Advancing Geothermal Energy Supply Chains for a Resilient and Abundant Energy Future
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Geosciences↗
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Chain-based Adaptive Reconfiguration Over Lattices for Hallucination Reduction
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97 MATHEMATICS AND COMPUTING↗
Impact of Alkyl Chain Length on Low-Temperature Oxidation of Methyl, Ethyl, and Propyl Cyclohexanes
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Chemistry↗
Effects of Tethered Polymers on Dynamics of Nanoparticles in Unentangled Polymer Melts
Polymer-tethered nanoparticles (NPs) are commonly added to a polymer matrix to improve the material properties. Critical to the fabrication and processing of such composites is the mobility of the tethered NPs. Here, we study the motion of tethered NPs in unentangled polymer melts using molecular dynamics simulations, which offer a precise control of the grafted chain length N g and the number z of grafted chains per particle. As Ng increases, there is a crossover from particle-dominated to tethered-chain-dominated terminal diffusion of NPs with the same z. The mean squared displacement of loosely tethered NPs in the case of tethered-chain-dominated terminal diffusion exhibits two subdiffusive regimes at intermediate time scales for small z. The first one at shorter time scales arises from the dynamical coupling of the particle and matrix chains, while the one at longer time scales is due to the participation of the particle in the dynamics of the tethered chains. The friction of loosely grafted chains in unentangled melts scales linearly with the total number of monomers in the chains, as the friction of individual monomers is additive in the absence of hydrodynamic coupling. As more chains are grafted to a particle, hydrodynamic interactions between grafted chains emerge. As a result, there is a nondraining layer of hydrodynamically coupled chain segments surrounding the bare particle. Outside the nondraining layer is a free-draining layer of grafted chain segments with no hydrodynamic coupling. The boundary of the two layers is the stick surface where the shear stress due to the relative melt flow is balanced by the friction between the grafted and melt chains in the interpenetration layer. The stick surface is located further away from the bare surface of the particle with higher grafting density.
42 ENGINEERING↗
A multiscale anisotropic polymer network model coupled with phase field fracture
The study of polymers has continued to gain substantial attention due to their expanding range of applications, spanning essential engineering fields to emerging domains like stretchable electronics, soft robotics, and implantable sensors. These materials exhibit remarkable properties, primarily stemming from their intricate polymer chain network, which, in turn, increases the complexity of precisely modeling their behavior. Especially for modeling elastomers and their fracture behavior, accurately accounting for the deformations of the polymer chains is vital for predicting the rupture in highly stretched chains. Despite the importance, many robust multiscale continuum frameworks for modeling elastomer fracture tend to simplify network deformations by assuming uniform behavior among chains in all directions. Recognizing this limitation, our study proposes a multiscale fracture model that accounts for the anisotropic nature of elastomer network responses. At the microscale, damage in the chains is assumed to be driven by both the chain's entropy and the internal energy due to molecular bond distortions. In order to bridge the stretching in the chains to the macroscale deformation, we employ the maximal advance path constraint network model, inherently accommodating anisotropic network responses. As a result, chains oriented differently can be predicted to exhibit varying stretch and, consequently, different damage levels. To drive macroscale fracture based on damages in these chains, we utilize the micromorphic regularization theory, which involves the introduction of dual local-global damage variables at the macroscale. The macroscale local damage variable is obtained through the homogenization of the chain damage values, resulting in the prediction of an isotropic material response. The macroscale global damage variable is subjected to nonlocal effects and boundary conditions in a thermodynamically consistent phase field continuum formulation. Moreover, the total dissipation in the system is considered to be mainly due to the breaking of the molecular bonds at the microscale. To validate our model, we employ the double-edge notched tensile test as a benchmark, comparing simulation predictions with existing experimental data. Additionally, to enhance our understanding of the fracturing process, we conduct uniaxial tensile experiments on a square film made up of polydimethylsiloxane (PDMS) rubber embedded with a hole and notches and then compare our simulation predictions with the experimental observations. Furthermore, we visualize the evolution of stretch and damage values in chains oriented along different directions to assess the predictive capacity of the model. In conclusion, the results are also compared with another existing model to evaluate the utility of our model in accurately simulating the fracture behavior of rubber-like materials.
42 ENGINEERING↗
Building Environmental Justice and Equity into the Development of Critical Mineral Industries
The global transition toward low-carbon energy not only means an increase in demand for clean electricity and renewable resources, but also an increase in demand for the critical minerals (CMs) and rare earth elements (REEs) that these technologies rely upon. Indeed, low-carbon energy technologies, such as those used for wind turbines and electric vehicle motors, require significantly more lithium, nickel, cobalt, manganese, graphite, and other CMs than fossil-based energy technologies. The growing demand for new forms of low- carbon energy will necessitate a proportional scale-up of CM and REE extraction and processing. Presently, the majority of extraction and processing activities for CMs and REEs are concentrated in very few countries, primarily in China and the Global South. CM and REE supply chain activities conducted in or controlled by these countries are commonly associated with widespread and well- documented human rights abuses and environmental degradation. As a result of concerns related to supply chain security, worker welfare, and the overall need for additional sources of CMs and REEs, governments worldwide have begun to explore policy pathways for the development of new supply chains. The development of new supply chains for CMs and REEs re s a multifold opportunity to accelerate the global deployment of low-carbon energy fleets, reduce global carbon emissions, build political resilience—and also to enhance policy objectives of environmental justice and equity in the clean energy transition. Fulfilling these policy objectives requires energy producers to navigate a maze of global supply chain policies designed to shape and accelerate the growth of new markets. In the United States, for instance, President Biden recently implemented fiscal and trade policies that incentivize both domestic and global reliance on U.S.-produced CMs and REEs, leveraging key relationships in Asia and Europe to ensure the accelerated buildout of the U.S. supply chain. The Biden Administration’s framework also emphasizes that new supply chains for CMs, REEs, and other low-carbon energy pathways must generate benefits for marginalized and disadvantaged communities, build energy equity, and contribute to the Biden Administration’s vision of environmental justice. present CM and REE supply chains include several stages, including mining, processing, transport, utilization, and disposal, each of which involves different environmental justice considerations and potential injustices. This study explores how technical innovation, paired with responsible community engagement and empowerment, can help inform the development of energy equity and environmental justice at all stages of new supply chains. The study highlights these opportunities on a broad scale. We also lend a specific focus to research at the University of Wyoming School of Energy Resources that aims to guide the development of CM and REE industries in communities with high economic dependence on coal and other fossil fuel industries, identifying pathways to grow a U.S. domestic supply chain by producing CMs from coal, coal by-products, and coal waste streams. These production pathways represent a potential new supply for CMs across the U.S. and elsewhere, thereby enhancing national security and accelerating the widespread deployment of low-carbon energy technologies, while also generating alternative applications for remaining coal reserves and aiding in a just transition for rural energy-producing communities.
Gerace, Selena↗
Robust production of monovalent bispecific IgG antibodies through novel electrostatic steering mutations at the C H 1-C λ interface
Bispecific antibodies represent an increasingly large fraction of biologics in therapeutic development due to their expanded scope in functional capabilities. Asymmetric monovalent bispecific IgGs (bsIgGs) have the additional advantage of maintaining a native antibody-like structure, which can provide favorable pharmacology and pharmacokinetic profiles. The production of correctly assembled asymmetric monovalent bsIgGs, however, is a complex engineering endeavor due to the propensity for non-cognate heavy and light chains to mis-pair. Previously, we introduced the DuetMab platform as a general solution for the production of bsIgGs, which utilizes an engineered interchain disulfide bond in one of the C H 1-C L domains to promote orthogonal chain pairing between heavy and light chains. While highly effective in promoting cognate heavy and light chain pairing, residual chain mispairing could be detected for specific combinations of Fv pairs. Here, we present enhancements to the DuetMab design that improve chain pairing and production through the introduction of novel electrostatic steering mutations at the C H 1-C L interface with lambda light chains (C H 1-C λ ). These mutations work together with previously established charge-pair mutations at the C H 1-C L interface with kappa light chains (C H 1-C κ ) and Fab disulfide engineering to promote cognate heavy and light chain pairing and enable the reliable production of bsIgGs. Importantly, these enhanced DuetMabs do not require engineering of the variable domains and are robust when applied to a panel of bsIgGs with diverse Fv sequences. We present a comprehensive biochemical, biophysical, and functional characterization of the resulting DuetMabs to demonstrate compatibility with industrial production benchmarks. Overall, this enhanced DuetMab platform substantially streamlines process development of these disruptive biotherapeutics.
60 APPLIED LIFE SCIENCES↗
Ionic Liquid‐Driven Modulation of DNA Brush Morphology on Nanoparticle Surfaces
Here, the morphology of DNA is strongly influenced by its surrounding environment, including factors such as pH, salt type and valency, and the presence of polymers. Inorganic salts are known to reduce the DNA chain length through mechanisms like electrostatic screening and ion bridging. In contrast, ionic liquids, a new class of organic salts, have previously been found to increase the DNA chain length, indicating a distinct mode of interaction between the ionic liquid and DNA chains. This study utilizes self-assembled DNA-AuNPs as a model system to examine changes in the DNA chain morphology and the nanoscale interaction mechanisms in an ionic liquid environment. The DNA chain lengths are measured in solution using X-ray scattering measurements at varying concentrations of two imidazolium ([$BMIM$] acetate and [$EMIM$] acetate) based ionic liquids. Additionally, Molecular Dynamics (MD) simulations are performed mimicking the experimental system. Our results suggest an interplay of electrostatic and groove-binding interactions governing the DNA chain morphology, which depends on IL concentration and the composition of the DNA chains. It has been found that for DNA chains with majority ssDNA, electrostatic interaction dominate, however with increasing composition of double strands, the DNA chains exhibit compaction due to a non-electrostatic hydrophobic groove-binding mechanism.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Effect of reaction media on hydrogenolysis of polyethylene plastic waste: Polymer-surface interactions in small alkane/polymer blends
The polymer reaction media and its properties can be altered by recycling a fraction of liquid products or adding alkane solvents. Less clear is whether this strategy affects hydrogenolysis. Herein, we investigated the effect of short-chain alkanes C n consisting of n carbons (n=8, 16, and 32) on the upcycling of high-density polyethylene (HDPE) plastic waste to lubricant-range products over Ru/TiO 2 catalysts by multiscale simulations and experiments. First, we trained a force field for polymer/surface interactions on a Ru 22 nanoparticle (NP) supported on TiO 2 . Using replica exchange molecular dynamics simulations, we studied the effect of small hydrocarbons on the adsorption of a surrogate polymer, C 142 , on the catalyst. We found segregation of long chains (C 142 ) at the catalyst surface due to the enthalpy gained by adsorbing more C-C bonds of the long chains, compensating for entropic losses upon adsorption. Short-chain molecules decrease the adsorbed carbons of long chains on the Ru NP due to blocking Ru active sites. Compared to the bulk chains, competitive adsorption results in a broader, heavy-tailed distribution of end-to-end distance of adsorbed chains. Our experiments demonstrated that catalyst activity declines significantly beyond simple dilution due to changes in polymer adsorption, and tuning the reaction media by creating suitable blends impacts hydrogenolysis. Density distributions for a 50:50%wt mixture of PP and PE show that PE chains are segregated at the surface, so they are prone to C-C bond breaking much faster than PP chains. H/D exchange experiments show preferential deuteration of PE, while CH 3 groups of PP remain undeuterated. Furthermore, this may be explained by the preferential sorption of PE over PP, leading to specific distribution in the polymer blend.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Topological Effects Near Order–Disorder Transitions in Symmetric Diblock Copolymer Melts
The effects of polymer chain topology on the order–disorder transition of symmetric AB diblock copolymer melts are studied using coarse-grained molecular dynamics simulations. Specifically, we compared chain conformations near the lamellar-disordered transition in melts of symmetric (i.e., 50–50) AB diblock copolymers of linear chains, rings, and trefoil knots at the same chain lengths. The order (lamellar)–disorder transition temperature and the domain sizes both shifted to lower values with the introduction of topological constraints, leading to the following sequence: linear chains > rings > trefoil knots. Furthermore, investigation of the polymer chain conformations in terms of their radii of gyration, their writhe values (a measure for the degree of intertwining of a chain around itself), and their Jones polynomials (a method to measure entanglement of curves) showed that linear chains and rings remained stretched, while knots were stretched and tightened in disordered melts close to the lamellar-disorder transition. This work highlights chain topology as an important factor in affecting microphase separation in block copolymers.
36 MATERIALS SCIENCE↗
A modular and extensible CHARMM-compatible model for all-atom simulation of polypeptoids
Peptoids (N-substituted glycines) are a class of sequence-defined synthetic peptidomimetic polymers with applications including drug delivery, catalysis, and biomimicry. Classical molecular simulations have been used to predict and understand the conformational dynamics of single chains and their self-assembly into morphologies including sheets, tubes, spheres, and fibrils. The CGenFF-NTOID model based on the CHARMM General Force Field has demonstrated success in accurate all-atom molecular modeling of peptoid structure and thermodynamics. Extension of this force field to new peptoid side chains has historically required reparameterization of side chain bonded interactions against ab initio data. This fitting protocol improves the accuracy of the force field but is also burdensome and precludes modular extensibility of the model to arbitrary peptoid sequences. In this work, we develop and demonstrate a Modular Side Chain CGenFF-NTOID (MoSiC-CGenFF-NTOID) as an extension of CGenFF-NTOID employing a modular decomposition of the peptoid backbone and side chain parameterizations, wherein arbitrary side chains within the large family of substituted methyl groups (i.e., –CH 3 , –CH 2 R, –CHRR', and –CRR'R") are directly ported from CGenFF. We validate this approach against ab initio calculations and experimental data to develop a MoSiC-CGenFF-NTOID model for all 20 natural amino acid side chains along with 13 commonly used synthetic side chains and present an extensible paradigm to efficiently determine whether a novel side chain can be directly incorporated into the model or whether refitting of the CGenFF parameters is warranted. We make the model freely available to the community along with a tool to perform automated initial structure generation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Development of Coarse-Grained Models for Poly(4-vinylphenol) and Poly(2-vinylpyridine): Polymer Chemistries with Hydrogen Bonding
In this paper, we identify the modifications needed in a recently developed generic coarse-grained (CG) model that captured directional interactions in polymers to specifically represent two exemplary hydrogen bonding polymer chemistries—poly(4-vinylphenol) and poly(2-vinylpyridine). We use atomistically observed monomer-level structures (e.g., bond, angle and torsion distribution) and chain structures (e.g., end-to-end distance distribution and persistence length) of poly(4-vinylphenol) and poly(2-vinylpyridine) in an explicitly represented good solvent (tetrahydrofuran) to identify the appropriate modifications in the generic CG model in implicit solvent. For both chemistries, the modified CG model is developed based on atomistic simulations of a single 24-mer chain. This modified CG model is then used to simulate longer (36-mer) and shorter (18-mer and 12-mer) chain lengths and compared against the corresponding atomistic simulation results. We find that with one to two simple modifications (e.g., incorporating intra-chain attraction, torsional constraint) to the generic CG model, we are able to reproduce atomistically observed bond, angle and torsion distributions, persistence length, and end-to-end distance distribution for chain lengths ranging from 12 to 36 monomers. We also show that this modified CG model, meant to reproduce atomistic structure, does not reproduce atomistically observed chain relaxation and hydrogen bond dynamics, as expected. Simulations with the modified CG model have significantly faster chain relaxation than atomistic simulations and slower decorrelation of formed hydrogen bonds than in atomistic simulations, with no apparent dependence on chain length.
36 MATERIALS SCIENCE↗
Developing a Carbon Negative Biorefinery for Organic Waste Valorization
Production of bio-based chemicals have become increasingly attractive as efforts to meet carbon neutrality goals expand. Diverse organic waste feedstocks can be valorized via arrested anaerobic digestion and chain elongation to produce important key intermediates, such as medium chain carboxylic acids. Our work aims to develop a carbon negative biorefinery that funnels multiple organic waste feedstocks into a chemically consistent stream of carboxylic acids that are then upgraded to exemplary carbon negative products. The pairing of a hydrolysis reactor with a chain elongation reactor will allow each biological step to be optimized to improve the ability to valorize a variety of organic waste streams. Specifically, this work has so far been aimed at screening for potential chain elongating organisms to produce VFAs and MCCAs of interest. Four chain elongating organisms were tested for their chain elongation potential with diverse single and mixed substrates. So far, Megasphaera elsdenii and Actinobacillus succinogenes have been tested to determine potential differences in titer as well as product speciation due to variations in pH. To do this, each organism was tested under 3 different substrate combinations with pH maintained at either 5.5, 6, or 7. With better understanding of their metabolic needs and optimal operating conditions, these chain elongating organisms could provide a valuable option to facilitate the chain elongation necessary to produce precursor molecules. In addition to optimizing the bioconversion steps, downstream processing of carboxylic acids is also a key component for the overall feasibility of the process. Our group previously developed a downstream in-situ product recovery (ISPR) process for continuously recovering bio-based carboxylic acids from fermentation broth. The ISPR includes: (i) a solid-liquid separation as a cell retention device, (ii) a liquid-liquid extraction (LLE) to selectively extract the desired bio-based acids, and (iii) a distillation to obtain the neat product. The integrated process was demonstrated at bench-scale and is now scaled up for pilot-scale operations. A more cost-efficient membrane-based emulsion separation is introduced for LLE in downstream separation process with greatly promoted mass transfer, leading to -2800 times smaller needed membrane area than membrane contactors to achieve the same butyric acid extraction rate.
BIOMASS FUELS↗
Specific molecular design of polycarboxylate polymers exhibiting optimal compatibility with clay contaminants in concrete
Highlights: • Allyl ether-based PCEs with short side chain length and low side chain density presented superior clay resistance. • PCEs with medium side chain density exhibited best clay robustness when compared at the absolute dosed quantities. • The proportion of PCE being intercalated into the layered structure of clay was quantified. It is widely recognized that the dispersing ability of polycarboxylate superplasticizers (PCEs) could be hindered due to the presence of clay contaminants in concrete. In this study, a series of allyl ether-based polycarboxylate superplasticizers possessing short polyethylene glycol side chains was successfully synthesized and probed for their clay tolerance. The resulting PCE polymers were characterized via Size Exclusion Chromatography (SEC) to obtain their molecular properties. Thereafter, their dispersing ability was probed in the absence and presence of sodium bentonite. Allyl ether-based polycarboxylate (APEG) polymers possessing short side chains were found to exhibit enhanced clay resistance as compared to that of conventional MPEG PCEs holding long pendant chains. The mode of interaction between APEG PCEs and bentonite was investigated via sorption and XRD measurements. The data revealed that APEG PCEs possessing a lower side chain density intercalate less into the interlayer space of bentonite than those exhibiting higher side chain density.
36 MATERIALS SCIENCE↗
Understanding the origin of softness in structurally tailored and engineered macromolecular (STEM) gels: A DPD study
Structurally tailored and engineered macromolecular (STEM) gels are polymer networks containing a primary network (the “STEM-0” gel) and side chains that are anchored to this network (forming the “STEM-1” gel). The ability to vary the features of the side chains provides a robust means of tailoring the macroscopic properties of the material. We use dissipative particle dynamics (DPD) simulations to determine the mechanical response of STEM-1 gels to uniaxial compression for various values of the side chain length, n sc . While the Young’s modulus of the material is significantly decreased with increasing n sc (at a fixed density of grafted side chains), above a certain saturation value, increasing n sc does not lead to any further softening of the sample. Using the simulations, we calculate the relevant stresses, which are related to the Young’s modulus and the number of entanglements in the network. We show that the backbone chains become more spread out upon addition of sidechains, leading to a decrease in the physical entanglements between backbone segments. This observation accounts for the decrease of stress in the backbone network and the softening of the networks through the addition of sidechains. For long chains, however, the number density of physical crosslinks between side chains is independent of side chain length; this observation explains the observed stress saturation in the STEM-1 gels. Our approach allows us to correlate the molecular architecture of the gels to the resultant macroscopic mechanical behavior and provide guidelines for fabricating STEM gels with well-defined mechanical properties, which allow the materials to be used for a variety of applications.
36 MATERIALS SCIENCE↗
Investigation of Hierarchical Structure Formation in Merocyanine Photovoltaics
Merocyanines (MCs) are a versatile class of small-molecule dyes. Their optoelectronic properties are easily tunable by chemically controlling their donor–acceptor strength, and their structural properties can be tuned by simple side-chain substitution. This paper demonstrates a novel series of MCs featuring an indoline donor with varying hydrocarbon side-chain length (from 6 to 12 carbons) and a tert-butyl-thiazole acceptor, labeled InTBT. Bulk heterojunction organic photovoltaics are fabricated with a [6,6]-phenyl-C 61 -butyric acid methyl ester (PCBM) acceptor and characterized. Films composed of I8TBT:PCBM and I9TBT:PCBM produced the highest power conversion efficiency of 4.5%, which suggests that the morphology is optimized by controlling the side-chain length. Hierarchical structure formation in InTBT:PCBM films is studied using grazing incidence X-ray diffraction (GIXRD), small-angle neutron scattering (SANS), and atomic force microscopy (AFM). When mixed with PCBM, InTBTs with ≤8 side-chain carbons form pure crystalline domains, while InTBTs with ≥9 side-chain carbons mix well with PCBM. SANS demonstrates that increasing side-chain length increases the InTBT-rich domain size. In addition, a branched hexyl–dodecyl side-chain IHDTBT:PCBM film was studied and found to exhibit the worst-performance organic photovoltaic (OPV) device. The large-branched side chain inhibited mixing between IHDTBT and PCBM resulting in large segregated phases.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Cyclic Topology Enhancing Structural Ordering and Stability of Comb-Shaped Polypeptoid Thin Films against Melt-Induced Dewetting
We investigated the effect of cyclic chain topology on the molecular ordering and thermal stability of comb-shaped polypeptoid thin films on silicon (Si) substrates. Cyclic and linear poly(N-decylglycine) (PNDG) bearing long n-decyl side chains were synthesized by ring-opening polymerization of N-decylglycine-derived N-carboxyanhydrides. When the spin-coated thin films were subjected to thermal annealing at temperatures above the melting temperature (T > T m ), the cyclic PNDG films exhibited significantly enhanced stability against melt-induced dewetting than the linear counterparts (l-PNDG). When recrystallized at temperatures below the crystallization temperature (T < T c ), the homogeneous c-PNDG films exhibit enhanced crystalline ordering relative to the macroscopically dewetted l-PNDG films. Both cyclic and linear PNDG molecules adopt cis-amide conformations in the crystalline film, which transition into trans-amide conformations upon melting. A top-down solvent leaching treatment of both l/c-PNDG films revealed the formation of an irreversibly physisorbed monolayer with similar thickness (ca. 3 nm) on the Si substrate. The physisorbed monolayers are more disordered relative to the respective thicker crystalline films for both cyclic and linear PNDGs. Upon heating above T m , the adsorbed c-PNDG chains adopt trans-amide backbone conformation identical with the free c-PNDG molecules in the molten film. By contrast, the backbone conformations of l-PNDG chains in the adsorbed layers are notably different from those of the free chains in the molten film. We postulate that the conformational disparity between the chains in the physically adsorbed layers versus the free chains in the molten film is an important factor to account for the difference in the thermal stability of PNDG thin films. These findings highlight the use of cyclic chain topology to suppress the melt-induced dewetting in polymer thin films.
36 MATERIALS SCIENCE↗
Structure, Dynamics, and Hydrogen Transport in Amorphous Polymers: An Analysis of the Interplay between Free Volume Element Distribution and Local Segmental Dynamics from Molecular Dynamics Simulations
Polymers are attractive membrane materials owing to their mechanical robustness and relatively inexpensive fabrication. An important indicator of membrane performance are free volume elements (FVE): microporous void spaces created by the inefficient packing of bulky groups along the polymer chain. FVEs tend to degrade over time, as polymer chains reorganize irreversibly. While it is widely accepted that polymer flexibility has an impact on membrane transport properties, the molecular nature of this impact is still not well understood. By the establishment of a correlation between local chain dynamics and the distribution of free volume elements (FVEs), penetrant transport can be regulated more efficiently in amorphous polymer membranes. In this work, we implement all-atom molecular dynamics (MD) simulations to explore the relationship between chain dynamics and free volume in three polymers with different levels of backbone flexibility: polymethylpentene (PMP), polystyrene (PS), and HAB-6FDA thermally rearranged polymer (TRP). We construct these polymers at different temperatures and examine how temperature impacts the FVE distribution and segmental mobility. Our analysis shows that chain segments near FVEs have higher mobility compared with the atoms in the bulk; the extent of this difference increases with chain flexibility. Increasing the chain flexibility by increasing the temperature results in a broader FVE distribution. Rigid polymers such as TRP show the most robust FVE distribution and are not significantly affected by the temperature change. To capture penetrant diffusion through the polymer matrix, hydrogen is inserted and the diffusion is measured at different temperatures; hydrogen mobility is influenced by the FVE structure and overall mobility of polymer chains. Lastly, at low temperatures, hydrogen mobility is influenced by void distribution, while at high temperatures, polymer dynamics dictate hydrogen transport.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗