Abstract
Polarised Raman spectroscopy is a vibrational spectroscopic technique that is used widely for the chemical and physical analyses of materials since it is both non-destructive and suitable for remote analysis. In particularly over the last 40 years, the technique has been developed and applied for the study of molecular orientation distributions in polymers. Compared to other analytical techniques, polarised Raman spectroscopy has the following advantages, (1) quantitative and precise measurement of molecular orientation distributions, and (2) study of these distributions in both the crystalline and amorphous phases. Knowledge obtained from the technique is of both academic and industrial interest to study relationships between microstructure and macroscopic physical properties in polymers. In this paper, polarised Raman spectroscopy is reviewed with regard to the study of molecular orientation distributions in polymeric materials. The basis of polarised Raman scattering is first described, and this is followed by the procedure for obtaining spectra. It is shown how Raman scattering intensities for different polarised scattering geometries can be interpreted to give parameters and functions representing quantitative measures of the degree of molecular orientation. Factors affecting the evaluation of these parameters are also summarised. Finally, the usefulness of the technique is demonstrated by practical applications including a study of molecular orientation distributions in poly(ethylene terephthalate) (PET) fibres.
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References
L. E. ALEXANDER, in “X-ray Diffraction Methods in Polymer Science” (Wiley-Interscience, John Wiley & Sons, Inc., New York, 1969).
H. KAWAI, S. NOMURA, I. KIMURA and M. KAGIYAMA, J. Polym. Sci.: Part A-2 8 (1970) 383.
A. H. WINDLE, in “Measurement of Molecular Orientation and Structure in Non-Crystalline Polymers by Wide Angle X-Ray Diffraction”, in “Developments in Oriented Polymers-1”, edited by I. M. WARD (Applied Science Publishers, London, 1982).
P. LAPERSONNE, J.-F. TASSIN, L. MONNERIE and J. BEAUTEMPS, Polym. 32 (1991) 3331.
A. CUNNINGHAM, G. R. DAVIES and I. M. WARD, ibid. 15 (1974) 743.
A. CUNNINGHAM, I. M. WARD, H. A. WILLIS and V. ZICHY, Polym. 15 (1974) 749.
D. A. JARVIS, I. J. HUTCHINSON, D. I. BOWER and I. M. WARD, Polym. 21 (1980) 41.
I. M. WARD, in “Determination of Molecular Orientation by Spectroscopic Techniques”, in “Advances in Polymer Science”, edited by H. H. KAUSCH and H. G. ZACHMANN (Springer-Verlag, Berlin, 1985).
R.-J. ROE, J. Polym. Sci.: Part A-2 8 (1970) 1187.
V. J. MCBRIERTY and I. M. WARD, Brit. J. Appl. Phys. 1 (1968) 1529.
N. J. CLAYDEN, J. G. EAVES and L. CROOT, Polym. 38 (1997) 159.
M. BOTEV, R. NEFFATI and J. RAULT, Polym. 40 (1999) 5227.
M. E. R. ROBINSON, D. I. BOWER and W. F. MADDAMS, J. Polym. Sci.: Polym. Phys. Ed. 16 (1978) 2115.
S. K. SATIJA and C. H. WANG, J. Chem. Phys. 69 (1978) 2739.
D. Y. YOON, C. CHANG and R. S. STEIN, J. Polym. Sci.: Polym. Phys. Ed. 12 (1974) 2091.
V. PETRACCONE, I. C. SANCHEZ and R. S. STEIN, J. Polym. Sci.: Polym. Phys. Ed. 13 (1975) 1991.
G. VOYIATZIS, G. PETEKIDIS, D. VLASSOPOULOS, E. I. KAMITSOS and A. BRUGGEMAN, Macromolecules 29 (1996) 2244.
J. H. NOBBS, D. I. BOWER, I. M. WARD and D. PATTERSON, Polym. 15 (1974) 287.
F. PINAUD, J. P. JARRY, PH. SERGOT and L. MONNERIE, ibdi. 23 (1982) 1575.
P. LAPERSONNE, J. F. TASSIN, P. SERGOT, L. MONNERIE and G. BOURVELLEC, ibid. 30 (1989) 1558.
A. ELLIOTT, in “Infra-red Spectra and Structure of Organic Long-chain Polymers” (Edward Arnold, London, 1969).
J. H. NOBBS, D. I. BOWER and I. M. WARD, J. Polym. Sci.: Polym. Phys. Ed. 17 (1979) 259.
P. LAPERSONNE, D. I. BOWER and I. M. WARD, Polym. 33 (1992) 1266.
D. I. BOWER, J. Polym. Sci.: Polym. Phys. Ed. 10 (1972) 2135.
C. V. RAMAN and K. S. KRISHNAN, Nature 121 (1928) 501.
J. J. LASERNA (ed.) in “Modern Techniques in Raman Spectroscopy” (John Wiley & Sons, Chichester, 1996).
C. N. BANWELL and E. M. MCCASH, in “Fundamentals of Molecular Spectroscopy” (The McGraw-Hill Companies, London, 1994).
J. L. KOENIG, in “Spectroscopy of Polymers” (Elsevier, Oxford, 1999).
H. J. BOWLEY, D. J. GARDINER, D. L. GERRARD, P. R. GRAVES, J. D. LOUDEN and G. TURRELL, in “Practical Raman Spectroscopy” (Springer-Verlag, London, 1989).
J. G. GRASSELLI, M. K. SNAVELY and B. J. BULKIN, Phys. Reports 65 (1980) 231.
L. N. OVANDER, Opt. Spectrosc. 9 (1960) 302.
R. LOUDON, Adv. Phys. 13 (1964) 423.
Idem., ibid. 14 (1965) 621.
R.-J. ROE, J. Appl. Phys. 36 (1965) 2024.
S. P. S. PORTO, J. Opt. Soc. Am. 56 (1966) 1585.
J. R. SCHERER, S. KINT and G. F. BAILEY, J. Mol. Spectrosc. 39 (1971) 146.
C. V. RAMAN and K. S. KRISHNAN, Nature 122 (1928) 169.
R. G. SNYDER, J. Mol. Spectrosc. 37 (1971) 353.
D. I. BOWER, J. Phys. B: Atom. Mol. Phys. 9 (1976) 3275.
D. I. BOWER, J. Polym. Sci.: Polym. Phys. Ed. 19 (1981) 93.
S. NOMURA, N. NAKAMURA and H. KAWAI, J. Polym. Sci.: Part A-2 9 (1971) 407.
B. J. BERNE, P. PECHUKAS and G. D. HARP, J. Chem. Phys. 49 (1968) 3125.
H. POTTEL, W. HERREMAN, B. W. VAN DER MEER and M. AMELOOT, Chem. Phys. 102 (1986) 37.
F. L. LABARTHET, T. BUFFETEAU and C. SOURISSEAU, Appl. Spectrosc. 54 (2000) 699.
D. I. BOWER, Polym. 23 (1982) 1251.
D. I. BOWER, D. A. JARVIS and I. M. WARD, J. Polym. Sci.: Part B: Polym. Phys. 24 (1986) 1459.
N. E. SCHLOTTER and J. F. RABOLT, Polym. 25 (1984) 165.
G. Y. NIKOLAEVA, L. E. SEMENOVA, K. A. PROKHOROV and S. A. GORDEYEV, Laser Phys. 7 (1997) 403.
G. Y. NIKOLAEVA, L. E. SEMENOVA, K. A. PROKHOROV and S. A. GORDEYEV, Opt. Spectrosc. 85 (1998) 416.
K. PROKHOROV, S. GORDEYEV, G. NIKOLAEVA, P. PASHININ, R. WITHNALL, I. DUNKIN and S. SHILTON, Macromol. Symp. 184 (2002) 123.
I. W. SHEPHERD, in “Chapter 4: Raman Polarization Techniques in the Study of Macromolecules”, in “Advances in Infrared and Raman Spectroscopy”, edited by R. E. HESTER and R. J. H. CLARK (Heyden & Son, London, 1977).
J. STOKR, B. SCHNEIDER, D. DOSKOCILOVA, J. LOVY and P. SEDLACEK, Polym. 23 (1982) 714.
S. JEN, N. A. CLARK, P. S. PERSHAN and E. B. PRIESTLEY, Phys. Rev. Lett. 31 (1973) 1552.
S. MICHIELSEN, “Application of Raman Spectroscopy to Organic Fibers and Films” in “Handbook of Raman Spectroscopy”, edited by I. R. LEWIS and H. G. M. EDWARDS (Marcel Dekker, New York, 2001).
N. J. EVERALL, Appl. Spectrosc. 52 (1998) 1498.
T. C. DAMEN, S. P. S. PORTO and B. TELL, Phys. Rev. 142 (1966) 570.
E. HECHT, in “Optics” (Addison-Wesley, Reading, 1987).
H. C. VAN DE HULST, in “Light Scattering by Small Particles” (Dover, New York, 1981).
L. D. CAMBON, J. L. RAMONJA and D. V. LUU, J. Raman Spectrosc. 18 (1987) 129.
S. YANG and S. MICHIELSEN, Macromolecules 35 (2002) 10108.
R. J. ROE and W. R. KRIGBAUM, J. Appl. Phys. 35 (1964) 2215.
R.-J. ROE and W. R. KRIGBAUM, J. Chem. Phys. 40 (1964) 2608.
S. K. FREEMAN, in “Applications of Laser Raman Spectroscopy” (John Wiley & Sons, London, 1973).
I. M. WARD, in “Structure and Properties of Oriented Polymers, 2nd Ed.” (Chapman & Hall, London, 1997).
C.-P. LAFRANCE, P. CHABOT, M. PIGEON, R. E. PRUD'HOMME and M. PEZOLET, Polym. 34 (1993) 5029.
C. C. C. LESKO, J. F. RABOLT, R. M. IKEDA, B. CHASE and A. KENNEDY, J. Mol. Struct. 521 (2000) 127.
P. R. MORRIS, J. Appl. Phys. 40 (1969) 447.
P. H. HERMANS, in “Physics and Chemistry of Cellulose Fibres -with particular Reference to Rayon” (Elsevier Publishing Company, Inc., New York, 1949).
W. J. JONES, D. K. THOMAS, D. W. THOMAS and G. WILLIAMS, J. Mol. Struct. 614 (2002) 75.
V. B. GUPTA and S. KUMAR, J. Polym. Sci.: Polym. Phys. Ed. 17 (1979) 1307.
E. L. V. LEWIS, D. I. BOWER and I. M. WARD, Polym. 36 (1995) 4741.
R. T. BAILEY, A. J. HYDE and J. J. KIM, Spectrochim. Acta 30A (1974) 91.
M. J. GALL, P. J. HENDRA, C. J. PEACOCK, M. E. A. CUDBY and H. A. WILLIS, Spectrochim. Acta 28A (1972) 1485.
M. PIGEON, R. E. PRUD'HOMME and M. PEZOLET, Macromolecules 24 (1991) 5687.
I. W. SHEPHERD, in “Chapter 4: Raman Polarization Techniques in the Study of Macromolecules”, in “Advances in Infrared and Raman Spectroscopy Vol. 3,” edited by R. E. Hester, R. J. H. Clark (Heyden, London, 1977).
N. EVERALL, K. DAVIS, H. OWEN, M. J. PELLETIER and J. SLATER, Appl. Spectrosc. 50 (1996) 388.
S. P. S. PORTO, J. A. GIORDMAINE and T. C. DAMEN, Phys. Rev. 147 (1966) 608.
D. I. BOWER and I. M. WARD, Polym. 23 (1982) 645.
J. MAXFIELD, R. S. STEIN and M. C. CHEN, J. Polym. Sci.: Polym. Phys. Ed. 16 (1978) 37.
J. PURVIS and D. I. BOWER, J. Polym. Sci.: Polym. Phys. Ed. 14 (1976) 1461.
J. PURVIS and D. I. BOWER, Polym. 15 (1974) 645.
W. T. WILSER and D. B. FITCHEN, J. Chem. Phys. 62 (1975) 720.
P. D. VASKO and J. L. KOENIG, Macromolecules 3 (1970) 597.
N. EVERALL, H. OWEN and J. SLATER, Appl. Spectrosc. 49 (1995) 610.
M. A. DE BAEZ, P. J. HENDRA and M. JUDKINS, Spectrochim. Acta A51 (1995) 2117.
S. JEN, N. A. CLARK, P. S. PERSHAN and E. B. PRIESTLEY, J. Chem. Phys. 66 (1977) 4635.
W. T. WILSER and D. B. FITCHEN, Biopolymers 13 (1974) 1435.
J. L. DEROUAULT, P. J. HENDRA, M. E. A. CUDBY and H. A. WILLIS, J. Chem. Soc., Chem. Comm. (1972) 1187.
B. FANCONI, B. TOMLINSON, L. A. NAFIE, W. SMALL and W. L. PETICOLAS, J. Chem. Phys. 51 (1969) 3993.
E. L. V. LEWIS and D. I. BOWER, J. Raman Spectrosc. 18 (1987) 61.
G. TURRELL, C. BREMARD, P. DHAMELINCOURT and J. LAUREYNS, Appl. Spectrosc. 39 (1985) 1036.
R. E. PRUD'HOMME, L. BOURLAND, R. T. NATARAJAN and R. S. STEIN, J. Polym. Sci., Polym. Phys. Ed. 12 (1974) 1955.
M. J. CITRA, D. B. CHASE, R. M. IKEDA and K. H. GARDNER, Macromolecules 28 (1995) 4007.
C. BREMARD, P. DHAMELINCOURT, J. LAUREYNS and G. TURRELL, J. Mol. Struct. 142 (1986) 13.
M. E. ANDERSEN and R. Z. MUGGLI, Anal. Chem. 53 (1981) 1772.
F. ADAR and H. NOETHER, Polym. 26 (1985) 1935.
G. TURRELL and J. CORSET (Ed.), in “Raman Microscopy Development and Applications” (Harcourt Brace & Company, London, 1996).
G. TURRELL, J. Raman Spectrosc. 15 (1984) 103.
C. BREMARD, J. LAUREYNS and G. TURRELL, Can. J. Spectrosc. 32 (1987) 70.
B. JASSE and J. L. KOENIG, J. Polym. Sci.: Polym. Phys. Ed. 18 (1980) 731.
J. A. TOPP and W. KLEFER, Appl. Spectrosc. 28 (1974) 26.
W. F. MADDAMS, Spectrochim. Acta 50A (1994) 1967.
B. H. STUART, Vib. Spectrosc. 10 (1996) 79.
K. MIYANO, J. Chem. Phys. 69 (1978) 4807.
C.-P. LAFRANCE, P. CHABOT, M. PIGEON, R. E. PRUD'HOMME and M. PEZOLET, Polym. 34 (1993) 5029.
S. LU, A. E. RUSSELL and P. J. HENDRA, J. Mater. Sci. 33 (1998) 4721.
J. PURVIS, D. I. BOWER and I. M. WARD, Polym. 14 (1973) 398.
F. J. BOERIO and R. A. BAILEY, Polym. Lett. Ed. 12 (1974) 433.
J. C. RODRIGUEZ-CABELLO, J. C. MERINO, L. QUINTANILLA and J. M. PASTOR, J. Appl. Polym. Sci. 62 (1996) 1953.
S. NATARAJAN and S. MICHIELSEN, J. Appl. Polym. Sci. 73 (1999) 943.
R. A. HUIJTS and S. M. PETERS, Polym. 35 (1994) 3119.
S. YANG and S. MICHIELSEN, Macromolecules 36 (2003) 6484.
S. YANG and S. MICHIELSEN, J. Polym. Sci.: Part B: Polym. Phys. 42 (2004) 47.
N. EVERALL, P. TAYLER, J. M. CHALMERS, D. MCKERRON, R. FERWERDA and J. H. VAN DER MAAS, Polym. 35 (1994) 3184.
N. J. EVERALL, J. LUMSDON, J. M. CHALMERS and N. MASON, Spectrochim. Acta 47A (1991) 1305.
P. J. HENDRA and T. R. GILSON (Ed.), “Laser Raman Spectroscopy” (Wiley, London, 1970) Chap.7.
S. FRISK, R. M. IKEDA, D. B. CHASE, A. KENNEDY and J. F. RABOLT, Macromolecules 37 (2004) 6027.
A. S. NIELSEN and R. PYRZ, Composites Sci. Technol. 62 (2002) 2219.
N. EVERALL, J. CHALMERS and P. MILLS, Appl. Spectrosc. 50 (1996) 1229.
R. J. SAMUELS, J. Polym. Sci.: Part A 3 (1965) 1741.
I. KARACAN, A. K. TARAIYA, D. I. BOWER and I. M. WARD, Polym. 34 (1993) 2691.
J. M. PASTOR, T. JAWHARI, J. C. MERINO and J. FRAILE, Makromol. Chem., Macromol. Symp. 72 (1993) 131.
C. H. WANG and D. B. CAVANAUGH, J. Appl. Phys. 52 (1981) 6003.
X. WANG and S. MICHIELSEN, J. Appl. Polym. Sci. 82 (2001) 1330.
D. GARCIA-LOPEZ, J. C. MERINO and J. M. PASTOR, ibid. 88 (2003) 947.
H. DOSHI, S. KUMAR, M. SRINIVASRAO, J. O. PARK and D. A. SCHIRALDI, Polym. 43 (2002) 1701.
M. R. FERNANDEZ, J. C. MERINO, M. I. GOBERNADO-MITRE and J. M. PASTOR, Appl. Spectrosc. 54 (2000) 1105.
A. R. BHATTACHARYA, T. V. SREEKUMAR, T. LIU, S. KUMAR, K. M. ERICSON, R. H. HAUGE and R. E. SMALLEY, Polym. 44 (2003) 2373.
M. J. FOLKES, M. KASHIWAGI and I. M. WARD, ibid. 12 (1971) 697.
B. JASSE, R. S. CHAO and J. L. KOENIG, J. Polym. Sci.: Polym. Phys. Ed. 16 (1978) 2157.
J. F. RABOLT and B. FANCONI, Macromolecules 11 (1978) 740.
K. ZABEL, N. E. SCHLOTTER and J. F. RABOLT, Macromolecules 16 (1983) 446.
P. B. SMITH, A. LEUGERS, S. KANG, X. YANG and S. L. HSU, Macromol. Symp. 175 (2001) 81.
P. B. SMITH, A. LEUGERS, S. KANG, S. L. HSU and X. YANG, J. Appl. Polym. Sci. 82 (2001) 2497.
H. TAKEUCHI, M. MATSUNO, S. A. OVERMAN and G. J. THOMAS JR, J. Am. Chem. Soc. 118 (1996) 3498.
M. TSUBOI, S. A. OVERMAN and G. J. THOMAS, JR, Biochemistry 35 (1996) 10403.
M. TSUBOI, M. SUZUKI, S. A. OVERMAN and G. J. THOMAS, JR, Biochemistry 39 (2000) 2677.
M.-E. ROUSSEAU, T. LEFEVRE, L. BEAULIEU, T. ASAKURA and M. PEZOLET, Biomacromolecules 5 (2004) 2247.
S.-H. LEE and S. KRIMM, J. Raman Spectrosc. 29 (1998) 73.
S. A. OVERMAN, M. TSUBOI and G. J. THOMAS, JR, J. Mol. Biol. 259 (1996) 331.
W.-Y. YEH and R. J. YOUNG, J. Macromol. Sci.-Phys. B37 (1998) 83.
S. KOUTEVA-ARGUIROVA, W. SEIFERT, M. KITTLER and J. REIF, Mater. Sci. Eng. B102 (2003) 37.
V. B. GUPTA, S. K. SATT and D. D. DEORUKHKAR, Polym. Comm. 30 (1989) 341.
S. K. BAHL, D. D. CORNELL, F. J. BOERIO and G. E. MCGRAW, Polym. Lett. Ed. 12 (1974) 13.
C. W. BUNN, R. P. DAUBENY and C. J. BROWN, Proc. Roy. Soc. Lond. A226 (1955) 531.
I. M. WARD, Proc. Phys. Soc. 80 (1962) 1176.
I. M. WARD, in “Mechanical Properties of Solid Polymers, 2nd ed.” (John Wiley & Sons, Chichester, 1983).
A. REUSS, Zeit. Angew. Math. Mech. 9 (1929) 49.
T. NISHINO, K. NAKAMAE, F. YOKOYAMA and T. MATSUMOTO, J. Macromol. Sci.-Phys. B27 (1988) 407.
K. KAJI and I. SAKURADA, Makromol. Chem., Suppl. 1 (1975) 599.
C. E. SHANNON, Bell Sys. Tech. J. 27 (1948) 379.
C. E. SHANNON and W. WEAVER, in “Mathematical Theory of Communication” (University of Illinois Press, Urbana Illinois, 1949).
A. H. W. BECK, in “Statistical Mechanics, Fluctuations, and Noise” (Edward Arnold, London, 1976).
E. T. JAYNES, in “Information Theory and Statistical Mechanics”, in “Statistical Physics”, edited by K. W. FORD (W. A. Benjamin Inc., New York, 1963).
E. S. R. GOPAL, in “Statistical Mechanics and Properties of Matter Theory and Applications” (Ellis Horwood Limited, Chichester, 1974).
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Tanaka, M., Young, R.J. Review Polarised Raman spectroscopy for the study of molecular orientation distributions in polymers. J Mater Sci 41, 963–991 (2006). https://doi.org/10.1007/s10853-006-6595-7
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DOI: https://doi.org/10.1007/s10853-006-6595-7