Abstract
By utilizing a biconcave refractive neutron lens (MgF2) 5-inch size & high resolution position sensitive area photomultiplier with scintillator (ZnS), we constructed a focusing ultra-small-angle neutron scattering (USANS) spectrometer (SANS-J-II) at research reactor JRR3, Tokai, Japan. SANS-J-II can successfully reach to qmin=0.0003 Å−1, where q (=4πsin(θ)/λ) is the magnitude of scattering vector given by wavelength λ and scattering angle 2θ, and simultaneously cover conventional small-angle neutron scattering (SANS) region to q=0.004 Å−1. Focusing USANS, thus realized, plays an important role to investigate the time-evolution of hierarchically ordered structures in the living radical polymerization solution, preparing poly(methyl methacrylate)-block-polystyrene (PMMA-b-PS). In the reaction process to synthesize a PS block chain from the end of PMMA block chain, we found the interplay between macro- and microphase separation. SANS at q>0.001 Å−1 determined time-evolving microdomain structures; as the polymerization proceeds, (i) first by order-disorder transition, a lamellar microdomain appears and (ii) second by order-order transitions, the morphologies of microdomains change to PMMA cylinder and successively to PMMA sphere. USANS at q<0.001 Å−1, exhibiting power law scattering (∼q−α) due to macrophase separation between PMMA-b-PS and PS homopolymer (appeared as by product). The exponent α varies from 4 to 2, reflecting a grain boundary of macrodomain rich-in PMMA-b-PS; when a lamellar microdomain appears, Porod law gives α=4, whereas when cylinder and sphere appear, α=2, due to inhomogeniety of the microdomain spatial distribution of the microdomains.
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S. Koizumi, H. Iwase, J. Suzuki, T. Oku, R. Motokawa, H. Sasao, H. Tanaka, D. Yamaguchi, H. M. Shimizu, and T. Hashimoto, J. Appl. Crystallogr., 40, s474 (2007).
S.-M. Choi, J. G. Barker, C. J. Glinka, Y. T. Cheng, and P. L. Gammel, J. Appl. Crystallogr., 33, 793 (2000).
U. Bonse and M. Hart, Appl. Phys. Lett., 7, 238 (1965).
J. Chiefari, Y. K. Ercole, C. J. Glinka, F. Krstina, J. Jeffery, T. P. T. Le, R. T. A. Mayadunne, G. F. Meijs, C. L. Moad, G. Moad, E. Rizzardo, and S. H. Thang, Macromolecules, 31, 5559 (1998).
Y. K. Chong, J. Krstina, T. P. T. Le, G. Moad, A. Postma, E. Rizzardo, and S. H. Thang, Macromolecules, 36, 2256 (2003).
E. Helfand and Y. J. Tagami, J. Chem. Phys., 56, 3592 (1972).
T. Hashimoto, M. Shibayama, and H. Kawai, Macromolecules, 16, 1093 (1983).
P. G. de Gennes, in “Scaling Concepts in Polymer Physics,” Cornell University Press, N.Y., Ithaca, 1979.
I. W. Hamley, in “The Physics of Block Copolymers,” Oxford University Press, New York, 1998.
K. Yamauchi, H. Hasegawa, T. Hashimoto, H. Tanaka, R. Motokawa, and S. Koizumi, Macromolecules, 39, 4531 (2006).
R. Motokawa, S. Koizumi, Y. Zhao, and T. Hashimoto, J. Appl. Crystallogr., 40, s645 (2007).
F. Q. John, R. Ezio, and T. P. Davis, Chem. Commun., 1044 (2001).
K. S. Khuong, W. H. Jones, W. A. Pryor, and K. N. Houk, J. Am. Chem. Soc., 127, 1265 (2005).
L. Rosta, Physica B, 156–157, 615 (1989).
S. Koizumi, H. Iwase, J. Suzuki, T. Oku, R. Motokawa, H. Sasao, H. Tanaka, D. Yamaguchi, H. M. Shimizu, and T. Hashimoto, Physica B, 385–386, 1000 (2006).
A. Guinier and G. Fournet, in “Small-Angle Neutron Scattering of X-rays,” John Wiley and Sons, Inc., New York, 1955.
W. J. Ruland, J. Appl. Crystallogr., 4, 70 (1971).
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Motokawa, R., Iida, Y., Zhao, Y. et al. Living Polymerization Induced Macro- and Microdomain Investigated by Focusing Ultra-small-angle Neutron Scattering. Polym J 39, 1312–1318 (2007). https://doi.org/10.1295/polymj.PJ2007099
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DOI: https://doi.org/10.1295/polymj.PJ2007099