폴리에틸렌 열분해의 속도론적 연구

김명수; 오세천; 이해평; 김희택; 류경옥

Journal of the Korean Industrial and Engineering Chemistry, Vol.10, No.4, 548-556, June, 1999

Export Citation

폴리에틸렌 열분해의 속도론적 연구

A Study on the Kinetics of Thermal Degradation of Polyethylene

김명수, 오세천, 이해평, 김희택, 류경옥

초록

질소 분위기에서 폴리에틸렌 열분해의 속도론적 연구를 10 ℃/min와 50 ℃/min 사이의 여러 가지 가열속도에서 비등온 질량감소 기술을 이용하여 수행하였다. 속도 상수들에 대한 정보를 얻기 위하여 질량감소 곡선 및 그 미분값을 Kissinger, Freeman-Carroll, Flynn-Wall, Coats-Redfern, Chatterjee-Conrad, Friedman, Horowitz-Metzger 및 Ozawa 방법과 Denq 방법을 이용하여 해석하였다. 연구에 사용된 수학적인 방법에 따라 속도 상수의 결과값에 많은 차이가 있음을 알 수 있었으며, 따라서 열분해의 속도 상수 결정에 있어서는 각 방법의 장·단점에 대한 비교 분석 연구가 선행되어야 할 것으로 판단되었다. 본 연구로부터 HDPE의 겉보기 활성화 에너지의 값이 LDPE의 값보다 크게 나타냄을 확인할 수 있었다.

The thermal degradation of polyethylene has been studied using a nonisothermal thermogravimetric technique under a nitrogen atmosphere condition at several heating rates from 10 to 50 ℃/min. To obtain information on the kinetic parameters, the dynamic thermogravimetric analysis curve and its derivative have been analyzed by a variety of analytical methods such as Kissinger, Freeman-Carroll, Flynn-Wall, Coats-Redfern, Chatterjee-Conrad, Friedman, Horowitz-Metzger, Ozawa and Denq methods. The comparative works for the kinetic results obtained from various methods should be performed to determine the kinetic parameters, because three are tremendous differences in the calculated kinetic parameters depending upon the mathematical method taken in the analysis. From this work, it was found that the apparent activation energy of HDPE was larger than those of LDPE and LLDPE.

Keywords:Polyethylene;Thermal degradation kinetic analysis

[References]

Sircar AK, Lamond TG, Rubber Chem. Technol., 48, 301 (1975)
Kim S, Ph.D. Dissertation, Wisconsin-Madison University, U.S.A. (1995)
Yang J, Kaliaguine S, Roy C, Rubber Chem. Technol., 66, 213 (1993)
Salin IM, Seferis JC, J. Appl. Polym. Sci., 47, 847 (1993)
Rao VK, Bardon MF, Combust. Flame, 102, 219 (1995)
Jimenez A, Berenguer V, Lopez J, Sanchez A, J. Appl. Polym. Sci., 50, 1565 (1993)
Ghim YS, HWAHAK KONGHAK, 29(4), 503 (1991)
Park SW, Lee JK, Seul SD, HWAHAK KONGHAK, 23(2), 125 (1985)
Levchik SV, Levchik GF, Lesnikovich AI, J. Appl. Polym. Sci., 37, 1319 (1989)
Cooney JD, Day M, Wiles DM, J. Appl. Polym. Sci., 28, 2887 (1983)
Ozawa T, Bull. Chem. Soc. Jpn., 38, 1881 (1965)
Westerhout RW, Waanders J, Kuipers JA, Vanswaaij WP, Ind. Eng. Chem. Res., 36(6), 1955 (1997)
Denq BL, Chiu WY, Lin KF, J. Appl. Polym. Sci., 66(10), 1855 (1997)
Rao SS, "Optimization: Theory and Applications," 2nd ed., 345, John Wiley & Sons, Inc,. New York (1984)
Flynn JH, Wall LA, J. Res. National Bureau Standards, 70A, 487 (1966)
Regnier N, Cuide C, Polym. Degrad. Stabil., 55, 165 (1997)
Mucha M, J. Polym. Sci. Symp., 7, 25 (1976)
Urzendowski SR, J. Therm. Anal., 3, 379 (1971)
Wu CH, Chang CY, Hor JL, Shih SM, Chen LW, Chang FW, Pyrolysis Kinet. Waste Manag., 13, 221 (1993)
Jellinek HHG, J. Polym. Sci., 4, 378 (1950)

[Referenced By]

[1] Sircar AK, Lamond TG, Rubber Chem. Technol., 48, 301 (1975)

[2] Kim S, Ph.D. Dissertation, Wisconsin-Madison University, U.S.A. (1995)

[3] Yang J, Kaliaguine S, Roy C, Rubber Chem. Technol., 66, 213 (1993)

[4] Salin IM, Seferis JC, J. Appl. Polym. Sci., 47, 847 (1993)

[5] Rao VK, Bardon MF, Combust. Flame, 102, 219 (1995)

[6] Jimenez A, Berenguer V, Lopez J, Sanchez A, J. Appl. Polym. Sci., 50, 1565 (1993)

[7] Ghim YS, HWAHAK KONGHAK, 29(4), 503 (1991)

[8] Park SW, Lee JK, Seul SD, HWAHAK KONGHAK, 23(2), 125 (1985)

[9] Levchik SV, Levchik GF, Lesnikovich AI, J. Appl. Polym. Sci., 37, 1319 (1989)

[10] Cooney JD, Day M, Wiles DM, J. Appl. Polym. Sci., 28, 2887 (1983)

[11] Ozawa T, Bull. Chem. Soc. Jpn., 38, 1881 (1965)

[12] Westerhout RW, Waanders J, Kuipers JA, Vanswaaij WP, Ind. Eng. Chem. Res., 36(6), 1955 (1997)

[13] Denq BL, Chiu WY, Lin KF, J. Appl. Polym. Sci., 66(10), 1855 (1997)

[14] Rao SS, "Optimization: Theory and Applications," 2nd ed., 345, John Wiley & Sons, Inc,. New York (1984)

[15] Flynn JH, Wall LA, J. Res. National Bureau Standards, 70A, 487 (1966)

[16] Regnier N, Cuide C, Polym. Degrad. Stabil., 55, 165 (1997)

[17] Mucha M, J. Polym. Sci. Symp., 7, 25 (1976)

[18] Urzendowski SR, J. Therm. Anal., 3, 379 (1971)

[19] Wu CH, Chang CY, Hor JL, Shih SM, Chen LW, Chang FW, Pyrolysis Kinet. Waste Manag., 13, 221 (1993)

[20] Jellinek HHG, J. Polym. Sci., 4, 378 (1950)