Charge Density Analysis of a Pentaborate Ion in an Ammonium Borate: Toward the Understanding of Topological Features in Borate Minerals

Structural and charge density distribution studies have been carried out on a single crystal data of an ammonium borate, [C(10)H(26)N(4)][B(5)O(6)(OH)(4)](2), synthesized by solvothermal method. Further, the experimentally observed geometry is used for the theoretical charge density calculations using the B3LYP/6-31G** level of theory, and the results are compared with the experimental values. Topological analysis of charge density based on the Atoms in Molecules approach for B-O bonds exhibit mixed covalent/ionic character. Detailed analysis of the hydrogen bonds in the crystal structure in the ammonium borate provides insights into the understanding of the reaction pathways that net atomic charges and electrostatic potential isosurfaces also give additional such systems. could result in the formation of borate minerals. The input to evaluate chemical and physical properties in such systems.

Preparation of a thermally sensitive ammonium perchlorate

The effect of ultrasound on the thermal decomposition behaviour of ammonium perchlorate (AP) has been investigated. It was observed that significant changes in the thermal behaviour of A-P, followed using differential thermal analysis and thermogravimetry, was observed when AP was subjected to power ultrasound in water saturated with oxygen-nitrogen mixture. The decomposition temperature of AP was found to have been lowered by nearly 25degreesC. A similar thermal sensitization was observed in AP when subjected to sonication in the presence of transition metal oxides. Kinetic parameters were calculated for AP, modified AP and catalyzed AP decomposition using non-isothermal kinetics. The activation energy for the decomposition of the sonicated AP samples were found to be lower than normal AP.

In-situ measurements of concentration and temperature during transient solidification of aqueous solution of ammonium chloride using laser interferometry

The variation in temperature and concentration plays a crucial role in predicting the final microstructure during solidification of a binary alloy. Most of the experimental techniques used to measure concentration and temperature are intrusive in nature and affect the flow field. In this paper, the main focus is laid on in-situ, non-intrusive, transient measurement of concentration and temperature during the solidification of a binary mixture of aqueous ammonium chloride solution (a metal-analog system) in a top cooled cavity using laser based Mach-Zehnder Interferometric technique. It was found from the interferogram, that the angular deviation of fringe pattern and the total number of fringes exhibit significant sensitivity to refractive index and hence are functions of the local temperature and concentration of the NH4Cl solution inside the cavity. Using the fringe characteristics, calibration curves were established for the range of temperature and concentration levels expected during the solidification process. In the actual solidification experiment, two hypoeutectic solutions (5% and 15% NH4Cl) were chosen. The calibration curves were used to determine the temperature and concentration of the solution inside the cavity during solidification of 5% and 15% NH4Cl solution at different instants of time. The measurement was carried out at a fixed point in the cavity, and the concentration variation with time was recorded as the solid-liquid interface approached the measurement point. The measurement exhibited distinct zones of concentration distribution caused by solute rejection and Rayleigh Benard convection. Further studies involving flow visualization with laser scattering confirmed the Rayleigh Benard convection. Computational modeling was also performed, which corroborated the experimental findings. (C) 2011 Elsevier Ltd. All rights reserved.

Exceptional activity of mesoporous beta-MnO2 in the catalytic thermal sensitization of ammonium perchlorate

Mesoporous beta-MnO2 has been prepared, characterized and demonstrated to possess excellent catalytic activity in the thermal decomposition of ammonium perchlorate. The observed unprecedentedly low decomposition temperatures, fast reaction rates and enhanced heat releases in the catalysed formulations make mesoporous beta-MnO2 promising as a high-performing ballistic modifier in AP-based composite solid rocket propellants.

Surfactant solubility and micellization in ternary eutectic melt (acetamide plus urea plus ammonium nitrate)

Cationic surfactants such as dodecyltrimethylammonium bromide (DTAB), tetradecyltrimehtylammonium bromide (TTAB) and hexadecyltrimethylammonium bromide (HTAB); and anionic surfactants such as sodium decyl sulphate (SDeS), sodium dodecyl sulphate (SDS) and sodium tetradecyl sulphate (STDS) have been used to determine their solubility and micellization in ternary eutectic melt (acetamide + urea + ammonium nitrate) at 50 degrees C. We employed the electrical conductivity and the surface tension measurement techniques to determine the critical micelle concentration (CMC). The deviation in the slope of the specific conductance/surface tension against surfactant concentration plots indicated the aggregations of surfactants and hence, their CMC. CMC decreases with increase of alkyl chain length due to the increased van der Waals forces. The calculated increment in Gibb's energy per methylene group for cationic and anionic surfactants is about -6 kJ mol(-1) and -4 kJ mol(-1) respectively. It is found that, the CMCs of the surfactants in the ternary melt are higher than the CMCs of same surfactants in water (similar to 25 degrees C). (C) 2012 Elsevier B.V. All rights reserved.

Small-Angle Neutron-Scattering Studies of Mixed Micellar Structures Made of Dimeric Surfactants Having Imidazolium and Ammonium Headgroups

Planar imidazolium cation based gemini surfactants 16-Im-n-Im-16], 2Br(-) (where n = 2, 3, 4, 5, 6, 8, 10, and 12), exhibit different morphologies and internal packing arrangements by adopting different supramolecular assemblies in aqueous media depending on their number of spacer methylene units (CH2)(n). Detailed measurements of the small-angle neutron-scattering (SANS) cross sections from different imidazolium-based surfactant micelles in aqueous media (D2O) are reported. The SANS data, containing the information of aggregation behavior of such surfactants in the molecular level, have been analyzed on the basis of the Hayter and Penfold model for the macro ion solution to compute the interparticle structure factor S(Q) taking into account the screened Coulomb interactions between the dimeric surfactant micelles. The characteristic changes in the SANS spectra of the dimeric surfactant with n = 4 due to variation of temperature have also been investigated. These data are then compared with the SANS characterization data of the corresponding gemini micelles containing tetrahedral ammonium ion based polar headgroups. The critical micellar concentration of each surfactant micelle (cmc) has been determined using pyrene as an extrinsic fluorescence probe. The variation of cmc as a function of spacer chain length has been explained in terms of conformational variation and progressive looping of the spacer into the micellar interior upon increasing the n values. Small-angle neutron-scattering (SANS) cross sections from different mixed micelles composed of surfactants with ammonium headgroups, 16-A(0), 16-Am-n-Am-16], 2Br(-) (where n = 4), 16-I-0, and 16-Im-n-Im-16], 2Br(-) (where n = 4), in aqueous media (D2O) have also been analyzed. The aggregate composition matches with that predicted from the ideal mixing model.

Silicon surface texturing with a combination of potassium hydroxide and tetra-methyl ammonium hydroxide etching

A two step silicon surface texturing, consisting of potassium hydroxide (KOH) etching followed by tetra-methyl ammonium hydroxide etching is presented. This combined texturing results in 13.8% reflectivity at 600 nm compared to 16.1% reflectivity for KOH etching due to the modification of microstructure of etched pyramids. This combined etching also results in significantly lower flat-band voltage (V-FB) (-0.19V compared to -1.3 V) and interface trap density (D-it) (2.13 x 10(12) cm(-2) eV(-1) compared to 3.2 x 10(12) cm(-2) eV(-1)). (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4776733]

Binding of carboxylatopillar5]arene with alkyl and aryl ammonium salts in aqueous medium

The complex formation of alkyl ammonium salts by water-soluble carboxylatopillar5] arene (CP5A) in aqueous medium is reported. p-Xylene diammonium salt and a series of secondary alkyl ammonium salts with various alkyl groups have been prepared and investigated for complex formation. All the ammonium salts exhibit strong host-guest complexation with CP5A under neutral aqueous conditions. H-1 NMR, H-1 DOSY and 2D NOESY NMR experiments have been performed to characterize these inclusion complexes. In this study, the hydrophobic and electrostatic interactions govern the complex formation leading to the formation of pseudorotaxane species. Five pseudo2] rotaxanes and one pseudo3] rotaxane were obtained whose association constant values and stoichiometry were evaluated by an NMR titration method. The results indicate the use of ammonium salts as new complimentary synthons for CP5A in aqueous medium, adding to the repertoire of existing recognition motifs such as paraquat and 1,4-bis(pyridinium) derivatives.

Surface modification of mild steel by a self-assembled cetyl-trimethyl ammonium bromide (CTAB) monolayer: Evaluation of its corrosion protection property

The surface of mild steel was modified by generating cetyl-trimethyl ammonium bromide (CTAB) self-assembled monolayer (SAM) to enhance the corrosion resistance property. The experimental parameters (pH and time) for SAM generation were optimized. The modified surface was characterized by infrared reflection absorption spectroscopy (IRRAS) and contact angle measurements. The SAM generated in 1 mM solution of CTAB at pH 2.5 for 2 h showed a regimented monolayer. Polarization and electrochemical impedance spectroscopic (EIS) studies demonstrated a significant enhancement in the corrosion resistance property of the SAM protected steel in both 1 M HCl and 3.5% NaCl solution. The CTAB SAM surface substantially reduced the corrosion rate by approximately 4 times in 1 M HCl and 1.5 times in 3.5% NaCl media as compared to bare steel. Scanning electron microscopy images confirmed the formation of lesser amounts of corrosion products on the SAM protected surface. (C) 2015 Elsevier B.V. All rights reserved.

Variable-Temperature EPR and Transport Studies on Poly(4,4'-methylenedianiline): Evidence for Bipolarons

The correlation between magnetic and transport properties is examined by studying poly(4,4'-methylenedianiline)(PMDA) salts and their bases using EPR and conductivity measurements. Five different PMDA salts (doped polymers)were prepared by chemical polymerization of 4,4'-methylenedianiline using different protonic acids. The PMDA bases were obtained by dedoping the salts using ammonium hydroxide. Ambient temperature electrical conductivity measurements show evidence for the doped PMDA system to be highly disordered. The EPR spectra of the samples were recorded in the range 20-200 "C, and the results were analyzed on the basis of the polaron-bipolaron model, which is typical of nondegenerate systems. Both PMDA salts and their bases consist of self-trapped, highly mobile polarons or radical cations. EPR studies on PMDA salts show evidence for the presence of thermally activated and temperature independent (or Pauli type) paramagnetism while the bases show thermally activated, Pauli and Curie-Weiss types of paramagnetism. The paramagnetism arises due to polarons.It is proposed that charge transport takes place through both polarons and bipolarons.

Ultrasonic Degradation of Poly(acrylic acid)

The ultrasonic degradation of poly(acrylic acid), a water-soluble polymer, was studied in the presence of persulfates at different temperatures in binary solvent Mixtures of methanol and water. The degraded samples were analyzed by gel permeation chromatography for the time evolution of the molecular weight distributions. A continuous distribution kinetics model based on midpoint chain scission was developed, and the degradation rate coefficients were determined. The decline in the rate of degradation of poly(acrylic acid) with increasing temperature and with an increment in the methanol content in the binary solvent mixture of methanol and water was attributed to the increased vapor pressure of the solutions. The experimental data showed an augmentation of the degradation rate of the polymer with increasing oxidizing agent (persulfate) concentrations. Different concentrations of three persulfates-potassium persulfate, ammonium persulfate, and sodium persulfate-were used. It was found that the ratio of the polymer degradation rate coefficient to the dissociation rate constant of the persulfate was constant. This implies that the ultrasonic degradation rate of poly(acrylic acid) can be determined a priori in the presence of any initiator.

A rapid and highly selective method for the estimation of pyro-,tri- and orthophosphates

A rapid, highly selective and simple method has been developed for the quantitative determination of pyro-, tri- and orthophosphates. The method is based on the formation of a solid complex of bis(ethylenediamine)cobalt(III) species with pyrophosphate at pH 4.2-4.3, with triphosphate at pH 2.0-2.1 and with orthophosphate at pH 8.2-8.6. The proposed method for pyro- and triphosphates differs from the available method, which is based on the formation of an adduct with tris(ethylenediamine)cobalt(III) species. The complexes have the composition [Co(en)(2)HP2O7]4H(2)O and [Co(en)(2)H2P3O10]2H(2)O, respectively. The precipitation is instantaneous and quantitative under the recommended optimum conditions giving 99.5% gravimetric yield in both cases. There is no interferences from orthophosphate, trimetaphosphate and pyrophosphate species in the triphosphate estimation up to 5% of each component. The efficacy of the method has been established by determining pyrophosphate and triphosphate contents in various matrices. In the case of orthophosphate, the proposed method differs from the available methods such as ammonium phosphomolybdate, vanadophosphomolybdate and quinoline phosphomolybdate, which are based on the formation of a precipitate, followed by either titrimetry or gravimetry. The precipitation is instantaneous and the method is simple. Under the recommended pH and other reaction conditions, gravimetric yields of 99.6-100% are obtainable. The method is applicable to orthophosphoric acid and a variety of phosphate salts.

Rapid Synthesis And Properties Of Fevo4, Alvo4, Yvo4, And Eu3+-Doped Yvo4

Fine particle FeVO4, AIVO4, YVO4 and Yo.95Eu0.05VO4 have been prepared by the combustion of aqueous solutions containing corresponding metal nitrate, ammonium metavanadate, ammonium nitrate and 3-methyl-5-pyrazolone.The solutions containing the redox mixtures, when rapidly heated at 370 °C, ignite and undergo self-propagating,gas-producing, exothermic reactions to yield fine particle metal vanadates. Formation of crystalline vanadates was confirmed by powder X-ray diffraction patterns,27A1 nuclear magnetic resonance, IR and fluorescence spectra.

Action of Transition Metal Oxides on Composite Solid Propellants

The catalytic effects of Fe2O3, Ni2O3, MnO2, and Co2O3 transition metal oxides (TMO) on the combustion of polystyrene and carboxyl-terminated polybutadiene were investigated. The order of activity of TMO's was explained by the presence of Co and absence of Fe and Ni in their lattice systems along with a reduced electron-transfer process; in systems which induce the metal ions to enter the lattice, the electron transfer process is much greater. The thermal decomposition of ammonium perchlorate propellants was enhanced to a greater extent by Co2O3 and MnO2 than by Fe2O3 and Ni2O3.