Effect of MnC2O4 nanoparticles on the thermal decomposition of TEGDN/NC propellant

The effect of MnC₂O₄ nanoparticles on the thermal decomposition of double-base propellant composed of nitrocellulose (NC) and triethylene glycol dinitrate (TEGDN) has been investigated by TG/DSC?CMS?CFTIR coupling technique. The results show that the decomposition of TEGDN/NC propellant has two stages, the first stage is the volatility and decomposition of TEGDN, the second is the decomposition of NC. The addition of MnC₂O₄ nanoparticles gets the onset temperature of first stage higher, and makes the activation energy of decomposition of TEGDN grow by about 20?C30?kJ/mol. The catalytic also accelerates the total weight loss, and makes the peak temperatures of DSC curves higher. The activation energy of the second stage has a decrease of 20?C40?kJ/mol. MS and FTIR analysis show that the catalyst gets the gas products of macromolecular significantly reduce, while small molecules increase significantly. It also results in the decrease of H₂O, N₂O, and NO₂, and the increase of NO and HCN. Above all, the catalytic improves the thermal stability of TEGDN/NC propellant, make it more safety in storage, and make the decomposition easier and more thorough in main reaction zone.     

Nanosized low-temperature phases of titanium(<Emphasis Type="SmallCaps">iv</Emphasis>) oxide with anatase and η-phase structures: composition,structure, and photocatalytic properties

Nanosized low-temperature modifications of titanium(iv) oxide with the anatase and η-phase (TiO_2–x?mH₂O) structures were prepared by the sulfate method (pH <3) and for the first time characterized by a complex of methods (X-ray diffractometry, scanning electron microscopy, IR spectroscopy, Raman spectroscopy, differential scanning calorimetry, low-temperature sorption capacity of samples to nitrogen, and differentiating dissolution). The physicochemical properties of the modifications were compared. Differences in compositions of the surface and volumes of the samples, compositions and structures of the phases (structure of η-phase is superstructure to anatase), and microstructure elements (sizes of crystallites, nanoparticles, and specific surface area; volume of nano- and ultrananopores) were revealed. The region of η-phase stability was found in the coordinates of temperature (T = 50–95 °C) and hydrolysis duration (τ = 10–80 min) and temperature (T≤200 °C) and annealing duration (τ <6 h). The distinctions in the thermal behavior of the nanosized anatase and η-phase were studied. The photocatalytic activity (PCA) is determined by the physicochemical characteristics of the samples and phases and also by the composition and structure of the decomposed substrate. In the case of difenoxazole, the PCA is affected by the compositions of the samples, phases, and surface (the presence of OH groups) and specific surface area, whereas the composition of the samples and specific surface area affect the PCA in the case of thiamethoxam.     

Biodegradable poly(butylene succinate-<Emphasis Type="Italic">co</Emphasis>-butylene dimerized fatty acid)s: Synthesis,crystallization, mechanical properties,and rheology

Poly(butylene succinate-co-butylene dimerized fatty acid) (P(BS-co-BDFA)) copolyesters were synthesized from succinic acid (SA) and dimerized fatty acid (DFA) with 1,4-butanediol (BDO) through a two-step process of esterification and polycondensation. The polyester compositions and physical properties of copolyesters were investigated by GPC, ¹H NMR and ¹³C NMR, DSC, WAXD, DMA, TGA, tensile and rheology test. The melting temperature (T_m), and crystallization temperature (T_c) decreased gradually as the content of DFA monomer increased. P(BS-co-BDFA) copolyesters showed the same crystal structure as the PBS homopolyester. Besides, TGA results indicated that P(BS-co-BDFA)s were of higher thermal stabilities. Moreover, it was found that the synthesized P(BS-co-BDFA)s showed the maximum elongation at break (591%) as the DFA contents were 10 mol%. Rheology analysis indicated that the viscoelastic behavior of the polyesters greatly depended on the molecular weight of polyesters.     

Bulk properties of a liquid phase mixture {ethylene glycol+<Emphasis Type="Italic">tert</Emphasis>-butanol} in the temperature range 278.15–348.15 K and pressures of 0.1–100 MPa. II. Molar isothermal compressibility,molar isobaric expansibility,thermal pressure coefficient,and internal pressure

Based on the experimental data, the molar isothermal compressibilities, molar isobaric expansibilities, thermal pressure coefficients, internal pressures of a liquid phase mixture {ethylene glycol (1) + tert-butanol (2)} are calculated for a wide spectrum of compositions in the range of pressures of 0.1–100 MPa and temperatures of 278.15–323.15 K. Shown that the dependences of molar isothermal compressibilities K _{T, m} , molar isobaric expansibilities E _{P, m} , and isochoric thermal pressure coefficients β on the mole fraction of tert-butanol in the mixture are characterized by the absence of extrema typical of aqueous systems. The manifestation of negative partial expansibility and negative partial expansibility of ethylene glycol in the mixture is found. The thermal pressure coefficients decrease with an increase in the mole fraction of tert-butanol at all pressures and temperatures. A rise in the pressure increases the thermal pressure coefficient, while a rise in the temperature decreases its value due to a decrease of free space in the mixture. An increase in the concentration of tert-butanol leads to an increase in the negative temperature coefficient of internal pressure ΔP _int/ΔT, which indicates a weakening of intermolecular interaction at these compositions.     

Copper and copper oxides nanopowders in the oxidative condensations of phenylacetylene and <Emphasis Type="Italic">tert</Emphasis>-butylacetylene

Transformations of phenylacetylene and tert-butylacetylene in the presence of copper and copper oxide (Cu₂O, CuO) nanopowders prepared by gas-phase condensation of copper in argon were studied. The reaction of phenylacetylene with copper oxide nanopowders having different phase compositions in the absence of a solvent at room temperature resulted in oxidative condensation of phenylacetylene and complex formation of the condensation product. The complex undergoes decomposition by the action of acids, bases, and compounds capable of forming complexes. According to the X-ray diffraction data, one of the products is a new “parquet” modification of diphenyldiacetylene. Under analogous conditions, tert-butylacetylene gave rise to a complex mixture of products among which di-tert-butyldiacetylene was identified by gas chromatography-mass spectrometry. No copper complexes with the tert-butylacetylene condensation products were detected.     

Heat capacities and thermal diffusivities of <Emphasis Type="Italic">n</Emphasis>-alkane acid ethyl esters—biodiesel fuel components

The heat capacities and thermal diffusivities of ethyl esters of liquid n-alkane acids C _n H_2n–1O₂C₂H₅ with the number of carbon atoms in the parent acid n = 10, 11, 12, 14, and 16 are measured. The heat capacities are measured using a DSC 204 F1 Phoenix heat flux differential scanning calorimeter (Netzsch, Germany) in the temperature range of 305–375 K. Thermal diffusivities are measured by means of laser flash method on an LFA-457 instrument (Netzsch, Germany) at temperatures of 305–400 K. An equation is derived for the dependence of the molar heat capacities of the investigated esters on temperature. It is shown that the dependence of molar heat capacity C _p,m (298.15 K) on n (n = 1–6) is close to linear. The dependence of thermal diffusivity on temperature in the investigated temperature range is described by a first-degree polynomial, but thermal diffusivity a (298.15 K) as a function of n has a minimum at n = 5.     

Preparation and thermal reliability of <Emphasis Type="Italic">N</Emphasis>-butyl stearate/methyl palmitate composite phase change material

In this study, a series of binary mixtures of N-butyl stearate (nBS) and methyl palmitate (MP) were used to produce a novel composite phase change material (CPCM) for potential application in the eastern China, and their thermal properties were investigated by differential scanning calorimetry (DSC). The results of DSC indicated that the mixture consisting of 10 mass% nBS and 90 mass% MP is optimum as the CPCM in terms of the phase change temperature ranges (T _f = 19.74–5.59 °C; T _m = 18.34–33.80 °C) and latent heats (ΔH _f = 176.8 J g^?1; ΔH _m = 189.3 J g^?1). On the other hand, the thermal reliability and chemical stability of the CPCM after 120, 180, 240, 300, 360 and 500 accelerated thermal cycling tests were studied by DSC and fourier transform infrared (FTIR) analysis. The results demonstrated that the CPCM had good thermal reliability and chemical stability.     

Study on the thermal decomposition kinetics of<Emphasis Type="Italic">cis/trans-</Emphasis>[Cu(gly)<Subscript>2</Subscript>] • H<Subscript>2</Subscript>O

The thermal decomposition reactions of the complexescis/trans-[Cu(gly)₂] ? H₂O were studied by TG-DSC methods. The results showed that they have similar decomposition process, which occur in two steps. The first step is the loss of water and the second step is the decomposition of anhydrous complexes. But forcis-[Cu(gly)₂]?H₂O, the temperature of losing water is higher than that oftrans-isomer. Their reaction mechanisms of the two-step decomposition were also proposed.     

Analysis of structure transition and compatibility of PTT/PC blend without transesterification

Poly(trimethylene terephthalate)/polycarbonate (PTT/PC) blends were prepared by solvent mixing to avoid transesterification during high temperature blending. The influences of compositions on the thermal behavior, crystallization morphology and structure of the blends were studied. FTIR results indicated that there was no COO linking to two phenyl groups on each side chain and DSC results supported no transesterification reaction. DSC curves showed that T _c and T _mc increased to maximum range when PC contents were between 7 wt%-15 wt%, however, T _m decreased constantly with the increase of PC contents. It was observed from POM that PTT spherulitic morphology and crystallization kinetics were obviously influenced by the change of PC contents. Structural evolutions during cooling were investigated by SAXS which showed L _c of PTT remained a constant with different PC contents and also fixed during crystallization, nevertheless, it revealed a maximum value of L _nc for sample PTT₉₃. It was concluded that PC chains could be permeated into not only amorphous crystallite structure but also amorphous lamellae structure and 7 wt% PC content was supposed to be the “proper” penetration amount into PTT lamellae structure which led to a maximum capacity of amorphous lamellar layer. Fringedmicelle crystal model was adopted to illustrate semi-crystalline physical structures of the blend in two kinds of component aggregation states.     

Thermal stability of chlorophyll <Emphasis Type="Italic">a</Emphasis> derivatives containing hydrophilic groups

Trends in thermal stability of aromatic macroheterocycles based of pheophorbide a and chlorin e ₆ containing hydrophilic groups have been revealed by means of thermogravimetric analysis at 298–1223 K under inert atmosphere. Methylpheophorbide a and 13(1)-N-methylamide of chlorin e ₆ are the most stable, the decomposition onset temperature being t _o 351 and 333°С. Their functional substitution leads t _o the reduction in thermal stability. Depending on the macrocycle structure the decrease in t _o can reach 20–200°С.     

Calorimetric study of Sb-modified Ge–Se–Te glassy alloys

The glassy compositions of Ge ₁₆ Se ₅₂ Te _32?x Sb _x system, obtained using rapid melt quenching technique, have been characterized by calorimetric study at different heating rates in this study. A systematic investigation of the crystallization kinetics is carried out for these compositions. Composition corresponding to atomic % 8 of Sb has good thermal stability. The material exhibits the unique thermal properties, which makes it suitable to use for electrical or memory switching devices. Various thermal parameters, activation energies of glass transition and crystallization are calculated using relevant approaches.     

Study of the thermal decomposition of historical metal threads

A complex of copper perchlorate coordinated with imidazole Cu(C₃N₂H₄)₄(ClO₄)₂ was synthesized and characterized by X-ray single-crystal diffraction. The complex is centrosymmetric in the monoclinic P2(1)/c space group. The low-temperature molar heat capacities and thermodynamic properties of the complex were studied with adiabatic calorimetry (AC). The thermodynamic functions [H _T–H _298.15] and [S _T–S _298.15] were derived in the temperature range from 80 to 370 K with temperature interval of 5 K. Thermal decomposition behavior of the complex in nitrogen atmosphere was studied by thermogravimetric (TG) analysis and differential scanning calorimetry (DSC). The mechanism of the decomposition was deduced to be the breaking up the two Cl–O bonds of the Cl–O–Cu and the Cu–N bonds of the imidazole rings in succession.     

Molecular structure,quantum chemical investigation,and thermal behavior of (DNAZ-CO)<Subscript>2</Subscript>

Bis-(3,3-dinitroazetidinyl)-oxamide ((DNAZ-CO)₂) is an acyl derivative of 3,3-dinitroazetidine (DNAZ). It is prepared and its crystal structure is determined. The crystal is orthorhombic, Fdd2 space group, a = 13.136(14) Å, b = 19.48(3) Å, c = 10.326(14) Å, V = 2642 (6) ų, Z = 8. A density functional theory (DFT) method of the Amsterdam Density Functional (ADF) package is used to calculate the geometry, frequencies, and properties. The optimized geometry, frontier orbital energy, and main atomic orbital percentage are obtained. The thermal behavior is studied under a non-isothermal condition by DSC and TG/DTG methods. The apparent activation energy (E _a) and pre-exponential factor (A) of the exothermic decomposition reaction of (DNAZ-CO)₂ are 164.10 kJmol^?1 and 10^13.38 s^?1 respectively. The critical temperature of thermal explosion is 272.20°C. The values of ΔS ^≠, ΔH ^≠, and ΔG ^≠ of this reaction are 6.44 Jmol^?1·K^?1, 163.76 kJmol^?1 and 160.34 kJmol^?1 respectively.     

The thermal properties of water-n,n-dimethylformamide solutions at 278–323.15 K and 0.1–100 MPa

The isothermal compressibility coefficients κ _T , volumetric thermal expansion coefficients α, and pressure coefficients (?p/?T) _v were calculated for water-N,N-dimethylformamide (DMFA) mixtures of 12 compositions over the temperature and pressure ranges 278–323.15 K and 0.1–100 MPa. The composition dependences of κ _T passed minima, and the corresponding α and (?p/?T) _v dependences passed maxima. The structural features of water and hydrophobic hydration effects were found to play a determining role in changes in the thermodynamic properties of water-DMFA solutions.     

An AEE-active polymer containing tetraphenylethene and 9,10-distyrylanthracene moieties with remarkable mechanochromism

A polymer(poly(9,10-anthracenevinylene-alt-4,4'-(9,9-bis(4-(4'-(1,2,2'-triphenylvinyl)phenoxy)butyl)-9Hfluorene-2,7-diyl) dibenzaldehyde), P1) was successfully synthesized through the Wittig-Horner reaction by employing fluorene and 9,10-distyrylanthracene moieties as building blocks for backbone and tetraphenylethenes as pendant groups. Photophysical and thermal properties of the resulting polymeric emitter were fully characterized by ultraviolet-visible(UVVis) absorption and photoluminescence(PL) spectra, thermogravimetric analysis(TGA) and differential scanning calorimetry(DSC). While P1 emits an orange-light centered at 567 nm in dilute tetrahydrofuran(THF) solution, the solid powder of the polymer exhibits strong yellow emission peaked at 541 nm. It is also found that the as-synthesized polymer shows unique property of aggregation-enhanced emission(AEE). In addition, P1 possesses high thermal stability with a decomposition temperature(T_(d,5%)) of 430 °C and high morphological stability with a glass transition temperature(T_g) of 171 °C. Under the stimulus of mechanical force, the emission of P1 can be changed from yellow to red(Δλ_(max)=61 nm), showing a remarkable mechanochromism. The results from XRD analysis suggest that such mechanochromic phenomenonof P1 is probably caused by the destruction of crystalline structure, which leads to the conformational planarization of the distyrylanthracene moieties forming by the polymerization and the increase of molecular conjugation of the backbone.     

Evaporation of Plasticizer from NEPE Type Propellant

Using the method of dynamic thermogravimetry and differential scanning calorimetry in the heating rate range 0.46–10.0 deg^–1 min^–1, evaporation of the plasticizer from propellant samples of the NEPE type was investigated. The experiments were carried out in an open system in a flow of pure argon at atmospheric pressure. Nitroglycerin is the main mass fraction of the plasticizer. The activation energy E of the gross evaporation–diffusion process is determined by various methods. Heat of evaporation of the plasticizer ΔH_v is estimated. It is shown that in the early stage of evaporation the values of E and ΔH_v practically coincide. At a temperature of 298.15 K ΔH_v = 89 ± 4 kJ mol^–1, which is in satisfactory agreement with the literature data for heat of evaporation of pure nitroglycerin. With any way of preventing free removal of the plasticizer from the surface of the samples on the DSC thermograms successive exothermic peaks of the thermal decomposition of the plasticizer and the octogen are observed, which are not realized in the open system for the indicated heating rates at T < 190°C.     

Surface tension of tin and its alloys with lead

The temperature and concentration dependencies of the surface tension of high-purity tin and its alloys with lead were investigated in an ultrahigh vacuum by the large-drop method. It was shown that the tin surface-tension polytherm obeyed the equation σ(T) = 570.0 ? 0.08(T ? T _m). Lead was found to possess high surface activity in the range of its low concentrations in tin. Estimate was made for the limiting lead surface activity in tin-based alloys. Our conclusions about lead surface activity in alloys with tin are consistent with the literature data obtained by the modern electron-spectrometric methods for the surface compositions of the alloys studied.     

Catalytic effect investigation of α-Fe2O3 and α-Fe2O3-CMS nanocomposites on the thermal behavior of NC/DEGDN mixture: DSC measurements and kinetic modeling

In this work, the thermal behavior and kinetics of energetic systems containing α-Fe₂O₃ and iron oxide–carbon mesospheres (α-Fe₂O₃-CMS) with nitrocellulose (NC)/diethylene glycol dinitrate (DEGDN)-based composites have been investigated using differential scanning calorimetry DSC and four isoconversional kinetic methods, respectively. The obtained results indicate that NC/DEGDN show only one decomposition peak, corresponding to the decomposition of the nitrate esters. Furthermore, the introduction of α-Fe₂O₃ and α-Fe₂O₃-CMS have lowered the peak temperature by 3.1 °C and 4.7 °C, respectively. Besides, the activation energy of the thermal decomposition of NC/DEGDN was decreased by 11.9 kJ/mol and 27.97 kJ/mol, after the introduction of α-Fe₂O₃ NPs and α-Fe₂O₃ NPs supported on CMS. These results confirm the good catalytic effect of the added catalysts on the thermal decomposition of the NC/DEGDN mixtures. However, the best catalytic effect was provided by the α-Fe₂O₃-CMS. Furthermore, the three considered systems were found to decompose according to different integral models g(α).     

Temperature-dependent AC electrical conductivity,thermal stability and different DC conductivity modelling of novel poly(vinyl cinnamate)/zinc oxide nanocomposites

Thermal analysis on organically modified Ca²⁺-montmorillonite (OMON) and its source materials—octadecylamine (ODA) and Ca²⁺-montmorillonite (Ca²⁺-Mon)—was studied using thermally stimulated current (TSC) technique. The appearance of ρ _MON peak with the T _max = 75 °C shows the ability of the developed TSC system to demonstrate the relaxation effects of dehydration in Ca²⁺-Mon. It appeared within the temperature range of DSC endothermic peak (30–100 °C) where the T _mMON = 58 °C. Segmental motions of ODA chains and structural disruptions in the modifier agent compound produced TSC α _ODA, ρ _ODA and ρ _1ODA peaks that are comparable to thermal transition and endothermic peaks in DSC profile (T _gODA, T _m1ODA and T _m2ODA). The effect of localized motion in ODA chains as revealed by the TSC β_OMON peak (T _max = ?23 °C), however, is absent in the DSC profile of OMON. It shows TSC technique has high sensitivity in detecting various relaxation behaviors at molecular level. More evidences are demonstrated by the ρ _OMON (T _max = 86 °C) and ρ _1OMON (T _max = 105 °C) peak originated from the ODA chains structures. These peaks also confirm the intercalation of the modifier cations inside the Ca²⁺-Mon gallery.     

High-Temperature X-Ray Diffraction Investigation of the Decomposition Process in Manganese-Gallium Spinel Mn<Subscript>1.5</Subscript>Ga<Subscript>1.5</Subscript>O<Subscript>4</Subscript>

The stability of spinel-type mixed Mn_1.5Ga_1.5O₄ oxide prepared in an inert medium (1000 °C, Ar) is studied by thermogravimetry and high-temperature X-ray diffraction in air in a wide temperature range 30–1000 °C. On heating, reversible decomposition processes of initial spinel are observed. From 30 °C to 600 °C oxygen atoms attach to the surface layer of initial Mn_1.5Ga_1.5O₄ spinel to form a new phase distinct from parent oxide by the oxygen stoichiometry (cation vacancies are formed). The product of decomposition is two oxides: Mn_1.5Ga_1.5O₄ and Mn_1.5–xGa_1.5–x[·]_xO₄. On the contrary, above 600 °C a loss of oxygen occurs, the concentration of cation vacancies decreases in Mn_1.5–xGa_1.5–x[·]_xO₄, and the reverse process of single phase oxide crystallization takes place. At 1000 °C the spinel phase forms again whose composition is similar to that of the initial parent phase Mn_1.5Ga_1.5O₄. On cooling the decomposition of this phase is again observed due to oxygen attachment.