Abstract
Over time, nuclear magnetic resonance (NMR) spectroscopy has proven to be a remarkably versatile tool for the description of molecular structure and dynamics. This versatility arises from the wide range of nuclear interactions affecting the NMR signal. Because these interactions depend on different nuclear and molecular parameters, one can manipulate them to extract very specific information. Since the development, in the mid-1970s, of solid-state pulse techniques, it has been possible to tailor an NMR experiment to highlight the specific interaction of interest [1–4], leading to a finer description of chemical structure, morphology, orientation, and chain dynamics [5–7].
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References
Gerstein, B.C. and Dybowski, C. (1985) Transient Techniques in the NMR of Solids: An Introduction to Theory and Practice, Academic Press, New York.
Mehring, M. (1993) High Resolution NMR in Solids, Springer-Verlag, Berlin.
Haeberlen, U. (1970) High Resolution NMR in Solids: Selective Averaging, Academic Press, New York.
Munowitz, M. (1990) Approaches to high-resolution NMR in solids. Trends in Analytical Chemistry, 9 253–63.
Komoroski, R.A. (ed.) (1986) High Resolution NMR Spectroscopy of Synthetic Polymers in Bulk, VCH Publishers, Deerfield Beach, FL.
Fyfe, C.A. (1983) Solid State NMR for Chemists, CFC Press, Guelph, ON.
Koenig, J.L. (1992) Spectroscopy of Polymers, American Chemical Society, Washington, DC.
Cheng, H.N. (1991) NMR characterization of polymers, in Modern Methods of Polymer Characterization, (eds H.G. Barth and J.W. Mays), John Wiley and Sons, New York, pp. 409–93.
Yu, T. and Guo, M. (1990) Recent developments in 13C solid-state high-resolution NMR of polymers. Prog. Polym. Sci. 15 825–908.
Bluemich, B., Hagemeyer, A., Schaefer, D. et al. (1990) Solid-state NMR spectroscopy in polymer science. Adv. Mat. 2 72–81.
Laupetre, F. (1990) Applications of high-resolution solid-state carbon-13 NMR to polymers. Prog. Polym. Sci. 15 425–74.
Kinsey, R.A. (1990) Solid-state NMR of elastomers. Rubb. Chem. Tech. 63 407–25.
Axelson, D.E. and Russell, K.E. (1985) Characterization of polymers by means of 13C NMR spectroscopy. Prog. Polym. Sci. 11 221–82.
Jelinski, L.W. and Melchior, M.T. (1987) High-resolution NMR of solids, in NMR Spectroscopy Techniques, (eds C. Dybowski and R.L. Lichter). Marcel Dekker, New York, pp. 253–329.
Jelinski, L.W. (1982) Solid-state NMR of macromolecules, in Chain Structure and Conformation of Macromolecules, (ed. F.A. Bovey), Academic Press, New York, pp. 223–49.
Spiess, H.W. (1991) Structure and dynamics of solid polymers from 2D- and 3D-NMR. Chem. Rev. 91 1321–38.
Spiess, H.W. (1989) Two-dimensional NMR methods for studying solid polymers. Makromol. Chem., Macromol. Symp. 26 197–207.
Harris, R.K. and Mann, B.E. (1978) NMR and the Periodic Table, Academic Press, London.
Crosby, R.C. and Haw, J.F. (1987) Magic-angle spinning NMR of polyphosphazenes. Macromolecules, 20 2324–8.
Powell, D.G. and Mathias, L.J. (1990) Characterization of nylon-6 by 15N solid-state nuclear magnetic resonance. J. Am. Chem. Soc. 112 669–75.
Powell, D.G. and Mathias, L.J. (1990) 15N NMR powder spectra of semicrystalline nylon-6. Polym. Comm. 31 58–60.
Mathias, L.J. and Johnson, C.G. (1991) Solid-state NMR investigation of nylon-12. Macromolecules, 24 6114–22.
Hatfield, G.R., Glans, J.H. and Hammond, W.B. (1990) Characterization of structure and morphology in nylon-6 by solid-state 13C and 15N NMR. Macromolecules, 23 1654–8.
Asakura, T., Yoshimizu, H. and Yoshizawa, F. (1988) NMR of silk fibroin. Sequence and conformation analyses of the silk fibroins from Bombyx mori and Philosaia cynthia ricini by 15N NMR spectroscopy. Macromolecules, 21 2038–41.
Beshah, K., Mark, J.E. and Ackerman, J.L. (1986) Topology of poly(dimethylsiloxane) elastomeric networks studied by variable-temperature solid-state nuclear magnetic resonance. Macromolecules, 19 2194–6.
Beshah, K., Mark, J.E., Ackerman, J.L. and Himstedt, A. (1986) Characterization of PDMS model junctions and networks by solution and solid-state silicon-29 NMR spectroscopy. J. Polym. Sci. B: Polym. Phys. 24 1207–25.
Litvinov, V.M., Whittaker, A.K., Hagemeyer, A. and Spiess, H.W. (1989) Molecular motions in poly(dimethylsiloxane) studied by solid-state 29Si NMR. Colloid Polym. Sci. 267 681–6.
Dickinson, L.C., MacKnight, W.J., Connolly, J.M. and Chien, J.C.W. (1987) 23Na NMR of solid-state ionomers: lineshape, shift, and hydration effects. Polym. Bull. 17, 459–64.
Dickinson, L.C., Chien, J.C.W, and MacKnight, W.J. (1988) Cross-link point mobility in swollen polymer networks by phosphorus-31 spin-lattice relaxation in the rotating frame. Macromolecules, 21 2959–63.
Kambour, R.P., Kelly, J.M., McKinley, B.J. et al. (1988) Spectroscopic studies of diluent motion in glassy plastiazed blends. Macromolecules, 21, 2937–40.
Carduner, K.R., Carter, R.O., Cheung, M.F. et al. (1990) Studies on the role of organophosphites in polyester blends: I. 3lP nuclear magnetic resonance spectroscopy. J. Appl. Polym. Sci. 40 963–75.
Dybowski, C., Bansal, N. and Duncan, T.M. (1991) NMR spectroscopy of xenon in confined spaces: clathrates, intercalates, and zeolites. Annu. Rev. Phys.Chem. 42 433–64.
Stengle, T.R. and Williamson, K.L. (1987) Nuclear magnetic resonance of xenon absorbed in solid polymers: a probe of the amorphous state. Macromolecules, 20 1428–30.
Kennedy, G.J. (1990) Xenon-129 NMR as a probe of the effect of crosslinking on the amorphous phase structure of polymers. Polym. Bull. 23 605–8.
Kentgens, A.P.M., von Boxtel, H.A., Verweel, R.-J. and Veeman, W.S (1991) Line-broadening effect for 129Xe absorbed in the amorphous state of solid polymers. Macromolecules, 24 3713–14.
Brownstein, S.K., Roovers, J.E.L. and Worsfold, D.J. (1988) 129Xe line widths in block copolymers. Magn. Res. Chem. 26 392–3.
Linder, M., Henrichs, P.M., Hewitt, J.M. and Massa, D.J. (1985) Use of carbon-carbon nuclear spin diffusion for the study of miscibility of polymer blends. J. Chem. Phys. 82 1585–98.
Clements, J., Davies, G.R. and Ward, I.M. (1985) A broad line NMR study of oriented poly(vinylidene fluoride). Polymer, 26 208–18.
Kauffman, J.S. and Dybowski, C. (1989) Determination of transition temperatures and crystalline content of linear, high-molecular-weight polyethylene by proton NMR spectroscopy. J. Polym. Sci. B: Polym. Phys. 27 2203–9.
Goldman, M. and Shen, L. (1966) Spin-spin relaxation in LaF3. Phys Rev. 144 321–31.
Cheung, T.T.P., Gerstein, B.C., Ryan, L.M. et al. (1980) Chem. Phys. 73 6059–67.
van der Hart, D.L. (1990) Proton spin diffusion as a tool for characterizing polymer blends. Makromol. Chem., Macromol. Symp. 34 125–59.
Miller, J.B., McGrath, K.J., Roland, C.M. et al. (1990) Nuclear magnetic resonance study of polyisoprene/poly(vinylethylene) miscible blends. Macromolecules, 23 4543–7.
Caravatti, P., Neuenschwander, P. and Ernst, R.R. (1986) Characterization of polymer blends by selective proton spin-diffusion nuclear magnetic resonance measurements. Macromolecules, 29 1889–95.
Caravatti, P., Neuenschwander, P. and Ernst, R.R. (1985) Characterization of heterogeneous polymer blends by two-dimensional proton spin diffusion spectroscopy. Macromolecules, 28 119–22.
Jelinski, L.W., Schilling, F.C. and Bovey, F.A. (1981) Carbon-13 nuclear magnetic resonance studies of solid segmented copolymers. 1. Mobile domains of a polyester thermoplastic elastomer. Macromolecules, 14 581–6.
Pines, A., Gibby, M.G. and Waugh, J.S. (1973) Proton-enhanced NMR of dilute spins in solids. J. Chem. Phys. 59 569–90.
Parmer, J.F., Dickinson, L.C., Chien, J.C.W, and Porter, R.S. (1987) Polymer-polymer miscibility determination via CP-MAS NMR in blends of deuterated and protonated polymers. Macromolecules, 20 2308–10.
Gobbi, G.C., Silvestri, R., Russell, T.P. et al. (1987) Intermolecular polarization transfer study of polymer blend compatibility. J. Polym. Sci. C: Polym. Lett. 25 61–5.
Zhang, X., Natansohn, A. and Eisenberg, A. (1990) Intermolecular cross-polarization studies of the miscibility enhancement of PS/PMMA blends through ionic interactions. Macromolecules, 23 412–16.
Zumbulyadis, N. and Reilly, J.M. (1991) Polarization transfer across interfaces. 1. 29Si cross-polarization dynamics at the poly(vinyl alcohol)-silica sol-gel interface. Macromolecules, 24, 5294–8.
Duff, D.W. and Maciel, G.E. (1991) Monitoring postcure reaction chemistry of residual isocyanate in 4,4′-methylenebis(phenyl isocyanate) based isocyanurate resins by 15N and 13C CP/MAS NMR. Macromolecules, 24 387–97.
Duff, D.W. and Maciel, G.E. (1991) Monitoring the thermal degradation of an isocyanurate-rich MDI-based resin by 15N and 13C CP/MAS NMR. Macromolecules, 24, 651–8.
Duff, D.W. and Maciel, G.E. (1990) 13C and 15N CP/MAS NMR characterization of MDI-polyisocyanurate resin systems. Macromolecules, 23 3069–79.
Schmidt-Rohr, K., Clauss, J., Bluemich, B. and Spiess, H.W. (1990) Miscibility of polymer blends investigated by 1H spin diffusion and 13C NMR detection. Magn. Res. Chem., 28 S3–9.
Hughes, C.D., Sethi, N.K., Baltisberger, J.H. and Grant, D.M. (1989) Polyethylene crystallinity from static, solid-state NMR spectra. Macromolecules, 22 2551–4.
Brandolini, A.J., Apple, T.M., Dybowski, C. and Pembleton, R.G. (1982) Solid-state 19F NMR of deformed PTFE. Polymer, 23 39–42.
Brandolini, A.J. and Dybowski, C. (1983) Determination of orientation distribution functions using solid-state nuclear magnetic resonance. J. Polym. Sci.: Lett. Ed., 21 423–8.
Brandolini, A.J., Alvey, M.D. and Dybowski, C. (1983) The crystallite orientation distribution functions of deformed polytetrafluoroethylene: multiple-pulse 19F NMR spectroscopy. J. Polym. Sci. Phys. Ed., 21 2511–34.
Brandolini, A.J., Rocco, K.J. and Dybowski, C. (1984) Solid-state 19F NMR investigations of annealed polytetrafluoroethylene. Macromolecules, 17 1455–8.
Henrichs, P.M. (1987) Molecular orientation and structure in solid polymers with 13C NMR: a study of biaxial films of poly(ethylene terephthalate). Macromolecules, 20, 2099.
Schaefer, J. Stejskal, E.O. and Buchdahl, R. (1977) Magic-angle 13C NMR analysis of motion in solid glassy polymers. Macromolecules, 10 384–405.
Takahashi, M., Ookubo, M. and Takenaka, H. (1991) Solid-state 13C NMR spectra analysis of alkalicellulose. Polymer, 23, 1009–14.
Brueckner, S., Meille, S.V., Sozzani, P. and Torri, G. (1990) Gamma isotactic polypropylene: an MAS 13C NMR study of a crystalline polymer with non-parallel chains. Makromol. Chem. Rapid Comm., 11 55–60.
Kaji, A., Ohta, Y., Yasuda, H. and Murano, M. (1990) Phase structural analysis of ultra high-molecular weight polyethylene fibers by solid-state high-resolution NMR. Polym. J. 22 455–62.
Dec, S.F., Wind, R.A. and Maciel, G.E. (1987) Solid-state fluorine-19 nuclear magnetic resonance study of fluorocarbon polymers. Macromolecules, 20 2754–61.
Taylor, P.C., Baugher, J.F. and Kriz, H.M. (1975) Chem. Rev. 75 203.
Jelinski, L.W. (1986) Deuterium NMR of solid polymers, in High-Resolution NMR Spectroscopy of Synthetic Polymers in Bulk, (ed. R.A. Komoroski), VCH Publishers, Deerfield Beach FL, pp. 335–64.
Dumais, J.J., Jelinski, L.W., Leung, L.M. et al. (1985) Phase separation in polyurethanes — a deuterium NMR study. Macromolecules, 18 116–9.
Kornfeld, J.A., Spiess, H.W., Nefzger, H. et al. (1991) Deuteron NMR measurements of order and mobility in the hard segments of a model polyurethane. Macromolecules, 24 4787–95.
Dumais, J.J., Cholli, A.L., Jelinski, L.W. et al. (1986) Molecular basis of the β-transition in poly(arylene ether sulfones). Macromolecules, 29, 1884–9.
Cholli, A.L., Dumais, J.J., Engel, A.K. and Jelinski, L.W. (1984) Aromatic ring flips in a semicrystalline polymer. Macromolecules, 17 2399–404.
Schaefer, D., Spiess, H.W., Suter, U.W. and Fleming, W.W. (1990) Two-dimensional solid-state NMR studies of ultraslow chain motion: glass transition in atactic polypropylene versus helical jumps in isotactic polypropylene. Macromolecules, 23, 3431–9.
Doverspike, M.A., Conradi, M.S., DeReggi, A.S. and Cais, R.E. (1989) Deuterium magnetic resonance study of orientation and poling in poly(vinylidene fluoride) and poly(vinylidene fluoride-co-tetrafluoroethylene. J. Appl.Phys. 65 541–7.
Ballinger, J.M., Kasuboski, L.A. and Dybowski, C. (1987) Spin-lattice relaxation of dipolar energy of polypropylenes. Macromolecules, 20 1012–4.
Chu, C.W., Dickinson, L.C. and Chien, J.C.W. (1990) Study of critical phenomena of polystyrene-polyvinyl methyl ether blends by solid-state NMR. J. Appl. Polym. Sci. 41 2311–25.
Percec, S. and Hammond, T. (1990) Phase behavior of blend systems containing nitrile copolymers examined by solid-state nuclear magnetic resonance and differential scanning calorimetry. Polymer, 32 1252–7.
Liu, Y., Roy, A.K. and Jones, A.A. (1990) An NMR study of plasticization and antiplasticization of a polymeric glass. Macromolecules, 23 968–77.
Webb, A.G. and Hall, L.D. (1991) An experimental overview of the use of nuclear magnetic resonance imaging to follow solvent ingress into polymers. Polymer, 32 2926–38.
Weisenberger, L.A. and Koenig, J.L. (1989) NMR imaging of solvent diffusion in polymers. Appl. Spectrosc., 43 1117–26.
Perry, B.C. and Koenig, J.L. (1989) A 1H magnetic resonance imaging study of porosity in polyurethane foams. J. Polym. Sci. A: Polym. Chem. 27 3429–38.
Smith, S.R. and Koenig, J.L. (1991) Observation of cross-link density dispersion in sulfur donor-vulcanized polybutadiene using NMR imaging. Macromolecules, 24 3496–504.
Bluemler, P. and Bluemlich, B. (1991) Aging and phase separation of elastomers investigated by NMR imaging. Macromolecules, 24 2183–8.
Chang, C. and Komoroski, R.A. (1989) NMR imaging of elastomeric networks. Macromolecules, 22 600–7.
Garrido, L., Mark, J.E., Sun, C.C. et al. (1991) NMR characterization of elastomers reinforced with in situ precipitated silica. Macromolecules, 24 4067–72.
Jackson, P., Clayden, N.J., Walton, N.J. et al. (1991) Magnetic resonance imaging studies of the polymerization of methylmethacrylate. Polym. Intl. 24 139–43.
Guenther, E., Bluemich, B. and Spiess, H.W. (1990) Deuteron double-quantum NMR imaging of molecular order and mobility in solid polymers. Mol. Phys. 71 477–89.
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Dybowski, C., Brandolini, A.J. (1994). NMR spectroscopy of solid polymer systems. In: Spells, S.J. (eds) Characterization of Solid Polymers. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-1262-8_7
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DOI: https://doi.org/10.1007/978-94-011-1262-8_7
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