• Bulletin of the Korean Chemical Society
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• v.19 no.8
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• pp.868-874
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• 1998

An equivalent retention has been experimentally observed in thermal field-flow fractionation (ThFFF) for different polymer-solvent systems. It is shown that iso-retention between two sets of polymer-solvent systems can be obtained by adjusting the temperature difference (ΔT) according to the difference in the ratio of ordinary diffusion coefficient to thermal diffusion coefficient. This method uses a compensation of field strength (ΔT) in ThFFF at a fixed condition of cold wall temperature. It is applied for the calculation of molecular weight of polymers based on a calibration run of different standards obtained at an adjusted AT. The polymer standards used in this study are polystyrene (PS), polymethylmethacrylate (PMMA), and polytetrahydrofuran (PTHF). Three carrier solvents, tetrahydrofuran (THF), methylethylketone (MEK) and ethylacetate (ETAc) were employed. Though the accuracy in the calculation of molecular weight is dependent on the difference in the slope of log λ vs. log M which is related to Mark-Houwink constant a, it shows reasonable agreement within about 6% of relative error in molecular weight calculation for the polymer-solvent systems having similar a value.

• Bulletin of the Korean Chemical Society
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• v.21 no.1
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• pp.69-74
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• 2000

Applicability of Thermal field flow fractionation (ThFFF) was investigated for the analysis of masticated natural rubber (NR) adhesives produced bya hot melt mastication process. An optimum ThFFF condition for NR analysis was found by using tetrahydrofuran (THF) as a solvent/carrier and a field-programming. Low flowrate (0.3 mL/min) was used to avoid stopping the flow for the sample relaxation. Measured molecular weight distribution was used to monitor degradation of rubber during the mastication process. Rubber samples collected at three different stages of the mastication process and were analyzed by ThFFF. It was found that in an anaerobic process rubber degradation occurs at the resin-mixing (compounding) zone as well as in the initial break-down zone, while in an aerobic process most of degradation occurs at the initial breakdown zone. It was also found that E-beam radiation on NR causes a slight increase in the NR molecular weight due to the formation of a branched structure.

• Analytical Science and Technology
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• v.6 no.5
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• pp.453-462
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• 1993

The retention behaviors of polystyrenes influenced by mixed solvents are examined in thermal field-flow fractionation(ThFFF). Experimental data are obtained with polystyrene samples of molecular weights of 35,000, 110,000, 200,000 and 470,000 dissolved in organic solvents. The pure and mixed solvents are tetrahydrofuran(THF), chloroform(CHL), cyclohexane(CH), and benzene(BZ), respectively. The values of retention ratio(R) and thermal diffusion coefficient($D_T$) are measured with change of molecular weight and composition of mixed solvents. Atempts are then made to correlate the measured values with various physicochemical parameters of polymers and solvents. Studies suggest that R is significantly increased with the density of solvent and a good correlation is found between them. $D_T$ values decreases in the mixed solvent having has a higher concentration of poor solvent.

• Proceedings of the Membrane Society of Korea Conference
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• 2004.05b
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• pp.192-194
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• 2004

FFF에서 외부장은 시료의 종류에 따라 선택적으로 사용되며, 그 외부장의 종류에 따라 세부기술로 구분되어진다. 원심력(gravitational or centrifugal field)을 외부장으로 사용하는 침강장-흐름분획법(sedimentation FFF)은 지름이 0,05∼1um정도인 콜로이드 입자의 분리에 좋은 방법이다. 온도구배(thermal fradient)를 이용하는 열장-흐름분획법(thermal FFF)은 유기 고분자의 분리 및 고분자의 물성연구에 이용된다.(중략)

• Journal of the Korean Chemical Society
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• v.39 no.11
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• pp.848-855
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• 1995

The influence of gravitational effect on the retention behaviors of polystyrene (PS) and polymethylmethacrylate (PMMA) in flat type thermal field flow fractionation (Thermal FFF) was studied. In the case of downward flow of mobile phase, the gravitational effect acting in the same direction of mobile phase flow increases as the angle of the system from the horizontal line (0˚to 60˚) increases. The decreasement of retention time of PS & PMMA was found. Also, the increasement of dimensionless λ values was found. And the difference in the retention time of PS & PMMA having different molecular weight decreases and also the resolution decreases. In the case of upward flow of mobile phase, the gravitational effect acting in the opposite direction of mobile phase flow increases as the angle of the system from the horizontal line (0˚to 60˚) increases. The increasement of retention time of PS & PMMA was found. Also, the decreasement of dimensionless λ values was found. And the difference in the retention time of PS & PMMA having different molecular weight increases and also the resolution increases.

• Journal of the Korean Chemical Society
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• v.36 no.3
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• pp.419-427
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• 1992

The performance of homemade thermal field-flow fractionation (ThFFF) and the optimization for separation are investigated in terms of retention parameters and selectivity using polystyrene standards. The ribbonlike channel was constructed by sandwiching two Mylar spacers between two highly polished copper bars which serve as channel walls. The hot bar was heated by two electrical cartridge heaters and the cold bar had holes through the entire length, allowing tap water as coolant to enter. It has been observed that the retention of polystyrenes increases as the temperature gradient increases. And the retention decreases as the cold wall temperature increases from 20 to $45^{\circ}C$. In comparison with size exclusion chromatography, ThFFF is more selective but has relatively low efficiency. It has been found that the plate height is proportional to the flow velocity and good estimates of polydispersities can be made directly from the ThFFF data.

• Journal of the Korean Chemical Society
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• v.38 no.6
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• pp.427-434
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• 1994

The retention behaviors of poly(ethylene-co-vinyl acetate)s have been studied by thermal field-flow fractionation(ThFFF) with respect to effective separation and characterization of thermal diffusion coefficients($D_{\tau}$) as one of the physicochemical properties of polymers. The eight copolymers are different in vinyl acetate composition ranging from 25% to 70% and in molecular weight ranging from 110,000 to 285,000. The carrier solvents are THF, toluene and chlorobenzene which have different viscosities and thermal conductivities. It is shown that the retention of a copolymer is dependent on the type of the carrier, the molecular weight and chemical composition of the copolymer. The results show that the retention of a copolymer increases when either vinyl acetate composition or the molecular weight increase. $D_{\tau}$ values measured by experiments vary from 1.36∼5.97 $\cm^2/(s.K)$ depending on the copolymer composition and the type of the carrier solvent. These values increase $(r^2{\geq}0.928)$ with increase of weight % of vinyl acetate. THF is found to be the proper carrier solvent for separation of copolymers employed in this study due to the fact that a $D_{\tau}$ value greatly changes with variation of copolymer composition. From the above results, ThFFF can be used for separation of copolymers with similar molecular sizes but different compositions.

• Analytical Science and Technology
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• v.22 no.4
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• pp.285-292
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• 2009

It has been observed that, after long term storage, some ammunitions are misfired by tamping (combustionstopping) due to aging of the chemicals loaded in the ammunitions. Used in ammunitions are percussion powder which provides the initial energy, igniter which ignites the percussion powder, and a delay system that delays the combustion for a period of time. The percussion powder is loaded first, followed by the igniter and then the delay system, and the ammunitions explode by the energy being transferred in the same order. Tamping occurs by combustion-stopping of the igniter or insufficient energy transfer from the igniter to the delay system or the combustion-stopping of the delay system, which are suspected to be caused by low purity of the components, inappropriate mixing ratio, size distribution of particulate components, type of the binder, blending method, hydrolysis by the humidity penetrated during the long term storage, and chemical changes of the components by high temperature. Goal of this study is to find the causes of the combustion-stopping of the igniter and the delay system of the ammunitions after long term storage. In this study, a method was developed for testing of the combustion-stopping, and the size distributions of the particulate components were analyzed with field-flow fractionation (FFF), and then the mechanism of chemical change during long term storage was investigated by thermal analysis (differential scanning calorimetry), XRD (X-ray diffractometry), and XPS (X-ray photoelectron spectroscopy). For the ignition system, M (metal)-O (oxygen) and M-OH peaks were observed at the oxygen's 1s position in the XPS spectrum. It was also found by XRD that $Fe_3O_4$ was produced. Thus it can be concluded that the combustion-stopping is caused by reduction in energy due to oxidation of the igniter.