• Membrane Journal
• /
• v.8 no.1
• /
• pp.1-10
• /
• 1998

액체 상태에서 물질이 확산되는 현상을 자유 부피의 개념으로 해석하고자 하는 노력은 1959년에 Cohen과 Turnbull에 의해서 시작되었다. 그들은 액체의 부피를 두 부분으로 나누었는데, 하나는 분자가 차지하고 있는 점유 부피(Occupied volume)이고, 다른 하나는 자유 부피(Free-volume)로서 무작정한 열적 유동에 의해서 재분배된다. 온도의 변화에 의해 부피가 변하는 것은 이 자유 부피의 변화때문이며, 점유 부피는 온도에는 무관함 것으로 갖주하였다. 분자가 액체 상태에서 이동하려면 이웃에 충분한 크기의 자유 부피 공간이 존재해야한다. 따라서, 분자의 확산은 분자가 이들 자유 부피 공간들로 도약하는 것이다. Cohen-Turnbull의 이론에서는 순수한 액체의 자기 확산 계수(Self-diffusion conefficient)는 자유 부피의 무작정한 유동에 의하여 임계 크기의 공간이 생성되는 확률과 관련이 있다. Cohen-Turnbull 자유 부피 이론은 그 후 많은 사람들에 의해서 수정되었고, 그중에서 현재 가장 널리 사용되는 것은 Fujita의 이론과 Vrentas-Duda의 이론이다. 두 이론 모두 확산 데이터를 correlation하는데는 문제가 없으나, Vrentas-Duda의 이론만이 확산계수를 예측할 수 있는 능력이 있다. 또한, 고분자와 용매의 도약 단위의 몰 질량이 같을때에 Vrentas-Duda의 이론은 Fujita의 이론과 같아지므로, Fujita의 이론은 Vrentas-Duda의 이론의 특수한 경우라고 할 수 있다. 따라서, 본 논문에서는 Vrentas-Duda 자유 부피 이론만을 다루기로 하겠다.

• Membrane Journal
• /
• v.22 no.5
• /
• pp.352-358
• /
• 2012

In this study, we found structure-property relationship for pressure retarded osmosis (PRO) membrane, between BPS-XX and BisA-XX having similar structure but different free volume. And this comparison was subdivided by controlling its sulfonation degree. BPS-XX and BisA-XX were prepared via a polycondensation reaction. The degree of sulfonation were 20 to 60 mol.%. And they were fabricated to membrane. Characteristics were analyzed to verify of free volume. And the results showed that increase of free volume normally lead to increase permeability and decrease selectivity in equivalent molecule structure. Finally, in the permeability-selectivity results, we conclude high permeability and selectivity membrane can be prepared by controlling molecular structure and free volume.

• Journal of the Korean Society of Radiology
• /
• v.6 no.6
• /
• pp.489-493
• /
• 2012

Positron Annihilation Lifetime Spectroscopy is a non-destructive technique to study voids and defects in solids by the measurement of gammas from electron-positron annihilation. In this study, we measured the lifetime of CR, EPDM, NBR, all of which are widely used polymer in various fields. A conventional fast-fast coincidence system in KAERI(Korea Atomic Energy Research Institute) has been used to measure the lifetime spectra, Three lifetime components were analyzed from each lifetime spectra. According to Tao-Eldrup model equation, the size and fraction of free-volume were calculated. Mean radius and free volume fraction of CR, EPDM NBR are $0.1217nm^3$(1.9103%), $0.14780nm^3$(5.3147%), $0.1216nm^3$(2.6381%), respectively. Through these measurements, we identified the feasibility of the PAL system for polymer analysis.

• Membrane Journal
• /
• v.29 no.4
• /
• pp.191-201
• /
• 2019

Before the commercialization of polymeric membranes applicable for industrial application, the homework remains for the high-performance polymers to overcome the practical challenge: long-term stability for prolonged service time. Polymers of intrinsic microporosity (PIMs), exhibiting exceptionally high fractional free volume and high permeability, are susceptible to physical aging where the extra volume created by the inefficient ladder-type packing will lead them from the volumetric equilibrium and reduce the free volume/permeability over time. Here, we will re-examine the physical aging of polymers of intrinsic microporosity, and discuss some of the most prominent attempts to mitigate physical aging in PIMs.

• Journal of the Korean Institute of Gas
• /
• v.5 no.1
• /
• pp.29-36
• /
• 2001

The permeation properties of $O_2\;and\;N_2$ were measured for bromobisphenol A polysulfone(BPSf), bisphenol A trimethylsilylated polysulfone(TMSPSf) and their blend membrane to investigate the structure-properties relationships. BPSf shows relatively high permselectivity. It can be explained that the strong polarity of bromine in BPSf increases chain packing ability. In this case the distance of polymer chains is reduced by increasing of interchain interaction by induced dipole. TMSPSf shows relatively high permeability. The higher value of permeability coefficients for TMSPSf is due to the substitution of very bulky trimethylsilyl groups. The replacement of phenyl hydrogens of bisphenol A polysulfone(PSf) with trimethylsilyl groups results in higher fractional free volume(FFV). In this work, taking into account the complimentary features of BPSf and TMSPSf, BPSf/TMSPSf blend was prepared and the compatibility in mixing are examined. The BPSf/TMSPSf blend shows higher permeability than commercial PSf, with minimum loss of selectivity. The miscibility of the BPSf/TMSPSf blend is confirmed by the single glass transition temperature.

• KSBB Journal
• /
• v.14 no.6
• /
• pp.696-701
• /
• 1999

The enzymatic hydrolysis of Castor oil for the mass production of ricinoleic acid was studied to find out the optimum conditions such as solvents and the weight ratio of substrate to enzyme. Three different lipases were tested for the hydrolysis of castor oil: lipase from Porcine Pancrease(lipsase PP), lipase from Candida cylindracea(lipase CC), lipase from Candida Rugosa(lipase CR). The poor mass transfer in water caused a low degree of hydrolysis of castor oil. To overcome this problem, organic solvents were used. Among organic solvents tested, hydrophobic solvents gave better results of hydrolysis than hydrophilic solvents. Organic solvents also lowered or changed the effect of pH. Isopropyl ether made complete hydrolysis of castor oil. The ratio of water to isopropyl ether and the ratio of weight ratio of lipase to castor oil were important for the hydrolysis of castor oil. At 30$^{\circ}C$ castor oil was completely hydrolyzed by 4 wt% of lipase in the mixture of isopropyl ether and water(1:1 in volume).

• Journal of the Korean Chemical Society
• /
• v.37 no.12
• /
• pp.1003-1009
• /
• 1993

The viscosities of benzene have been determined at several temperatures and pressures to investigate the effect of temperature and pressure on the viscosity of benzene in liquid phase. When a falling ball viscometer with a constant volume contained a given amount of liquid benzene at desired temperatures and pressures, the viscosities of benzene in the viscometer could be evaluated from the measurements of the falling time of a skinker. The variations of the specific volume and the free volume of liquid benzene with temperature and pressure were, from the results, searched out. Finally, the effects of temperature and pressure on the viscosity of benzene were discussed by means of the variations of free volume with temperature and pressure.

• Proceedings of the Computational Structural Engineering Institute Conference
• /
• 2011.04a
• /
• pp.112-115
• /
• 2011

본 연구는 분자동역학 전산모사를 통하여 나일론 6 고분자재료 및 나이론 6 고분자재료를 기지재료로 사용하는 나노복합재에 대하여 인장하중을 부여하고, 인장에 의하여 발생하는 구조적 변화 및 물질의 구조적 특성과 열전도 특성 사이의 상관관계를 규명하였다. 나노복합재의 열전도특성을 변화시키는 주요 인자로는 나노입자, 인장에 의한 고분자 사슬의 배열 변화, 자유부피(free volume)의 변화이다. 고분자 사슬이 열전달 방향으로 배열될 경우 음양자(phonon)의 흐름을 가속화하여 열전도특성이 증가하며, 반면 자유부피의 증가는 음양자의 산란을 증가시켜 열전도특성이 저하된다. 따라서 서로 상반작용을 하는 두 인자가 복합적으로 작용하여 열전도 특성을 결정한다. 인장 하중이 부여됨에 따라 시스템의 열전도특성이 증가하며, 각 시스템의 증가 정도는 시스템의 구조적 특성에 따라 서로 다르다.

• Journal of the Korean Chemical Society
• /
• v.10 no.2
• /
• pp.91-97
• /
• 1966

The partition function for liquid water is developed according to the transient state theory of significant liquid structure proposed by Pak, Ahn and Chang. This theory assumes that the molecules may possess solid-like, transient and gas-like degrees of freedom in liquid state. Although liquid water has several special properties, for example, minimum molar volume at 4^{\circ}C$, the general theory of liquid can be applied successfully. The theoretically calculated values for thermodynamic properties at the liquid temperature range and for the critical properties are in good agreement with the observed values.

• Proceedings of the Korea Air Pollution Research Association Conference
• /
• 2001.11a
• /
• pp.395-396
• /
• 2001

고온의 산업공정에서 발생하는 에어로졸 입자들은 많은 기본입자(primary particle)들로 이루어진 불규칙한 사슬구조를 가진다 (Matsoukas and Friedlander, 1991). 이러한 비구형 프랙탈 입자들의 거동은 구형 입자들과 비교할 때 큰 차이를 보인다. 프랙탈 입자들의 부피는 충돌반경의 거듭제곱으로 나타낼 수 있으며, 프랙탈 차원이라 불리는 그 지수는 1에서 3 사이의 값을 가진다. 자유분자영역에서의 브라운 응집에 대한 해석해는 Lee et al.(1990)에 의해 제시된 바 있으나, 이는 구형입자를 가정한 결과였고, 비구형 프랙탈 입자의 거동을 해석하려 할 때는 이로 인한 오차가 발생하게 된다. (중략)