Deuteration effects on the miscibility and phase separation kinetics of polymer blends

Yang, Hsinjin; Shibayama, Mitsuhiro; Stein, Richard S.; Sato, Nobuyuki; Hashimoto, Takeji

doi:10.1021/ma00160a032

Cited by 134 publications

(116 citation statements)

References 16 publications

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“…Here, polystyrene/poly(vinyl methyl ether) (PS/PVME) blend has been chosen as a model system. This blend exhibits a typical lower critical solution temperature (LCST) behavior [31][32][33], which is illustrated by the schematic polymerpolymer phase diagram in Figure 1. In this work, the interfacial adhesion of nanoparticles in PS/PVME blends has been quantitatively characterized by intrinsic fluorescence combining with a simple model based on decomposition reaction.…”

Section: Introductionmentioning

confidence: 99%

Interfacial adhesion of nanoparticles in polymer blends by intrinsic fluorescence spectra

Yang¹,

He²,

Zhang³

et al. 2011

Express Polym. Lett.

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Abstract.Intrinsic fluorescence was applied to quantitatively describe the interfacial adhesion of nanoparticles in polystyrene/poly(vinyl methyl ether) (PS/PVME) blends. Due to the aggregation of aromatic rings on PS chains, the temperature dependence of excimer fluorescence intensity (I 324 ) showed the high sensitivity to the phase separation process. Consistent with Ginzburg thermodynamic model, it was found that the addition of spherical hydrophilic nanoparticles shifted the phase separation temperature to higher temperatures due to the aggregation of silica into PVME chains leading to the free energy reduction and slowing down the phase separation dynamics. A certain composition of polymer blend, i.e. 2/8, was focused on to shed light on the dynamic of spinodal decomposition (SD) phase separation by using decomposition reaction model. It was shown that the addition of nanoparticles to polymer blends resulted in the deviation of linear relationship between the initial SD phase separation rate (R p0 ) and thermodynamic driving force (!f SD ). Besides, for PS/PVME (2/8) with 2 vol% silica nanoparticles, the apparent activation energy of phase separation (E a ) was 196.61 kJ/mol, which was higher than that of neat PS/PVME (2/8) blend (E a = 173.68 kJ/mol), which strongly confirmed the interfacial adhesion effect of silica nanoparticles as compatibilizers.

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Section: Introductionmentioning

confidence: 99%

Interfacial adhesion of nanoparticles in polymer blends by intrinsic fluorescence spectra

Yang¹,

He²,

Zhang³

et al. 2011

Express Polym. Lett.

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“…As an example, in blends involving polystyrene (PS) and poly(vinyl methyl ether) (PVME), deuteration of the PS component leads to roughly a 40 degree increase in the lower critical solution temperature (LCST). 7 However, an analogous H-D switch in a blend of PS with tetramethyl polycarbonate (TMPC) has a much smaller effect on the LCST. 9 There appear to be no obvious trends associated with deuterium substitution, and the lack of predictability therefore represents a theoretical opportunity.…”

Section: Introductionmentioning

confidence: 99%

Effect of Deuterium Substitution on the Physical Properties of Polymer Melts and Blends

2010

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Using our simple lattice-based equation of state we capture the effect of deuterium substitution in polystyrene (PS), predicting both the pure component melt properties as well as the remarkable shift in the coexistence curve when hPS is replaced by dPS in forming a blend with poly(vinyl methyl ether) (PVME). Taking advantage of a rare opportunity to compare with experimental pure component data, we demonstrate that by characterizing the deuterated component through analysis of neutron scattering data we are able to make predictions for the pure dPS PVT properties which are in superb agreement with experiment. Calculations and measurement show that the dPS volume (per repeat unit) is slightly larger than that for hPS at low pressure, an effect which can be correlated with a difference in the model energetic parameter, (ε). In addition, we find that the dPS coefficient of thermal expansion (α) is larger than that for hPS and thus closer to the value for PVME. We propose that the increased similarity of the α's for dPS and PVME is connected to the increased miscibility of the dPS/PVME blend, a linkage which may be helpful to experimentalists in anticipating the potential effect on phase stability of polymer blends when deuterium substitution is employed.

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“…The miscibilities of PS and PVME were demonstrated by the observations of a single T g at all compositions for temperatures below the LCST (about 100°C). 4,5 In 1974, Kwei, Nishi, and Roberts 6 determined the composition of each phase-separated domain of a 50/50 PS/PVME blend by measuring the 13 C NMR spin-lattice relaxation time of single-phase and two-phase blends.…”

Section: Introductionmentioning

confidence: 99%

Late Stages of Phase Separation in a Binary Polymer Blend Studied by Rheology, Optical and Electron Microscopy, and Solid State NMR

et al. 1997

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The relation between rheology and the time dependent morphology of a phase-separating binary blend of polystyrene and poly(vinyl methyl ether) was investigated by heating a sample from the single-phase (at 90°C) into the two-phase regime (at 124°C, 16 K above the LCST) and maintaining its temperature there while measuring the evolution of the dynamic moduli G′ and G′′. Morphological changes occurred slowly so that there was sufficient time to cycle the dynamic mechanical measurements repeatedly over five decades in frequency. The morphology was observed on length scales from 1 mm down to 1 nm by conventional optical microscopy combined with digital image analysis, Hoffman modulation microscopy, TEM, and WISE NMR with spin diffusion. NMR shows that major compositional changes occur mostly in the first 20 min and then the composition remains constant at about 60:40 PS/PVME for the PS-rich matrix and 5:95 PS/PVME for the PVME-rich microdomains. The PVME-rich microdomains are separated by thin layers of the PS-rich phase which forms the matrix. On a larger scale, shape and geometry change during the entire experiment (42 h). The linear domain growth appears to be consistent with the theories of Siggia and Doi-Ohta. The initial increase of the dynamic moduli is attributed to the formation of highly interconnected PVME-rich and PS-rich phases during spinodal decomposition. The subsequent decrease of the values of the dynamic moduli is considered to be the result of the loss of the interconnectivity between the two phases due to the breakup of the PS-rich phase network and the coalescence of the PVME-rich domains.

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Deuteration effects on the miscibility and phase separation kinetics of polymer blends

Cited by 134 publications

References 16 publications

Interfacial adhesion of nanoparticles in polymer blends by intrinsic fluorescence spectra

Interfacial adhesion of nanoparticles in polymer blends by intrinsic fluorescence spectra

Effect of Deuterium Substitution on the Physical Properties of Polymer Melts and Blends

Late Stages of Phase Separation in a Binary Polymer Blend Studied by Rheology, Optical and Electron Microscopy, and Solid State NMR

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