Nitrate-Citrate 혼합 전구체로부터 ZnO 입자의 합성반응 특성

양시우; 이승호; 임대호; 유동준; 강용; Si Woo Yang; Seung Ho Lee; Dae Ho Lim; Dong Jun Yoo; Yong Kang

Korean Chemical Engineering Research, Vol.54, No.3, 299-304, June, 2016

DOI10.9713/kcer.2016.54.3.299 Export Citation

Nitrate-Citrate 혼합 전구체로부터 ZnO 입자의 합성반응 특성

Synthesis Characteristics of ZnO Powder from Precursors Composed of Nitrate-Citrate Compounds

양시우, 이승호, 임대호, 유동준, 강용 ^†

충남대학교 화학공학과, 34134 대전시 유성구 대학로 99

Si Woo Yang, Seung Ho Lee, Dae Ho Lim, Dong Jun Yoo, and Yong Kang^†

Department of Chemical Engineering, Chungnam National University, 99, Daehak-ro, Yuseong-gu, Daejeon, 34134, Korea

E-mail:

초록

Nitrate-citrate 혼합 전구체로부터 ZnO 입자 합성을 위한 자체진행 반응(Self-propagating reaction)의 특성을 고찰하였다. 질화물과 Citrate 그룹간의 자체진행 반응을 위해 탄소/질소 성분의 비는 0.7~0.8 수준으로 유지하였으며, 출발물질의 시료를 TGA방법에 의해 열분해하였다. 반응의 후반부인 반응 전환율이 0.5 이상에서 자체진행 반응의 특성을 나타내었으며 시료는 매우 짧은 시간에 많은 열을 방출하며 분해되었다. 반응의 전반부(X<0.5)가 전체반응의 율속단계로 나타났으며, 이 율속단계에서 반응의 특성을 Friedman, Ozawa-Flynn-Wall 그리고 Vyazovkin의 방법들을 사용하여 해석하였다. 율속단계에서 활성화 에너지는 46~130 (kJ/mol)의 범위로 반응 전환율이 증가함에 따라 증가하였으며, 반응차수는 2.9~0.9, 그리고 반응속도의 빈도인자(Frequency factor)는 85~287 (min-1)의 범위에서 승온속도가 증가함에 따라 각각 전자는 감소하고 후자는 증가하였다.

Characteristics of self-propagating reaction for the preparation of ZnO powder from precursors composed of nitrate and citrate compounds were examined. The ratio of C/N was maintained in range of 0.7~0.8 to initiate the selfpropagating reaction between the reducing citrate and oxidizing nitrate groups. The samples were decomposed thermally by using TGA. The sudden decomposition occurred in the range of X > 0.5 in a very short time with a very sharp decrease of mass, indicating that the self-propagating reaction would occur. Friedman, Ozawa-Flynn-Wall and Vyazovkin methods were employed to predict the activation energy, reaction order and frequency factor of the reaction rate in the rate determining step of X < 0.5 range. The activation energy increased with increasing fractional conversion in the range of 46~130 (kJ/min). The reaction order decreased in the range of 2.9~0.9, while the frequency factor increased in the range of 85~278 (min-1), respectively, with increasing the rate of temperature increase.

Keywords:Self-propagating reaction;Activation energy;Reaction order;Frequency factor;ZnO powder;Nitrate-Citrate precursor

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[2] Lee SH, Yang SW, Lim DH, Yoo DJ, Lee CK, Kang GM, Kang Y, Korean Chem. Eng. Res., 53(5), 597 (2015)

[3] Liu SZ, Zhang YC, Wang TX, Yang FX, Mater. Lett., 71, 154 (2012)

[4] Zeng Y, Qiao L, Bing Y, Wen M, Zou B, Zheng W, Zhang T, Zou G, Sens. Actuators B-Chem., 173, 897 (2012)

[5] Chaudhari SP, Bodade AB, Chaudhari GN, Korean J. Chem. Eng., 30(11), 2001 (2013)

[6] Thongrom B, Amornpitoksuk P, Suwanboon S, Baltrusaitis J, Korean J. Chem. Eng., 31(4), 587 (2014)

[7] Yu HF, Chou HY, Powder Technol., 233, 201 (2013)

[8] Lu CH, Lai YC, Kale RB, J. Alloy. Compd., 477, 523 (2009)

[9] Chakraborty A, Devi PS, Maiti HS, Mater. Lett., 20, 63 (1994)

[10] Chakraborty A, Devi PS, Roy S, Maiti HS, J. Mater. Res., 9, 986 (1994)

[11] Chakraborty A, Devi PS, Maiti HS, J. Mater. Res., 10, 918 (1995)

[12] Bell RJ, Millar GJ, Drennan J, Solid State Ion., 131(3-4), 211 (2000)

[13] Blank DHA, Kruidhof H, Flokstra J, J. Phys. D-Appl. Phys., 21, 226 (1988)

[14] Mancic L, Milosevic O, Marinkovic B, Lopez S, Rizzo F, Physica C.-Superconductivity, 341-348, 503 (2000)

[15] Friedman HL, J. Polym. Sci. Part C, 6, 183 (1964)

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[17] Pielichowski K, Solid State Ion., 104(1-2), 123 (1997)

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[20] Vyazovkin S, Wight CA, Int’l. Rev. Phy. Chem., 17, 407 (1998)

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