Activated magnetite (Fe3O4-δ) has the capability of decomposing CO2 proportional to the δ-value at comparativelylow temperature of 300oC. To enhance the CO2 decomposition capability of Fe3O4-δ, (Fe1-xCox)3O4-δ and (Fe1-xMnx)3O4-δ weresynthesized and then reacted with CO2. Fe1-xCoxC2O4·2H2O powders having Fe to Co mixing ratios of 9:1, 8:2, 7:3, 6:4, and5:5 were synthesized by co-precipitation of FeSO4·7H2O and CoSO4·7H2O solutions with a (NH4)2C2O4·H2O solution. The samemethod was used to synthesize Fe1-xMnxC2O4·2H2O powders having Fe to Mn mixing ratios of 9:1, 8:2, 7:3, 6:4, 5:5 with aMnSO4·4H2O solution. The thermal decomposition of synthesized Fe1-xCoxC2O4·2H2O and Fe1-xMnxC2O4·2H2O was analyzedin an Ar atmosphere with TG/DTA. The synthesized powders were heat-treated for 3 hours in an Ar atmosphere at 450oCto produce activated powders of (Fe1-xCox)3O4-δ and (Fe1-xMnx)3O4-δ. The activated powders were reacted with a mixed gas(Ar:85%, CO2:15%) at 300oC for 12 hours. The exhaust gas was analyzed for CO2 with a CO2 gas analyzer. The decom-position of CO2 was estimated by measuring CO2 content in the exhaust gas after the reaction with CO2. For (Fe1-xMnx)3O4-δ,the amount of Mn2+ oxidized to Mn3+ increased as x increased. The δ value and CO2 decomposition efficiency decreased asx increased. When the δ value was below 0.641, CO2 was not decomposed. For (Fe1-xCox)3O4-δ, the δ value and CO2decomposition efficiency increased as x increased. At a δ value of 0.857, an active state was maintained even after 12 hoursof reaction and the amount of decomposed CO2 was 52.844cm3 per 1g of (Fe0.5Co0.5)3O4-δ.

A general synthetic method to make Fe3O4-δ (activated magnetite) is the reduction of Fe3O4 by H2 atmosphere. However, this process has an explosion risk. Therefore, we studied the process of synthesis of Fe3O4-δ depending on heat-treatment conditions using FeC2O4·2H2O in Ar atmosphere. The thermal decomposition characteristics of FeC2O4·2H2O and the δ-value of Fe3O4-δ were analyzed with TG/DTA in Ar atmosphere. β-FeC2O4·2H2O was synthesized by precipitation method using FeSO4·7H2O and (NH4)2C2O4·H2O. The concentration of the solution was 0.1 M and the equivalent ratio was 1.0. β-FeC2O4·2H2O was decomposed to H2O and FeC2O4 from 150˚C to 200˚C. FeC2O4 was decomposed to CO, CO2, and Fe3O4 from 200˚C to 250˚C. Single phase Fe3O4 was formed by the decomposition of β-FeC2O4·2H2O in Ar atmosphere. However, Fe3C, Fe and Fe4N were formed as minor phases when β-FeC2O4·2H2O was decomposed in N2 atmosphere. Then, Fe3O4 was reduced to Fe3O4-δ by decomposion of CO. The reduction of Fe3O4 to Fe3O4-δ progressed from 320˚C to 400˚C; the reaction was exothermic. The degree of exothermal reaction was varied with heat treatment temperature, heating rate, Ar flow rate, and holding time. The δ-value of Fe3O4-δ was greatly influenced by the heat treatment temperature and the heating rate. However, Ar flow rate and holding time had a minor effect on δ-value.

Activated magnetite (Fe3O4-δ) was applied to reducing CO2 gas emissions to avoid greenhouse effects. Wet and dry methods were developed as a CO2 removal process. One of the typical dry methods is CO2 decomposition using activated magnetite (Fe3O4-δ). Generally, Fe3O4-δ is manufactured by reduction of Fe3O4 by H2 gas. This process has an explosion risk. Therefore, a non-explosive process to make Fe3O4-δ was studied using FeC2O4·2H2O and N2. FeSO4·7H2O and (NH4)2C2O4·H2O were used as starting materials. So, α-FeC2O4·2H2O was synthesized by precipitation method. During the calcination process, FeC2O4·2H2O was decomposed to Fe3O4, CO, and CO2. The specific surface area of the activated magnetite varied with the calcination temperature from 15.43 m2/g to 9.32 m2/g. The densities of FeC2O4·2H2O and Fe3O4 were 2.28 g/cm3 and 5.2 g/cm3, respectively. Also, the Fe3O4 was reduced to Fe3O4-δ by CO. From the TGA results in air of the specimen that was calcined at 450˚C for three hours in N2 atmosphere, the δ-value of Fe3O4-δ was estimated. The δ-value of Fe3O4-δ was 0.3170 when the sample was heat treated at 400˚C for 3 hours and 0.6583 when the sample was heat treated at 450˚C for 3 hours. Fe3O4-δ was oxidized to Fe3O4 when Fe3O4-δ was reacted with CO2 because CO2 is decomposed to C and O2.

열차폐코팅층의 박리는 세라믹/금속접합층 계면에서 취성이 큰 스피텔의 생성, 금속과 세라믹의 열팽창계수의 차이, 세라믹층의 상변태, 코팅층의 잔류응력에 기인한다. 본 연구에서는 인코넬 713C에 전자빔 코팅 및 플라즈마 용사법으로 코팅된 안정화지르코니아/CoNiCrAIY 계면의 산화거동을 조사하기 위하여 900˚C에서 등온산화시험동안 생성되는 산화막층과 스피넬 생성 거동을 관찰, 분석하였다. 코팅 직후 코팅층에 고르게 분포하고 있는 Co,Ni,Cr,AI,Zr의 원소들이 산화시간에 따라 확산하여 산화반응을 하였다. 초기 20시간의 산화기시간에 안정화지르코니아/CoNiCrAIY 계면에 주요 성분이 α-AI2O3인 산화막층이 생성되었고, CoNiCrAIY층에는 AI의 외부확산으로 인한 AI 결핍지역이 생성되었다. 산화시험동안 α-AI2O층이 임계두께까지 성장한 후에 산화막층의 성장속도는 감소하였고, 안정화지르코니아/산화막층 계면에 스피넬, Cr2O3, CO2CrO4의 형성으로 인한 크랙이 관찰되었다.