Vibrational Spectroscopy를 이용한 n-Paraffin의 고체상 전이 연구

김도균; 김성수; 송기국; Do-Gyun Kim; Sung Soo Kim; Kigook Song

Polymer(Korea), Vol.23, No.6, 877-883, November, 1999

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Vibrational Spectroscopy를 이용한 n-Paraffin의 고체상 전이 연구

Vibrational Spectroscopic Studies of Solid-Solid Transitions in n-Paraffins

김도균 , 김성수 , 송기국 ^†

경희대학교 화학공학과, 재료과학연구소

Do-Gyun Kim , Sung Soo Kim , and Kigook Song^†

Department of Chemical Engineering and Institute of Materials Science, Kyung Hee University, Yongin, Kyunggi-do 449-701, Korea

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초록

폴리에틸렌과 같이 orthorhombic 결정형태를 형성하는 n-paraffin의 온도 변화에 따른 결정 및 사슬 구조의 변화를 분자의 진동운동에 의한 분광학적인 실험방법인 FTIR과 FT-Raman spectroscopy를 이용하여 조사하였다. 상온에서 orthorhombic 결정구조를 가지는 n-paraffin의 온도를 증가시켜면 용융점 이하에서 결종구조의 전이가 일어나 hexagonal 결정구조로 변화하는데, 이러한 고체 상에서의 전이현상은 사슬 끝에 gauche 구조가 나타나 orthorhombic 결정구조의 packing 정도를 약하게 하여 일어나는 라멜라 표면의 변화로부터 유도되는 결과이다.

The changes in the crystal structure and conformation of n-paraffins, whose crystal structure is orthorhomibc as in polyethylene, with temperature were investigated using bibrational spectroscopy such as FTIR and FT-Raman spectroscopy. The crystal structure of n-paraffin changes from orthorhombic to hexagonal at below its melting temperature with increasing temperature. Such a solid state transition is attributed to the changes in lamellar surface resulting from the introduction of gauche structures at the chain ends inducing reduction of the packing strength of chains in the orthorhombic crystal structure.

Keywords:n-paraffin;FTIR;FT-Raman;crystal structure;conformation

[References]

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Olf HG, Fanconi B, J. Chem. Phys., 69, 534 (1973)
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Casal HL, Mantsch HH, Cameron DG, Snyder RG, J. Chem. Phys., 77, 2825 (1982)
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Pietralla M, Hotz R, Engst T, Siems R, J. Polym. Sci. B: Polym. Phys., 35(1), 47 (1997)
Schaufele RF, Shimanouchi T, J. Chem. Phys., 47, 3605 (1967)
Song K, Krimm S, Macromolecules, 23, 1946 (1990)

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[1] Strobl G, Ewen B, Fischor EW, Piesczek W, J. Chem. Phys., 61, 5257 (1974)

[2] Kim Y, Strauss HL, Snyder RG, J. Phys. Chem., 93, 7520 (1989)

[3] Broadhurst MG, J. Res. NBS, 66A, 241 (1962)

[4] Strobl GR, Hagedorn W, J. Polym. Sci., 16, 1181 (1978)

[5] Stribeck N, Alamo RG, Mandelkern L, Zachmann HG, Macromolecules, 28(14), 5029 (1995)

[6] Snyder RG, J. Mol. Spectr., 7, 116 (1961)

[7] Olf HG, Fanconi B, J. Chem. Phys., 69, 534 (1973)

[8] Bank MI, Krimm S, Randall HM, J. Polym. Sci. A: Polym. Chem., 7, 1785 (1969)

[9] Casal HL, Mantsch HH, Cameron DG, Snyder RG, J. Chem. Phys., 77, 2825 (1982)

[10] Abbate S, Gussoni M, Zerbi G, J. Chem. Phys., 70(8), 3577 (1979)

[11] Ishii K, Nukaga M, Hibino Y, Hagiwara S, Nakayama H, Bull. Chem. Soc. Jpn., 68, 1323 (1995)

[12] Lee KS, Wegner G, Hsu SL, Polymer, 28, 889 (1987)

[13] Grossmann HP, Arnold R, Burhle KR, Polym. Bull., 3, 135 (1980)

[14] Hendra PJ, Jobic HP, Marsden EP, Bloor D, Spectrochimica Acta, 33A, 445 (1977)

[15] Snyder RG, Hsu SL, Krimm S, Spectrochimica Acta, 34A, 395 (1978)

[16] MacPhail RA, Strauss HL, Snyder RG, Elliger CA, J. Phys. Chem., 88, 334 (1984)

[17] Muller A, Proc. R. Soc. London Ser. A, 138, 514 (1932)

[18] Maroncelli M, Qi SP, Strauss HL, Snyder RG, J. Am. Chem. Soc., 104, 6237 (1982)

[19] Zerbi G, Roncone P, Longhi G, Wunder SL, J. Chem. Phys., 89, 166 (1988)

[20] Maroncelli M, Strauss HL, Snyder RG, J. Chem. Phys., 82, 2811 (1985)

[21] Snyder RG, Conti G, Strauss HL, Dorset DL, J. Phys. Chem., 97, 7342 (1993)

[22] Pietralla M, Hotz R, Engst T, Siems R, J. Polym. Sci. B: Polym. Phys., 35(1), 47 (1997)

[23] Schaufele RF, Shimanouchi T, J. Chem. Phys., 47, 3605 (1967)

[24] Song K, Krimm S, Macromolecules, 23, 1946 (1990)