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Isothermal cure characterization of dicyclopentadiene

The glass transition temperature and conversion

Journal of Thermal Analysis and Calorimetry
Authors:
X. Liu
,
X. Sheng
,
J. Lee
, and
M. Kessler

Abstract  

Conversion (α) and the glass transition temperature (T g) were investigated during the isothermal cure of endo-dicyclopentadiene (DCPD) with a Grubbs catalyst for different temperatures using differential scanning calorimetry. Conversion vs. In (time) data at an arbitrary reference temperature were superposed by horizontal shift and the shift factors were used to calculate an Arrhenius activation energy. Glass transition temperature vs. conversion data fell on a single curve independent of cure temperature, implying that reaction of the norbornene and cyclopentene ring of DCPD proceeds in a sequential fashion. Implications of the isothermal reaction kinetics for self-healing composites are discussed.

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Abstract  

The addition of suitable cross-linking agents with norbornene-based monomers has significant effects on the thermal properties of the resulting polymers formed by olefin metathesis. Ethylidene norbornene (ENB) and endo-dicyclopentadiene (endo-DCPD) were mixed separately with various loadings of three different cross-linking agents and then polymerized with the addition of Grubbs’ catalyst. The polymerization kinetics and resulting glass transition temperature (T g) of the systems were evaluated by differential scanning calorimetry (DSC). The addition of the first cross-linking agent, norbornadiene (CL-1), to both endo-DCPD and ENB resulted in decreasing glass transition temperatures with increasing concentrations. In contrast, the addition of the other two cross-linking agents (CL-2 and CL-3), which were both custom synthesized bifunctional norbornyl systems, to both endo-DCPD and ENB resulted in a monotonic increases in T g with cross-linker concentration. By tailoring the loading of these custom cross-linking agents, the properties of these polymer systems can be controlled for various applications, including self-healing composites.

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Abstract  

Resin injection repair is a common method to repair delamination damage in polymer matrix composites (PMCs). To repair high-temperature PMCs, the resin should have a very low viscosity, yet cure into a compatible adhesive with high temperature stability. Normally, thermosetting polymers with high glass transition temperatures (T g) are made from monomers with high room temperature viscosities. Among the high temperature resins, bisphenol E cyanate ester (BECy, 1,1’-bis(4-cyanatophenyl)ethane), is unique because it has an extremely low viscosity of 0.09–0.12 Pa s at room temperature yet polymerizes as a cross-linked thermoset with a high T g of 274°C. BECy monomer is cured via a trimerization reaction, without volatile products, to form the high T g amorphous network. In this study, the cure kinetics of BECy is investigated by differential scanning calorimetry (DSC). Both dynamic and isothermal experiments were carried out to obtain the kinetic parameters. An autocatalytic model was successfully used to model isothermal curing. The activation energy from the autocatalytic model is 60.3 kJ mol−1 and the total reaction order is about 2.4. The empirical DiBenedetto equation was used to evaluate the relationship between T g and conversion. The activation energy of BECy from the dynamic experiments is 66.7 kJ mol−1 based on Kissinger’s method, while isoconversional analysis shows the activation energy changes as the reaction progresses.

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Abstract  

A radioactive multitracer solution obtained from the nuclear reaction of selenium with 25 MeV/nucleon40Ar ions was applied to the investigation of the trace elements behavior in feces and urine of mouse. The excretion rates of 23 elements, Na, K, Rb, Mg, Ca, Sr, Ga, As, Sc, V, Cr, Mn, Co, Fe, Zn, Y, Zr, Mo, Nb, Tc, Ru, Ag and In were simultaneously detected under strictly identical experimental conditions, in order to clarify the excretion behavior of the elements in mice. Fecal and urinary excretion rates of the elements in mice reached the highest value separately at 48 and 24 hours. The total excretion of Mo, Tc and Co within 96 hours were all larger, more than 60%. Accumulative excretion rates of Ca, Nb, Mg, Sr, V, Sc, Na, Cr, Fe, Ag, Mn and Zr were 60-30%. The total rates of Ru, K, As, Zn, Rb, Y, Ga and In were less than 30%, and low excretion. The main excretion pathway of Mo, Co, Mg, Fe and Ag was through urine, and Na, K, As and Rb were eliminated from the body also in urine. But fecal excretion of Tc, Nb, Sr, Y, Ru, and In were larger than urinary excretion, and Ca, Sc, Mn, Zr, Zn were eliminated from the body in feces.

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Cereal Research Communications
Authors:
H. Yu
,
Y. Yang
,
X.Y. Chen
,
G.X. Lin
,
J.Y. Sheng
,
J.Y. Nie
,
Q.J. Wang
,
E.J. Zhang
,
X.R. Yu
,
Z. Wang
, and
F. Xiong

The waxy wheat shows special starch quality due to high amylopectin content. However, little information is available concerning the development and degradation of amyloplast from waxy wheat endosperm. To address this problem, waxy wheat variety, Yangnuo 1, and a non-waxy wheat variety, Yangmai 13, were chosen to investigate the development and degradation of endosperm amyloplast during wheat caryopsis development and germination stage respectively using histochemical staining and light microscopy. Changes of morphology, the soluble sugar and total starch content were indistinguishable in the process of caryopsis development of two wheat varieties. The developing endosperm of non-waxy was stained blue-black by I2-KI while the endosperm of waxy wheat was stained reddish-brown, but the pericarp of waxy and non-waxy wheat was stained blue-black. In contrast to nonwaxy wheat, endosperm amyloplast of waxy wheat had better development status and higher proportion of small amyloplast. During seed germination many small dissolution pores appeared on the surface of endosperm amyloplast and the pores became bigger and deeper until amyloplast disintegrated. The rate of degradation of waxy wheat endosperm amyloplast was faster than non-waxy wheat. Our results may also be helpful to the use of waxy starch in food and nonfood industry.

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Cereal Research Communications
Authors:
H.Q. Zhao
,
L. Wang
,
J. Hong
,
X.Y. Zhao
,
X.H. Yu
,
L. Sheng
,
C.Z. Hang
,
Y. Zhao
,
A.A. Lin
,
W.H. Si
, and
F.S. Hong

Salt stress impaired Mn imbalance and resulted in accumulation of ROS, and caused oxidative stress to plants. However, very little is known about the oxidative damage of maize roots caused by exposure to a combination of both salt stress and Mn deprivation. Thus the main aim of this study was to determine the effects of a combination of salt stress and Mn deprivation on antioxidative defense system in maize roots. Maize plants were cultivated in Hoagland’s media. They were subjected to 80 mM NaCl administered in the Mn-present Hoagland’s or Mn-deficient Hoagland’s media for 14 days. The findings indicated that the growth and root activity of maize seedlings cultivated in a combination of both salt stress and Mn deprivation were significantly inhibited; the compatible solute accumulation, malondialdehyde, carbonyl, 8-OHdG, and ROS were higher than those of the individual salt stress or Mn deprivation as expected. Nevertheless, the antioxidative enzymes such as superoxide dismutase, ascorbate peroxidase, glutathione reductase, glutathione-S-transferase and antioxidants such as ascorbic acid, glutathione and thiol were lower than those of the individual salt stress or Mn deprivation. In view of the fact that salt stress impaired Mn nutrition of maize seedlings, the findings suggested that Mn deprivation at the cellular level may be a contributory factor to salt-induced oxidative stress and related oxidative damage of maize roots.

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Abstract  

The complex from reaction of neodymium chloride six-hydrate with salicylic acid and 8-hydroxyquinoline, Nd(C7H5O3)2·(C9H6NO), was synthesized and characterized by IR, elemental analysis, molar conductance, and thermogravimatric analysis. The standard molar enthalpies of solution of [NdCl3·6H2O(s)], [2C7H6O3(s)], [C9H7NO(s)] and [Nd(C7H5O3)2·(C9H6NO)(s)] in a mixed solvent of anhydrous ethanol, dimethyl formamide (DMF) and perchloric acid were determined by calorimetry at 298.15 K. Based on Hess’ law, a new chemical cycle was designed, and the enthalpy change of the reaction

\documentclass{aastex} \usepackage{amsbsy} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{bm} \usepackage{mathrsfs} \usepackage{pifont} \usepackage{stmaryrd} \usepackage{textcomp} \usepackage{upgreek} \usepackage{portland,xspace} \usepackage{amsmath,amsxtra} \pagestyle{empty} \DeclareMathSizes{10}{9}{7}{6} \begin{document} $$NdCl_3 \cdot 6H_2 O(s) + 2C_7 H_6 O_3 (s) + C_9 H_7 NO(s) = Nd(C_7 H_5 O_3 )_2 \cdot (C_9 H_6 NO)(s) + 3HCl(g) + 6H_2 O(l)$$ \end{document}
((1)) was determined to be Δr H m Θ=117.89±0.37 kJ mol−1. From data in the literature, through Hess’ law, the standard molar enthalpy of formation of Nd(C7H5O3)2·(C9H7NO)(s) was estimated to be Δf H m Θ[Nd(C7H5O3)2·(C9H6NO)(s), 298.15 K]=−2031.80±8.6 kJ mol−1.

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Present research on prebiotics focuses on either polysaccharides or polyphenols. This study compared the individual and combined impact of polysaccharide, quercetin, and gallic acid (GA) treatment on three human faecal strains. In vitro pure culturing and correlation analysis confirmed that the growth of both beneficial microbe B. longum subsp. longum (0.695, 0.205: R2, slope, respectively) and pathogenic C. perfringens (0.712, 0.085: R2, slope, respectively) increased due to polysaccharide treatment, and only GA treatment would inhibit C. perfringens (0.789, –0.165: R2, slope, respectively) growth. In vivo studies also revealed that genome copies of Bifidobacterium increased and C. perfringens decreased in the faeces, when a blend of the three nutrients rather than single polysaccharide or polyphenols were fed to rats. These data suggested that combined prebiotic treatment improved human faecal strain composition better than single treatment.

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A new, sensitive, and selective high-performance liquid chromatography-tandem mass spectrometric method (HPLC-MS/MS) has been developed for the quantification of six flavonoids (sophoricoside, genistin, genistein, rutin, quercetin, and kaempferol) in rat bile and urine. The sample pretreatment was simple by liquid-liquid extraction. Sulfamethalazole was used as internal standard (IS). During method development, the effect of extraction volume, mobile phase composition, column temperature, and injection volume were varied to optimize sensitivity and achieve a run time as short as possible. Chromatographic separation was accomplished on a C18 column with a simple linear gradient elution within 9 min. Full validation of the assay was in accordance with the requirement of the validation of the method in vivo and implemented including specificity, linearity, accuracy, precision, recovery, and matrix effect. This is the first report on determination of the major flavones in rat bile and urine after oral administration of Fructus Sophorae extract. The method has been used successfully in excretion studies of six major flavonoids in rat bile and urine.

Open access