So far, many of our works, especially those pertaining to the study of polymer CaRI
dynamics, are limited to unentangled polymer. We have verified that entangled, high
molecular weight polymers can infiltrate into NP packings, in spite of the extreme
nanoconfinement imposed by the NPs. However, our preliminary experiments to quantify
and describe the infiltration dynamics of highly entangled polymer into NP packings using
in situ spectroscopic ellipsometry with multilayer Cauchy-model data fitting show different infiltration behavior than what is observed in the unentangled polymer case. More
117
uniform, clear front, which is characteristic to capillary rise infiltration. Instead, the
polymer may be forming prewetting layer in the NP packing which spreads along the NP
surface, followed by a clear front that catches up gradually. Prior studies have reported this
distinctive filling processes of polymer in nanopores.50 The quick surface wetting is
attributed to a stronger adhesive force than cohesive force, whereby the polymer favors
spreading on the solid surface to reduce the interfacial energy.50 The cohesive force needed
to sustain a continuous bulk filling is weakened by the strong physical confinement effect.
Furthermore, the deviation of entangled polymer infiltration dynamics may be related to
the high entropic penalty to transport through the narrow pores, as well as disentanglement
effects under extreme nanoconfinement.42,90,94,119 Moreover, the front broadening of a
liquid imbibition front in a nanoporous matrix may be more substantial in the case of
entangled polymer undergoing CaRI.246,247
We have performed preliminary experiments on entangled polymer systems using in situ
spectroscopic ellipsometry and analyzed the data using the three-layer Cauchy model with
a graded composite layer as described in the Method sections in Chapter 4. Figure 6.1
shows the plot of refractive index versus distance from substrate of a bilayer film composed
of SiO2 NP packing on a 173k PS film at various stages of annealing at T = 180°C. Initially,
there are 2 refractive indices value, corresponding to the NP layer (n = 1.31) and the PS
layer (n = 1.58), respectively. As we anneal the sample, a third refractive index value, that
of the composite layer, emerges between the NP and PS layer. The refractive index,
alongside the thickness of the composite layer, continuously increase throughout CaRI.
118
front. The challenge with pinpointing the exact infiltration dynamic is that the
interpretation can vary depending on the model used to analyze the data. For instance,
modeling the composite layer without gradient would still give reasonable fit to the data
but with provides a different picture on the polymer infiltration dynamics. Furthermore, we
have attempted fitting the composite with 2 distinct Cauchy layers, one describing the
cohesive invading front and one describing the diffuse prewetting layer. With the additional
layer however, the solution uniqueness is no longer guaranteed when there are too many
119
Figure 6.1 Refractive index of the film as a function of distance from substrate at various annealing intervals. The bilayer film is composed of a ~210 nm 22 nm SiO2 NP layer (nNP = 1.31) on a ~240 nm (nPS = 1.58) and
the film is annealed at 180 °C.
Because of this deviation in entangled polymer infiltration dynamics, we are unable to
apply the Lucas-Washburn analysis and derive the confined entangled polymer viscosity.
In addition, it is challenging to accurately describe the nature of the infiltration front based
solely on a model-dependent technique, such as in situ spectroscopic ellipsometry, whereby it is sometimes challenging to reconcile different model interpretations of the infiltration
120
to understand the infiltration behavior of high molecular weight (entangled) polymers in
nanoparticle packings. These complementary techniques may include elastic recoil
detection (ERD), small angle X-ray scattering (SAXS), and small angle neutron scattering
(SANS).
Another future direction involves the fabrication of biomimetic CaRI PINFs, where we use
instead high aspect ratio nanoparticles to more accurately mimic the morphology of natural
composites, for instance nanoplatelets in nacre. While there is abundant literature on nacre-
like nanocomposites, and we believe it would be advantageous to validate CaRI as a viable
process to achieve desirable optical and mechanical properties for applications in structural
coatings.
Figure 6.2. Schematic illustration of generating nacre-inspired polymer-infiltrated nanoparticle films using CaRI. The proposed nanoparticle is gibbsite nanoplatelet, which are thin hexagonal platelets with aspect ratio ~ 10, and poly(methylmethacrylate) (PMMA) as the polymer.
In our preliminary work, we synthesize gibbsite nanoplatelets with average width of 300.4
± 35.2 nm and average thickness of 28.4 ± 5.1 nm, using a hydrothermal method,248 as
shown in Figure 6.3. To deposit a gibbsite nanoplatelet layer, an aqueous suspension of the
nanoplatelet is prepared, and the pH of the suspension is adjusted to pH ~ 0 - 1 using 1 M
121
packings and 8k PS using spin-coating (Figure 6.4a), and successfully demonstrated in
Figure 6.4b that polymer undergoes CaRI into the gibbsite nanoplatelet layer. To more
accurately mimic the morphology of nacre, we also explore other avenues of depositing
the gibbsite nanoplatelets, such as flow coating or blade coating,249,250 to increase the
alignment of nanoplatelets. Figure 6.5(a) shows preliminary results of films fabricated
using doctor blading at various coating speed, and Figure 6.5(b) shows that this approach
is promising to increase the alignment of nanoplatelets. Thus, further extensive
characterizations are warranted to correlate the deposition parameters with the film
morphology including alignment parameter and film thickness. Next, future work to
establish the processing-structure-property relationship of the gibbsite/polymer
nanocomposite films is to follow.
Figure 6.3. The scanning electron microscopy (SEM) image of gibbsite nanoplatelets synthesized using a hydrothermal method. The nanoplatelets have an average width of 300.4 ± 35.2 nm and average thickness of 28.4 ± 5.1 nm. The scale bar is 500 nm.
122
Figure 6.4. The cross-sectional SEM image of the bilayer film of gibbsite nanoplatelet packing and 8k PS (a) before and (b) after CaRI. The scale bar is 500 nm.
Figure 6.5. (a) Gibbsite nanoplatelet films fabricated using doctor blading at decreasing coating speed from left to right. (b) The cross-sectional SEM image of the gibbsite nanoplatelet film deposited at low deposition speed. The scale bar is 500 nm.
123
APPENDIX
A1. Bulk polymer viscosity value from literature
This appendix section is meant to supplement the details pertaining to bulk polymer viscosity values in Chapter 2 and Chapter 3 for polystyrene (PS) and poly(2-vinylpyridine) (P2VP).
The bulk polystyrene (PS) viscosity value is extracted from literature133 based on Figure 6
and Figure 10. Figure 6 shows the plot of (Log ηT/η217) versus 1/T, whereas Figure 10 plots
Log viscosity versus M̅w1/2 at T = 217℃. We first extract the normalized viscosity as a function of reciprocal temperature for 21k PS from curve 1 (valid for MW ~ 25,5000 –
134,000 g mol-1), and 8k PS from curve 2 (M
W ~ 11,000 – 13,5000 g mol-1) and curve 3
(MW ~ 7400 g mol-1). We then extract the viscosities of 8k and 21k PS at T = 217℃ are
extracted using the linear interpolation of the high slope region at low M̅w1/2 values in Figure 10. The viscosity values as a function of temperature can then be calculated for both 8k and 21k PS. Since the normalized viscosity values extracted from step 1 is only valid at T > 130℃, the viscosity values of PS at T < 130℃ are obtained based on Williams-Landel- Ferry model of PS73,81:
log(𝑎𝑇) = log ( 𝜏 1000) =
−𝐶1(𝑇 − 𝑇𝑔)
𝐶2+ 𝑇 − 𝑇𝑔
Where C1 = 13.35; C2 = 42.00. aT is the shift factor and τ is the relaxation time. Viscosity
and relaxation time are related through a vertical shift factor (b), that is determine by fitting the data to the data for bulk polymer in literature.
124
−log 𝜇 = −𝑙𝑜𝑔𝜏 − 𝑏
The bulk poly(2-vinyl pyridine) (P2VP) viscosity value is extracted from literature156 based
on Figure 1 and Figure 4. Figure 1 shows the plot of log aT versus T, whereas Figure 4
plots η versus MW of bulk P2VP at T = 160 ℃. From Figure 1, we extract log aT versus T
using data from VPL8 (8,400 g mol-1) for 8k P2VP and from VPK7 (17,000 g mol-1) for
22k P2VP. Then, we linearly interpolate the low slope region at low 𝑀𝑊 values (MW ~
5,000 – 22,000 g mol-1) in Figure 4 to obtain the viscosity values for 8k and 22k P2VP at
T = 160 ℃. Finally, we obtain the viscosity value as a function of temperature by solving for aT = μ/μ160, where μ160 refers to the viscosity at reference temperature T = 160 ℃
125
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