DSC combined with chemiluminescence for studying polymer oxidation

The oxidation of (Ti,W)C ceramics have been studied as a part of the program to investigate of properties of powder materials. Thermogravimetry, derivative thermogravimetry (TG-DTG), and differential thermal analysis DSC have been used in the non-isothermal study of powder oxidation (Ti,W)C in dry air atmosphere. The powder of crystalline carbide cermets with a ratio of W:Ti equals 0.3 was used in this study. The diagrams were recorded on a sample mass 3.42 mg on the Setaram apparatus in temperatures ranging from 25 to 1000°C. Seven different heating rates were used. The analytical techniques SEM, WDX, EDX and XRD were used in the research. The kinetics of the oxidation process was followed by the integral method by applying the Coats-Redfern's approximation. The kinetic models of particular stages of (Ti,W)C oxidation were evaluated from the dynamic mass losses data. The values of apparent activation energy E and the pre-exponential factor A of each stage of the oxidation were calculated. This revised version was published online in July 2006 with corrections to the Cover Date.     

Eine Ab?nderung der Kjeldahlschen Stickstoffbestimmungsmethode

Ohne Zusammenfassung     

Alkohole

Analytical and Bioanalytical Chemistry -     

Multi-beam second-harmonic generation in beta barium borate with a spatial light modulator and application to internal structuring in poly(methyl methacrylate)

Parallel beam frequency doubling of 170 fs, NIR pulses is demonstrated by placing a thin beta barium borate (BBO) nonlinear crystal after a spatial light modulator. Computer-generated holograms applied to the spatial light modulator create 18 parallel diffracted beams at the fundamental wavelength λ=775 nm, then frequency doubled to λ=387 nm and focussed inside the poly(methyl methacrylate) (PMMA) substrate for refractive index structuring. This procedure, demonstrated for the first time in PMMA, requires careful attention to phase matching of multiple beams and opens up dynamic parallel processing at UV wavelengths where nematic liquid crystal devices are more sensitive to optical damage. By overlapping filamentary modifications, an efficient, stable volume phase grating with dimensions 5×5×2.0 mm³ and pitch Λ=15 μm was fabricated in 18 minutes and reached a first-order diffraction efficiency of 70 % at the Bragg angle.     

Accelerating effect of poly(methyl methacrylate) on rubber oxidation, Part 1: A chemiluminescence study

The oxidative stability of blends of poly(methyl methacrylate) (PMMA) with four types of rubber, poly(ethylene-stat-propylene-stat-5-methylene-2-norbornene) (EPDM), poly(ethylene-stat-vinyl acetate) (EVA), dicarboxy terminated poly(acrylonitrile-stat-butadiene) (NBR) and poly(1,3-butadiene-stat-styrene) (SBR), has been investigated as models for rubber-toughened PMMA. Chemiluminescence was used to monitor the oxidation of the rubber in the blends, revealing an unexpected accelerating effect of PMMA on the oxidation of all the rubbers investigated. The effect varies according to the type of rubber and the temperature. The thermo-oxidative stability of PMMA has also been found to decrease in the presence of the rubber as proved by thermogravimetry, confirming mutually antagonistic effects of PMMA and rubber in the blend oxidation. On the basis of results from all techniques, including identification of oxidation products by FTIR spectroscopy, a possible mechanism is suggested, involving the formation of mobile radicals in PMMA induced by rubber oxidation. These radicals are suggested to play a crucial role in enhancing rubber phase oxidation.