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At least 127 records · Page 7

Machine-Learned Manifold-Based Models for Large Eddy Simulation of Turbulent Combustion

Reduced-order manifold combustion models are commonly used to lower the cost of reacting Large Eddy Simulations (LES) and may be derived either from physical principles as in flamelet models or from data-driven methods like Principal Component Analysis (PCA). In either case, neural networks are increasingly used as part of these models to provide a nonlinear mapping between a small set of pre-defined variables that parameterize the manifold and outputs of interest, such as reaction rates. In this work, we propose a new manifold-based modeling approach that combines the definition of the manifold-parameterizing variables (linear combinations of species), the nonlinear mapping to the outputs, and closure of filtered quantities for LES into the structure of a single neural network. This allows the process used to train the neural network to simultaneously optimize both the functional form of the model and the identities of the inputs to the model. The new approach can flexibly incorporate thermochemical data from any combustion system; if trained on data from 1D flames it can be interpreted as an optimized flamelet model, but it can also be used to learn models from data from more complex configurations. This work presents a priori evaluations of the new approach in both contexts. Evaluation using data from 1D premixed flames demonstrates the physical interpretability of the manifold variables generated by the new approach. Evaluation using data from direct numerical simulations of turbulent flames shows improved predictions relative to either flamelet or PCA-based models in a more complex configuration.

47 OTHER INSTRUMENTATION↗

Dynamic Bertrand Oligopoly

We study continuous time Bertrand oligopolies in which a small number of firms producing similar goods compete with one another by setting prices. We first analyze a static version of this game in order to better understand the strategies played in the dynamic setting. Within the static game, we characterize the Nash equilibrium when there are N players with heterogeneous costs. In the dynamic game with uncertain market demand, firms of different sizes have different lifetime capacities which deplete over time according to the market demand for their good. We setup the nonzero-sum stochastic differential game and its associated system of HJB partial differential equations in the case of linear demand functions. We characterize certain qualitative features of the game using an asymptotic approximation in the limit of small competition. The equilibrium of the game is further studied using numerical solutions. We find that consumers benefit the most when a market is structured with many firms of the same relative size producing highly substitutable goods. However, a large degree of substitutability does not always lead to large drops in price, for example when two firms have a large difference in their size.

97 MATHEMATICS AND COMPUTING↗

Design of light- and chemically responsive protein assemblies through host-guest interactions

Host-guest (HG) interactions have been widely used to build responsive materials and molecular machines owing to their inherently dynamic nature, interaction specificity, and responsiveness to diverse stimuli. Here, in this work, we have set out to exploit these advantages of HG chemistry in the design of dynamic protein assemblies, using a C 4 symmetric protein, C98 RhuA, as a building block. We show that a C98 RhuA variant individually modified with β-cyclodextrin (βCD) (host) or azobenzene (guest) functionalities can specifically pair with each other to form highly ordered 1D and 2D assemblies. Association and dissociation of βCD RhuA- azo RhuA assemblies can be controlled by UV and visible light as well as by small-molecule modulators of βCD-azobenzene interactions. Kinetics analyses reveal that βCD RhuA- azo RhuA nanotubes assemble without a nucleation barrier, a highly unusual occurrence for helical supramolecular systems. Taken together, our findings provide a compelling example for achieving complex structural and dynamic outcomes in protein assembly through simple chemical design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cosmology and stellar equilibrium using Newtonian hydrodynamics with general relativistic pressure

We revisit the analysis made by Hwang and Noh [JCAP 1310 (2013)] aiming the construction of a Newtonian set of equations incorporating pressure effects typical of the General Relativity theory. We explicitly derive the Hwang-Noh equations, comparing them with similar computations found in the literature. Then, we investigate i ) the cosmological expansion, ii ) linear cosmological perturbations theory and iii ) stellar equilibrium by using the new set of equations and comparing the results with those coming from the usual Newtonian theory, from the Neo-Newtonian theory and from the General Relativity theory. We show that the predictions for the background evolution of the Universe are deeply changed with respect to the General Relativity theory: the acceleration of the Universe is achieved with positive pressure. On the other hand, the behaviour of small cosmological perturbations reproduces the one found in the relativistic context, even if only at small scales. We argue that this last result may open new possibilities for numerical simulations for structure formation in the Universe. Finally, the properties of neutron stars are qualitatively reproduced by Hwang-Noh equations, but the upper mass limit is at least one order of magnitude higher than the one obtained in General Relativity.

79 ASTRONOMY AND ASTROPHYSICS↗

3D Printed Silicones with Shape Memory

Direct ink writing enables the layer-by-layer manufacture of ordered, porous structures whose mechanical behavior is driven by architecture and material properties. Here, we incorporate two different gas filled microsphere pore formers to evaluate the effect of shell stiffness and T g on compressive behavior and compression set in siloxane matrix printed structures. The lower T g microsphere structures exhibit substantial compression set when heated near and above T g , with full structural recovery upon reheating without constraint. By contrast, the higher T g microsphere structures exhibit reduced compression set with no recovery upon reheating. Aside from their role in tuning the mechanical behavior of direct ink write structures, polymer microspheres are good candidates for shape memory elastomers requiring structural complexity, with potential applications toward tandem shape memory polymers.

36 MATERIALS SCIENCE↗

Harmonic analysis of discrete tracers of large-scale structure

It is commonplace in cosmology to analyze fields projected onto the celestial sphere, and in particular density fields that are defined by a set of points e.g. galaxies. When performing an harmonic-space analysis of such data (e.g. an angular power spectrum) using a pixelized map one has to deal with aliasing of small-scale power and pixel window functions. We compare and contrast the approaches to this problem taken in the cosmic microwave background and large-scale structure communities, and advocate for a direct approach that avoids pixelization. We describe a method for performing a pseudo-spectrum analysis of a galaxy data set and show that it can be implemented efficiently using well-known algorithms for special functions that are suited to acceleration by graphics processing units (GPUs). The method returns the same spectra as the more traditional map-based approach if in the latter the number of pixels is taken to be sufficiently large and the mask is well sampled. The method is readily generalizable to cross-spectra and higher-order functions. It also provides a convenient route for distributing the information in a galaxy catalog directly in harmonic space, as a complement to releasing the configuration-space positions and weights, and a route to spectral apodization. Finally, we make public a code enabling the application of our method to existing and upcoming datasets.

79 ASTRONOMY AND ASTROPHYSICS↗

Customizable wave tailoring nonlinear materials enabled by bilevel inverse design

Abstract Passive wave transformation via nonlinearity is ubiquitous in settings from acoustics to optics and electromagnetics. It is well known that different nonlinearities yield different effects on propagating signals, which raises the question of “what precise nonlinearity is the best for a given wave tailoring application?” In this work, considering a one-dimensional spring-mass chain connected by polynomial springs (a variant of the Fermi-Pasta-Ulam-Tsingou system), we introduce a bilevel inverse design method which couples the shape optimization of structures for tailored constitutive responses with reduced-order nonlinear dynamical inverse design. We apply it to two qualitatively distinct problems—minimization of peak transmitted kinetic energy from impact, and pulse shape transformation—demonstrating our method’s breadth of applicability. For the impact problem, we obtain two fundamental insights. First, small differences in nonlinearity can drastically change the dynamic response of the system, from severely under- to outperforming a comparative linear system. Second, the oft-used strategy of impact mitigation via “energy locking” bistability can be significantly outperformed by our optimal nonlinearity. We validate this case with impact experiments and find excellent agreement. This study establishes a framework for broader passive nonlinear mechanical wave tailoring material design, with applications to computing, signal processing, shock mitigation, and autonomous materials.

Science & Technology - Other Topics↗

Temperature-dependent radiation sensitivity and order of 70S ribosome crystals

All evidence to date indicates that at T = 100 K all protein crystals exhibit comparable sensitivity to X-ray damage when quantified using global metrics such as change in scaling B factor or integrated intensity versus dose. This is consistent with observations in cryo-electron microscopy, and results because nearly all diffusive motions of protein and solvent, including motions induced by radiation damage, are frozen out. But how do the sensitivities of different proteins compare at room temperature, where radiation-induced radicals are free to diffuse and protein and lattice structures are free to relax in response to local damage? It might be expected that a large complex with extensive conformational degrees of freedom would be more radiation sensitive than a small, compact globular protein. As a test case, the radiation sensitivity of 70S ribosome crystals has been examined. At T = 100 and 300 K, the half doses are 64 MGy (at 3 Å resolution) and 150 kGy (at 5 Å resolution), respectively. The maximum tolerable dose in a crystallography experiment depends upon the initial or desired resolution. When differences in initial data-set resolution are accounted for, the former half dose is roughly consistent with that for model proteins, and the 100/300 K half-dose ratio is roughly a factor of ten larger. 70S ribosome crystals exhibit substantially increased resolution at 100 K relative to 300 K owing to cooling-induced ordering and not to reduced radiation sensitivity and slower radiation damage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermoelectric characterization of suspended single silicon%3CU%2B2010%3Egermanium alloy nanowires.

The use of nanowires for thermoelectric energy generation has gained momentum in recent years as an approach to improve the figure of merit (ZT) due in part to larger phonon scattering at the boundary resulting in reduced thermal conductivity while electrical conductivity is not significantly affected. Silicon-germanium (SiGe) alloy nanowires are promising candidates to further reduce thermal conductivity by phonon scattering because bulk SiGe alloys already have thermal conductivity comparable to reported Si nanowires. In this work, we show that thermal and electrical conductivity can be measured for the same single nanowire eliminating the uncertainties in ZT estimation due to measuring the thermal conduction on one set of wires and the electrical conduction on another set. In order to do so, we use nanomanipulation to place vapor-liquid-solid boron-doped SiGe alloy nanowires on predefined surface structures. Furthermore, we developed a contact-annealing technique to achieve negligible electrical contact resistance for the placed nanowires that allows us, for the first time, to measure electrical and thermal properties on the same device. We observe that thermal conductivity for SiGe nanowires is dominated by alloy scattering for nanowires down to 100 nm in diameter between the temperature range 40-300 K. The estimated electronic contribution of the thermal conductivity as given by the Wiedemann-Franz relationship is about 1 order of magnitude smaller than the measured thermal conductivity which indicates that phonons carry a large portion of the heat even at such small dimensions.

36 MATERIALS SCIENCE↗

Fast Real-Time Time-Dependent Density Functional Theory Calculations with the Parallel Transport Gauge

Real-time time-dependent density functional theory (RT-TDDFT) is known to be hindered by the very small time step (attosecond or smaller) needed in the numerical simulation, because of the fast oscillation of electron wave functions, which significantly limits its range of applicability for the study of ultrafast dynamics. In this paper, we demonstrate that such oscillation can be considerably reduced by optimizing the gauge choice using the parallel transport formalism. RT-TDDFT calculations can thus be significantly accelerated using a combination of the parallel transport gauge and implicit integrators, and the resulting scheme can be used to accelerate any electronic structure software that uses a Schrödinger representation. Here, using absorption spectrum, ultrashort laser pulse, and Ehrenfest dynamics calculations for example, we show that the new method can utilize a time step that is on the order of 10–100 attoseconds using a planewave basis set. Thanks to the significant increase of the size of the time step, we also demonstrate that the new method is more than 10 times faster, in terms of the wall clock time, when compared to the standard explicit fourth-order Runge–Kutta time integrator for silicon systems ranging from 32 to 1024 atoms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Advancing Understanding of the Role of Belowground Processes in Terrestrial Carbon Sinks trhrough Ground-Penetrating Radar. Final Report

Coarse roots play a significant role in belowground carbon cycling and will likely play an increasingly crucial role in belowground carbon sequestration as atmospheric CO 2 levels continue to rise, yet they are one of the most difficult ecosystem parameters to quantify. Despite promising results with ground-penetrating radar (GPR) as a nondestructive method of quantifying biomass of coarse roots, this application of GPR is in its infancy and neither the complete potential nor limitations of the technology have been fully evaluated. The primary goals and questions of this study fell into four groups: (1) GPR methods: Can GPR detect change in root biomass over time, differentiate live roots from dead roots, differentiate between coarse roots, fine roots bundled together, and a fine root mat, remain effective with varied soil moisture, and detect shadowed roots (roots hidden below larger roots); (2) CO 2 enrichment study at Kennedy Space Center in Brevard County, Florida: Are there post-fire legacy effects of CO 2 fertilization on plant carbon pools following the end of CO 2 application ? (3) Disney Wilderness Study: What is the overall coarse root biomass and potential for belowground carbon storage in a restored longleaf pine flatwoods system? Can GPR effectively quantify coarse roots in soils that are wetter than the previous sites and that have a high percentage of saw palmetto rhizomes present? (4) Can GPR accurately represent root architecture in a three-dimensional model? When the user is familiar with the equipment and software in a setting that minimizes unsuitable conditions, GPR is a relatively precise, non-destructive, useful tool for estimating coarse root biomass. However, there are a number of cautions and guidelines that should be followed to minimize inaccuracies or situations that are untenable for GPR use. GPR appears to be precise as it routinely predicts highly similar values for a given area across multiple scanning events; however, it appears to lack sufficient accuracy at small scales. Knowledge of soil conditions and their effects on GPR wave propagation and reception are paramount for the collection of useful data. Strong familiarity with the software and equipment is both important and necessary for GPR use in estimating coarse root biomass. GPR must be utilized at low soil moisture levels in order to accurately represent existing coarse root structures. Our results from Disney Wilderness Preserve highlight the need for a strong understanding of the limitations of GPR, specifically knowledge of root structures (saw palmetto rhizomes) or environmental factors (low moisture content) that may hinder its application within a given system. The 3D modeling of course roots with GPR appears quite promising, as it has become more accurate and precise as the software has advanced and become more robust, but there is still a need for more precision before it will likely be able to model anything more than simple root systems comprised mostly of large diameter roots. Our results from Kennedy Space Center suggest that there are legacy effects from CO 2 fertilization in the form of more root mass providing a greater capacity for aboveground plant regrowth following fire, even 7 years after treatment ended.

54 ENVIRONMENTAL SCIENCES↗

PRELUDE TO A DOUBLE DEGENERATE MERGER: THE ONSET OF MASS TRANSFER AND ITS IMPACT ON GRAVITATIONAL WAVES AND SURFACE DETONATIONS

We present the results of a systematic numerical study of the onset of mass transfer in double degenerate binary systems and its impact on the subsequent evolution. All investigated systems belong to the regime of direct impact, unstable mass transfer. In all of the investigated cases, even those considered unstable by conventional stability analysis, we find a long-lived mass transfer phase continuing for as many as several dozen orbital periods. This settles a recent debate sparked by a discrepancy between earlier smoothed particle hydrodynamics (SPH) calculations that showed disruptions after a few orbital periods and newer grid-based studies in which mass transfer continued for tens of orbits. The number of orbits a binary survives sensitively depends on the exact initial conditions. We find that the approximate initial conditions that have been used in most previous SPH calculations have a serious impact on all stages of the evolution from the onset of mass transfer up to the final structure of the remnant. We compare 'approximate' initial conditions where spherical stars are placed at an initial separation obtained from an estimate of the Roche lobe size with 'accurate' initial conditions that were constructed by carefully driving the binary system to equilibrium by a relaxation scheme. Simulations that use the approximate initial conditions underestimate the initial separation when mass transfer sets in, which yields a binary that only survives for only a few orbits and thus a rapidly fading gravitational wave signal. Conversely, the accurate initial conditions produce a binary system in which the mass transfer phase is extended by almost two orders of magnitude in time, resulting in a gravitational wave signal with amplitude and frequency that remain essentially constant up until merger. As we show that these binaries can survive at small separation for hundreds of orbital periods, their associated gravitational wave signal should be included when calculating the gravitational wave foreground (although expected to be below Laser Interferometer Space Antenna's sensitivity at these high frequencies). We also show that the inclusion of the entropy increase associated with shock heating of the accreted material reduces the number of orbits a binary survives given the same initial conditions, although the effect is not as pronounced when using the appropriate initial conditions. The use of accurate initial conditions and a correct treatment of shock heating allows for a reliable time evolution of the temperature, density, and angular momentum, which are important when considering thermonuclear events that may occur during the mass transfer phase and/or after merger. Our treatment allows us to accurately identify when surface detonations may occur in the lead-up to the merger, as well as the properties of final merger products.

79 ASTRONOMY AND ASTROPHYSICS↗

CombAlign: a code for generating a one-to-many sequence alignment from a set of pairwise structure-based sequence alignments

In order to better define regions of similarity among related protein structures, it is useful to identify the residue-residue correspondences among proteins. Few codes exist for constructing a one-to-many multiple sequence alignment derived from a set of structure or sequence alignments, and a need was evident for creating such a tool for combining pairwise structure alignments that would allow for insertion of gaps in the reference structure. This report describes a new Python code, CombAlign, which takes as input a set of pairwise sequence alignments (which may be structure based) and generates a one-to-many, gapped, multiple structure- or sequence based sequence alignment (MSSA). The use and utility of CombAlign was demonstrated by generating gapped MSSAs using sets of pairwise structure-based sequence alignments between structure models of the matrix protein (VP40) and pre-small/secreted glycoprotein (sGP) of Reston Ebolavirus and the corresponding proteins of several other filoviruses. The gapped MSSAs revealed structure-based residue-residue correspondences, which enabled identification of structurally similar versus differing regions in the Reston proteins compared to each of the other corresponding proteins. CombAlign is a new Python code that generates a one-to-many, gapped, multiple structure- or sequence-based sequence alignment (MSSA) given a set of pairwise sequence alignments (which may be structure based). CombAlign has utility in assisting the user in distinguishing structurally conserved versus divergent regions on a reference protein structure relative to other closely related proteins. CombAlign was developed in Python 2.6, and the source code is available for download from the GitHub code repository.

59 BASIC BIOLOGICAL SCIENCES↗

Dust-acoustic rogue waves in a nonextensive plasma

We present an investigation for the generation of a dust-acoustic rogue wave in a dusty plasma composed of negatively charged dust grains, as well as nonextensive electrons and ions. For this purpose, the reductive perturbation technique is used to obtain a nonlinear Schroedinger equation. The critical wave-number threshold k{sub c}, which indicates where the modulational instability sets in, has been determined precisely for various regimes. Two different behaviors of k{sub c} against the nonextensive parameter q are found. For small k{sub c}, it is found that increasing q would lead to an increase of k{sub c} until q approaches a certain value q{sub c}, then further increase of q beyond q{sub c} decreases the value of k{sub c}. For large k{sub c}, the critical wave-number threshold k{sub c} is always increasing with q. Within the modulational instability region, a random perturbation of the amplitude grows and thus creates dust-acoustic rogue waves. In order to show that the characteristics of the rogue waves are influenced by the plasma parameters, the relevant numerical analysis of the appropriate nonlinear solution is presented. The nonlinear structure, as reported here, could be useful for controlling and maximizing highly energetic pulses in dusty plasmas.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

The second-order differential phase contrast and its retrieval for imaging with x-ray Talbot interferometry

Purpose: The x-ray differential phase contrast imaging implemented with the Talbot interferometry has recently been reported to be capable of providing tomographic images corresponding to attenuation-contrast, phase-contrast, and dark-field contrast, simultaneously, from a single set of projection data. The authors believe that, along with small-angle x-ray scattering, the second-order phase derivative {Phi}{sup Double-Prime }{sub s}(x) plays a role in the generation of dark-field contrast. In this paper, the authors derive the analytic formulae to characterize the contribution made by the second-order phase derivative to the dark-field contrast (namely, second-order differential phase contrast) and validate them via computer simulation study. By proposing a practical retrieval method, the authors investigate the potential of second-order differential phase contrast imaging for extensive applications. Methods: The theoretical derivation starts at assuming that the refractive index decrement of an object can be decomposed into {delta}={delta}{sub s}+{delta}{sub f}, where {delta}{sub f} corresponds to the object's fine structures and manifests itself in the dark-field contrast via small-angle scattering. Based on the paraxial Fresnel-Kirchhoff theory, the analytic formulae to characterize the contribution made by {delta}{sub s}, which corresponds to the object's smooth structures, to the dark-field contrast are derived. Through computer simulation with specially designed numerical phantoms, an x-ray differential phase contrast imaging system implemented with the Talbot interferometry is utilized to evaluate and validate the derived formulae. The same imaging system is also utilized to evaluate and verify the capability of the proposed method to retrieve the second-order differential phase contrast for imaging, as well as its robustness over the dimension of detector cell and the number of steps in grating shifting. Results: Both analytic formulae and computer simulations show that, in addition to small-angle scattering, the contrast generated by the second-order derivative is magnified substantially by the ratio of detector cell dimension over grating period, which plays a significant role in dark-field imaging implemented with the Talbot interferometry. Conclusions: The analytic formulae derived in this work to characterize the second-order differential phase contrast in the dark-field imaging implemented with the Talbot interferometry are of significance, which may initiate more activities in the research and development of x-ray differential phase contrast imaging for extensive preclinical and eventually clinical applications.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Similarity Downselection: Finding the n Most Dissimilar Molecular Conformers for Reference-Free Metabolomics

Computational methods for creating in silico libraries of molecular descriptors (e.g., collision cross sections) are becoming increasingly prevalent due to the limited number of authentic reference materials available for traditional library building. These so-called “reference-free metabolomics” methods require sampling sets of molecular conformers in order to produce high accuracy property predictions. Due to the computational cost of the subsequent calculations for each conformer, there is a need to sample the most relevant subset and avoid repeating calculations on conformers that are nearly identical. The goal of this study is to introduce a heuristic method of finding the most dissimilar conformers from a larger population in order to help speed up reference-free calculation methods and maintain a high property prediction accuracy. Finding the set of the n items most dissimilar from each other out of a larger population becomes increasingly difficult and computationally expensive as either n or the population size grows large. Because there exists a pairwise relationship between each item and all other items in the population, finding the set of the n most dissimilar items is different than simply sorting an array of numbers. For instance, if you have a set of the most dissimilar n = 4 items, one or more of the items from n = 4 might not be in the set n = 5. An exact solution would have to search all possible combinations of size n in the population exhaustively. We present an open-source software called similarity downselection (SDS), written in Python and freely available on GitHub. SDS implements a heuristic algorithm for quickly finding the approximate set(s) of the n most dissimilar items. We benchmark SDS against a Monte Carlo method, which attempts to find the exact solution through repeated random sampling. We show that for SDS to find the set of n most dissimilar conformers, our method is not only orders of magnitude faster, but it is also more accurate than running Monte Carlo for 1,000,000 iterations, each searching for set sizes n = 3–7 out of a population of 50,000. We also benchmark SDS against the exact solution for example small populations, showing that SDS produces a solution close to the exact solution in these instances. Using theoretical approaches, we also demonstrate the constraints of the greedy algorithm and its efficacy as a ratio to the exact solution.

97 MATHEMATICS AND COMPUTING↗

Group Additivity Determination for Oxygenates, Oxonium Ions, and Oxygen-Containing Carbenium Ions

Bio-oil produced from biomass fast pyrolysis often requires catalytic upgrading to remove oxygen and acidic species over zeolite catalysts. The elementary reactions in the mechanism for this process involve carbenium and oxonium ions. In order to develop a detailed kinetic model for the catalytic upgrading of biomass, rate constants are required for these elementary reactions. The parameters in the Arrhenius equation can be related to thermodynamic properties through structure-reactivity relationships, such as the Evans-Polanyi relationship. For this relationship, enthalpies of formation of each species are required, which can be reasonably estimated using group additivity. However, the literature previously lacked group additivity values for oxygenates, oxonium ions, and oxygen-containing carbenium ions. In this work, 71 group additivity values for these types of groups were regressed, 65 of which had not been reported previously and six of which were newly estimated based on regression in the context of the 65 new groups. Heats of formation based on atomization enthalpy calculations for a set of reference molecules and isodesmic reactions for a small set of larger species for which experimental data was available were used to demonstrate the accuracy of the Gaussian-4 quantum mechanical method in estimating enthalpies of formation for species involving the moieties of interest. Isodesmic reactions for a total of 195 species were constructed from the reference molecules to calculate enthalpies of formation that were used to regress the group additivity values. The results showed an average deviation of 1.95 kcal/mol between the values calculated from Gaussian-4 and isodesmic reactions versus those calculated from the group additivity values that were newly regressed. Importantly, the new groups enhance the database for group additivity values, especially those involving oxonium ions.

09 BIOMASS FUELS↗

Pendant Group Modifications Provide Graft Copolymer Silicones with Exceptionally Broad Thermomechanical Properties

Graft copolymers offer a versatile platform for the design of self-assembling materials; however, simple strategies for precisely and independently controlling the thermomechanical and morphological properties of graft copolymers remain elusive. Here, using a library of 92 polynorbornene-graft-polydimethylsiloxane (PDMS) copolymers, we discover a versatile backbone-pendant sequence-control strategy that addresses this challenge. Small structural variations of pendant groups, e.g., cyclohexyl versus n-hexyl, of small-molecule comonomers have dramatic impacts on order-to-disorder transitions, glass transitions, mechanical properties, and morphologies of statistical and block silicone-based graft copolymers, providing an exceptionally broad palette of designable materials properties. For example, statistical graft copolymers with high PDMS volume fractions yielded unbridged body-centered cubic morphologies that behaved as soft plastic crystals. By contrast, lamellae-forming graft copolymers provided robust, yet reprocessable silicone thermoplastics (TPs) with transition temperatures spanning over 160 °C and elastic moduli as high as 150 MPa despite being both unentangled and un-cross-linked. Altogether, this study reveals a new pendant-group-mediated self-assembly strategy that simplifies graft copolymer synthesis and enables access to a diverse family of silicone-based materials, setting the stage for the broader development of self-assembling materials with tailored performance specifications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗