Microscopic Dynamics and Topology of Polymer Rings Immersed in a Host Matrix of Longer Linear Polymers: Results from a Detailed Molecular Dynamics Simulation Study and Comparison with Experimental Data
Abstract
:1. Introduction
2. Molecular Model and Simulated Systems
3. Results and Discussion
3.1. Conformational Properties
3.2. Normal Mode Analysis
3.3. Dynamic Structure Factor
- (a)
- In the short L-02k blend (Figure 6a1), the computed curves for all q’s decay monotonically and smoothly over short and long time scales (that extend up to 600ns). The rate of decay is steeper at short times and deceases as the time increases, but in a very smooth way. As a result, only quantitative differences are observed from the corresponding spectra computed for the neat ring 20k PEO melt (Figure 6a2).
- (b)
- In the L-10k blend, a totally different picture emerges. Compared to the pure 20k ring or the behavior of rings in the unentangled L-02k blend, the simulation results here indicate an initial rapid decay at short times but then a rather asymptotic and time-independent behavior which leads to plateau values for that depend on the momentum transfer q. The time scale of the fast initial decay depends on the wavenumber q but overall is seen to be between 30 and 100 ns, i.e., on the order of the entanglement time τe for entangled linear PEO melts at 413K, see Section 3.4 and Section 3.6 below. A closer inspection reveals that the initial fast decay is even steeper than the one recorded in the corresponding pure ring PEO-20k melt, implying more freedom for motion. According to Goossen et al. [21], at these short times, rings in the L-10k blend enjoy free 3-d Rouse motion in the tubes formed by the surrounding (moderately entangled, number of entanglements Z ≅ 5) L-10k linear chains. At later times, strong topological interactions (hindrance effects [21]) set in, which cause to cross over to time-independent plateau values exhibiting no sign of any further decay.
- (c)
- In the longer L-20k blend, the dynamic structure factor exhibits the same qualitative behavior as in the L-10k blend. Again, we observe the rapid initial decay at very short times (on the order of 30 to 100 ns depending on the wavenumber q), followed by the time-independent behavior towards plateau values that are practically the same with those observed in the L-10k blend.
- (d)
- The qualitative agreement between predicted and experimentally measured spectra in the L-02k and L-20k blends is excellent. The quantitative agreement, on the other hand, is fairly good but improves for larger q values (larger than approximately 0.10 Å−1). For lower q values the simulation results systematically overpredict the measured NSE data. We believe that any quantitative differences between simulated and experimentally measured spectra should be attributed to the united-atom nature of the force-field employed in the MD simulations.
3.4. Mean Square Displacement of Atomistic Segments
3.5. Mean-Square-Displacement of Chains Centers-of-Mass
3.6. Topological Analysis
4. Conclusions
Acknowledgments
Author Contributions
Conflicts of Interest
References
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System | Host matrix | Number of ring PEO-20k molecules | Number of linear PEO chains | Volume fraction of ring molecules |
---|---|---|---|---|
1 | L-02k | 8 | 720 | 0.1 |
2 | L-10k | 8 | 144 | 0.1 |
3 | L-20k | 8 | 72 | 0.1 |
System | Ring molecules | Linear chains | |||
---|---|---|---|---|---|
(Å2) | (Å2) | (Å2) | (Å2) | ||
02k pure linear melt | - | - | 235 ± 55 | 1475 ± 140 | 6.3 ± 0.7 |
10k pure linear melt | - | - | 1410 ± 180 | 8420 ± 310 | 6.0 ± 0.8 |
20k pure linear melt | - | - | 2660 ± 320 | 17,015 ± 930 | 6.4 ± 1.0 |
L-02k blend | 1150 ± 120 | 3040 ± 260 | 240 ± 25 | 1525 ± 105 | 6.3 ± 1.4 |
L-10k blend | 885 ± 105 | 2320 ± 240 | 1380 ± 85 | 8160 ± 220 | 5.9 ± 08 |
L-20k blend | 815 ± 110 | 2055 ± 260 | 2975 ± 185 | 16,925 ± 500 | 5.7 ± 0.8 |
20k pure ring melt | 825 ± 63 | 2250 ± 120 | - | - | - |
System | of ring molecules (Å) | of ring molecules (Å) | of linear chains (Å) | of linear chains (Å) |
---|---|---|---|---|
02k pure linear melt | 12 ± 3 | 6.7 ± 0.4 | ||
10k pure linear melt | 12 ± 3 | 6.7 ± 0.4 | ||
20k pure linear melt | 11 ± 3 | 6.7 ± 0.4 | ||
20k pure ring melt | 35 ± 3 | 6.1 ± 0.4 | ||
L-02k blend | 28 ± 3 | 6.1 ± 0.4 | 13 ± 3 | 6.7 ± 0.4 |
L-10k blend | 31 ± 3 | 6.1 ± 0.4 | 12 ± 3 | 6.7 ± 0.4 |
L-20k blend | 38 ± 4 | 6.1 ± 0.4 | 12 ± 3 | 6.7 ± 0.4 |
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Papadopoulos, G.D.; Tsalikis, D.G.; Mavrantzas, V.G. Microscopic Dynamics and Topology of Polymer Rings Immersed in a Host Matrix of Longer Linear Polymers: Results from a Detailed Molecular Dynamics Simulation Study and Comparison with Experimental Data. Polymers 2016, 8, 283. https://doi.org/10.3390/polym8080283
Papadopoulos GD, Tsalikis DG, Mavrantzas VG. Microscopic Dynamics and Topology of Polymer Rings Immersed in a Host Matrix of Longer Linear Polymers: Results from a Detailed Molecular Dynamics Simulation Study and Comparison with Experimental Data. Polymers. 2016; 8(8):283. https://doi.org/10.3390/polym8080283
Chicago/Turabian StylePapadopoulos, George D., Dimitrios G. Tsalikis, and Vlasis G. Mavrantzas. 2016. "Microscopic Dynamics and Topology of Polymer Rings Immersed in a Host Matrix of Longer Linear Polymers: Results from a Detailed Molecular Dynamics Simulation Study and Comparison with Experimental Data" Polymers 8, no. 8: 283. https://doi.org/10.3390/polym8080283