연료전지용 프로톤 전도성 고분자로서 분지체 함량이 조절된 부분불소계 Sulfonated poly(arylene ether sulfone) 이오노머 블록공중합체막의 합성 및 특성에 관하여 연구하였다. 분지형태의 부분불소계 블록고분자 전해질막 제조를 위해 설폰화 활성이 높은 단량체, 설폰화 활성이 낮은 단량체 그리고 분지체를 합성하였고, 블록형성을 위해 biphenyl계 올리고머를 합성하였다. 분지체의 양에 따른 막 특성변화를 고찰하기 위해, biphenyl계 올리고머와 sulfonyl계 단량체의 몰 비를 4 : 6으로 고정하고 분지체의 함량을 2 mol%까지 늘려가면서 중부가형태의 열중합을 통하여, 다른 분지체의 함량을 가지는 공중합체를 얻었다(BBC-40Bx). 제조된 분지형태의 공중합체들을 chlorosulfonic acid (CSA)를 사용하여 후설폰화(post-sulfonation)하였다(SBBC-40Bx). 제조된 화합물, 단량체, 분지체 및 중합체들은 1H-NMR, 19F-NMR 및 FT-IR분석을 통하여 성공적으로 합성되었음을 확인하였다. 분지형태의 블록공중합체(SBBC-40Bx)는 분지체의 함량이 증가함에 따라 이온교환능력(IEC), 함수율 및 이온전도도가 증가하는 경향을 보였다.

To manufacture a carbon/carbon composite the coal tar pitch was used as the matrix precursor and the PAN (polyacrylonitrile)-based carbon fiber was used as the reinforcing material to weave 3-directional preform. For pressure carbonization HIP equipment was used to produce a maximum temperature of 1000℃ and a maximum pressure of 100 MPa. The carbonization was induced by altering the dwell temperature between 250℃ and 420℃, which is an ideal temperature for the moderate growth of the mesophase nucleus that forms within the molten pitch during the pressure carbonization process. The application of high pressure during the carbonization process inhibits the mesophase growth and leads to the formation of spherical carbon particles that are approximately 30 nm in size. Most particles were spherical, but some particles were irregularly shaped. The spread of the carbon particles was larger on the surface of the carbon fiber than in the interior of the matrix pocket.

The factors that influence ablation resistance in fiber composites are properties of the reinforced fiber and matrix, plugging quantity of fiber, geometrical arrangement, crack, pore size, and their distributions. To examine ablation resistance according to distribution of crack and pore size that exist in carbon/carbon composites, this study produced various sizes of unit cells of preforms. They were densified using high pressure impregnation and carbonization process. Reinforced fiber is PAN based carbon fiber and composites were heat-treated up to 2800℃. The finally acquired density of carbon/carbon composites reached more than 1.932 g/cm3. The ablation test was performed by a solid propellant rocket engine. The erosion rate of samples is below 0.0286 mm/s. In conclusion, in terms of ablation properties, the higher degree of graphitization is, the more fibers that are arranged vertically to the direction of combustion flame are, and the less interface between reinforced fiber bundle and matrix is, the better ablation resistance is shown.

Multidirectional reinforcement is aimed primarily at overcoming interlaminar weakness, hence a major interest lies in the mechanical properties of multidirectional carbon/carbon composites. Mechanical properties depend on the type of carbon fiber, the size of the fiber bundle, the spacing of the bundles, the angles of the bundles relative to the axes of the block, and matrix formation. In the present studies, PAN based carbon fiber preforms manufactured different size of unit cell have been prepared. Densification of these used high pressure infiltration and carbonization technique with coal tar pitch as matrix precursor was carried out. Scanning electron microscopy has been used to study the fracture behavior of composites. The size of unit cell of the preforms has considerably affected on the flexural properties as well as microstructure of the carbon/carbon composites.

This paper describes the physical properties of filled Nylon6 composites resin with nano-sized carbon black particle and graphite nanofibers prepared by melt extrusion method. In improving adhesions between resin and fillers, the surface of the carbon filler materials were chemically modified by thermo-oxidative treatments and followed by treatments of silane coupling agent. Crystallization temperature and rate of crystallization increased with increases in filler concentration which would act as nuclei for crystallization. The silane treatments on the filler materials showed effect of reduction in crystallization temperature, possibly from enhancement in wetting property of the surface of the filler materials. Percolation transition phenomenon at which the volume resistivity was sharply decreased was observed above 9 wt% of carbon black and above 6 wt% of graphite nanofiber. The graphite nanofibers contributed to more effectively in an increase in electrical conductivity than carbon black did, on the other hand, the silane coupling agent negatively affected to the electrical conductivity due to the insulating property of the silane. Positive temperature coefficient (PTC) phenomenon, was observed as usual in other composites, that is, temperature increase results conductivity increase. The dispersity of the fillers were excellently approached by melt extrusion of co-rotational twin screw type and it could be illustrated by X-ray diffraction and SEM.

In this study, AR (aromatic resin) pitch was employed as the matrix-precursor for carbon/carbon composite because it exhibits much higher coke yield than coal tar pitch. As a result, a fabrication process of carbon/carbon composites can be shortened. It has been known that the pitches may cause swolling problem during the carbonization process. In order to restrain the swelling occurrence, a small quantity of carbon black was added to the AR pitch. Due to addition of carbon black the swelling was decreased largely and the perform can be infiltrated with the AR pitch. The densification efficiency of the performs was compared with various matrix-precursors. The coke yield of matrixprecursors, the morphology and the degree of graphitization of carbon matrix were analyzed.

Chop molding composites and 2D carbon/carbon composites were manufactured by hot press molding method. Phenol resin of novolac type was used for matrix precursor and PAN-based carbon, PAN-based graphite and pitch-based carbon fiber were used for reinforcement and boron oxide was used for oxidation retardant. All of the composites were treated by 2000℃ and 2400℃ graphitization process, respectively. After graphitization process, amount of a boron residue in carbon/carbon composites is much according to irregularity of used raw materials. Under the presence of boron in carbon/carbon composites, catalytic effect of boron was a little at 2000℃ graphitization temperature. However, it was quite at 2400℃ graphitization.

Carbon/carbon composites are ideal candidates for a number of aerospace applications including structural materials for advanced vehicles, leading edges, structures of re-entry and hypersonic vehicles and propulsion systems. One serious defect for such application of the carbon/carbon composites is their poor oxidation resistance in high temperature oxidizing environments. SiC coating was employed to protect the composites from oxidation. It is mechanically and chemically stable under extreme thermal and oxidative environments, provides good adhesion to the substrate, and offers good thermal shock resistance. The SiC layer on the nozzle machined from the carbon/carbon composites was formed by pack-cementation method. Then, erosion characteristic of SiC coated carbon/carbon nozzle was examined by combustion test using a liquid rocket motor. The erosion rates were measured as function of combustion pressure, ratio of oxygen to fuel, combustion time, density of the composites and geometry of reinforced carbon fibre in the composites. The morphology change of the composites after combustion test was investigated using SEM and erosion mechanism also was discussed.

In this study, densified 4D carbon/carbon composites were made from carbon fiber and coal tar pitch through the process of pressure impregnation and carbonization and then followed by carbonization and graphitization. To improve the oxidative resistance of the prepared carbon/carbon composites, the surface of carbon/carbon composites was coated on SiC by the pack cementation method. The SiC coated layer was created by depending on the constitution of pack powder, and reaction time of pack-cementation. The morpology of crystalline and texture of these SiC coated carbon/carbon composites were investigated by XRD, SEM/EDS observation. So the coating mechanism of pack-cementation process was proposed. The oxidative res istance were observed through the air oxidation test, and then the optimal condition of pack cementation was found by them. Besides, the oxidative mechanism of SiC formed was proposed through the observation of SiC coated surface, which was undergone by oxidation test.

4D carbon fiber preforms were manufactured by weaving method and their carbon fiber volume fractions were 50% and 60%. In order to form carbon matrix on the preform, coal tar pitch was used for matrix precursor and high density carbon/carbon composites were obtained by high densification process. In this process, manufacture of high density composites was more effective according to pressure increasement. When densificating the preform of 60% fiber volume fraction with 900 bar, density of the composites reached at 1.90 g/cm3 after three times processing. Degree of pressure in the densification process controls macro pore but it can not affect micro pore. During the carbonization process, micro pore of the preform were filled fully by once or twice densification processing. But micro pore were not filled easily in the repeating process. Therefore, over three times densification processing is the filling micro pore.

The Carbon/Carbon composite was prepared from 3D carbon fiber preform and coal tar pitch as matrix precursor. In order to evaluate of ablative characteristics of the composite, liquid rocket system was employed Kerosene and liquid oxygen was used as propellants, operating at a nominal chamber pressure of 330 psi and a nominal mixture ratio (O/F) of 2.0. The results of an experimental evaluation were that high density composite exhibited high, while low density composites showed low erosion resistance. The erosion rate against heat flux was highly depended on the density of the materials. The morphology of eroded fiber showed differently according to collision angle with heat flux on the composite. The granular matrix which derived from carbonization pressure of 900 bar was more resistance to heat flux than well-developed flow type matrix.

It is well known that the fabrication process of carbon/carbon composites is very complex. Above all, the carbonization process have major effect on the morphology development of carbon matrix. Carbon/carbon composites of 4-directional fiber preform were fabricated using the coal tar based pitch as a matrix precursor in this study. According to carbonization pressure of 1 bar, 100 bar, 600 bar, and 900 bar, morphological changes of cokes and matrix of composites were discussed. As the carbonization pressure increased to 600 bar, the flow pattern morphology of bulk mesophse was well developed. On the contrary, mosaic pattern morphology was found in case of 900 bar of carbonization pressure. It is confirmed that the carbonization pressure have profound effect on the degree of graphitization and crystal size of carbon matrix. Even in the highly densified carbon/carbon composites, large voids were still found in the matrix pocket region.

Carbon fiber was reacted with gaseous silicon monoxide which is produced from pack-powder mixture at elevated temperature. As a result of the reaction, two kinds of SiC fiber were obtained. The first one was SiC fibers which were converted from carbon fiber. The fiber is constituted with polycrystal like fine grains or monolithic crystals that have a size from sub-micron to 10 μm. Their size depends on the temperature during the conversion reaction. The second one was ultra-fine SiC fibers that were found on the surface of the converted SiC fibers. The ultra-fine fibers have diameters from 0.08 to 0.2 μm and their aspect ratio were larger than 100. The chemical composit ion of the ultra-fine fibers was analyzed using an Auger electron spectroscopy. In result, the fibers consist of 51% silicon, 38% carbon and 11% oxygen by weight.