1932

Abstract

The first three decades of my research career closely map the development of neutron scattering techniques for the study of molecular behavior. At the same time, the theoretical understanding of organization and motion of polymer molecules, especially in the bulk state, was developing rapidly and providing many predictions crying out for experimental verification. Neutron scattering is an ideal technique for providing the necessary evidence. This autobiographical essay describes the applications by my research group and other collaborators of increasingly sophisticated neutron scattering techniques to observe and understand molecular behavior in polymeric materials. It has been a stimulating and rewarding journey.

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2016-06-07
2024-03-28
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Literature Cited

  1. Downes JS, White JW, Egelstaff PA, Ramsey V. 1.  1966. Localised vibrations of trapped molecules. Phys. Rev. Lett. 17:533 [Google Scholar]
  2. Egelstaff PA, Stretton Downes JS, White JW. 2.  1967. Molecular motion in molecular sieves by neutron scattering spectroscopy. Mol. Sieves (Chem. Ind.) 306:308–18 [Google Scholar]
  3. Downes JS. 3.  1968. Inelastic scattering of neutrons from clathrate inclusion compounds and molecules in molecular sieves DPhil Thesis, Oxford Univ., Oxford, UK
  4. Allen G, Higgins JS. 4.  1971. Spectroscopic studies of molecular motion in polymers. Molecular Spectroscopy P Heppel 261 London: Inst. Pet. [Google Scholar]
  5. Higgins JS, Allen G, Brier PN. 5.  1972. Methyl group motion in polypropylene oxide, polypropylene and polymethyl methacrylate. Polymer 13:157–63 [Google Scholar]
  6. Allen G, Wright CJ, Higgins JS. 6.  1974. Effect of polymer microstructure on methyl group torsional vibrations. Polymer 15:319–22 [Google Scholar]
  7. Allen G, Brier PN, Goodyear G, Higgins JS. 7.  1972. Motional broadening of the quasi-elastic peak in neutrons scattered from polymeric materials. Faraday Symp. Chem. Soc. 6:169–75 [Google Scholar]
  8. Higgins JS, Benoit HC. 8.  1994. Polymers and Neutron Scattering Oxford: Oxford Univ. Press
  9. Rouse PE. 9.  1953. A theory of the linear viscoelastic properties of dilute solutions of coiling polymers. J. Chem. Phys. 21:1272 [Google Scholar]
  10. Zimm B. 10.  1956. Dynamics of polymer molecules in dilute solution: viscoelasticity, flow birefringence and dielectric loss. J. Chem. Phys. 24:269–78 [Google Scholar]
  11. de Gennes PG. 11.  1967. Quasi-elastic scattering of neutrons by dilute polymer solutions: I. Free draining limit. Physics 3:37–45 [Google Scholar]
  12. Dubois-Violette E, de Gennes PG. 12.  1967. Quasi-elastic scattering of dilute, ideal, polymer solutions: II. Effects of hydrodynamic interactions. Physics 3:181–98 [Google Scholar]
  13. Allen G, Higgins JS, Wright CJ. 13.  1974. Segmental diffusion in rubbers studied by neutron quasi-elastic incoherent scattering. J. Chem. Soc. Faraday II 70:348–55 [Google Scholar]
  14. Benoît H, Decker D, Higgins JS, Picot C, Cotton JP. 14.  et al. 1973. Dimensions of a flexible polymer chain in the bulk and in solution. Nature 245:13–15 [Google Scholar]
  15. Kirste R, Kruse WA, Ibel K. 15.  1975. Determination of conformation of polymers in amorphous solid state and in concentrated solution by neutron diffraction. Polymer 16:120–24 [Google Scholar]
  16. Lieser G, Fischer EW, Ibel K. 16.  1975. Conformation of polyethylene molecules in the melt as revealed by small angle neutron scattering. J. Polym. Sci. Polym. Lett. Ed. 13:39–43 [Google Scholar]
  17. Allen G, Ghosh RE, Heidemann A, Higgins JS, Howells WS. 17.  1974. On the structure of the quasielastic incoherent neutron scattering from polydimethyl siloxane. Chem. Phys. Lett. 27:308–11 [Google Scholar]
  18. Higgins JS, Ghosh R, Howells WS. 18.  1977. Q4-dependent broadening in quasielastic incoherent neutron scattering from a polymer melt. J. Chem. Soc. Faraday Trans. II 73:40–47 [Google Scholar]
  19. Akcasu AZ, Higgins JS. 19.  1977. Quasielastic scattering of neutrons from freely jointed polymer chains in dilute solution. J. Polym. Sci. Polym. Phys. 15:1745–56 [Google Scholar]
  20. Ganazzoli F, Allegra G, Higgins JS, Roots JE, Bruckner S, Lucchelli E. 20.  1985. Chain dynamics of polydimethyl siloxane in the intermediate range. Macromolecules 18:435–42 [Google Scholar]
  21. Higgins JS, Nicholson LK, Hayter JB. 21.  1981. Observation of single chain motion in a polymer melt. Polymer 22:163–67 [Google Scholar]
  22. Higgins JS, Nicholson LK, Hayter JB. 22.  1981. Dynamics of dilute polymer solutions. Macromolecules 14:836–43 [Google Scholar]
  23. Arrighi V, Higgins JS, Burgess AN, Howells WS. 23.  1995. Rotation of methyl side groups in polymers: a Fourier transform approach to quasielastic neutron scattering. 1. Homopolymers.. Macromolecules 28:2745–53 [Google Scholar]
  24. de Gennes PG. 24.  1971. Reptation of a polymer chain in the presence of fixed obstacles. J. Chem. Phys. 55:572 [Google Scholar]
  25. Doi M, Edwards SF. 25.  1978. Dynamics of concentrated polymer systems. Part 1.—Brownian motion in equilibrium. J. Chem. Soc. Faraday Trans. II 74:1789–801 Doi M, Edwards SF. 1978. Dynamics of concentrated polymer systems. Part 2.—molecular motion under flow J. Chem. Soc. Faraday Trans. II 74:1802–17 [Google Scholar]
  26. de Gennes PG. 26.  1980. Coherent scattering by one reptating chain.. J. Phys 42:735–40 [Google Scholar]
  27. Ronca G. 27.  1983. Frequency spectrum and dynamic correlations of concentrated polymer liquids. J. Chem. Phys. 79:1031–43 [Google Scholar]
  28. Higgins JS, Roots JE. 28.  1985. Effects of entanglements on the single chain motion of polymer molecules in melt samples observed by neutron scattering. J. Chem. Soc. Faraday II 81:757–67 [Google Scholar]
  29. Koningsveld R, Stockmayer WJ, Nies E. 29.  2001. Polymer Phase Diagrams: A Textbook Oxford: Oxford Univ. Press
  30. Walsh DJ, Higgins JS, Zhikuan C. 30.  1982. The compatibility of poly(methyl methacrylate) and chlorinated polyethylene. Polymer 23:336–39 [Google Scholar]
  31. Zhikuan C, Ruona S, Walsh DJ, Higgins JS. 31.  1982. A thermodynamic interpretation of the compatibility of chlorinated polyethylene with poly(methyl methacrylate). Polymer 24:263–70 [Google Scholar]
  32. Walsh DJ, Higgins JS, Rostami S. 32.  1983. The compatibility of ethylene vinyl acetate copolymers with chlorinated polyethylene. 1. Compatibility and its variation with temperature. Macromolecules 16:388 Walsh DJ, Higgins JS, Rostami S, Weeraperuma K. 1983. 2. Investigation of thermodynamic parameters Macromolecules 16:391 [Google Scholar]
  33. Allen G, Chai Z, Chong CL, Higgins JS, Tripathi J. 33.  1984. Thermodynamics of oligomeric binary mixtures of polyethylene glycol and polypropylene glycol methyl ethers. Polymer 25:239–44 [Google Scholar]
  34. Warner M, Higgins JS, Carter AJ. 34.  1983. Chain dimension and interaction parameters in neutron scattering from polymer blends with a labelled component. Macromolecules 16:1931–35 [Google Scholar]
  35. Higgins JS, Carter AJ. 35.  1984. Molecular conformation and interactions in oligomeric mixtures of poly-ethylene glycol and polypropylene glycol methyl ethers: a neutron scattering study. Macromolecules 17:2197–202 [Google Scholar]
  36. Snyder HL, Meakin P, Reich S. 36.  1983. Dynamical aspects of phase separation in polymer blends. Macromolecules 16:757–62 [Google Scholar]
  37. Hill RG, Tomlins PE, Higgins JS. 37.  1985. A preliminary study of phase separation in oligomeric polystyrene/polybutadiene blends. Polymer 26:1708–12 [Google Scholar]
  38. Hill RG, Tomlins PE, Higgins JS. 38.  1985. A preliminary study of the kinetics of phase separation in high molecular weight polymethyl methacrylate/solution chlorinated polyethylene blends. Macromolecules 18:2555–60 [Google Scholar]
  39. Cahn JW. 39.  1968. Spinodal decomposition. Trans. Metal. Soc. AIME 242:168–80 Huston EL, Cahn JW, Hilliard JE. 1966. Spinodal decomposition during continuous cooling Acta Metall. 14:1053–62 Cook HE. 1970. Brownian motion in spinodal decomposition. Acta Metall. 18:297–306 [Google Scholar]
  40. Fruitwala H, Higgins JS, Tomlins PE. 40.  1989. Correlation of phase separation behaviour in polymer blends with thermodynamic measurements in the one phase region. Macromolecules 22:3674–81 [Google Scholar]
  41. Higgins JS, Fruitwala H, Tomlins PE. 41.  1988. Prediction of phase separation behaviour from thermodynamic measurements in the one-phase region. Makromol. Chem. Makromol. Symp. 16:313–27 [Google Scholar]
  42. Clark J, Fernandez ML, Tomlins PE, Higgins JS. 42.  1993. Small angle neutron scattering studies of phase equilibria in blend of deuterated polymethyl methacrylate with solution chlorinated polyethylene. Macromolecules 26:5897–907 [Google Scholar]
  43. Cabral JT, Gerard H, Clarke N, Higgins JS. 43.  2000. Phase separation of polymer blend TMPC/PS: dependence on blending method. Phys. B Condens. Matt. 276–278:408–9 [Google Scholar]
  44. Cabral JT, Higgins JS, McLeish TCB, Strausser S, Magonov S. 44.  2001. Bulk spinodal decomposition studied by atomic force microscopy and light scattering. Macromolecules 34:3748–56 [Google Scholar]
  45. Cabral JT, Higgins JS, Yeruna NA, Magonov SN. 45.  2002. Topography of phase separated critical and off-critical polymer mixtures. Macromolecules 35:1941–50 [Google Scholar]
  46. Hindawi I, Higgins JS, Galambos AF, Weiss RA. 46.  1990. Flow-induced mixing of blends of poly(ethylene-vinylacetate) and solution chlorinated polyethylene. Macromolecules 23:670–74 [Google Scholar]
  47. Hindawi I, Higgins JS, Weiss RA. 47.  1992. Flow-induced mixing and demixing in polymer blends. Polymer 33:2522–29 [Google Scholar]
  48. Fernandez ML, Higgins JS, Richardson SM. 48.  1993. When rheology interacts with thermodynamics in polymer blends. Trans. IChemE 71:239–44 [Google Scholar]
  49. Fernandez ML, Higgins JS, Richardson SM. 49.  1995. Flow instabilities in polymer blends under shear. Polymer 36:931–39 [Google Scholar]
  50. Soontanaranan W, Higgins JS, Papathanasiou T. 50.  1996. Shear flow and the behaviour of polymer blends. Fluid Phase Equilib. 121:273–92 [Google Scholar]
  51. Aelmans NJJ, Reid MC, Higgins JS. 51.  1999. Change of phase behaviour of SMA/PMMA blends during processing at high deformation rates. Polymer 40:5051–62 [Google Scholar]
  52. Clarke N, McLeish TCB, Pavawongsak S, Higgins JS. 52.  1997. Viscoelastic effects on the early stages of phase separation in polymer blends. Macromolecules 30:4459–63 [Google Scholar]
  53. Pavawongsak S, Higgins JS, Clarke N, McLeish TCB, Peiffer D. 53.  2000. Phase separation in entangled polystyrene/poly(vinyl methyl ether) blends. Polymer 41:757–63 [Google Scholar]
  54. Gerard H, Cabral JT, Higgins JS. 54.  2003. Flow-induced enhancement of concentration fluctuations on polymer mixtures. Philos. Trans. R. Soc. Lond. A 361:767–79 [Google Scholar]
  55. Fernandez ML, Higgins JS, Penfold J, Shackleton CS. 55.  1990. Structure of thin deuterated poly(methyl methacrylate) films as studied by the specular reflection of neutrons. Polym. Commun. 31:134 [Google Scholar]
  56. Walsh DJ, Sauer BB, Higgins JS, Fernandez ML. 56.  1990. Reflection methods for the study of polymer interfaces. Polym. Eng. Sci. 30:1085–89 [Google Scholar]
  57. Fernandez ML, Higgins JS, Penfold J, Shackleton C. 57.  1991. Interfacial structure for a compatible polymer blend for short and intermediate annealing times. J. Chem. Soc. Faraday Trans. 87:2055–61 [Google Scholar]
  58. Bucknall DG, Higgins JS, Penfold J. 58.  1992. The effect of a diblock copolymer compatibilizer on the interface between immiscible polymers. Phys. B Condens. Matt. 180:468–70 [Google Scholar]
  59. Bucknall DG, Higgins JS, Penfold J, Rostami S. 59.  1993. Segregation behaviour of deuterated P(s-b-MMA) diblock copolymer in the presence of PMMA homopolymer. Polymer 34:451 [Google Scholar]
  60. Hermes HE, Bucknall DG, Higgins JS, Scherrenberg RL. 60.  1998. The ordering of semi-crystalline PS-b-hPB copolymers at a PS/PB interface and their effects on interfacial strength. Polymer 39:3099 [Google Scholar]
  61. Butler SA, Bucknall DG, Higgins JS. 61.  1999. Real-time measurement of polymer diffusion coefficients using neutron reflection. Macromolecules 32:5453–56 [Google Scholar]
  62. Bucknall DG, Higgins JS, Butler SA. 62.  2004. Real-time neutron reflectivity study of the early stages of diffusion into and dissolution of glassy polymers. J. Polym. Sci. B Polym. Phys. 42:3267–81 [Google Scholar]
  63. Allegra G, Higgins JS, Ganazzoli F, Luccheli E, Bruckner S. 63.  1984. Dynamics of atactic polystyrene in solution. Macromolecules 17:1253–63 [Google Scholar]
  64. Gerard H, Higgins JS, Clarke N. 64.  1999. Shear-induced demixing in polystyrene/poly(vinyl methyl ether) blends. 1. Early stages of shear-induced demixing. Macromolecules 32:5411–22 [Google Scholar]
  65. Arrighi V, Higgins JS, Burgess AN, Howells WS. 65.  1995. Rotation of methyl side groups in polymers: a Fourier transform approach to quasielastic neutron scattering. 2. Polymer blends. Macromolecules 28:4622–30 [Google Scholar]
  66. Arrighi V, Gagliardi S, Zhang C, Ganazzoli F, Higgins JS. 66.  et al. 2003. A unified picture of the local dynamics of poly (dimethylsiloxane) across the melting point. Macromolecules 36:8738–48 [Google Scholar]
  67. Hermes HE, Higgins JS, Bucknall DG. 67.  1997. Investigation of the melt interface between polyethylene and polystyrene using neutron reflectivity. Polymer 38:985–89 [Google Scholar]
  68. Cabral JT, Higgins JS. 68.  2009. Small angle neutron scattering from the highly interacting polymer mixture TMPC/PSd: no evidence of spatially dependent χ parameter. Macromolecules 42:9528–36 [Google Scholar]
  69. Higgins JS, Dodgson K, Semlyen JA. 69.  1979. Studies of cyclic and linear polydimethyl siloxanes: 3. Neutron scattering measurements of the dimensions of ring and chain polymers. Polymer 20:553–58 [Google Scholar]
  70. Arrighi V, Gagliardi S, Dagger AC, Semlyen JA, Higgins JS, Shenton MJ. 70.  2004. Conformation of cyclic and linear chain polymers in bulk by SANS. Macromolecules 37:8057–65 [Google Scholar]
  71. Higgins JS, Ma K, Nicholson LK, Hayter JB, Dodgson K, Semlyen JA. 71.  1983. Studies of cyclic and linear poly(dimethyl siloxane): 12. Observation of diffusion behaviour by quasi-elastic neutron scattering. Polymer 24:793–99 [Google Scholar]
  72. Higgins JS, Dawkins JV, Taylor G. 72.  1980. Non-aqueous polymer dispersions: dimensions of adsorbed AB block copolymers of polystyrene and polydimethyl siloxane by small angle neutron scattering. Polymer 21:627–31 [Google Scholar]
  73. Higgins JS, Tomlins PE, Dawkins JV, Maghami GG, Shakir SA. 73.  1988. Non-aqueous polymer dispersions - investigation of anchor blocks in the adsorbed diblock copolymer poly(styrene-b-ethylene-co-propylene) by SANS. Polymer 29:121–25 [Google Scholar]
  74. Higgins JS, Dawkins JV, Maghami GG, Shakir SA. 74.  1986. Study of micelle formation by the diblock copolymer polystyrene-b-ethylene-co-propylene in dodecane by SANS. Polymer 27:931–36 [Google Scholar]
  75. Higgins JS, Blake S, Tomlins PE, Ross-Murphy SB, Staples E. 75.  et al. 1988. Comparison of the structural and rheological consequences of micelle formation in solutions of a model di-block copolymer. Polymer 29:1968–78 [Google Scholar]
  76. Earnest TR, Higgins JS, MacKnight WJ. 76.  1981. Small angle neutron scattering from sulfonate ionomers. Macromolecules 14:192–96 [Google Scholar]
  77. Earnest TR, Higgins JS, MacKnight WJ. 77.  1982. Small angle neutron scattering from polypentenamer sulfonates. Macromolecules 15:1390–95 [Google Scholar]
  78. Forsman WC, MacKnight WJ, Higgins JS. 78.  1984. Aggregation of ion pairs in polystyrene sulfonate ionomers: theory and experiment. Macromolecules 17:490–94 [Google Scholar]
  79. Arrighi V, Higgins JS, Abis L, Weiss RA. 79.  1996. Characterization of a main-chain semi-flexible liquid crystal polymer: degree of orientational order. Polymer 37:141–48 [Google Scholar]
  80. Arrighi V, Higgins JS. 80.  1997. Molecular dynamics of a main-chain liquid crystal polymer below the crystalline to nematic phase transition. J. Chem. Soc. Faraday Trans. 93:1605–12 [Google Scholar]
  81. Peiffer DG, Kaladao J, Duvdevani I. 81.  1987. Time- and shear-rate-dependent rheology of ionomer solution. Macromolecules 20:1397–400 [Google Scholar]
  82. Lantmann CW, MacKnight WJ, Higgins JS, Peiffer DG, Sinha SK, Lundberg RD. 82.  1988. Small angle neutron scattering from sulfonate ionomer solutions. I. Associating polymer behaviour. Macromolecules 21:1339–43 [Google Scholar]
  83. Gabrys B, Higgins JS, Lantmann CW, MacKnight WJ, Pedley AM. 83.  et al. 1989. Single-chain dimensions in semi-dilute ionomer solutions: a small-angle neutron scattering study. Macromolecules 22:3746–51 [Google Scholar]
  84. Pedley AM, Higgins JS, Peiffer DG, Rennie AR. 84.  1990. Thermodynamics of the aggregation phenomenon in associating polymer solutions. Macromolecules 23:2494–500 [Google Scholar]
  85. Pedley AM, Higgins JS, Peiffer DG, Burchard W. 85.  1990. Light scattering from sulphonate ionomers in xylene. Macromolecules 23:1434–37 [Google Scholar]
  86. Young M, Higgins JS, Peiffer DG, Rennie AR. 86.  1996. Effect of sulfonation level on the single chain dimensions and aggregation of sulfonated polystyrene ionomers in xylene. Polymer 36:691–97 [Google Scholar]
  87. Young AM, Brigault C, Hanan R, Higgins JS, Peiffer DG. 87.  1998. Small angle neutron scattering from ionomer gels. Polymer 39:6685–96 [Google Scholar]
  88. Kanaya T, Kaji K, Kitamaru R, Gabrus B, Higgins JS. 88.  1988. Local motions of counter-ions in polyelectrolyte solutions without added salts studied by neutron quasi-elastic scattering. J. Chem. Soc. Faraday I 84:3487–500 [Google Scholar]
  89. Roots JE, Nyström B, Higgins JS. 89.  1985. Effect of temperature on dynamics of isotactic polystyrene in solution observed by quasi-elastic scattering. Polymer 26:229–31 [Google Scholar]
  90. Nyström B, Roots JE, Gabrys B, Higgins JS, Peiffer D. 90.  et al. 1986. Dynamics of polystyrene sulfonate ionomers in solution: a neutron spin-echo study. J. Polym. Sci. C Polym. Lett. 24:273–81 [Google Scholar]
  91. Higgins JS, Tambasco M, Lipson JEG. 91.  2005. Polymer blends: stretching what we can learn through the combination of experiment and theory. Prog. Polym. Sci. 30:832–43 [Google Scholar]
  92. Tambasco M, Lipson JEG, Higgins JS. 92.  2006. Blend miscibility and the Flory-Huggins interaction parameter: a critical examination. Macromolecules 39:4860–68 [Google Scholar]
  93. Higgins JS, Lipson JEG, White RP. 93.  2010. A simple approach to polymer mixture miscibility. Philos. Trans. R. Soc. Lond. A 368:1009 [Google Scholar]
  94. White RP, Lipson JEG, Higgins JS. 94.  2012. New correlations in polymer blend miscibility. Macromolecules 45:1076–84 [Google Scholar]
  95. White RP, Lipson JEG, Higgins JS. 95.  2012. How pure components control polymer blend miscibility. Macromolecules 45:8861–71 [Google Scholar]
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