Polymer Behavior Under Rigid Symmetric Confinement · in confinement, suggesting competing forces,...
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ID confined simulation pore bulk simulation box cylindrical pore 14σ confined unconfined r pore 6-7 μm 30 nm 68 nm Aluminum Al 2 O 3 *not to scale 30 nm dPS film *not to scale Before Aſter λ x , λ y , λ z are the x, y (confined) and z (unconfined) components of the average R g . e change in the D is related to a confinement parameter, ID/2R g 1 e randomness of the nanoparticle distribution creates a variety of confinement lengthscales and orientations making other confined properties difficult to measure. All chains experience similar confinement and domains are aligned so anisotropic effects can be measured. Previous simulations show properties deviate more strongly as pore radius decreases, similar to the behavior observed in nanocomposites. 1 Lin, et al., Macromol., 2013, 46; 2 Sussman, et al., Macromol., 2014, 47; 3 Tung, et al., Macromol., 2015, 48 - 25-500 bead polymer chains, N - 2.5-7σ radius pores, r - Discrete pore wall - NVT with a Langevin thermostat, T=1 - Standard Kremer-Grest model, FENE bonds - Repulsive LJ potentials - Athermal polymer-wall interactions - 290 kg mol -1 polystyrene (PS) matrix polymer - 100-800 kg mol -1 deuterated PS (dPS) tracer polymer - 15 nm radius anodic aluminum oxide (AAO) pores - Phenyl-capped pore walls for athermal interactions - 160 °C annealing temperature e average R g increases slightly in the unconfined direction, with a greater increase for larger chain lengths. In the confined direction, the average R g asymptotes to a maximum value of r pore /2. is value is equivalent to the radius of gyration of the pore cross-section. Relative shape anisotropy as a function of confinement ratio collapses to a single line, suggesting confined chain conformation can be fully described by the confinement ratio. Unlike conformation polymer diffusion in confinement is not fully described by a confinement parameter. Apparent behavior in D as pore size decreases suggests two competing forces, most likely chain disentanglement (increased diffusivity) and polymer wall friction (decreased diffusivity). Confined chain conformation is dependent on the ratio between the confining length and the polymer size. In the confining dimension the average R g asymptotes, with increasing polymer size, to a maximum value of r pore /2. Polymer diffusion appears to exhibit a non-monotonic behavior in confinement, suggesting competing forces, most likely chain disentanglement and polymer-wall friction. Experimental studies are underway to determine if the same trends observed in simulations occur experimentally. 2 = 3 2 λ 4 x + λ 4 y + λ 4 z ( λ 2 x + λ 2 y + λ 2 z ) 2 1 2 κ 2 = 0 κ 2 = 1 points are spherically symmetric points lie on a line End-to-end distance, R ee Entanglements per Chain, Z Diffusion Coefficient, D Elastic Recoil Detection (ERD) is used to measure the depth profile of the tracer dPS. A Fickian diffusion profile, convoluted with a Gaussian beam resolu- tion is used to fit the depth profile and extract a diffusion coefficient. DOE BES-DE-SC0016421 James F. Pressly † , Robert A. Riggleman ‡ , Karen I. Winey †,‡ University of Pennsylvania † Department of Materials Science and Engineering and ‡ Department of Chemical and Biomolecular Engineering Polymer Behavior Under Rigid Symmetric Confinement Polymers experience confinement in nanocomposites Polymer Conformation Polymer Diffusion Cylindrical pores create a controlled system for studying polymer behavior in confinement Polymer properties change under nanoscale confinement Simulation Methods Experimental Methods Radius of Gyration, R g Relative Shape Anisotropy, κ 2 Conclusions Simulation Experimental
Transcript of Polymer Behavior Under Rigid Symmetric Confinement · in confinement, suggesting competing forces,...
ID
confined simulation pore bulk simulation box
cylindrical pore
14σ
confined
unconfined
rpore
6-7 μm 30 nm 68 nm
AluminumAl2O3
*not to scale
30 nm dPS film
*not to scale
Before After
λx, λy, λz are the x, y (confined) and z (unconfined) components of the average Rg.
The change in the D is related to a confinement parameter, ID/2Rg1
The randomness of the nanoparticle distribution creates a variety of confinement lengthscales and orientations making other confined properties difficult to measure.
All chains experience similar confinement and domains are aligned so anisotropic effects can be measured.
Previous simulations show properties deviate more strongly as pore radius decreases, similar to the behavior observed in nanocomposites.
1Lin, et al., Macromol., 2013, 46; 2Sussman, et al., Macromol., 2014, 47; 3Tung, et al., Macromol., 2015, 48
- 25-500 bead polymer chains, N - 2.5-7σ radius pores, r - Discrete pore wall - NVT with a Langevin thermostat, T=1 - Standard Kremer-Grest model, FENE bonds - Repulsive LJ potentials - Athermal polymer-wall interactions
- 290 kg mol-1 polystyrene (PS) matrix polymer - 100-800 kg mol-1 deuterated PS (dPS) tracer polymer - 15 nm radius anodic aluminum oxide (AAO) pores - Phenyl-capped pore walls for athermal interactions - 160 °C annealing temperature
The average Rg increases slightly in the unconfined direction, with a greater increase for larger chain lengths.
In the confined direction, the average Rg asymptotes to a maximum value of rpore/2. This value is equivalent to the radius of gyration of the pore cross-section.
Relative shape anisotropy as a function of confinement ratio collapses to a single line, suggesting confined chain conformation can be fully described by the confinement ratio.
Unlike conformation polymer diffusion in confinement is not fully described by a confinement parameter.
Apparent behavior in D as pore size decreases suggests two competing forces, most likely chain disentanglement (increased diffusivity) and polymer wall friction (decreased diffusivity).
Confined chain conformation is dependent on the ratio between the confining length and the polymer size.
In the confining dimension the average Rg asymptotes, with increasing polymer size, to a maximum value of rpore/2.
Polymer diffusion appears to exhibit a non-monotonic behavior in confinement, suggesting competing forces, most likely chain disentanglement and polymer-wall friction.
Experimental studies are underway to determine if the same trends observed in simulations occur experimentally.
2 =3
2
λ4x
+ λ4y
+ λ4z(
λ2x
+ λ2y
+ λ2z
)2 1
2
κ2 = 0
κ2 = 1
points are spherically symmetric
points lie on a line
End-to-end distance, Ree Entanglements per Chain, Z Diffusion Coefficient, D
Elastic Recoil Detection (ERD) is used to measure the depth profile of the tracer dPS.
A Fickian diffusion profile, convoluted with a Gaussian beam resolu-tion is used to fit the depth profile and extract a diffusion coefficient.
DOE BES-DE-SC0016421
James F. Pressly†, Robert A. Riggleman‡, Karen I. Winey†,‡
University of Pennsylvania †Department of Materials Science and Engineering and ‡Department of Chemical and Biomolecular Engineering
Polymer Behavior Under Rigid Symmetric Confinement
Polymers experience confinement in nanocomposites
Polymer Conformation Polymer Diffusion
Cylindrical pores create a controlled system for studying polymer behavior in confinement
Polymer properties change under nanoscale confinement
Simulation Methods Experimental Methods
Radius of Gyration, Rg
Relative Shape Anisotropy, κ2
Conclusions
Simulation
Experimental
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