Hartree analysis of 蠂 for a pressure-responsive diblock copolymer: Temperature-pressure superposition

详细信息    查看全文

• 作者：Junhan Cho (1) jhcho@dankook.ac.kr
• 关键词：SANS χ ; &#8211 ; Hartree fluctuation correction analysis &#8211 ; temperature ; pressure superposition &#8211 ; polydispersity
• 刊名：Macromolecular Research
• 出版年：2012
• 出版时间：May 2012
• 年：2012
• 卷：20
• 期：5
• 页码：534-539
• 全文大小：412.4 KB
• 参考文献：1. I. W. Hamley, Prog. Polym. Sci., 34, 1161 (2009).
  2. A. K. Khandpur, S. Forster, F. S. Bates, I. W. Hamley, A. J. Ryan, W. Bras, K. Almdal, and K. Mortensen, Macromolecules, 28, 8796 (1995).
  3. T. Hashimoto, Thermoplastic Elastomers, G. Holden, N. R. Legge, R. P. Quirk, and H. E. Schroeder, Eds., Hanser, New York, 1996.
  4. N. Hadjichristidis, S. Pispas, and G. A. Floudas, Block Copolymers: Synthetic Strategies, Physical Properties, and Applications, John Wiley & Sons, Inc., Hoboken, 2003.
  5. F. S. Bates and G. H. Fredrickson, Annu. Rev. Phys. Chem., 41, 525 (1990).
  6. T. P. Russell, T. E. Karis, Y. Gallot, and A. M. Mayes, Nature, 386, 729 (1994).
  7. A.-V. G. Ruzette, P. Banerjee, A. M. Mayes, M. Pollard, T. P. Russell, R. Jerome, T. Slawecki, R. Hjelm, and P. Thiyagarajan, Macromolecules, 31, 8509 (1998).
  8. D. Y. Ryu, C. Shin, J. Cho, D. H. Lee, J. K. Kim, K. A. Lavery, and T. P. Russell, Macromolecules, 40, 7644 (2007).
  9. D. A. Hajduk, S. M. Gruner, S. Erramilli, R. A. Register, and L. J. Fetters, Macromolecules, 29, 1473 (1996).
  10. A.-V. Ruzette, A. M. Mayes, M. Pollard, T. P. Russell, and B. Hammouda, Macromolecules, 36, 3351 (2003).
  11. J. A. Gonzalez-Leon, M. H. Acar, S. W. Ryu, A.-V. Ruzette, and A. M. Mayes, Nature, 426, 424 (2003).
  12. I. W. Hamley, Ed., Developments in Block Copolymer Science and Technology, John Wiley & Sons Ltd., Chichester, 2004.
  13. L. Leibler, Macromolecules, 13, 1602 (1980).
  14. G. H. Fredrickson and E. Helfand, J. Chem. Phys., 87, 697 (1987).
  15. M. Olvera de la Cruz, Phys. Rev. Lett., 67, 85 (1991).
  16. D. Y. Ryu, U. Jeong, J. K. Kim, and T. P. Russell, Nat. Mater., 1, 114 (2002).
  17. D. Y. Ryu, D. H. Lee, J. K. Kim, K. A. Lavery, T. P. Russell, Y. S. Han, B. S. Seong, C. H. Lee, and P. Thiyagarajan, Phys. Rev. Lett., 90, 235501 (2003).
  18. H. J. Kim, S. B. Kim, J. K. Kim, and Y. M. Jung, J. Phys. Chem. B, 112, 15295 (2008).
  19. A. R. Jo, W. C. Joo, W. H. Jin, H. J. Nam, and J. K. Kim, Nat. Nanotechnol., 4, 727 (2009).
  20. J. Cho, Macromolecules, 33, 2228 (2000).
  21. J. Cho, J. Chem. Phys., 119, 5711 (2003).
  22. J. Cho, J. Chem. Phys., 120, 9831 (2004).
  23. J. Cho, Macromolecules, 37, 10101 (2004).
  24. J. Cho, Polymer, 48, 429 (2007).
  25. J. Cho and I. C. Sanchez, Macromolecules, 31, 6650 (1998).
  26. I. C. Sanchez, J. Cho, and W.-J. Chen, J. Phys. Chem., 97, 6120 (1993).
  27. I. C. Sanchez, J. Cho, and W.-J. Chen, Macromolecules, 26, 4234 (1993).
  28. I. C. Sanchez and J. Cho, Polymer, 36, 2929 (1995).
  29. J. Lee, D. Y. Ryu, and J. Cho, Macromolecules, 44, 2387 (2011).
  30. C. Burger, W. Ruland, and A. N. Semenov, Macromolecules, 23, 3339 (1990).
  31. The experimental volume of a molten polymer is almost perfectly represented by a functional form as V/V a=exp[{ ω/ (1−ω)B 1}{1−(1+B 1 P/ ωB a)1−ω}] with B 1=10.2 and ω=0.9, where V a and B a are volume and bulk modulus at ambient pressure P a.27,28 PS possesses 1/V a=1.2247−5.3781脳10−4 T and lnB a= 8.8737−0.0038T while PPrMA reveals 1/V a=1.2848−6.7654脳 10−4 T and lnB a=9.1289−0.0049T.23,28 The regressed volumetric data for PS are taken as those for dPS in estimating the bulk modulus. The bulk modulus B 0 at P 0=13.79 MPa for the symmetric copolymer is estimated as the average of those of the two block constituents as lnB 0=8.8925−0.0039T.
  32. K. Huang, Statistical Mechanics, 2nd ed., Wiley, New York, 1987.
• 作者单位：1. Department of Polymer Science & Engineering and Center for Photofunctional Energy Materials, Dankook University, Gyeonggi, 448-701 Korea
• 刊物类别：Chemistry and Materials Science
• 刊物主题：Chemistry
  Physical Chemistry
  Polymer Sciences
  Characterization and Evaluation of Materials
  Soft and Granular Matter, Complex Fluids and Microfluidics
  Nanochemistry
  Nanotec
  
• 出版者：The Polymer Society of Korea, co-published with Springer
• ISSN：2092-7673

文摘

The response of small-angle neutron scattering (SANS) to pressure for a molten block copolymer in the disordered state has been studied through a Hartree (fluctuation correction) analysis. A slightly polydisperse diblock copolymer from deuterated polystyrene and poly(n-propyl methacrylate), denoted as dPS-b-PPrMA, was chosen for our purpose, because its ordering transition is highly sensitive to pressure. It was shown that the isotherms of effective Flory-Huggins parameters χ’s from the Hartree analysis are superposed into a characteristic curve when χ is scaled by χ(P ₀) at a reference pressure P ₀, and plotted against pressure difference ΔP (≡P-P ₀) divided by temperature dependent bulk modulus B ₀ at P ₀. Such a procedure required a scale factor τ, which was completely determined by B ₀. The established superposition yielded the interconvertibility of temperature and pressure effects on the Hartree χ. This behavior of χ was revealed to manifest that components of χ rely on the ratio of volume V to V ₀ at the reference P ₀, which is an exclusive function of ΔP/B ₀ to satisfy the temperature-pressure superposition concept in volumetric properties of polymeric liquids.