Composition and characteristics of primary combustion products of boron-based propellants

Primary combustion products of boron-based propellants are incomplete combustion products that are emitted from the gas generator of a solid ducted rocket. Studying the composition of primary combustion products provides valuable information about the primary combustion process and also helps to better understand the secondary combustion process. The particle size of the primary combustion products is analyzed by a laser particle size analyzer. The qualitative analysis of the sample composition is performed by using x-ray diffraction, x-ray photoelectron spectroscopy, and thermogravimetry–differential scanning calorimetry experiments. Based on these results, an integrated quantitative analysis of the sample composition is conducted. The quantitative analysis methods include tube furnace heating, ion chromatography, infrared spectroscopy, and inductively coupled plasma chromatography. In addition, scanning electron microscopy and energy dispersive spectrometry are also used to analyze the micro-morphology and distribution of different components in the sample. The primary combustion products mainly contain B, C, B _m C _n , H₃BO₃, B₂O₃, BN, Mg, MgCl₂, and NH₄Cl. B _m C _n (22–24%), H₃BO₃ (20%), and B (16.8%) are the three major components, while B _m C _n , B, and C (9.8–11.8%) are the three combustible components present in the highest amounts. The oxidant NH₄ClO₄ is completely consumed during the primary combustion, while the metal additive Mg does not show much reactivity. The micro-morphology and distribution of B _m C _n , H₃BO₃ (or B₂O₃), B, Mg, and C in the sample are investigated. Some components in the primary combustion products are found to be agglomerated, while some components are dispersed. Large particles in the sample mainly include B and Mg, while B _m C _n , H₃BO₃ (or B₂O₃), and C particles are small. In general, the combustion completeness of the primary combustion products is rather low. Therefore, better understanding and controlling of the secondary combustion process is very important to improve the performance of B-based propellants.     

Crystal structure and thermal expansion of ammonium pentaborate NH<Subscript>4</Subscript>B<Subscript>5</Subscript>O<Subscript>8</Subscript>

Anhydrous ammonium pentaborate NH₄B₅O₈ has been synthesized by thermal dehydration of larderellite NH₄[B₅O₇(OH)₂] · H₂O at a temperature of 290°C for 7 h. The crystal structure has been determined from the X-ray powder diffraction data: a = 7.58667(5) Å, b = 12.00354(8) Å, c = 14.71199(8) Å, R _p = 6.23, R _wp = 7.98, R _B = 12.7, R _F = 8.95, and β-KB₅O₈ structure type. The double interpenetrating framework is formed by pentaborate groups, each consisting of a boron-oxygen tetrahedron and four triangles, in which all oxygen atoms are bridging. The thermal behavior of the NH₄B₅O₈ compound has been investigated using thermal X-ray diffraction. As for other pentaborates of this type, the thermal expansion of the NH₄B₅O₈ compound is anisotropic and reaches a maximum along the a axis. The thermal expansion coefficients are as follows: α _a = 39 × 10^?6, α _b = 6 × 10^?6, α _c = 20 × 10^?6, and α _V = 65 × 10^?6 °C^?1.     

Thermogravimetric characteristics of <Emphasis Type="Italic">α</Emphasis>-cellulose and decomposition kinetics in a micro-tubing reactor

The pyrolysis characteristics and kinetics of α-cellulose were investigated using thermogravimetric analyzer (TGA) and micro tubing reactor, respectively. Most of the α-cellulose decomposed between 250 and 400 °C at heating rate of 5–20 °C/min. The apparent activation energy was observed in the range of 263.02 kJ mol^?1 to 306.21 kJ mol^?1 at the conversion of 10-80%. The kinetic parameters were determined by nonlinear least-squares regression of the experimental data, assuming first-order kinetics. It was found from the kinetic rate constants that the predominant reaction pathway was A(α-cellulose) to B(bio-oil) rather than A(α-cellulose) to C(gas; C₁-C₄) and/or to B(bio-oil) to C(gas; C₁-C₄) at temperatures of 340-360 °C.     

Sulfonic acid cation-exchange resins in the synthesis of straight-chain alkylphenols

Kinetic characteristics of reactions occurring in the alkylation of phenol with straight-chain alkenes (C₉, C₁₆) over the Amberlyst 15 Dry, Amberlyst 35 Dry, Amberlyst 36 Dry, Amberlyst 70, Amberlyst DT, Tulsion 66 MP, Lewatit K2640, Lewatit K 2431, and Relite EXC8D sulfonic acid cation-exchange resins have been determined experimentally. The activities of these catalysts in different types of reactions have been compared. The rate constants of all reactions decrease on passing from 1-nonene to straight-chain hexadecene. In the alkylations of phenol with straight-chain alkenes, the ortho-alkylphenol/para-alkylphenol ratio is practically equal to the statistical ratio for all of the resins examined in their operation range.     

A Comprehensive Study on the Synthesis and Micellization of Disymmetric Gemini Imidazolium Surfactants

Two groups of disymmetric Gemini imidazolium surfactants, [C₁₄C₄C _m im]Br₂ (m = 10, 12, 14) and [C _m C₄C _n im]Br₂ (m + n = 24, m = 12, 14, 16, 18) surfactants, were synthesized and their structures were confirmed by ¹H NMR and ESI–MS spectroscopy. Their adsorption at the air/water interface, thermodynamic parameters and aggregation behavior were explored by means of surface tension, electrical conductivity and steady-state fluorescence. A series of surface activity parameters, including cmc, γ _cmc, π _cmc, pC ₂₀, cmc/C ₂₀, Γ _max and A _min, were obtained from surface tension measurements. The results revealed that the overall hydrophobic chain length (N _c) for [C₁₄C₄C _m im]Br₂ and the disymmetry (m/n) for [C _m C₄C _n im]Br₂ had a significant effect on the surface activity. The cmc values decreased with an increase of N _c or m/n. The thermodynamic parameters of micellization (ΔG _m ^θ , ΔH _m ^θ , ΔS _m ^θ ) derived from the electrical conductivity indicated that the micellization process of [C₁₄C₄C _m im]Br₂ and [C _m C₄C _n im]Br₂ was entropy-driven at different temperatures, but the contribution of ΔH _m ^θ to ΔG _m ^θ was enhanced by increasing N _c or m/n. The micropolarity and micellar aggregation number (N _agg) were estimated by steady-state fluorescence measurements. The results showed that the surfactant with higher N _c or m/n can form larger micelles, due to a tighter micellar structure.     

On the critical displacement of excited kinetic units in liquids and glasses

The critical displacement of an atom (a group of atoms) in inorganic glasses Δr _m, which corresponds to the maximum of the interatomic attractive force, is calculated using available data on the surface tension and elastic constants. It is found that the critical atomic displacement Δr _m is close in order of magnitude to the linear dimension of the activation volume of atomic excitation v _h ^1/3 for glasses in the As-S and Ge-As-S systems with a chain structure and is considerably less than the value of v _h ^1/3 for alkali silicate glasses and glasses in the Cd-As system with a structure involving ionic sublattices. A relationship for calculating the activation volume of the atomic excitation from data on the glass transition temperature and elastic constants is derived within the model of an excited state.     

Mixed Stability and Antimicrobial Properties of Gluconamide-Type Cationic Surfactants

The stability of anionic-cationic surfactant solutions and the antimicrobial properties of novel N,N-dimethyl-N-[3-(gluconamide/lactobionamide)]propyl-N-alkylammonium bromides (CnDGPB and CnDLPB), N-methyl-N-hydroxyethyl group-N-[3-(gluconamide)-propyl]-N-alkylammonium bromide (CnMHGPB) and star-shaped gluconamide-type cationic surfactants N-dodecyl-N,N-bis[(3-d-gluconylamido)propyl]-N-alkylammonium bromide (CnDBGB) were investigated. Mixed stability in combination with sodium n-alkylbenzenesulfonate (LAS) was determined via transmittance; stability is achieved when percent transmittance was greater than 90 %. Transmittance results suggest that these cationic surfactants can form stable solutions with anionic surfactants over a broad concentration range. The inhibition activity of C _n DBGB is the best among the three kinds of glucocationic surfactants. Antimicrobial activity of C₁₂ surfactants was the best, C₁₄ was the second and C₁₀ was the worst. Moreover, antibacterial activity of glucose-based cationic surfactants was greater than lactose-based cationic surfactants.     

Analysis and Modeling of the Hydroisomerization Process for <Emphasis Type="Italic">n</Emphasis>-Hexane

A stage six-path mechanism for the reaction of n-hexane hydroisomerization on a BEA Pt-zeolite catalyst has been proposed. The mass flow rate of n-hexane in the feed stream varies in the range of 0.7?2.8 h^?1; the mole ratio of hydrogen to the n-hexane range of 2.7–14.6; the reactor temperature falls in the range from 453 to 573 K; and the gas flow pressure varies in the range of 1.0–10.0 atm. Thirty experiments have been carried out. In the product stream, the concentrations of n-hexane, 2-methylpentane, 3-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, propane, C₁-alkanes, and C₂-alkanes are analyzed by gas chromatography. A kinetic model has been constructed for the six-path mechanism of the reaction of n-hexane hydroisomerization, which contains 15 kinetic constants. Based on the results of laboratory experiments, the kinetic constants of the model have been estimated by the method of nonlinear least squares. The model has been shown to correspond with the experiment in the selected field of experimentation.     

Change of the thermal behavior of 55Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> ⋅ 45B<Subscript>2</Subscript>O<Subscript>3</Subscript> glass at annealing close to the vitrification temperature

The characteristic properties of relaxation processes for 55Bi₂O₃ ? 45B₂O₃ glass were described. The pattern of changes of the vitrification temperature (T _g ) is found to be quasi-periodic; the value of the endothermic effect near T _g (ΔC’ _p ) and the difference between the softening point and the vitrification temperature (T _m –T _g ) were determined. The temperature-time parameters of the transition from quasi-periodic to the continuous change of the properties were determined and an explanation of such behavior of the system was offered.     

Solid-phase synthesis and characterization of rare-earth chromates

Simple chromates(V) MCrO₄ (M = Sc, Y, Gd, Er, or Yb) and chromate(V) vanadates Gd(CrO₄) _x (VO₄)_{1 ? x} have been synthesized by a solid-phase method. All compounds crystallize in the xenotime-type structure, space group I4₁/amd, Z = 4. The unit cell parameters have been calculated as follows: for GdCrO₄, a = 7.209(5) Å, c = 6.318(4) Å; for ErCrO₄, a = 7.088(2) Å, c = 6.231(1) Å; for YbCrO₄, a = 7.034(1) Å, c = 6.205(2) Å; for YCrO₄, a = 7.108(3) Å, c = 6.254(3) Å; and for ScCrO₄, a = 7.012(2) Å, c = 6.188(2) Å. Symmetry D _2d , established for the CrO₄ tetrahedron during the Rietveld structure refinement, is verified by IR spectroscopy. The MCrO₄ simple chromates are paramagnets; their magnetic moments range from 1.7 to 8.1 μ _B .     

EPR and optical studies on binary mixed alkali-alkaline earth oxide borate glasses doped with Cu<Superscript>2+</Superscript> ions

Mixed alkali alkaline earth oxide borate glasses of the composition (25 – x)Li₂O–xK₂O–12.5BaO–12.5MgO–49B₂O₃–1CuO (x = 0, 5, 10, 15 and 20 mol %) were prepared by the melt quenching technique. The X-ray diffractograms of all the glass samples were recorded at room temperature. Peak free X-ray spectra revealed the amorphous nature of all the prepared glasses. Modulated differential scanning calorimetry (MDSC) was used to determine the glass-transition temperature (T _g ). The probable mixed alkali effect was investigated using experimental techniques like density, molar volume, MDSC, electron paramagnetic resonance (EPR), and optical absorption studies. From the EPR spectra the spin-Hamiltonian parameters were evaluated. The spin-Hamiltonian parameter values indicated that the ground state of \(C{u^{2 + }}is{\kern 1pt} {d_{{x^2} - {y^2}}}\) orbital (²B_1g) and the site symmetry around Cu² is tetragonally distorted octahedral. The variation of g _|| and A _|| as a function of Li₂O content was found to be nonlinear. A broad optical absorption band was observed in all the glasses containing Cu² ions corresponding to ²B_1g → ²B_2g transition. From the optical absorption studies the values of the optical band gap (E _opt) for indirect, direct transitions and Urbarch energy (ΔE) have been evaluated. By co-relating the EPR and optical absorption data, bonding parameters α², β² and β ₁ ² were evaluated.     

Esterification of acrylic acid with ethanol using pervaporation membrane reactor

Esterification of acrylic acid with ethanol was carried out using an in-situ reactor with an integrated pervaporation assembly (IPAE) made of polyvinyl alcohol (PVA) membrane and was compared with a non-integrated (NIE) system. Effect of reaction temperature (T _r ), catalyst loading (C _C ), molar ratios of reactants (MR) and ratio of effective membrane area to unit volume of reaction mixture (S/V _o ) on kinetics of esterification reaction were studied. Conversions achieved in IPAE were found to be distinctly higher than the NIE. The highest conversion of acrylic acid was obtained as 83.3% at T _r =60 °C, M _R =3 : 1, C _C =2% and S/V _o =14.1 m^?1. Equilibrium conversion of acrylic acid in NIE was obtained as 55.1% at 60 °C, 1 : 1 in 7 h, while using IPAE conversion enhances to 67.6%. Esterification of acrylic acid and ethanol with presently studied operating parameters provides a new approach to existing literature reported esterification-pervaporation system.     

Stability of polymer structures based on fullerene C<Subscript>60</Subscript> under their oxidation with oxygen

A comparative study of the oxidative destruction of the monomer face-centered cubic (FCC) lattice and various polymer [dimeric (D), orthorhombic (O), tetragonal (T), and rhombohedral (R)] phases of C₆₀ in an atmosphere of oxygen has been performed in the temperature range of 100–500°C with the use of a flow microunit connected to a gas chromatograph. From direct measurements of the content of CO₂ in the gaseous products of destruction, the temperature dependences of oxidation rates are measured for the materials under study. It has been established that, with respect to stability against oxidative destruction, different forms of C₆₀ may be arranged as follows: the monomer FCC phase of C₆₀ > D > O > T > R. The reasons behind this tendency are discussed.     

Mixed Micellization Study of Alkyltrimethylammonium and Alkyltriphenylphosphonium Bromides in Aqueous Solution

Mixed micellization study of cationic surfactants viz. alkyltrimethylammonium bromides (C_nTAB) and alkyltriphenylphosphonium bromides (C_nTPPB) with similar hydrophobic groups (C₁₂-, C₁₄-, and C₁₆-) was performed using tensiometry and UV–visible light spectrophotometry techniques. Critical micelle concentration (CMC) values of the single and binary surfactant mixtures were obtained from a plot of surface tension versus the logarithm of surfactant concentration (C _s). The degree of synergy and various mixed micelle parameters like interaction parameter (β), activity coefficients (f ^m ) and interfacial parameters like surface pressure (π _CMC), packing parameter (P), surface excess concentration (Г _max), surface tension at the CMC (γ _CMC), and minimum area per molecule (A _min) were evaluated using the regular solution theory (RST). Thermodynamic parameters were calculated using several proposed models which suggest the mixed micellar system to be more thermodynamically stable than their respective individual components. In addition, a dye solubilization study was performed using a spectrophotometric method to validate the CMC data obtained from tensiometric method. Conductometric measurements were also carried out for the mixture of C₁₂TAB + C₁₂TPPB only as it showed a more negative β, indicating a higher degree of synergism.     

FTIR spectra and elastic properties of Cd-substituted Ni–Zn ferrites

Solid solutions Ni_0.5–x Cd _x Zn_0.5Fe₂O₄ (x = 0, 0.15, 0.30) were prepared by solid-state synthesis and characterized by FTIR spectroscopy. The FTIR spectra of synthesized ferrites showed two absorption bands (ν₁ and ν₂) in the range 400–600 cm^–1 belonging to tetrahedral (A) and octahedral (B) interstitial sites in the spinel lattice. The force constants for tetrahedral (K _t) and octahedral sites (K _o) were determined, as well as Young’s modulus (E), rigidity modulus (G), bulk modulus (B), Debye temperature (Θ_D), and velocity of transverse (V _t) and longitudinal (V _l) elastic waves. The relevant interionic cation–anion, cation–cation distances and bond angles are also reported.     

Structural Analysis of Nano Ferrites Synthesized by Combustion and Microwave Methods

We suggest a new approach to synthesis of nano nickel ferrites via combustion synthesis in electric and microwave ovens. The oxidation of organic compounds, decomposition of salts, and their degradation were explored by TGA–DTA. As-prepared nanopowders were characterized by X-ray powder diffraction. Structures of both ferrites were slightly different. Detailed material parameters such as crystallite size (D), lattice constant (a), micro strain (ε), X-ray density (Δ_X), dislocation density (ρ_X), hopping lengths (L_A and L_B), bond lengths (A–O and B–O), ionic radii (r_A and r_B), texture coefficient [TC(hkl)], and mechanical properties were measured and comparatively analyzed.     

Synthesis and Characterization of Novel Aryl Alkyl Sulfonates Based on Nonylphenol

A series of nonylphenol-substituted alkyl sulfonates (C _x NPAS, x = 8, 10, 12, 14, 16) with two hydrocarbon chains and two different hydrophilic groups has been synthesized from α-olefins and nonylphenol. The respective products have a “pseudo-gemini” surfactant structure. The structures of the C _x NPAS have been characterized by IR, UV, ¹H nuclear magnetic resonance, electrospray ionization mass spectrometry, and elemental analysis. The effects of carbon chain length of the obtained surfactants on properties such as the critical micelle concentrations (CMC) in aqueous solutions, surface tension at the CMC (γ _CMC), and efficiency of adsorption at the water/air interface (pC ₂₀) have been determined. The γ _CMC of the surfactants first decreased and then increased with increasing length of the carbon chain x, and reached a minimum of 29.25 mN/m at x = 10, which is much lower than that of α-olefin sulfonate (AOS) (33.52 mN/m). The CMC decreased and pC ₂₀ increased with increasing x. The introduction of the hydroxyl group is responsible for multiple molecular conformations at the water/air interface and leads to a greater molecular area A _min and smaller Γ_max than those of AOS.     

Search of high-capacity cathode materials based on lithium–iron silicate compounds

The crystal structures of 197 lithium–silicate compounds have been analyzed using the method of crystal chemistry analysis (TOPOS software package). The compounds whose structures are characterized with a combination of high values of such parameters as the channel radius, stability, gravimetric capacity, and capacity per volume unit have been revealed: LiFeSiO₄ (R3?), Li₄Fe₂Si₃O₁₀ (C2/c), Li₂FeSiO₄ (Pc2₁ n), and Li₂FeSiO₄ (C222₁). It has been demonstrated that lithium–iron silicates of the monoclinic syngony have high values of the capacity per volume unit, as compared to those of the rhombic syngony. The structural stability of the Li₂FeSiO₄ (Pc2₁ n) framework has been corroborated using the method of computer simulation within the scopes of the electron density functional theory. The obtained information could facilitate creation of novel cathode materials of high capacity and specific accumulated energy.     

Purification,Surface Tensions,and Miscibility Gaps of Alkyldimethyl and Alkyldiethylphosphine Oxides

Alkyldimethyl (C _n DMPO) with chain lengths of n = 8 (octyl), 10 (decyl), 12 (dodecyl), and 14 (tetradecyl) as well as alkyldiethyl (C _n DEPO) phosphine oxides with chain lengths of n = 10, 12, and 14 were synthesized and purified to study how the adsorption properties and the location of the miscibility gap of these surfactants depend on the size of the head group and on the length of the alkyl chain. After surfactant purification, the surface tension isotherms were determined from which the cmc, the minimum surface tension σ_cmc, the maximum surface concentration Γ_max, and the minimum surface area A _min were obtained. As expected, for one homologous series, a decrease in the cmc and an increase in Γ_max was observed with increasing alkyl chain length. For two surfactants of the same alkyl chain length, the cmc values of the C _n DEPO surfactants are approximately two times lower than those of the C _n DMPO surfactants. However, the Γ_max values of C _n DEPO are lower than those of C _n DMPO as two ethyl chains are sterically more demanding than two methyl chains. In addition to the adsorption properties, the location of the miscibility gap as a function of the alkyl chain length and the head group size was studied. Its location depends on the total number of carbon atoms and not primarily on the length of the main alkyl chain. This observation reflects the decreasing water solubility which can be tuned by increasing the length of either the main alkyl chain or of the shorter head group chains.     

Synthesis and Structural Analysis of Co–Zn–Cd Ferrite by Williamson–Hall and Size–Strain Plot Methods

The work aimed at studying the structural properties of Cd-doped cobalt zinc ferrite (Co_0.5Zn_0.5Cd_0.2Fe_1.8O₄) prepared by simple, low-cost solid-state reaction method and characterized by XRD techniques. The X-ray analysis confirms the formation of ferrite particles with a cubic spinel structure. Crystallite size D, lattice constant a, micro strain ε, X-ray density Δ_X, dislocation density ρ _D , hopping lengths (L_A and L_B), bond lengths (A–O and B–O), ionic radii (r_A and r_B), texture coefficients [TC(hkl)], and mechanical properties are also reported.