Load-bearing entanglements in polymer glasses
Cynthia Bukowski, Tianren Zhang, Robert A. Riggleman, Alfred J. Crosby
Introduction to polymer science (CHEE 6377); Presented by: Yogita Pal
MOTIVATION
It is broadly acknowledged that entanglements between polymer molecules
play a critical role in determining strength. Below a certain threshold of
entanglement density, polymer materials tend to be excessively brittle,
whereas above this threshold, they dissipate energy through various
mechanisms to enhance strength and toughness. There is a need to minimize
entanglements in polymer processing to reduce environmental costs
associated with volatile solvents and high temperatures. However, a
comprehensive molecular view of how entanglements influence strength and
toughness is lacking, hindering efficient polymer material design.
PRIOR-WORK
Previous research has extensively studied deformation mechanisms such as
crazes and shear deformation zones in polymer glasses. Crazes form at low
entanglement densities, while shear deformation zones form at high
entanglement densities. The stability of crazes and their resistance to
breakdown are influenced by factors including entanglement density,
temperature, and strain rate. Experimental studies have focused on
morphologically tracking these deformation mechanisms using techniques
such as optical and transmission electron microscopy. Despite the insights
gained from prior research, linking these deformation mechanisms to the
mechanical strength of polymer glasses has been challenging. This is partly
due to limitations in measuring mechanical strength in thin films, which are
ideal for studying entanglement networks but have been traditionally restricted
to thicker, bulk specimens.
OBJECTIVE
The study aims to quantify the significance of entanglements in determining the
mechanical properties of glassy polymer blends. The study overcomes
limitations in previous research by using ultrathin polymer films to measure
mechanical strength while systematically altering entanglement states.
Fracture Energy Prediction:
Strength Prediction:
These equations, derived from prior scaling theories are modified based on
insights from molecular dynamics (MD) simulations, provide a framework for
understanding the relationship between entanglements and mechanical
properties in polymer glasses. . This integrated approach enables the
development and validation of a scaling theory to quantitatively describe the
number of strength-contributing entanglements per polymer chain.
EXPERIMENTAL METHODS
Polystyrene with different molecular weights:
Mn = 150.9 kDa (Mw = 157.2 kDa, PDI = 1.04);
Mn = 59.5 kDa (Mw = 70.7 kDa, PDI = 1.19);
Mn = 13.7 kDa (Mw = 14.2 kDa, PDI = 1.04);
Mn = 1.928 MDa (Mw = 2.257 MDa, PDI = 1.17)
Differential scanning calorimetry and gel permeation chromatography were
used to characterize the polymers. Blend samples of 100 nm thickness were
prepared by spin coating polystyrene solutions onto mica substrates. Samples
were vacuum annealed at 170°C and then cooled to room temperature. Films
were cut into a dog-bone shape using a laser.
TUTTUT Experiments:
Uniaxial tests were conducted in a reverse osmosis water bath with a strain rate
of 0.0077 s-1. Film thickness was measured by ellipsometry (RI = 1.59). Previous
studies ensured no significant differences between freestanding films and
water-supported films.
EXPERIMENTAL AND COMPUTATIONAL RESULTS
Fig. 1. Blended homopolymer thin films. Macroscopic experimental dog bone–shaped specimen
(pictured) loaded in TUTTUT for uniaxial extension. Molecular-level simulations depict chains sliding past
one another to form openings in the film as it is strained. Blended systems are composed of long (dark
blue) and short (light blue) chains where most load-bearing entanglements (orange dots), if not all, are
among the long polymer chains.
Fig. 2. Stress-strain behavior of polymer blends. (A)
Representative uniaxial deformation stress-strain
response for each blend tested experimentally on TUTTUT.
Ф represents the volume fraction of long chains in the
system. The top graph is blends with 13.7 kDa as the short
chain diluent and the bottom with 59.5 kDa. (B) Uniaxial
deformation stress-strain responses of N = 250 (⟨Z⟩ = 15.9)
blended with N = 30 (top) and 60 (bottom) at a temperature
of T/Tg = 0.71. ⟨Z⟩ is 1.8 and 3.6 for each short chain,
respectively. Low-strain response is included in the inset of
each section. (C) The elastic modulus (E) for each
experimentally measured blend. (D)average maximum
stress for each blend measured experimentally.
Fig. 4. Force distribution on entanglements.
(A) Simulation snapshots at various levels of
strain. A single chain, highlighted in red in the
top row, is shown in the row below at each of
the indicated strains. The single chains are
colored to show varying levels of average bond
stress on each primitive path (PP) along the
chain. (B) The average bond stress as a function
of strain on each PP in a blend of N = 250 and 30
at = 0.50. The schematic next to the graph
outlines where each mentioned PP is located.
PPs are color coded to match the plotted
points. Entanglements occur at each orange
dot. Hollow orange dots represent non–load-
bearing entanglements at the end of chains. (C
and D) Solid symbols represent calculations
that consider all entanglements in the blend
systems, and hollow symbols only consider
load-bearing entanglements. (C) The density of
entanglements, , in each simulated system as
a function of dilution, calculated as the total
number of entanglements divided by the
system volume. Note that there is a solid blue
star at point (0,0).(D) The average number of entanglements per chain, ⟨Z⟩, as a
function of dilution. The dashed line corresponds to N = 60, and the dotted line
corresponds to N = 30 as the diluent chain.
Error bars are 1 SD of five to nine averaged films. Open symbols
represent blends that were attempted but too brittle to manipulate
in TUTTUT and stretch uniaxially. (E) The elastic modulus for each
simulated blend. (F) The toughness value for each simulated blend.
Fig. 3. Data plotted against the Mikos and Peppas model.
Normalized experimental maximum stress, σmax/σ∞ (A), and
normalized simulated toughness, Г/Г∞ (B), as a function of
entanglements, ⟨Z⟩. Here, ⟨Z⟩ is the Mn obtained from gel
permeation chromatography of each blend divided by the Me of
polystyrene (18.1 kDa). For simulations, ⟨Z⟩ is average chain length
N for each blend divided by Ne (16). Maximum stress and toughness
are normalized by the maximum stress of polystyrene chains Mn =
1.928 MDa and the toughness of chains N = 250, respectively.
Fig. 5. Strength and toughness of materials as a function of load-
bearing entanglements. Normalization is carried out by the
undiluted maximum stress of polystyrene at Mn = 1.928 MDa and
the undiluted toughness of N = 250 for the experimental and
simulation results, respectively. Experimental data are represented
by solid symbols, and simulation data are represented by hollow
symbols. The lines represent the modified Mikos and Peppas model
calculated for both the experiment (solid line) and simulation
(dashed line) including only load-bearing entanglements. Each
shaded region represents 1 SD of error in each line. The schematic
on the right shows a system of entanglements with long chains (dark
blue) and short chains (light blue). Solid orange dots represent load-
bearing entanglements. Orange hollow dots represent
entanglements that cannot bear load because they contain a first
PP. Green hollow dots represent non–load-bearing entanglements
that are made with a short species of chain. Ends of long chains are
highlighted in red.
COMPUTATIONAL METHODS
MD simulations were conducted using a modified version of the coarse-grained
bead-spring KG model. Nonbonded monomers interacted through a Lennard-
Jones (LJ) potential, described by the equation:
where r ≤ rcut= 2.5σ. Here, ϵ represents the potential strength, σ is the monomer
size, and r is the distance between monomers. Bonded interactions between
successive monomers were governed by a finitely extensible nonlinear elastic
potential k = 30ε/σ2 and R0 = 1.5σ. This potential does not allow bond breaking
during the uniaxial deformation process. An angular harmonic potential was
introduced to increase the average number of entanglements per chain:
here Kθ = 10 per radian2 and θ0=120∘ is the equilibrium bond angle. The
introduced angular potential aimed to achieve an average number of monomers
between entanglements ⟨Ne⟩ of ~16. Used monomer chains of lengths (N = 10,
30, 60, 250). Adjusted (N/Ne) ratios accordingly: roughly (0, 1.8, 3.75, 15.9),
respectively. Incorporated short chains N = 10, 30, or 60 as diluents into long-
chain systems N = 250. Maintained a thickness of H = 20σ. Simulation box
dimension is 70σ × 70 σ × H with system density ~0.85σ-3 in melted state.
Random polymer growth with top and bottom walls. Soft potentials prevented
monomer overlap; walls removed to create films along z direction. Accelerated
equilibration with connectivity-altering Monte Carlo moves. Cooled films from
high to low temperatures generate glassy polymer thin films. Films deformed
under constant temperature with uniaxial tension in x direction. Simulations
conducted using Large-scale Atomic/Molecular Massively Parallel Simulator MD
package with NVT ensemble and appropriate algorithms.
CONCLUSIONS
Through systematic adjustments of entanglement density using bidisperse
blends, both experimental tensile tests and MD simulations reveal a decrease in
maximum stress and toughness with added diluent. Microscopic analysis from
simulations shows that certain entanglements are unable to bear substantial
stress at large deformations, leading to the development of a model describing
the number of effective entanglements per chain. The findings align well with an
exponential scaling between film toughness and maximum stress, supported by
the model's incorporation of load-bearing entanglements. This enhanced
understanding provides insights into polymer failure mechanisms across
multiple scales and offers a framework for tuning mechanical properties based
on molecular composition. While differences between simulations and
experiments persist, addressing these disparities could further refine our
understanding of material behavior, especially regarding ultimate failure modes
and the influence of defects and contaminants.
RELEVANCE
Researchers are exploring this study extensively to understand:
1. Polymer Blend Systems: how altering polymer blend compositions affects
mechanical properties, particularly toughness, in thin films.
2. Chain Entanglements: The role of effective entanglements per chain in
determining mechanical properties is examined, revealing an exponential
relationship with film strength.
3. Experimental-Simulation Comparison: combining MD simulations with
experimental data to get an insights into the mechanical behavior of polymer thin
films.
4. Material Design Implications: strategies for enhancing material properties through
structural modifications, such as introducing nano-/micro-fibrous structures or
topological entanglements.
5. Challenges and Future Directions: Despite progress, challenges remain in
understanding phenomena like ductile fracture in thermosets, highlighting the need
for further investigation into factors influencing polymer network behavior.