Polyacrylonitrile (PAN) fibers were pre-oxidized in a temperature range of 180-275℃. The effects of positive and negative stretching on the structure and morphology of PAN fiber in the pre-oxidation process were studied by FTIR spectroscopy, XRD, and SEM. Mechanical property changes were also investigated. No changes in the movement and intensity of functional groups of PAN fibers were caused by positive stretching of up to 10% and negative stretching down to -8%. The crystal structure can be affected by the positive stretching and negative stretching. The maximum strength is 479.81 MPa when the stretching is positive, and the maximum strength is 420.55 MPa when the stretching is negative.
PAN precursor fibers were produced via wet-spinning process, and effects of polymerization and spinning processes, especially the stretching process, were investigated on mechanical properties and micro-morphologies of precursor fibers. An increase in molecular weight, dope solid and densification and a decrease in surface defects were possible by controlling polymerization temperature, the number of heating rollers for densification and the jet stretch ratio, which improved the mechanical properties of precursor fibers. The curves for strength, modulus, tensile power and diameter as a function of stretch ratio can be divided into three stages: steady change area, little change area and sudden change area. With the increase of stretch ratio, the fiber diameter became smaller, the degree of crystallization increased and the structure of precursor fibers became compact and homogeneous, which resulted in the increase of strength, modulus and tensile power of precursor fibers. Empirical relationship between fiber strength and stretch ratio was studied by using the sub-cluster statistical theory. It was successfully predicted when the strengths were 0.8 GPa and 1.0 GPa under a certain technical condition, the corresponding stretch ratio of the fiber were 11.16 and 12.83 respectively.
Propellant waste was impregnated on the surface of activated carbon fiber and heat-treated at different temperature to introduce newly developed functional groups on the ACF surface. Functional groups of nitrogen and oxygen such as pyridine, pyridone, pyrrol, lacton and carboxyl were newly introduced on the surface of modified activated carbon fiber. The porosity, specific surface area, and morphology of those modified ACFs were changed as increasing the heat-treated temperature from 200 to 500℃. The optimum heat-treatment temperature was suggested to 500℃, because lower temperature given rise to the decrease of specific surface area and higher temperature resulted in the decrease of weight loss. Propellant waste can be used as an useful surface modifier to porous carbons.
The precipitation polymerization of acrylonitrile (AN) was carried out in a mixture solution of dimethyl sulfoxide (DMSO) and water at 50~65℃ using α,α'-azobisisobutyronitrile (AIBN) as an initiator. The increased molecular weight polyacrylonitrile (PAN) was prepared with increasing the H2O/DMSO ratio from 10/90 to 80/20. The viscosity average molecular weight of H2O/DMSO solvent was 4.4 times larger than that of H2O/DMF solvent, and precipitation polymerization was accelerlated due to the far decreased chain transfer effect of DMSO. Based on the experimental results, the increased PAN molecular weight was regarded as the summation of two mechanisms: i) particle-particle aggregation and ii) particle-radical attachment. The theoretical equation derived from the mechanisms was well coincided with the experimental results showing the linear relationship between the viscosity average molecular weight and the H2O/DMSO ratio.
Henequen fiber was air-stabilized, carbonized, and steam-activated to obtain high surface area activated henequen fiber (AHF). Thermal behavior of henequen fibers has been studied by TGA. The structural morphology and characteristics were observed by SEM and BET surface area measurement. The yield of AHF from natural henequen was in the range of 20~25 wt%. Mesopores (2~2.5 nm) were developed on the AHF as the activation temperature was raised up to 700℃, and the band of mesopore size distribution moved to 15~30 nm when the activation were carried out at 900℃ for 30 min. The specific surface area and the total pore volume were about 1394 m2/g and 1.30 cm3/g, respectively at this activation conditions.
Pitch-based carbon fiber tows were prepared from naphtha cracking bottom oil by reforming and carbonization. The relationship between exothermic heat and carbon contents of the fiber was investigated by changing the carbonization conditions. The carbon contents and the crystallinities of isotropic pitch-based carbon fibers were 86.8~93.8 wt% and 33.7~40.1%, respectively, which were linearly proportional to the increase of carbonization temperature from 700 to 1000℃. The exothermic heat (temperature increase) of fiber tows was measured in a short time, which was also linearly proportional to the increase of carbon contents due to the increase of crystallinity, even though the crystallinity was low. Therefore, the carbon contents or carbonization degree of fibers can rapidly and indirectly be estimated by measuring the surface temperature increase of fibers.
Naphtha Cracking Bottom (NCB) oil was heat reformed at various reforming temperature and time, and the volatile extracts were characterized including yields, molecular weight distributions, and representative compounds. The yield of extract increased as the increase of reforming temperature (360~420℃) and time (1~4 hr). Molecular weight of the as-received NCB oil was under 200, and those of extracts were distributed in the range of 100-250, and far smaller than those of precursor pitches of 380-550. Naphtalene-based compounds were more than 70% in the as-received NCB oil, and most of them were isomers of compounds bonding functional groups, such as methyl (CH3-) and ethyl (C2H5-). When the as-received NCB oil was reformed at 360℃ for 1 hr, the most prominent compound was 1,2-Butadien, 3-phenyl- (24.57%), while naphthalene became main component again as increasing the reforming temperature.
The oxygen and nitrogen enriched activated carbons were obtained from modification of commercial activated carbon by using nitric acid, sodium hydroxide and urea. Zeta-potentials of modified activated carbons were investigated in relation to copper ion adsorption. The structural properties of modified activated carbons were not so much changed, but the zeta-potentials and isoelectric points were considerably changed. The zeta-potential of nitric acid modified activated carbon was the most negative than other activated carbons in the entire pH region, and the pHIEP was shifted from pH 4.8 to 2.6, resulted in the largest copper ion adsorption capacities compare with other activated carbons in the range of pH 3~6.5. In case of urea modified activated carbon, copper ion adsorption was larger than that of the as-received activated carbon from pH 2 to pH 6.5 even though the pHIEP was shifted to pH 6.0, it was due to the coordination process operated between nitrogen functional groups and copper ion. The adsorption capacity of copper ion was much influenced by zeta-potential and pHIEP of carbon adsorbent.
Isotropic pitch-based carbon fiber has been activated by steam diluted in nitrogen in order to characterize the microporosity. Especially, 40 wt% burn-off ACFs were prepared from different conditions to compare the pore structure and size. The ACFs were thinly sliced to investigate the inside pores by TEM and image analyzer. As expected, the adsorption characteristics of these ACFs were quite different from one another because of different pore structure and size. Most pores are not slit-shaped but rather round. Small round micropores become broad and irregular as increasing the activation time and temperature.
Plasma polymerization of allylamine subsequently after plasma pre-treatment was conducted on the activated carbon fibers (ACFs) for the immobilization of amine groups in the surface of ACFs. The change of structural properties of ACFs with respect to different polymerization conditions was investigated through BET method. The change of surface morphologies of ACFs with respect to different plasma polymerization power was also studied through AFM. It was found that the structural properties such as specific surface area and micropore volume could be optimized under certain plasma deposition conditions. It was reckoned that treatment and deposition showed adverse effect on plasma polymerization, in which the former developed the micro-structures of the ACFs and the latter tended to block the micro pores. The Fourier transform infrared spectroscopy (FTIR) revealed that the poly(allylamine) was successfully immobilized on the surface of ACFs and the amount of the deposited polymer layer was related to the plasma polymerization power. SEM results showed that the plasma deposited polymer layer were small and homogenously distributed. The size and the distribution of particles deposited were closely related to the plasma polymerization power, too.
본 연구는 사용 후 핵연료의 금속전환 공정에서 발생되는 폐용융염을 고형화하는 방법으로 GRSS(Gel-Route Slabilization/Solidifcation)개념을 이용한 전처 리법을 제안하였다. Sodium silicate와 H3p04로 구성된 물질계에서는 SiO에 의해 형성되는 반응모듈 내에서 휘발성 핵종은 열적으로 안정한 화합물로 전환된다. 얻어진 생성물은 붕규산 유리매질과의 반응을 통하여 Li는 LiPO 형태로 유지되며 Cs 및 Sr은 유리매질내에 포용될 수 있다. 또한 sodium silicate, HPO 및 ZrCl로 이루어진 물질계를 이용하여 내구성이 우수한 WZP 세라믹 고화매질을 합성하였다. 이상에서 NZP구조가 형성되며, Cs가 Li보다 우선하여 NZP구조를 형성하였다. 이상의 결과로부터, GRSS를 이용한 폐용융염의 전처리는 단순한 공정과 열적 안정성을 통하여 검증된 고화매질로 고형화가 가능토록하는 유효한 접근법이라 할 수 있으며, 수화학적 안정성의 검증을 통하여 ANL의 제올라이트를 이용한 고화법에 대한 대안이 될 것으로 기대된다.
In this work, a nickel metal (Ni) electroplating on the activated carbon fiber (Ni/ACFs) surfaces was carried out to remove the toxic hydrogen chloride (HCl) gas. The surface properties of the treated ACFs were determined by using nitrogen adsorption isotherms at 77 K, SEM, and X-ray diffraction (XRD) measurements. HCl removal efficiency was confirmed by a gas-detecting tube technique. As a result, the nickel metal contents on the ACF surfaces were increased with increasing the plating time. And, it was found that the specific surface area or the micropore volume of the ACFs studied was slightly decreased as increasing the plating time. Whereas, it was revealed that the HCl removal efficiency containing nickel metal showed higher efficiency values than that of untreated ACFs. These results indicated that the presence of nickel metal on the ACF surfaces played an important role in improving the HCl removal over the Ni/ACFs, due to the catalytic reactions between nickel and chlorine.
Thermolysis of Cu(NO3)2·3H2O impregnated activated carbon fiber (ACF) was studied by means of XRD analysis to obtain Cu-impregnated ACF. Cu(NO3)2·3H2O was converted into Cu2O around 230℃. The Cu2O was reduced to Cu at 400℃, resulting in ACF-C(Cu). Some Cu particles have a tendency to aggregate through the heat treatment, resulting in the ununiform distribution in ACF. Catalytic decomposition of NO gas has been performed by Cu-impregnated ACF in a column reactor at 400℃. Initial NO concentration was 1300 ppm diluted in helium gas. NO gas was effectively decomposed by 5~10 wt% Cu-impregnated ACF at 400℃. The concentration of NO was maintained less than 200 ppm for 6 hours in this system. The ACF-C(Cu) deoxidized NO to N2 and was reduced to ACF-C(Cu2O) in the initial stage. The ACF-C(Cu2O) also deoxidized NO to N2 and reduced to ACF-C(CuO). This ACF-C(CuO) was converted again into ACF-C(Cu) by heating. There was no consumption of ACF in mass during thermolysis and catalytic decomposition of NO to N2 by copper. The catalytic decomposition was accelerated with increase of the reaction temperature.
The atmospheric pressure plasma treatments (Ar/O2 and Ar/N2) of activated carbon fibers (ACFs) were carried out to introduce hydrophilic functional groups on carbon surfaces in order to enhance the hydrogen chloride gas (HCl) adsorption. Surface properties of the ACFs were determined by XPS and SEM. N2/77 K adsorption isotherms were investigated by BET and D-R (Dubinin-Radushkevich) plot methods. The HCl removal efficiency was confirmed by HCl detecting tubes (range:1~40 or 40~1000 ppm). As experimental results, it was found that all plasma-treated ACFs showed the decrease in the pore volume, but the HCl removal efficiency showed higher level than that of the untreated ACFs. This result indicated that the plasma treatments led to the conformation of hydrophilic functional groups on the carbon surfaces, resulting in the increase of the interaction between the ACFs and HCl gas.
원자력시설에서 방사성요오드 제거용으로 사용되는 TEDA 첨착활성탄의 고온공정에서치 메틸요오드의 제거성능을 은이온제올라이트(AgX)와 상호 비교하였다. 3-40 온도범위에서 온도에 따른 메틸요오드의 흡착량 및 탈착후 잔존량을 측정한 결과, 비첨착활성탄의 흡착성능은 온도가 증가함에 따라 급격히 감소하지만 TEDA 첨착활성탄의 흡착성능은 10 부근에서도 AgX-10과 거의 유사한 값을 나타내었고, 탈착후 잔존량은 25 까지도 비첨착활성탄에 비하여 매우 높은 값을 유지하였다. 또한 10 이상의 고온공정에서 AgX 및 TEDA 첨착활성탄을 충전한 고정층 파과특성을 상호 비교한 결과 10 이상에서 AgX-10의 메틸요오드 흡착량 및 잔존량은 TEDA 첨착활성탄에 비하여 평균 30%정도 높은 값을 나타내어 고온에서 더 흡착성능이 우수함을 보여주고 있다. 흡착반응 후 생성된 기체의 성분을 분석한 결과를 토대로 AgX-10 흡착제를 충전한 고정층에서 메틸요오드 제거 메카니즘을 제안하였다.
Antibacterial behaviors of PAN-based activated carbon fibers (ACFs) containing silver metal were investigated. The effects of surface and pore structures of the ACFs were studied by N2/77 K adsorption and D-R plot as a function of silver loading content. The antibacterial activities were investigated by a dilution test against Staphylococcus aureus (S. aureus; gram positive) and Klebsiella pnemoniae (K. pnumoniae; gram negative). As experimental results, the ACFs showed some decreases in specific surface areas, micropore volumes, and total pore volume with an increase of silver content. However, the antibacterial activities of the ACFs were strongly increased against S. aureus as well as K. pnumoniae, which could be attributed to the presence of antibacterial metal in the ACFs system.
Based on the previous results of the equilibrium and batch adsorptions, the removal efficiency of the two-step surface-modified activated carbon (2ndAC) for heavy metal ions such as Pb, Cd, and Cr in fixed column was evaluated by comparing with that of the as-received activated carbon (AC) and the first surface-modified activated carbon (1stAC). The order of metal removal efficiency was found as 2ndAC 〉 1stAC 》 AC, and the efficiency of the 2ndAC maintained over 98% from the each metal solution. Increase of the removal efficiency by the second surface modification was contributed to maintain favorable pH condition of bulk solution during adsorption process. The removal of the heavy metals on the 2ndAC was selective with Pb being removed in preference to Cr and Cd in multicomponent solutions and slightly influenced by phenol as the organic material.
The two-step surface modifications of activated carbon was carried out to improve the adsorption capacity of toxic heavy metal ions in liquid phase. Physical and chemical properties of the as-received activated carbon (AC) and two kinds of surface-modified activated carbons (1stAC and 2ndAC) were evaluated through the BET analysis, surface acidity, and oxides measurements. Specific surface area and pore volume did not significantly change, but surface oxide-group remarkably increased by the surface modification. Equilibrium and batch adsorptions of the various metals, such as Pb, Cd, and Cr, using AC, 1stAC, and 2ndAC were performed at initial pH 5. The adsorption capacity and rate of 2ndAC were higher than those of AC and 1stAC. The carboxylic/sodium carboxylate complex groups were developed from the two-step surface modification of activated carbon, which strongly affected the adsorption of metal ions.
The surface treatment of C-type isotropic pitch-based carbon fiber was carried out by anodic oxidation in 5 wt% NH4NO3 electrolyte. The changes of fiber surface and carbon fiber/ABS resin composites were characterized by SEM, XPS and mechanical properties test. The oxygen functional groups on the surface, such as hydroxyl (-C-OH), carboxyl (-COOH) groups etc., increased after oxidation. Tensile strength, flexural strength and modulus of carbon fiber/ABS composites were also enhanced. However, the impact strength decreased with the improvement of the surface adhesion between CF and matrix.
A study on the electrosorption of Co2+ and Sr2+ ions onto a porous activated carbon fiber (ACF) was performed to treat radioactive liquid wastes resulting from chemical or electrochemical decontamination and to regenerate the spent carbon electrode. The result of batch electrosorption experiments showed that applied negative potential increased adsorption kinetics and capacity in comparison with open-circuit potential (OCP) adsorption for Co2+ and Sr2+ ions. The adsorbed Co2+ and Sr2+ ions are released from the carbon fiber by applying a positive potential on the electrode, showing the reversibility of the sorption process. The possibility of application of the electrosorption technique to the separation of radionuclides was examined. The result of a selective removal experiments of a single component from a mixed solution showed that perfect separation of Co2+ and Sr2+ ions was possible by the electrosorption process.