Evaluation of runaway thermal reactions of di-<Emphasis Type="Italic">tert</Emphasis>-butyl peroxide employing calorimetric approaches

Di-tert-butyl peroxide (DTBP) is an organic peroxide (OP) which has widespread use in the various chemical industries. In the past, thermal runaway reactions of OPs have been caused by their general thermal instability or by reactive incompatibility in storage or operation, which can create potential for thermal decomposition reaction. In this study, differential scanning calorimetry was applied to measure the heat of decomposition reactions, which can contribute to understand the reaction characteristics of DTBP. Vent sizing package 2 was also employed to evaluate rates of increase for temperature and pressure in decomposition reactions, and then the thermokinetic parameters of DTBP were estimated. Finally, hazard characteristics of the gassy system containing DTBP, specifically with respect to thermal criticality, were clearly identified.     

Crystallization kinetics and crystallization behavior of syndiotactic polystyrene/clay nanocomposites

We investigated the effects of montmorillonite (clay) on the crystallization kinetics of syndiotactic polystyrene (sPS) with isothermal differential scanning calorimetry analyses. The clay was dispersed into the sPS matrix via melt blending on a scale of 1–2 nm or up to about 100 nm, depending on the surfactant treatment. For a crystallization temperature of 240 °C, the isothermal crystallization data were fitted well with the Avrami crystallization equation. Crystallization data on the kinetic parameters (i.e., the crystallization rate constant, Avrami exponent, clay content, and clay/surfactant cation‐exchange ratio) were also investigated. Experimental results indicated that the crystallization rate constant of the sPS nanocomposite increased with increasing clay content. The clay played a vital role in facilitating the formation on the thermodynamically more favorable all‐β‐form crystal when the sPS was melt‐crystallized. © 2001 John Wiley & Sons, Inc. J Polym Sci Part B: Polym Phys 39: 2097–2107, 2001     

Polymerization and nanocomposites properties of multifunctional methylmethacrylate POSS

Thermally induced polymerization of multifunctional methylmethacrylate POSS (MMA‐POSS) was studied in this work for preparation of polymer/POSS nanocomposites. The polymerization of MMA‐POSS could be promoted with benzoyl peroxide (BPO). Self‐assembly of POSS into a layer‐by‐layer structure in the MMA‐POSS polymer (TP‐MMA‐POSS) is observed with a transmission electron microscopy. An ultra‐low‐k value of about 1.85 is measured with TP‐MMA‐POSS. In addition, polyimide‐POSS nanocomposites are also prepared. These nanocomposites demonstrate good homogeneity and enhanced mechanical properties. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 5157–5166, 2008     

Sorption of low-level radwaste by Spirulina

The feasibility of using spirulina as adsorbent for the treatment of low-level liquid radwaste is studied. The experimental results indicate that the sorption capacity of spirulina is good for the di- and trivalent metallic ions at pH 3-7, but rather poor for the mono-valent metallic ions and non-metallic ions. Some factors affecting metal ion uptake by spirulina such as the content of detergent, sodium ion in liquid radwaste and the stability of spirulina under gamma irradiation were also investigated.     

Phthalocyanines bearing bulky cycloalkylmethyl substituents on non-peripheral sites

Octasubstituted phthalocyanines bearing bulky (cyclopentyl)methyl- and (cyclohexyl)methyl-substituents in non-peripheral positions are prepared and characterised. The synthesis of the precursor phthalonitriles is achieved through nickel-catalysed cross-coupling employing alkylzinc reagents. In the case of the (cyclopentyl)methyl derivative the formal precursor is 5-hexenyl bromide which yields the cyclised material exclusively on formation of the zinc reagent and subsequent cross-coupling.     

Degradation induced variation of LC transition of poly(n-undecyl isocyanate)

The first-order thermal transitions including side-chain melting, crystal-LC, biphasic chimney-like, and isotropic transitions of poly(n-undecyl isocyanate) (PUDIC) were investigated by varying its thermal history. After annealing at 140 °C for different periods of time, it leads to different degrees of backbiting degradation into n-undecyl isocyanurate trimer which behaves as a solvent for the rest non-degraded/rigid PUDIC to change into a lyotropic LC from thermotropic transition. Based on the degree of degradation, various amounts of trimers are present and the PUDIC demonstrates different types of thermal transitions found in DSC thermograms due to the variation of the non-degraded PUDIC concentration in solvent trimers. Finally, a phase diagram includes all types of crystallines, LC, and isotropic regions can be drawn according to the DSC thermograms.     

Comparisons of <Emphasis Type="Italic">n</Emphasis>th-order kinetic algorithms and kinetic model simulation on HMX by DSC tests

Octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine (HMX) is a typical highly energetic material that has been widely used in national defense industries since the 1940s. The aim of this study was to establish a reaction kinetic model on thermal decomposition properties via differential scanning calorimetry (DSC) by well-known kinetic equations and kinetic model simulation. Furthermore, the aim also was to compare kinetic algorithms for thermal decomposition energy parameters under various conditions. Experimental results highly depended on the reliability of the kinetic concept applied, which is essentially defined by the proper choice of a mathematical model of a reaction. In addition, the correctness of the methods is used for kinetics evaluation.     

Effective Synthesis of N‐Arylformamide from α‐Halo‐N‐arylacetamides

A convenient synthetic method for N‐arylformamide derivatives was successfully developed by reacting α‐iodo‐N‐arylacetamides with formamide. This method was applicable to α‐iodo‐N‐arylacetamide substrates bearing electron‐donating or electron‐withdrawing groups, N‐(benzo[d][1,3]dioxol‐5‐yl)‐2‐iodoacetamide, 2‐iodo‐N‐(pyridin‐2‐yl)acetamide, and 2‐iodo‐N‐(naphthalen‐4‐yl)acetamide to give the corresponding N‐arylformamides in moderate to excellent yields (65–94%). A plausible mechanism was proposed to account for the new transformation.     

Rapid determination of aristolochic acids I and II in herbal products and biological samples by ultra-high-pressure liquid chromatography-tandem mass spectrometry

Aristolochic acids (AAs) are a mixture of structural-related compounds, in which aristolochic acid I (AA I) and aristolochic acid II (AA II) are reported to be correlated with Aristolochic acid nephropathy (AAN). In this work, a rapid and sensitive ultra-high-pressure liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) method was developed to determine AA I and AA II in herbal products and biological fluids. By using gradient elution with a mobile phase composed of a mixture of 10 mM ammonium formate buffer (pH 3.0) and acetonitrile, AAs could be determined within 10 min. Under optimum UHPLC-MS/MS conditions, the limit of detections was 0.14 and 0.26 ng mL⁻¹ for AA I and AA II, respectively. Run-to-run repeatability and intermediate precision of peak area for AA I and AA II were less than 5.74% relative standard deviation (RSD). Accuracy was tested by spiking 10, 100 and 1000 ng mL⁻¹ in rat serum and the recoveries were within 76.5-92.9%. Matrix effects were within 78.8-127.7%. The developed method was successfully applied to determine AA I and AA II in several herbal products and to investigate their pharmacokinetic behavior in female Wister rats. The result shows that the developed UHPLC-MS/MS method is efficient, sensitive, and accurate for the determination of AA I and AA II in herbal products and biological samples.     

Selective extraction of melamine using 11-mercaptoundecanoic acid-capped gold nanoparticles followed by capillary electrophoresis

This study describes the use of 11-mercaptoundecanoic acid-capped gold nanoparticles (MUA-AuNPs) for selective extraction of melamine prior to analysis by capillary electrophoresis with UV detection. The highest degree of melamine-induced aggregation of MUA-AuNPs was found to occur at pH 5.0, indicating that the NP aggregation is mainly because of hydrogen bonding between the carboxylate groups of MUA and the amine groups of melamine. Moreover, the degree of melamine-induced NP aggregation gradually increased when the chain length of the mercaptoalkanoic acid was increased from two to 12 carbon atoms. At pH 5.0, the extraction efficiency of melamine was highly dependent on the concentration of MUA-AuNPs, the concentration of dithiothreitol (DTT), the extraction time between MUA-AuNPs and melamine, and the incubation time between melamine-adsorbed AuNPs and DTT. The separation of the extracted melamine and DTT (releasing agent) was accomplished using a solution of 10 mM phosphate (pH 6.0) containing 1.6% (v/v) poly(diallyldimethylammonium chloride). Under the optimum extraction and separation conditions, the limit of detection at a signal-to-noise ratio of 3 was estimated to be 77 pM for melamine, with linear range of 1-1000 nM. The proposed method was successfully applied to the determination of melamine in tap water and in milk.