The process of carbonization followed by a high-temperature halogenation removal of radionuclides is a promising approach to convert low-radioactivity spent ion-exchange (IE) resins into freereleasable non-radioactive waste. The first step of this process is to convert spent ion-exchange resins into the carbon granules that are stable under high-temperature and corrosive-gas flowing conditions. This study investigated the kinetics of carbonization of cation exchange resin (CER) and the changes in structures during the course of carbonization to 1,273 K. Both of model-free and modelfitted kinetic analysis of mixed reactions occurring during the course of carbonization were first conducted based on the non-isothermal TGAs and TGA-FTIR analysis of CER to 1,272 K. The structural changes during the course of carbonization were investigated using the high-resolution FTIR and C-13 NMR of CER samples pyrolyzed to the peak temperature of each reaction steps established by the kinetic analysis. Four individual reaction steps were identified during the course of carbonization to 1,273 K. The first and the third steps were identified as the dehydration and the dissociation of the functional group of —SO3-H+ into SO2 and H2O, respectively. The second and the fourth steps were identified as the cleavage of styrene divinyl benzene copolymer and carbonization of pyrolysis product after the cleavage, respectively. The temperature and time positions of the peaks in the DTG plot are nearly identical to those of the peaks of the Gram Schmidt intensity of FTIR. The structural changes in carbonization identified by high-resolution FTIR and DTG are in agreement with those by C-13 NMR. The results of a detailed examination of the structural changes according to NMR and FTIR were in agreement with the pyrolysis gas evolution characteristics as examined by TGA-FTIR.
Modified pitch A (MPA) and modified pitch B (MPB) were prepared by oxidative polymerization and thermal polycondensation reaction with refined pitch as the raw material, respectively. The toluene soluble components (TS-1 and TS-2) were obtained by solvent extraction from MPA and MPB, separately. The Flynn-Wall-Ozawa method and Kissinger-Akahira- Sunose method were used to calculate the pyrolysis activation energy of TS. The Satava- Sestak method was used to investigate the pyrolysis kinetic parameters of TS. Moreover, the optical microstructure of the thermal conversion products (TS-1-P and TS-2-P) by calcination shows that TS-1-P has more contents of mosaic structure and lower contents of fine fiber structure than TS-2-P. The research result obtained by a combination of X-ray diffraction and the curve-fitting method revealed that the ratios of ordered carbon crystallite (Ig) in TS-1-P and TS-2-P were 0.3793 and 0.4417, respectively. The distributions of carbon crystallite on TS-1-P and TS-2-P were calculated by Raman spectrum and curve-fitting analysis. They show that the thermal conversion product of TS-2 has a better graphite crystallite structure than TS-1.
Microstructural evolution and the intermetallic compound (IMC) growth kinetics in an Au stud bump were studied via isothermal aging at 120, 150, and 180˚C for 300hrs. The AlAu4 phase was observed in an Al pad/Au stud interface, and its thickness was kept constant during the aging treatment. AuSn, AuSn2, and AuSn4 phases formed at interface between the Au stud and Sn. AuSn2, AuSn2/AuSn4, and AuSn phases dominantly grew as the aging time increased at 120˚C, 150˚C, and 180˚C, respectively, while (Au,Cu)6Sn5/Cu3Sn phases formed at Sn/Cu interface with a negligible growth rate. Kirkendall voids formed at AlAu4/Au, Au/Au-Sn IMC, and Cu3Sn/Cu interfaces and propagated continuously as the time increased. The apparent activation energy for the overall growth of the Au-Sn IMC was estimated to be 1.04 eV.
As a part of enhancing the performance of wood-plastic composites (WPC), polypropylene (PP)/ nanoclay (NC)/ wood flour (WF) nanocomposites were prepared using melt blending and injection molding process to evaluate their thermal stability. Thermogravimetric analysis (TGA) was employed to investigate thermal degradation kinetics of the nanocomposites both dynamic and isothermal conditions. Dynamic scans of the TGA showed an increased thermal stability of the nanocomposites at moderate wood flour concentrations (up to 20 phr, percentage based on hundred percent resin) while it decreased with the addition of 30 phr wood flour. The activation energy (Ea) of thermal degradation of nanocomposites increased when nanoclay was added and the concentration of wood flour increased. Different equations were used to evaluate isothermal degradation kinetics using the rate of thermal degradation of the composites, expressed as weight loss (%) from their isothermal TGA curves. Degradation occurred at faster rate in the initial stages of about 60 min., and then proceeded in a gradual manner. However, nanocomposites with wood flour of 30 phr heated at 300℃ showed a drastic difference in their degradation behavior, and reached almost a complete decomposition after 40 min. of the isothermal heating. The degree of decomposition was greater at higher temperatures, and the residual weight of isothermal degradation of nanocomposites greatly varied from about 10 to 90%, depending on isothermal temperatures. The isothermal degradation of nanocomposites also increased their thermal stability with the addition of 1 phr nanoclay and of wood flour up to 20 phr. But, the degradation of PP100/NC1/MAPP3/WF30 nanocomposites with 30 phr wood flour occurs at a faster rate compared to those of the others, indicating a decrease in their thermal stability.