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  • 1
    ISSN: 1572-8943
    Keywords: epoxy resin ; inorganic polymer glass ; reaction-induced phase separation ; reaction mechanism ; TMDSC ; unsaturated polyester resin
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The benefits of temperature-modulated differential scanning calorimetry to characterize reacting polymers are illustrated for different experimental systems. The effects of combined isothermal and non-isothermal cure paths on (de)vitrification, mobility-restricted reactions, and relaxation during vitrification are discussed for anhydride- and amine-cured epoxies. The simultaneous measurement of heat capacity, heat flow, and heat flow phase provides an excellent tool for mechanistic interpretations. The influence of the metakaolinite particle size on the production of inorganic silicate-metakaolinite polymer glasses is treated as an example. These principles are further illustrated for primary and secondary amine-epoxy step growth reactions, and for styrene-cured unsaturated polyester chain growth reactions with ‘gel effect’. Finally, the effects of isothermal cure and temperature on reaction-induced phase separation in a polyethersulfone modified epoxy-amine system are highlighted.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 59 (2000), S. 305-318 
    ISSN: 1572-8943
    Keywords: autoacceleration ; dynamic rheometry ; gelation ; gel effect ; TMDSC ; unsaturated polyester resin ; vitrification
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The free radical cross-linking copolymerization of an unsaturated polyester resin with styrene is studied in isothermal conditions using temperature modulated differential scanning calorimetry (TMDSC) and dynamic rheometry. The dynamic rheometry measurements show that gelation occurs at a conversion below 5%, while TMDSC measurements show that an important autoacceleration starts near 60% conversion, giving rise to a maximum cure rate closely before the (partial) vitrification of the system near 80%. This indicates that the autoacceleration is not due to the sharp increase in bulk viscosity at gelation, but rather to a change in molecular mobilities at higher conversion.
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  • 3
    Electronic Resource
    Electronic Resource
    Springer
    Journal of thermal analysis and calorimetry 62 (2000), S. 417-427 
    ISSN: 1572-8943
    Keywords: differential scanning calorimetry ; FTIR ; inorganic polymer glasses ; kaolinite ; metakaolinite ; TG
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The degree of dehydroxylation of kaolinite, DTG and DIR, respectively, is characterized by thermogravimetric analysis (TG) and Fourier transform infrared spectroscopy (FTIR). The relation between DTG and DIR based on the infrared absorptions at 3600–3700, 915, 810, and 540 cm−1 is established. Three regions can clearly be distinguished: the dehydroxylation region (DTG〈0.9), the metakaolinite region (0.9〈DTG〈1) and the ‘spinel’ region(DTG=1). The effect of the degree of dehydroxylation of kaolinite on the amount of reactive material is measured by the reaction enthalpy, ΔH, of the low-temperature reaction of the dehydroxylated kaolinite with a potassium silicate solution using differential scanning calorimetry (DSC). |ΔH| increases almost linearly with DTG in the dehydroxylation region. In the metakaolinite region, ΔH and thus the amount of reactive material, becomes constant. |ΔH| is sharply decreasing when metakaolinite transforms into other phases in the ‘spinel’ region. No significant differences in the reactivity of the dehydroxylates is detected with DSC. According to FTIR, the use of partially dehydroxylated kaolinite is not influencing the molecular structure of the low-temperature synthesized aluminosilicates, but residual kaolinite is retrieved as an additive.
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  • 4
    ISSN: 1573-4803
    Source: Springer Online Journal Archives 1860-2000
    Topics: Mechanical Engineering, Materials Science, Production Engineering, Mining and Metallurgy, Traffic Engineering, Precision Mechanics
    Notes: Abstract The low-temperature reaction between an aqueous sodium or potassium silicate solution and metakaolinite yields a solid aluminosilicate. The influence of the molar ratios H2O/R2O (between 6.6 and 21.0) and SiO2/R2O (between 0.0 and 2.3) of the silicate solution (R=Na or K) on the aluminosilicate's production, on the reaction stoichiometry and on the aluminosilicate's molecular structure is studied with differential scanning calorimetry, 27Al and 29Si magic angle spinning nuclear magnetic resonance (MAS NMR), cross-polarization MAS NMR, Fourier transform infrared spectroscopy and X-ray diffractometry. The reaction stoichiometry is determined by a one to one ratio for R/Al. H2O/R2O has no influence on the molecular structure of the aluminosilicate. Aluminium in the aluminosilicate is four-fold coordinated for the whole range of silicate solutions investigated. Moreover, Si and Al are homogeneously distributed and the ratio Al/Si in the aluminosilicate is the same as in the reaction mixture if the stoichiometric one-to-one ratio for R/Al is used. If SiO2/R2O in the Na-silicate solution is equal to or higher than 0.8, the low-temperature reaction yields an amorphous aluminosilicate or “inorganic polymer glass”. For smaller values of SiO2/R2O the Na-aluminosilicates are partially crystalline. Thermomechanical analysis and dynamic mechanical analysis indicate that a variation in the composition of the amorphous aluminosilicates can shift the glass transition over a few hundreds of degrees, with a minimum value of 650°C.
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 363-371 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the Diels-Alder additions of CH2 = CHCN, CH2 = C(CH3) CN, and cis- and trans-CH3CH = CHCN to cyclohexa-1, 3-diene have been studied in the gas phase. The stereochemistry of these reactions is discussed. In terms of a biradical mechanism, a minimum value of 4.1 ± 0.8 kcal mol-1 for the stabilizing effect of a CN group vis-à-vis a methyl group is shown to fit the experimental activation energies.
    Additional Material: 3 Ill.
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 19 (1987), S. 1063-1072 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the Diels-Alder additions of CH2 — CHCHO, CH2—C(CH3)CHO, and CH2—CHC(CH3)O to cyclohexa-1,3-diene (CHD) have been studied in the gas phase. The stereochemistry and the mechanism of these reactions are discussed. In contrast with other Diels-Alder additions involving CHD as diene, a biradical mechanism does not fit the experimental results.
    Additional Material: 4 Ill.
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 17 (1985), S. 709-711 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 8
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 28 (1996), S. 755-761 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of C2Cl6 has been studied between 652 and 735 K at pressures ranging from 19 to 50 torr. The observed total pressure- and Cl2 pressure-time curves show S-shapes with an induction period depending on temperature and pressure. Further, the total pressure goes through a maximum to finally reach a lower constant value. These curves are explained in terms of a recently proposed reaction model using a parameter optimization computer program. © 1996 John Wiley & Sons, Inc.
    Additional Material: 5 Ill.
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  • 9
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 9 (1977), S. 283-293 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal reaction of 1,3-butadiene (BD) has been studied between 464 and 557°K at pressures between 49 and 450 torr. The products are 4-vinylcyclohexene (VCH) and cis, cis-cycloocta-1,5-diene (COD), and their formations are second order. The rate constant (in 1/mol · sec) for VCH is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{10} k_{\rm V} = - (24,530 \pm 120)/4.576T + (6.95 \pm 0.05) $$\end{document} and that for COD by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log}_{10} k_{\rm C} = - (28,440 \pm 100)/4.576T + (7.65 \pm 0.04) $$\end{document}The thermal reaction of COD has also been studied. The temperature was varied from 505 to 586°K and the pressure from 15 to 51 torr. The rate constants (in sec-1) for the formations of VCH and BD are given by \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{l} {\rm log}_{10} k_{{\rm VCH}} = - (51,780 \pm 120)/4.576T + (15.34 \pm 0.05) \\ {\rm log}_{10} k_{{\rm BD}} = - (56,380 \pm 100)/4.576T + (16.46 \pm 0.04) \\ \end{array} $$\end{document}A biradical mechanism seems to fit these results. The heat of formation and the entropy of COD are estimated.
    Additional Material: 4 Ill.
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  • 10
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 10 (1978), S. 1183-1187 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
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