.

Термические свойства дипиколиновой кислоты и натриевой соли дипиколиновой кислоты NaH(COO)2C5H3N • H2(COO)2C5H3N • 3H2O

Pyridine-2,6-dicarboxylic acid (dipicolinic acid) are actively studied by scientists. Dicarboxylic acid can be used as a special biomarker of anthrax. The crystal structure of NaH(COO)2C5H3N•H2(COO)2C5H3N•3H2O (1) was redetermined from single crystal. In the structure of the sodium salt of dipicolinic acid, sodium is the central atom having two molecules of dipicolinic acid and three molecules of water as ligands. The dipicolinic anion coordinate sodium cation by both oxygens and one nitrogen atom. A network of hydrogen bonds connects water and dipicolinic acid molecules. Hydrogen bonds take part in the formation of building blocks and arranging them into chains which, in their turn, make up layers. The sodium salt of dipicolinic acid as well as its precursor – dipicolinic acid were studied by IR spectroscopy and simultaneous thermal analysis. According to thermal analysis dipicolinic acid is anhydrous substance, that decompose on melting at 252 °C forming only gaseous products, presumably CO2 and pyridine. Opposite to that, thermolysis of its sodium salt follow much more complicated way. According to thermogram the 1 has first stage of three water molecules removal at 105 °C. The measured mass loss is very close to expected mass loss. Heat of dehydratation reaction is 151 kJ/mole. On a further heating the sodium salt of dipicolinic acid was melted at 256 °C with large mass loss. The nature of products at 268 and 315 °C is hard to state. EDX elemental analysis of black residue after 700 °C state brutto-formula of “NaNC5O2” – Na cyanate or carbonate in glassy carbon matrix.

Thermal and bisphenol-A adsorption properties of a zinc ferrite/β-cyclodextrin polymer nanocomposite.

The present study investigated the use of a nanocomposite, produced by reinforcing nanosize zinc ferrite (ZnFe2O4) in a porous β-CD based polymeric matrix (β-CD-E-T/ZnFe2O4), for the removal of Bisphenol A (BPA) from aqueous solutions via adsorption. The thermal stability of the β-CD-based polymer and β-CD-E-T/ZnFe2O4 nanocomposite were investigated using simultaneous thermal analysis at four heating rates. Non-isothermal isoconversion methods were employed to study the thermal degradation kinetics of the β-CD based polymer before and after ZnFe2O4 nano-filling. The results showed that ZnFe2O4 nano-reinforcement increased the activation energy barrier for the thermal degradation of the β-CD-based polymeric matrix. Adsorption experiments showed that the β-CD-E-T/ZnFe2O4 nanocomposite exhibited very high BPA adsorption within 5 minutes. Isotherm, kinetics, and thermodynamic investigations revealed that the adsorption of BPA was via multilayer adsorption on a heterogeneous β-CD-E-T/ZnFe2O4 surface. The thermodynamic studies indicated that BPA adsorption on β-CD-E-T/ZnFe2O4 was spontaneous and exothermic. Overall, the β-CD-E-T/ZnFe2O4 nanocomposite showed less thermal degradation and high efficiency for removing BPA from contaminated water, indicating its potential as a promising material for wastewater treatment applications.

Thermal stability of emerging N6-type energetic materials: kinetic modeling of simultaneous thermal analysis data to explain sensitivity trends.

A number of new high-performing energetic materials possess explosophoric functionalities, high nitrogen content, and fused heterocyclic blocks. Two representatives of these materials have been synthesized recently, namely, 1,2,9,10-tetranitrodipyrazolo[1,5-d:5',1'-f][1,2,3,4]-tetrazine (1) and 2,9-dinitrobis([1,2,4]triazolo)[1,5-d:5',1'-f][1,2,3,4]tetrazine (2). The thermal stability of these energetic materials bearing the N-N-N = N-N-N fragment and three closely related compounds has been investigated for the first time. The thermal decomposition process of analyzed compounds was complicated by the appearance of the liquid phase, sublimation of the material, and autocatalysis by reaction products. In contrast to the traditional approach to the kinetic modeling based on data from either TGA or DSC, we use both signals' data measured at the same time and perform the joint kinetic analysis using the model-fitting technique to obtain the pertinent kinetic description of the process. Of the analyzed materials, 1 and 2 show the lowest thermal stability in melt with a characteristic rate constant of 2.6 × 10-3 s-1 at 250 °C. The kinetic parameters and calculated detonation performance data were used in the model to describe the mechanical sensitivity. The model output and the experimental friction sensitivity data show a respectable agreement, but more data are required to draw firm conclusions. In general, the provided thermal stability and kinetic data can be used for thermal response and storage modeling of these new N6-type energetic materials. The developed thermokinetic approach, joint model-fitting of several thermal analysis signals, can be applied to other complex thermally induced processes to increase the value and credibility of the kinetic findings.

Behaviour of single-crystal nickel alloy in the conditions of high-temperature hydrogen corrosion

This study presents the results of the investigation of the behaviour of ZhS32-VI single-crystal nickel alloy in hydrogen environment or argon atmosphere at 850°C. The microstructure and chemical composition of corrosion deposits were studied by scanning electron microscopy and X-ray energy-dispersive analysis. It has been established that in argon containing an admixture of oxygen a dense scale rich in cobalt and nickel oxides is formed. At atmosphere containing 65% hydrogen and 35% argon an increased content of aluminum in the surface composition was noted. The influence of 100% hydrogen leads to segregation of tungsten and rhenium with the formation of convex growths. The data of simultaneous thermal analysis revealed that the amount of desorbed hydrogen can be from 0.08 to 0.14%.

Degradation Processes of Medieval and Renaissance Glazed Ceramics.

Corrosion effects in deposit environments (soil, waste pit, etc.), together with the glaze adherence and fit, could cause severe deterioration accompanied by different types of defects or growth of corrosion products. The aim of this work was to identify the source of surface degradation of the lead-glazed ceramics sets from the Prague area from the Romanesque to the Renaissance period. A combination of X-ray fluorescence (XRF), X-ray diffraction (XRD), optical microscopy (OM), scanning electron microscopy with energy dispersive X-ray spectroscopy (SEM/EDS), and simultaneous thermal analysis (STA) techniques along with stress state calculations was used to study the defects. Based on the interpretation of the possible sources of the observed defects, four types of degradation effects were schematically expressed for the archaeological samples. It was shown that the glazes were already appropriately chosen during the production of the Romanesque tiles and that their degradation occurred only due to long-term exposure to unsuitable environmental conditions.