• Korea-Australia Rheology Journal
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• v.14 no.3
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• pp.129-138
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• 2002

A cationic surfactant, cetyltrimethylammonium $\rho$-toluenesufonate (CTA$\rho$TS), forms long threadlike micelles in aqueous solution. The threadlike micelles make concentrated entanglement networks, so that the solution shows pronounced viscoelastic behavior as concentrated polymer systems do. However, a mechanism for a process responsible for the longest relaxation time of the threadlike micellar system is different from that of semi-dilute to concentrated polymer systems. The threadlike micellar system exhibits unique viscoelasticity described by a Maxwell model. The longest relaxation time of the threadlike micellar system is not a function of the concentration of CTA$\rho$TS, but changes with that of $\rho$-toluenesufonate ($\rho$$TS^{-}$) ions in the bulk aqueous phase supplied by adding sodium $\rho$-toluenesulfonate (NapTS). The rates of molecular motions in the threadlike micelles are not influenced by the concentration of $\rho$$TS^{-}$ anions, therefore, molecular motions in the threadlike micelles (micro-dynamics) are independent of the longest relaxation mechanism (macro-dynamics). A nonionic surfactant, oleyldimethylamineoxide (ODAO), forms long threadlike micelles in aqueous solution without any additives. The aqueous threadlike micellar system of ODAO also shows Maxwell type viscoelastic behavior. However, the relaxation mechanism for the longest relaxation process in the system should be different from that in the threadlike micellar systems of CTA$\rho$TS, since the system of ODAO does not contain additive anions. Because increase in the average degree of protonation of head groups of ODAO molecules in micelles due to adding hydrogen bromide causes the relaxation time remarkably longer, changes in micro-structure and micro-dynamics in the threadlike micelle are closely related to macro-dynamics in contrast with the threadlike micellar system of CTA$\rho$TS.

• Macromolecular Research
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• v.17 no.10
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• pp.785-790
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• 2009

In this paper, the relaxation behavior of the regenerated silk fibroin (SF) films was investigated using dielectric thermal analysis (DETA), and compared with the dynamic mechanical behavior obtained from dynamic mechanical thermal analysis (DMTA), in order to gain a better understanding of the characteristics of dielectric behavior of SF film and identify the differences between the two analyses. Compared to DMTA, DETA exhibited a higher sensitivity on the molecular relaxation behaviors at low temperature ranges that showed a high $\gamma$-relaxation peak intensity without noise. However, it was not effective to examine the relaxation behaviors at high temperatures such as $\alpha-$ and ${\alpha}_c$-relaxations that showed a shoulder peak shape. On the contrary, DMTA provided more information regarding the relaxation behaviors at high temperatures, by exhibiting the changes in width, intensity and temperature shift of the $\alpha$-relaxation peak according to various crystallinities. Conclusively, DETA and DMTA can be utilized in a complementary manner to study the relaxation behavior of SF over a wide temperature range, due to the different sensitivity of each technique at different temperatures.

• Korea-Australia Rheology Journal
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• v.21 no.4
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• pp.235-244
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• 2009

Miscible polymer blends still have heterogeneity in their component chain concentration in the segmental length scale because of the chain connectivity (that results in the self-concentration of the segments of respective chains) as well as the dynamic fluctuation over various length scales. As a result, the blend components feel different dynamic environments to exhibit different temperature dependence in their segmental relaxation rates. This type of dynamic heterogeneity often results in a broad glass transition (sometimes seen as two separate transitions), a broad distribution of the local (segmental) relaxation modes, and the thermo-rheological complexity of this distribution. Furthermore, the dynamic heterogeneity also affects the global dynamics in the miscible blends if the component chains therein have a large dynamic asymmetry. Thus, the superficially simple miscible blends exhibit interesting dynamic behavior. This article gives a brief summary of the features of the segmental and global dynamics in those blends.

• Proceedings of the Korea Society for Energy Engineering kosee Conference
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• 1993.05a
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• pp.126-131
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• 1993

Differential Scanning Calorimetry (DSC) and solvent swelling technique have been applied for identifying physical transition temperatures in the macromolecular structure of coals. The transition processes seem to be associated with physical relaxation of the coal structure and are irreversible processes. In Pittsburgh No. 8 high volatile bituminous (hvb) coat one physical transition was noted at 250-30$0^{\circ}C$ (at 8$^{\circ}C$/min) without any significant accompanying weight loss. Coals of higher rank than high volatile bituminous, i.e., Upper Freeport medium volatile bituminous (mvb) and Pocahontas No.3 low volatile bituminous (lvb) coals, exhibit structural relaxation just before the major thermal decomposition process and a sharp increase in solvent swellability accompanies this relaxation. In the case of both the Pittsburgh No.8 and the Upper Freeport coat structural relaxations at around 36$0^{\circ}C$ seem to coincide with release of "guest molecules".les".uot;.

• Macromolecular Research
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• v.14 no.4
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• pp.416-423
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• 2006

The dynamic mechanical thermal properties of poly(hexamethylene terephthalate) (PHT), poly(1,4-cyclohexylenedimethylene terephthalate) (PCT) and their P(HT-co-CT) random copolymers in the amorphous state were examined as a function of temperature and frequency. All the samples exhibited two main relaxation processes in the plot of tan ${\delta}$ versus temperature: the primary ${\alpha}$-relaxation associated with the glass transition and the secondary ${\beta}$-relaxation attributed to the local segmental motions of mostly cyclohexylene rings for PCT and to cooperative motions of methylene, carboxyl, and phenylene groups for PHT. Both ${\alpha}$- and ${\beta}$-relaxation temperatures increased with increasing CT content. The activation energy of the ${\alpha}$-relaxation increased with increasing CT content, whereas that of the ${\beta}$-relaxation decreased. The sub-glassy secondary ${\beta}$-relaxation processes of PCT and PHT were investigated in terms of the cooperativity of main-chain segmental motions.

• Macromolecular Research
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• v.12 no.6
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• pp.559-563
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• 2004

Both the ultrasonic velocity at 3 MHz and the absorption coefficient in the frequency range from 0.2 to 2 MHz were measured for aqueous solutions of poly(sodium 4-styrenesulfonate) over the concentration range from 5 to $25\%$ (by weight). The pulse echo overlap method was employed to measure the ultrasonic velocity over the temperature range from 10 to $90^{\circ}C;$ the high-Q ultrasonic resonator method was used for the measurement of the absorption coefficient at $20^{\circ}C.$ The velocities exhibited their maximum values at ca. 55, 59, 63, 67, and $71^{\circ}C.$ for the 25, 20, 15, 10, and $5\%$ solutions, respectively. The velocity increased with respect to the poly(sodium 4-styrene-sulfonate) concentration at a given temperature. A study of the concentration dependence of the both the relaxation frequency and amplitude indicated that the relaxation at ca. 200 kHz is related to structural fluctuations of the polymer molecules, such as the segmental motions of the polymer chains and that the relaxation at ca. 1 MHz resulted from the proton transfer reactions of the oxygen sites of $SO_3.$ Both the absorption and the shear viscosity increase upon increasing the polymer concentration, but they decrease upon increasing the temperature.

• Journal of Pharmaceutical Investigation
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• v.19 no.4
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• pp.173-178
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• 1989

Drug release rates from copolymer hydrogels were controlled by their hydrophilic-hydrophobic balances. As a model copolymer hydrogel, poly(acrylamide-co-styrene) was synthesized at different monomer composition. Release mechanisms of propranolol-HCI from the copolymer matrices were investisated. Swelling rates of the copolymer hydrogels retarded as their hydrophobicity increased. Swelling kinetics of the copolymer hydrogels regulated drug release rates via polymer relaxation controlled release mechanisms. Zero order drug release could thus be achieved within certain periods.

• Macromolecular Research
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• v.14 no.6
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• pp.617-623
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• 2006

In order to achieve an oriental lacquer (OL) film with a thick consistency, UV-curable silicone acrylate (SA) was added to OL by a dual curing process. The addition of 5 wt% UV-curable SA to the OL fomulation enabled the preparation via a single drying step of a $77{\mu}m-thick$ film exhibiting excellent surface properties. FTIR-ATR was used to investigate the effect of UV-curable SA on the behavior of film formation during curing, and the relaxation behavior of the produced films was investigated by dielectric spectroscopy. Dielectric properties were measured in the frequency range $10^{-2}-10^5\;Hz$ at various temperatures between -100 and $200^{\circ}C$. The results demonstrated that OL modified by UV-curable SA has a higher glass transition temperature and stronger secondary relaxation at a lower temperature than the conventional OL system. The OL film modified with UV-curable SA was presumed to be harder at the surface and tougher than conventional OL film.

• Macromolecular Research
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• v.12 no.1
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• pp.141-143
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• 2004

We have investigated the dynamic mechanical behavior of ultra-high molecular weight polyethylene (UHMWPE) irradiated with varying doses of gamma rays. A relaxation peak in the loss factor curve, which has not been reported previously in the literature, is observed at a temperature above the crystal melting temperature. The peak is unique to UHMWPE and appears to be related to the high degree of entanglement. Because the temperature and intensity of the peak are reduced by irradiation-induced chain scission and crosslinking, respectively, we believe that the peak is associated with disentanglement relaxation. The behavior of the storage modulus in the melt state agrees with the classical theory of rubber elasticity.

• Investigative Magnetic Resonance Imaging
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• v.6 no.1
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• pp.35-40
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• 2002

Purpose : To evaluate the NMR relaxation properties and imaging characteristics of tissue-specificity for a newly developed macromolecular MR agent. Materials and methods : Phthalocyanine (PC) was chelated with paramagnetic ion, Mn.2.01g (5.2 mmol) of Phthalocyanine was mixed with 0.37g (1.4 mmol) of Mn chloride at $310^{\circ}C$ for 36 hours and then purified by chromatography (CHC13/CH3OH 98/2 v/v, Rf, 0.76) to obtain 1.04g (46%) of MnPC (molecular weight= 2000d). The $T1}T2$ relaxivity of MnPC was measured in 1.5T(64 MHz) MR using 0.1 mM MnPC. The MR image characteristics of MnPC was evaluated using spin-echo (TR/TE=500/14 msec) and gradient-echo (FLASH) (TR/TE=80/4 msec, flip angle=60) techniques in 1.57 MR scanner. The images of rabbit liver were obtained every 10 minutes up to 4 hours. To study the effect of concentration on image, 20 mM, 50 mM, 100 mM of MnPC were tested. Results : The relaxivities of MnPC at 1.5T(64MHz) were Rl=7.28 $mM^{-1}S^{-1},{\;}R2=55.56mM^{-1}S^{-1}$. Compared to the values of Gd-DTPA (Rl[=4.8 $mM^{-1}S^{-1})$], R2[=5.2 $mM^{-1}S^{-1}])$]), both T1/T2 relaxivities of MnPC were higher than those of Gd-DTPA. For both of SE and FLASH techniques, the contrast enhancement reached maximum at 10 minutes after bolus injection and the enhancement continued for more than 2 hours. When compared with small molecular weight liver agents such as Gd-EOB-DTPA, Gd-BOPTA and MnDPDP, MnPC was characterized by more prolonged enhancement time. The time course of MR images also revealed biliary excretion of MnPC. Conclusion : We developed a new macromolecular MR agent, MnPC. The relaxivities of MnPC were higher than those of small molecular weight Gd-chelate. Hepatic uptake and biliary excretion of MnPC suggests that this agent is a new liver-specific MR agent.