Effect of polymer addition amount and type on thermal decomposition behavior of spray-dried particles comprising ammonium nitrate,potassium nitrate,and polymer

Certain properties of ammonium nitrate (AN), such as high hygroscopicity and the thermal transformation of the crystal structure accompanied by volume changes, pose problems for industrial applications of AN. To solve these problems, we previously prepared AN-based particles by spray-drying. The particles contained potassium nitrate (PN) as a phase stabilizer and a polymer (e.g., PVA, CMCs, and Latex) to produce a moisture-resistant material. Herein, we investigate the thermal decomposition of spray-dried AN/PN/polymer particles by differential scanning calorimetry and Thermogravimetry–Differential thermal analysis. Comparison of the thermal decomposition of AN/PN/polymer materials with different amounts and types of polymers suggested that thermal decomposition at lower temperatures resulted from the reaction of AN with the molten polymer or decomposition products derived from the polymer. Therefore, it can be concluded that the thermal stability of the AN/PN/polymer was exclusively determined by the thermal properties of the polymer components.     

Size-controlled synthesis and characterization of polyvinyl alcohol coated palladium nanoparticles

In order to synthesize stable, catalytically active palladium nanoparticles with low polydispersity, a one-pot synthesis by the facile reduction of palladium chloride with citric acid in an aqueous solution of steric stabilizer polyvinyl alcohol (PVA) has been developed. The resulting nanoparticles are highly water-dispersible, excellent electro-catalysts, and have long shelf life. The palladium nanoparticles have been characterized by physico-chemical, spectroscopic, microscopic, and CV studies. The average size of the nanoparticles can be readily tuned from 8.1 to 53 nm by controlling the extent of reflux for mixtures containing suitable concentrations of metal ion, reducing agent and capping polymer, which also influence the size. Despite the surface-protecting action of PVA, the palladium nanoparticles are electro-catalytically active and exhibit size-dependent electro-catalytic behavior.     

The simulation of the thermal behavior of energetic materials based on DSC and HFC signals

Two small calibre and four medium calibre types of propellants were investigated non-isothermally (0.25–4K min⁻¹) by differential scanning calorimetry (DSC) in the range of RT-260°C and isothermally (60–100°C) by heat flow calorimetry (HFC). The data obtained from both techniques were used for the calculation and comparison of the kinetic parameters of the decomposition process. The application of HFC allowed to determine the kinetic parameters of the very early stage of the reaction (reaction progress α below 0.02) what, in turn, made possible the precise prediction of the reaction progress under temperature mode corresponding to real atmospheric changes according to STANAG 2895. In addition, the kinetic parameters obtained from DSC data enabled determination of self-accelerating decomposition temperature (SADT) and comparison of the predicted ignition temperature during slow cook-off with the experimental results. The study contains also the results of the calculation of the time to maximum rate (TMR_ad) of the propellants under adiabatic conditions.     

Green synthesis and characterization of cobalt oxide nanoparticles and its electrocatalytic behavior

Green synthesis of pure cobalt oxide nanoparticles (CoO-NPs) in aqueous medium has been carried out using gelatin. The main advantage of using gelatin as a stabilizing agent is that it provides long-term stability for nanoparticles by preventing particles agglomeration. The particles have been characterized using X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM), energy dispersive X-ray (EADX), and thermogravimetric analysis (TGA). TEM image shows the formation of CoO-NPs with average particle size of 28 nm which agrees well with the XRD data. Cobalt oxide nanoparticles modified carbon paste electrode (CoO-NPs/CPE) displayed excellent electrochemical catalytic activities towards the oxidation of glucose. The electrocatalytic response showed a wide linear range of 7–1000 µM, as well as its experimental limit of detection can be achieved 5.3 µM. The modified electrode for glucose determination is of the property of simple preparation, good stability and high sensitivity.     

Application of ionic liquids as a catalyst in the synthesis of polyvinyl butyral(PVB) polymer

Polyvinyl butyral(PVB) polymer was successfully synthesized using ionic liquid(IL) catalyst. The synthesis of PVB was achieved by acetalization of polyvinyl alcohol(PVA) and butyraldehyde(BA) in the presence of[HMIM]⁺HSO₄^- IL catalyst. The FT-IR, ¹H NMR, DSC, GPC and SEM characterizations were used to analyze the structure and properties of PVB. The effects of the concentration of PVA in water and the number of reuse cycles on the acetalization degree were investigated. The results indicated that the maximum acetalization degree of PVB obtained using[HMIM]⁺HSO₄^- IL catalyst was up to 72%. The comparison of the commercial PVB and the PVB obtained using[HMIM]⁺HSO₄^- IL catalyst showed that the self-made PVB has a larger molecular weight, higher viscosity, and higher acetalization degree than the commercial PVB.     

Facile solid-phase synthesis of the diammoniate of diborane and its thermal decomposition behavior

The recent mechanistic finding of the hydrogen release pathways from ammonia borane (AB) has sparked new interest in the chemistry and properties of the diammoniate of diborane (DADB), an ionic isomer of AB. We herein report a facile one-step solid-phase synthesis route of DADB using inexpensive starting materials. Our study found that mechanically milling a 1?:?1 NaBH(4)/NH(4)F powder mixture causes the formation of crystalline DADB via a NH(4)BH(4) intermediate. The produced DADB can be readily separated from the sodium fluoride (NaF) by-product by a purification procedure using liquid ammonia at -78 °C. The thermal decomposition behavior of DADB was studied using synchronous thermal analyses, particularly in comparison with AB. It was found that the decomposition steps and products of DADB are similar to those of AB. But meanwhile, DADB exhibits a series of advantages over AB that merit its potential hydrogen storage application, such as lower dehydrogenation temperature, free of foaming and lack of an induction period in the thermal decomposition process. Our study further found that the volatile non-hydrogen products from DADB can be effectively suppressed by milling with MgH(2).     

Triaminoguanidinium dinitramide-calculations, synthesis and characterization of a promising energetic compound

The highly energetic compound 1,3,5-triaminoguanidinium dinitramide (1) was prepared in high yield (82%) according to a new synthesis by the reaction of potassium dinitramide and triaminoguanidinium perchlorate. The heat of formation was calculated in an extensive computational study (CBS-4M). With this the detonation parameters of compound were computed using the EXPLO5 software: D = 8796 m s(-1), p = 299 kbar. In addition, a full characterization of the chemical properties (single X-ray diffraction, IR and Raman spectroscopy, multinuclear NMR spectroscopy, mass spectrometry and elemental analysis) as well as of the energetic characteristics (differential scanning calorimetry, thermal safety calorimetry, impact, friction and electrostatic tests) is given in this work. Due to the high impact (2 J) and friction sensitivity (24 N) several attempts to reduce these sensitivities were performed by the addition of wax. The performance of was tested applying a "Koenen" steel sleeve test resulting in a critical diameter of > or =10 mm.     

The use of advanced calorimetric techniques in polymer synthesis and characterization

Progress in the understanding of polymer synthesis, including the crucial step of initiation and undesired side reactions, and in characterization of polymers, especially their thermal behaviour, are directly related to advances in calorimetric technologies.

In polymer synthesis, since polymerization reactions are highly exothermic, reaction calorimetry (RC) is an appropriate technique for on-line process monitoring. Measurements are non-invasive, rapid, and straightforward. Viscosity increase and fouling at the reactor wall are typical features of many polymerizations. The global heat transfer coefficient, UA, also changes drastically when viscosity increases and affects the accuracy of calorimetric measurements. Our approach was focused on oscillating temperature calorimetry (TOC). Reactions were performed with two different reaction calorimeters, i.e. an isoperibolic calorimeter and a Calvet-type high sensitivity differential calorimeter, respectively. Special attention was paid to the interpretation of the measured signals to obtain reliable calorimetric data. The evolution of heat transfer coefficient was followed by performing two Joule effect calibration experiments, before and after the reaction, and the two values interpolated to obtain the desired profile of UA. A differentiation method based on the convolution of the measured heat flow by the generated one was used for determining the time constants and deconvoluting the measured heat flow.

With respect to polymer characterization, pressure-controlled scanning calorimetry, also called scanning transitiometry, is now a well established technique. The transitiometer was coupled to an ultracryostat to work at low temperature. The assembly was used to follow the pressure effect on phase change phenomena such as fusion/crystallization and glass transition temperature T_g of low molecular weight substances or high molecular weight polymers.     

Heating rate effect on the thermal behavior of ammonium nitrate and its blends with limestone and dolomite

The effect of heating rate on the thermal behavior of ammonium nitrate (AN) and on the kinetic parameters of decomposition of AN and its blends with limestone and dolomite was studied on the basis of commercial fertilizer-grade AN and several Estonian limestone and dolomite samples. Experiments were carried out under dynamic heating conditions up to 900 °C at heating rates of 2, 5, 10 and 20 °C min⁻¹ in a stream of dry air using Setaram Labsys 2000 equipment. For calculation of kinetic parameters, the TG data were processed by differential isoconversional method of Friedman. The variation of the value of activation energy E along the reaction progress α showed a complex character of decomposition of AN—interaction of AN with limestone and dolomite additives with the formation of nitrates as well as decomposition of these nitrates at higher temperatures.     

Novel synthesis of polymer and copolymer nanoparticles by atomized microemulsion technique and its characterization

The present paper relates to the atomized process for the synthesis of nanoparticles of polystyrene (nPS), polyacrylonitrile (nPAN), and poly(styrene/acrylonitrile) (nP[SAN]) copolymers with different monomer ratios and with controlled particle size in the range from 10 to 100 nm. In this process, ammonium persulfate (APS) was used as thermal initiator, along with sodium dodecyl sulfate (SDS) and n‐pentanol (n‐Pt) as surfactant and cosurfactant, respectively. The effect of different parameters on particle size and morphology of polymer nanoparticles has been reported in this work. Transmission electron microscopy (TEM) study showed the changes in particle morphology of pure nPS, nPAN, and their copolymers. Structural property and interaction of PS and PAN were investigated by Fourier transform infrared (FTIR) spectroscopy and X‐ray diffraction (XRD). The effect of particle size and crystalline structure on glass transition temperature (T_g) and melting temperature (T_m) were also investigated by differential scanning calorimetry (DSC). Thermal stability of polymer nanoparticles was studied by thermo gravimetric analyzer (TGA) and it showed that the copolymer nanoparticles of nP[SAN] were more stable with minimum weight loss (W_L). Copyright © 2010 John Wiley & Sons, Ltd.     

Micellar synthesis and characterization of ultradispersed powders of ammonium nitrate

Reverse micelles of oxyethylated nonylphenol (Triton N-42) were used to synthesize ultradispersed powder of ammonium nitrate with the yield 75% and content 79%. Its composition and morphology were examined by colorimetry, IR Fourier spectroscopy, scanning electron microscopy (SEM) and X-ray diffraction analysis (XRD). According to XRD, the sample is stable with time, although it is a mixture of three polymorphic forms of crystal ammonium nitrate — one stable and three metastable forms. The agglomerates consists of 20–50 nm nanoparticles; a part of nanoparticles form filaments of length 0.5–1.5 μm and thickness 25–30 nm, as estimated by SEM.     

Synthesis,characterization, thermal stability and compatibility properties of new energetic polymers

Four new cross-linked polymers poly(vinyl m-nitrobenzene)-polyglycidylazides (PVMNB-GAPs) were successfully synthesized using toluene diisocyanate as the cross-linking agent. Their structure was confirmed by their FTIR, UV–Vis, ¹H and ¹³C NMR spectroscopy. Moreover, the thermal properties of cross-linked polymers were evaluated by DTA, TGA and DSC techniques, which confirmed that synthesized polymers exhibited good resistance to thermal decomposition up to 200°C. In addition, their compatibility with the main energetic components of 2,4,6-trinitrotoluene-based melt-cast explosives were also evaluated by the non-isothermal differential thermal analysis method.     

Dioxidouranium isothiosemicarbazone coordination compounds: synthesis,characterization, crystal structure,and thermal behavior

Five uranium complexes with UO₂L′(solv) formula (L′: prepared by condensation reaction between 2-hydroxyacetophenon S-pentyl isothiosemicarbazone (H₂L) and 5-bromosalicylaldehyde (Sal); solv: ethanol (1), 2-propanol (2), 2-butanol (3), ethylene glycol (4), 1,2-propanediol (5)) were synthesized through template reactions between H₂L, Sal, and UO₂(CH₃COO)₂?2H₂O for 1 and recrystallization of 1 in appropriate solvents for the other complexes. The compounds are characterized by melting point, elemental analyses, FT-IR, ¹H NMR, ¹³C NMR, TGA, and X-ray crystallography. Molecular structures of the obtained crystals, determined by X-ray diffraction analysis, showed that the complexes have distorted pentagonal bipyramidal geometry. In all complexes, the bianionic tetradentate ligand (N₂O₂) with phenolic oxygens (O3, O4), thioamidic and azomethine nitrogen donor atoms is coordinated to the metal center in equatorial positions and the solv molecules occupied the fifth equatorial site and finally linear UO₂ is located in axial position. The thermal behavior of the complexes was studied with TGA and DTG data and the results revealed three weight loss stages. The Coats–Redfern method is used for all degradation steps to determine kinetic parameters.     

Controllable synthesis and characterization of porous polyvinyl alcohol/hydroxyapatite nanocomposite scaffolds via an in situ colloidal technique

During the last decades, there have been several attempts to combine bioactive materials with biocompatible and biodegradable polymers to create nanocomposite scaffolds with excellent biocompatibility, bioactivity, biodegradability and mechanical properties. In this research, the nanocomposite scaffolds with compositions based on PVA and HAp nanoparticles were successfully prepared using colloidal HAp nanoparticles combined with freeze-drying technique for tissue engineering applications. In addition, the effect of the pH value of the reactive solution and different percentages of PVA and HAp on the synthesis of PVA/HAp nanocomposites were investigated. The SEM observations revealed that the prepared scaffolds were porous with three dimensional microstructures, and in vitro experiments with osteoblast cells indicated an appropriate penetration of the cells into the scaffold's pores, and also the continuous increase in cell aggregation on the scaffolds with increase in the incubation time demonstrated the ability of the scaffolds to support cell growth. According to the obtained results, the nanocomposite scaffolds could be considered as highly bioactive and potential bone tissue engineering implants.     

Structure and morphology of nanocomposite films prepared from polyvinyl alcohol and silver nitrate: Influence of thermal treatment

Hybrid organic/inorganic films have been prepared from an aqueous solution of polyvinyl alcohol (PVA) and silver nitrate (AgNO₃). The silver nanoparticles have been generated in the PVA matrix by thermal treatments. The structure and the morphology of the hybrid films have been studied as a function of the silver precursor concentration and of the annealing conditions for a wide range of annealing temperatures. It was shown that in the uncured hybrid film most of the silver ions were initially coordinated with the polymer OH groups to form a chelate structure. A nanostructuration effect leading to the formation of crystalline silver nanoparticles was evidenced for annealing treatments performed at temperatures higher than 90 °C. For a curing temperature equal to 110 °C, the sizes of the formed nanoparticles were only slightly increasing as a function of annealing time and the effect of AgNO₃ complex amount in this curing condition was also significant, but slight. Annealing at a temperature equal to 160 °C thus at a temperature for which a part of the crystalline phase of PVA was melt led to an important increase of the size of the generated metal nanoparticles. The evolution of the morphology was discussed for each curing temperature as a function of the kinetics of the nanostructuration, of the size of the matrix amorphous lamellae and of the polymer chain mobility. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2657–2672, 2007     

Novel (1H-tetrazol-5-yl-NNO-azoxy)furazans and their energetic salts: synthesis,characterization and energetic properties

Six novel energetic furazans containing tetrazol-5-yl-NNO-azoxy moiety were synthesized using (cyano-NNO-azoxy)-furazans as starting compounds. The obtained compounds exhibit high enthalpies of formation (531–792 kcal kg^–1), acceptable densities (1.70–1.76 g cm^–3), good thermal stability (T_onset = 146–199 °C), and, as a result, excellent detonation performance (detonation velocities of 8.61–8.95 km s?1 and detonation pressures of 31.6–36.0 GPa).     

芳酰基硒脲合成及其对O~2清除作用的EPR研究

芳酰基硒脲的合成试剂芳酰基异硒氰酸脂是极不稳定的化合物。通过硒氰化铅在非极性溶剂苯中同芳酰氯反应能简便、稳定和可靠地合成芳酰基异硒氰酸脂、从而与芳胺反应能合成一系列芳酰基硒脲。经EFR 研究其对超氧阴离子自由基O~2具有明显的清除作用。