고분자 전해질 연료전지의 연료에 포함된 일산화탄소의 선택적 산화를 위하여, 귀금속 촉매를 대체하기 위한 CuO-CeO2 복합 산화물 촉매를 졸-겔법과 공침법으로 제조하였다. 졸-겔법으로 촉매 제조 시 Cu/Ce의 비와 가수분해 비를 변화시켰다. 제조한 촉매의 활성은 귀금속 촉매(Pt/γ-Al2O3)와 비교하였다. Cu/Ce의 비를 변화시키면서 제조한 촉매 중 Cu/Ce의 비가 4:16인 촉매가 가장 높은 CO 전환율(90%)과 선택도(60%)를 나타내었다. 촉매의 제조에서 가수분해 비가 증가할수록 촉매 표면적이 증가하였고, 아울러 촉매 활성 또한 증가하였다. 공침법으로 제조한 촉매와 1wt% Pt/γ-Al2O3 촉매의 가장 높은 CO 전환율은 각각 82% 및 81%인 반면, 졸-겔법으로 제조한 촉매의 경우는 90%가 얻어졌다. 이는 졸-겔법으로 제조한 촉매가 공침법으로 제조한 촉매나 귀금속 촉매보다 더 높은 촉매활성을 보임을 의미한다. CO-TPD 실험을 통하여, 낮은 온도(140℃)에서 CO를 탈착하는 촉매가 본 반응에서 더 높은 촉매활성을 보임을 알 수 있었다.

Methanol was directly produced by the partial oxidation of methane with four-component mixed oxide catalysts. Four-component(Mo-Bi-Cr-Si) mixed oxide catalysts were prepared by the co-precipitation and sol-gel methods. The catalyst prepared by the sol-gel method showed about eleven times higher surface area than that prepared by the co-precipitation method. From the O2-TPD experiment of the prepared catalysts, it was proven that there exists two types of oxygen species, and the oxygen species that participates in the partial oxidation reaction is the lattice oxygen desorbing around 750℃. The optimum reaction condition for methanol production was 420°C, 50 bar, flow rate of 115 mL/min, and CH4/O2 ratio of 10/1.5, providing methane conversion and methanol selectivity of 3.2 and 26.7%, respectively.

페롭스카이트 촉매와 Mo, Bi를 기본으로 하는 복합 산화물 촉매를 이용하여 천연가스의 주성분인 메탄의 부분산화를 통하여 메탄올을 직접 합성하였다. 페롭스카이트(ABO₃) 촉매는 A 및 B site 성분을 변화시키면서 사과산법으로 제조하였으며, Mo, Bi를 기본으로 하는 3성분계 복합 산화물 촉매는 공침법으로 제조하여 반응특성을 살펴보았다. 페롭스카이트 촉매에서 A site에 알칼리 금속인 Sr을, B site에 전이금속인 Cr을 도입한 SrCrO₃ 촉매가 400℃에서 메탄올 선택도 11%로 가장 우수한 결과를 보였다. Mo, Bi를 기본으로 하는 3성분계 복합 산화물 촉매의 경우 모든 촉매에서 메탄 전환율에는 큰 차이를 보이지 않았으며, Cr을 첨가한 Mo-Bi-Cr 복합 산화물 촉매가 400℃에서 메탄올 선택도 15.3% 로 가장 우수한 결과를 나타냈다. 3성분계 복합 산화물 촉매에서 촉매의 활성과 메탄올 선택도는 촉매의 표면적에 정비례하였다.

가시광선에 감응하는 광촉매를 제조하기 위하여 TiO2에 질소(N)를 도핑하여 N-TiO2를 제조하였다. 제조한 광촉매의 결정성, 입자 형상 및 도핑 상태는 XRD, FE-SEM 및 XPS를 이용하여 조사하였다. 제조한 광촉매의 활성 평가는 메틸렌블루의 광분해로 조사하였다. 제조한 광촉매는 anatase type이었으며, pH가 높을수록 결정화도가 향상되었다. 제조한 광촉매의 입자 크기는 pH 2.0에서 5.42 nm, pH 4.7에서 5.99 nm, pH 9.0에서 7.58 nm로, 입자 크기는 pH가 증가 할수록 약간씩 증가하였다. 광촉매의 활성은 결정화도에 비례하였다. TiO2에 N를 도핑하여 제조한 N-TiO2가 가시광선 하에서도 활성을 나타냈다. TiO2에 도핑한 N는 격자 속에 존재하는 것이 아니라 표면에 존재하였다.

The effects of La addition to Ni/CeO2 methane partial oxidation catalysts were investigated. Catalysts were prepared by the impregnation and urea methods. In the preparation of catalysts, La content was changed from 1 wt% to 3wt%. Catalysts that contain 2wt% La showed the highest methane conversion of about 80% and CO selectivity of 84% and H2 selectivity of 70%. This result may be stemmed from that, when La content is 2wt%, a fluorite oxide-type structure is well formed and carbon deposition is also decreased. Among the catalysts, 2.5wt% Ni/Ce(La)Ox showed the highest catalytic activity. From the experiment of changing reaction temperature with 2.5wt% Ni/Ce(La)Ox catalyst, it was found that the optimum reaction temperature is 750℃ and at this temperature methane conversion was about 90%, CO and H2 selectivities were 94 and 80%, respectively.

The flame-retardant coatings were prepared by blending the synthesized triphosphorus modified polyester in the previous paper and hexamethylene diisocyanate-trimer and curing it at room temperature. The characterization of the films of the prepared coatings was performed. It was confirmed that no deterioration of physical properties of PU coatings was observed with the increasing phenylphosphonic acid (PPA) contents. Flame retardancy was tested by a 45˚ Meckel burner method and LOI method. With the 45˚ Meckel burner method, CATBTP-20C and CATBTP-30C that contain 20 wt% and 30 wt% of PPA, flame retarding component, respectively, showed the first grade flame retardancy with 2.8~3.9 cm of char length ; and, with LOI method, they exhibited a good flame retardancy as a range of 30~32% of combustion values.

Catalytic activity changes of perovskite catalysts were examined with their A-site substitution. For the preparation of catalysts, Mn was used for B-site component and La, Ce, Sr, Ba, Ca, Ag were used for A-site component of the perovskite catalysts(ABO3) The effect of calcination temperature on methane combustion and perovskite structure was also investigated. The surface area and adsorbed oxygen species were tested with BET apparatus and O2-TPD, respectively. Perovskite catalysts whose A-site was partially substituted needed higher calcination temperature than un-substituted one to form the perovskite structure. From O2-TPD experiment, it was found that methane combustion activity was directly related to the oxygen desorbing ability of the catalysts. The prepared catalyst(LM-7) was stable at 600℃ for 72 hours of reaction.

Three different weather-resistant coatings were fabricated with the various weight ratios of a mill-base silicone/acrylic resin to let-down silicone /acrylic resin at 2:8, 3:7, and 4:6 respectively. The prepared coatings were tested to investigate the effect of composition of weather-resistant coatings on the physical properties. The thermal stability, salt spray exposure, and weather-resistance were improved with the increased silicone content. It was concluded that the optimum retio of mill-base silicone/acrylic resin to let-down silicone/acrylic resin would be 2:8 and the coating with 30 wt% of silicone content would have high weather-resistance.

In order to obtain the maximum flame retardancy with the minimal deterioration of physical properties of PU flame-retardant coatings, chlorine and phosphorous functional groups were introduced into the pre-polymer of modified polyesters. In the first step, the tetramethylene bis(orthophosphate) (TBOP) and neohexanediol dichloroacetate (DCA-adduct) intermediates were synthesized. In the second step, 1,4-butanediol and adipic acid monomers were polymerized with the two kind of intermediates to obtain copolymer. The modified polyesters containing chlorine and phosphorous (ATBA-10C, -20C, and -30C) were synthesized by adjusting the contents of chlorine compound (dichloroacetic acid, 10, 20, 30 wt%) with fixed the content of phosphorous compound (2 wt%). The PU flame-retardant coatings (TTBAH -10C, -20C, and -30C) were prepared using the synthesized ATBAs and HDI-trimer as curing agent at room temperature. The physical properties of PU flame-retardant coatings with chlorine and phosphorous were inferior to those with phosphorous only and the properties were getting worse with increasing chlorine content. Flame retardancy was tested with three methods. With the vertical method, Complete combustion time of ATBAHs were 259~347 seconds, which means that the prepared coatings are good flame-retardant. With the 45˚ Meckel burner method, char lengths of the three prepared coatings were less than 2.9 cm, which indicates that the prepared coatings are 1st grade flame retardancy. With the limiting oxygen index (LOI) method, the LOI values of the three prepared coatings were in the range of 30~35%, which proves good flame retardancy of the prepared coatings. From the results of flame retardancy tests of the specimens that contain the same amounts of flame retarding compounds, it was found that the coatings containing both phosphorous and chlorine show higher flame retardancy than the coatings containing phosphorous alone. This indicates that some synergy effect of flame retardancy exists between phosphorous and chlorine.

Methane combustion over perovskite catalysts was investigated. For the preparation of catalysts, Co, Mn, Fe, and Ni were used as B-site components of the perovskite catalysts (ABO3) and La was used as A-site component. The effect of calcination temperature on methane combustion and perovskite structure was also investigated. The structure of perovskites, surface area, and adsorbed oxygen species were tested with XRD, BET apparatus, and O2-TPD, respectively. The formation of perovskite structure was affected by the calcination temperature. The catalyst desorbing oxygen at a lower temperature showed better activity for the methane combustion, therefore, the oxygen species desorbing at lower temperatures is responsible for the methane combustion.

This study was focused on the maximization of flame-retardancy of polyesters by a synergism of simultaneously introduced chlorine and phosphorus into polymer chains of modified polyesters. To prepare modified polyesters, reaction intermediates, TD-adduct (prepared from trimethylolpropane/2,4-dichlorobenzoic acid (2,4-DCBA)) and TMBO (prepared from tetramethylene bis(orthophosphate)), were prepared first, then condensation polymerization of the prepared intermediates, adipic acid, and 1,4-butanediol were carried out. In the condensation polymerization, the content of phosphorus was fixed to be 2%, and the content of 2,4-DCBA that provides chlorine component was varied to be 10, 20, and 30wt%, and we designated the prepared modified polyesters containing chlorine and phosphorus as ABTT-10C, -20C, -30C. Two-component PU flame-retardant coatings (ABTTC, ABTTC-10C, ABTTC-20C, ABTTC-30C) were prepared by the curing of synthesized ABTTs with a curing agent of allophanate/trimer at room temperature. To examine the film properties of the prepared PU flame-retardant coatings, film specimens were prepared with the prepared coatings. The film properties of ABTTC, ABTTC-10C and ABTTC-20C, which contain 0, 10 and 20wt% 2,4-DCBA, respectively, were proved to be good, whereas the film properties of ABTTC-30C, which contains 30wt% 2,4-DCBA, was proved to be a little bit poor. Two kinds of flame retardancy tests, ˚45Meckel burner method and LOI method were performed. With the ˚45Meckel burner method, three flame-retardant coatings except ABTTC showed less than 3.4cm of char length, and showed less than 2 seconds of afterflaming and afterglow. From this result, the prepared flame-retardant coatings were proved to have the 1st grade flame retardancy. With the LOI method, the LOI values of the coatings containing more than 10wt% 2,4-DCBA were higher than 30%, which means that the coatings possess good flame retardancy. From these results, it was found that synergistic effect in flame retardancy was taken place by the introduced phosphorus and chlorine.

To prepare weather-resistant silicone/acrylic resin coatings for an architectural purpose, tetrapolymers were synthesized by a radical polymerization. 3-Methacryloxypropyltrimethoxysilane (MPTS) as a silicone monomer and n-butyl acrylate, methyl methacrylate, and n-butyl methacrylate as acrylic monomers were used. The compositions of monomers were adjusted to fix the glass transition temperature of acrylic polymer for 20℃. The composition of MPTS in the synthesized polymer were varied from 10 wt% to 30 wt%. On the basis of synthesized resin amber paints were prepared and their physical properties and effects for weatherability were examined. The presence of MPTS in silicone/acrylic resins generally resulted in low molecular weight and broad molecular weight distribution, and also lowered the viscosity of the copolymers. The coated films prepared from these resins showed good and balanced properties in general. Adhesion to the substrate was outstanding in particular. Weatherability tests were carried out in three different types such as outdoor exposure, QUV, and SWO. The test results showed that the silicone/acrylic resins containing 30 wt% of MPTS had weather-resistant properties.

The PU flame-retardant coatings (TTBAH, ATBAH-10C, -20C, and -30C) were prepared using the synthesized ATBAs and HDI-trimer as curing agent at room temperature. The physical properties of PU flame-retardant coatings with chlorine and phosphorus were inferior to those with phosphorus only and the properties were getting worse with increasing chlorine content. Flame retardancy was tested with three methods. With the vertical method, complete combustion time of ATBAHs were 259~347 seconds, which means that the prepared coatings are good flame-retardant. With the 45˚ Meckel burner method, char lengths of the three prepared coatings were less than 2.9 cm, which indicates that the prepared coatings are first grade. With the limiting oxygen index (LOI) method, the LOI values of the three prepared coatings were in the range of 30~35%, which proves good flame retardancy of the prepared coatings. from the result of flame retardancy tests of the specimens that contain the same amounts of flame retarding compounds. it was found that the coatings containing both phosphorus and chlorine show higher flame retardancy than the coatings containing only phosphorus. This indicates that there exists, some synergy effect between coexisting phosphorus and chlorine.

In order to prepare high-solid coatings, first acrylic resins (HSAs) which contain 80% solid were synthesized, and then the prepared resins were cured with isocyanate at room temperature. In the synthesis of HSAs, viscosity, number average molecular weight (Mn) and conversion were 1372~2700 cps, 1520~1650 and 83~87%, respectively. Among the four kinds of initiators used, tert-amylperoxy-2-ethyl hexanoate was the most proper one in the synthesis of HSAs. With increasing Tg values, viscosity increased rapidly and molecular weight increased slowly. As a result of the examination of coated films, it was found that 60˚ specular gloss, impact resistance, heat resistance and cross-hatch adhesion were good, and pencil hardness, drying time and pot life were poor.

PU type flame-retardant coatings (TBAO/L-75, TBAOL ; TBAO/N-100, TBAON) were prepared by blending bromine-containing modified polyester (TBAO) which was synthesized in our earlier work. with two kinds of isocyanate curing agents, Desmodur L-75 and Desmodur N-100. Physical properties of the prepared flame-retardant coatings were tested. TBAOL shows better hardness than TBAON, while TBAON shows better viscosity, accelerated weathering resistance, yellowness index and lightness index difference than TBAOL. There were no remarkable differences in fineness of grind, 60˚ specular gloss, cross-hatch adhesion, and abrasion resistance of TBAOL and TBAON. There was no discernable difference in flame-retardancy between the two flame-retardant coatings, TBAOL and TBAON. When the content of tribromo acetic acid, which is flame-retarding component, was 30wt% the LOI value was in a range of 29~30%, which indicates that the two coatings are good flame-retardant coatings.

Anti-corrosive coatings for steel structures with an alternative anti-corrosive pigment, polyaniline was prepared and anti-corrosive characteristics of the prepared coatings were investigated. The structure of the polyaniline was identified by using FT-IR, UV/Vis. and TGA analysis, and the anti-corrosive properties were analyzed from the results of the salt spray experiment. We found that the anti-corrosion properties of the prepared coatings varied in accordance with the types of primer coating resins as well as with the existence and nonexistence of the top coating. In this condition, the properties of adhesion, chemical resistance, and water resistance were found to be very satisfactory when using the single-packaged urethane resin as the primer coating resin and the urethane resin as the top coating resin.

Methanol and formaldehyde were produced directly by the partial oxidation of methane over mixed oxide catalysts. The catalysts were composed of Mo and Bi with late-transition metals, such as Mn, Fe, and Co. The reaction was carried out at 450℃, 50 bar in a fixed-bed differential reactor. The prepared catalysts were characterized by O2-TPD and BET apparatus. Among the catalysts used, the catalyst composed of 1:1:2.5 molar ratio of Mo:Bi:Mn showed the best methane conversion and methanol selectivity. The change in ratio of methane to oxygen affected at the conversion and selectivity, and the most proper ratio was 10:1.5. Methane conversion, methanol and formaldehyde selectivities increased with the surface areas of the catalysts. From the O2-TPD result, it was found that the oxygen species responsible for this reaction might be the lattice oxygen species desorbed at high temperature around 800℃.

Acrylic adhesives for automobiles protection were prepared by emulsion polymerization. Monomers used were n-butyl acrylate(BA), acrylonitrile (AN), butyl methacrylate(BMA), glycidyl methacrylate(GMA), and acrylic acid (AA). Emulsifiers used were sodium lauryl sulfate and polyoxyethylene lauryl ether, which are an anionic emulsifier and a nonionic emulsifier respectively. Potassium persulfate was used as an initiator and polyvinyl alcohol was used as a stabilizer. Emulsion polymerization was carried out in a semi-batch reactor at 70℃ and agitation speed was kept at 200 rpm. Water resistance, heat resistance, acid resistance, alkali resistance and smoke resistance were examined. As a result, when each 0.03 mole of GMA and AA was introduced, the adhesion properties and various above mentioned resistances of the prepared adhesives were satisfied the standard for automobiles.

In order to obtain the maximum flame retardancy as well as the minimum deterioration of physical properties of PU flame-retardant coatings, chlorine and phosphorus functional groups were introduced into the pre-polymer of modified polyesters. In the first step, the tetramethylene bis(orthophosphate) (TBOP) and neohexanediol dichloroacetate (DCA-adduct) intermediates were synthesized. In the second step, 1,4-butanediol and adipic acid monomers were polymerized with the two kinds of intermediates to obtain copolymers. The modified polyesters containing chlorine and phosphorus (ATBA-10C, -20C, and -30C) were synthesized by adjusting that the content of phosphorus compound was fixed as 2wt% and the contents of chlorine compound (dichloroacetic acid) were varied as 10, 20, and 30wt%. Average molecular weight and polydispersity index of the preparation of ATBAs were decreased with increasing DCA content because of the increase in hydroxyl group that retards reaction.

Modified polyesters (TTBA-10C, -20C, -30C) that contain phosphorus and chlorine were synthesized by the condensation polymerization of tetramethylene bis(orthophosphate), neohexanediol trichlorobenzoate, 1,4-butanediol and adipic acid, in which tetramethylene bis(orthophosphate) and neohexanediol trichlorobenzoate were prepared previously in our laboratory. In this study, two-component flame-retardant polyurethane coatings (TTBA-10C/HDI-trimer=TTHD-10C, TTBA-20C/ HDI-trimer= TTHD-20C, TTBA-30C/HDI-trimer= TTHD-30C) were obtained by curing at room temperature with the synthesized TTBAs and hexamethylene diisocyanate (HDI)-trimer as a curing agent. The obtained TTHDs were made into coating samples and used as test samples for various physical properties. The physical properties of the flame-retardant coatings containing chlorine and phosphorus groups were generally inferior to those containing only phosphorus group. Flame retardancy was tested by vertical and horizontal combustion method, and 45˚ Meckel burner method. Since the retardancy of flame-retardant coatings containing chlorine and phosphorus groups was better than that containing only phosphorus group, it could be concluded that the retardancy by the synergism effect of chlorine and phosphorus groups exhibited.