Overlap Concentration of Sodium Polystyrene Sulfonate in Solution.
Abstract not provided.
Stevens, Mark↗
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Experimental and computational study of polystyrene sulfonate depolymerization by a Fenton reaction
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Landera, Alexander↗
ORNL TSL evaluations for polyethylene, polystyrene, and lucite [Slides]
Abstract not provided.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Alternating Gyroid Network Structure in an ABC Miktoarm Terpolymer Comprised of Polystyrene and Two Polydienes
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99 GENERAL AND MISCELLANEOUS↗
Coexistence and Phase Behavior of Solvent-Polystyrene-Grafted Gold Nanoparticle Systems
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99 GENERAL AND MISCELLANEOUS↗
Total thermal neutron cross section measurements of hydrogen dense polymers from 0.0005–20 eV
Hydrogen dense polymers, specifically polyethylene, polystyrene, and Plexiglas, have served as neutron moderator and reflector materials in hundreds of separate critical benchmark experiments because of their low cost and abundance of hydrogen. In order to accurately model and simulate these critical benchmarks, the thermal scattering law (TSL) evaluation that governs how neutrons will thermalize must be well understood and rigorously validated. To support this validation, researchers at Rensselaer Polytechnic Institute performed total neutron cross section measurements for high-density polyethylene & polystyrene over the energy range 0.0005–20 eV and for Plexiglas G & Plexiglas G-UVT over the energy range 0.0005–3 eV. Comparisons were made between the measured cross section and that predicted by the ENDF/B-VIII.0 and Oak Ridge National Laboratory/European Spallation Source/Rensselaer Polytechnic Institute TSL evaluations for polyethylene, Plexiglas, and polystyrene, as available. These experiments represent the first total neutron cross section measurements for polystyrene.
73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
Integrating Flow Imaging Analysis and Single-Particle ICP-TOFMS for Comprehensive Micro- and Nanoplastic Characterization
Flow imaging analysis (FIA), provides composition-agnostic morphological characterization. These measurements of particle size and shape are valuable to mass-based analysis, such as single particle inductively coupled plasma time-of-flight mass spectrometry (sp-ICP-TOFMS), which provides quantitative data on elements within particles. Using these two methods together enables informed use of geometric assumptions required by sp-ICP-TOFMS, as particle mass is typically converted to a particle diameter using assumed-spherical geometry. To validate this concept, parallel measurements to determine particle diameters were performed by FIA and sp-ICP-TOFMS on four particle suspensions: 300 nm polystyrene Eu-doped nanoparticles, 1 μm Fe-rich beads, 3 μm four element calibration polystyrene beads and 5 μm polystyrene beads. The Fe-particles obtained the highest percent difference from the manufacturer’s nominal diameter, as the mean diameter obtained by FIA was overestimated by 21% and sp-ICP-TOFMS underestimated the mean diameter by 20.7%. Two types of particles were selected to test the effect of varying the particle number concentrations (PNC) on sizing accuracy, and both methods accurately sized each particle population at the PNC expected. Single particle analysis of carbon has continued to be a popular research topic, with direct applications to environmental pollutants in terms of nano- and micro- plastics. Real-world plastic particles were studied, and FIA’s measured circularity values demonstrated that the particles deviated from spherical geometries, therefore sp-ICP-TOFMS data should be interpreted as mass-based rather than size-based. Combining these techniques enables improved interpretation of particle populations and evaluation of particle sizes.
Szakas, Sarah [ORNL] (ORCID:0000000241332197)↗
Pore-Confined Polymers Enhance the Thermal Conductivity of Polymer Nanocomposites
In this work, molecularly confined polymer fillers in nanopores were found to give superior mechanical properties of polymer nanocomposites. In this work, we study the thermal conductivity of such nanocomposites and unveil the effect of polymer confinement on thermal conductivity. Using the time-domain thermoreflectance method, we measure the cross-plane thermal conductivity of polymer nanocomposites that consist of polystyrene fillers confined within a nanoporous organosilicate matrix. Compared to unconfined bulk polystyrene fillers, we find that pore-confined polystyrene fillers enhance the thermal conductivity of the polymer nanocomposites. This enhancement is attributed to the better aligned and less entangled chains in the confined phase, where chain–chain phonon scatterings are reduced. Our work provides essential insights into the thermal conductivity of polymer nanocomposites for multifunctional thermal and mechanical applications.
36 MATERIALS SCIENCE↗
Morphology of poly-3-hexyl-thiophene blends with styrene–isoprene–styrene block-copolymer elastomers from X-ray and neutron scattering
The nano- and micron scale morphology of poly(3-hexylthiophene) (P3HT) and polystyrene-block-polyisoprene-block-polystyrene (PS–PI–PS) elastomeric blends is investigated through the use of ultra-small and small angle X-ray and neutron scattering (USAXS, SAXS, SANS). It is demonstrated that loading P3HT into elastomer matrices is possible with little distortion of the elastomeric structure up to a loading of ~5 wt%. Increased loadings of conjugated polymer is found to significantly distort the matrix structure. Changes in processing conditions are also found to affect the blend morphology with especially strong dependence on processing temperature. Processing temperatures above the glass transition temperature (T g ) of polystyrene and the melting temperature (T m ) of the conjugated polymer additive (P3HT) creates significantly more organized mesophase domains. P3HT blends with PS–PI–PS can also be flow-aligned through processing, which results in an anisotropic structure that could be useful for the generation of anisotropic properties (e.g. conductivity). Moreover, the extent of flow alignment is significantly affected by the P3HT loading in the PS–PI–PS matrix. The work adds insight to the morphological understanding of a complex P3HT and PS–PI–PS polymer blend as conjugated polymer is added to the system. Here, we also provide studies isolating the effect of processing changes aiding in the understanding of the structural changes in this elastomeric conjugated polymer blend.
36 MATERIALS SCIENCE↗
Thermal Cross Section Measurements At The RPI LINAC
Recently, a cold moderator was designed and developed for use at the Rensselaer Polytechnic Institute Linear Accelerator (RPI LINAC). This cold moderator proved to easily and safely couple to an existing neutron producing target, while enhancing neutron flux below 0.02 eV by up to a factor of 8 by cooling polyethylene down to 29 K. This cold moderator capability allowed for significantly improved counting statistics below 0.02 eV not previously possible due to a poor signal to background ratio. Additionally, testing was performed to characterize the energy resolution of the new cold moderator system and found the system easily capable of resolving resonances in Ta-181 at 4 and 10 eV, while also clearly resolving the Bragg edges found in Be metal below 0.01 eV. Furthermore, following the design and development of a cold polyethylene moderator, a series of thermal total cross section measurements were performed for polyethylene, polystyrene, Plexiglas and yttrium hydride in the thermal region. These measurements serve to help validate thermal scattering law (TSL) evaluations in the 0.0005 – 1 eV energy range. For polyethylene and polystyrene, two sets of experiments were performed – one with the Enhanced Thermal Target (ETT) and another with the ETT plus the new cold moderator capability (ETTC). The yttrium hydride and Plexiglas measurements were only performed with the ETTC. The measurements for polyethylene help to validate the data processing methodology when using the ETTC, while extending the measured range of polyethylene down to 0.0005 eV. Two different Plexiglas, Plexiglas G and Plexiglas G-UVT, and two different concentrations of yttrium hydride, H/Y = 1.85 and 1.68, were measured. Overall, all materials had generally good agreement with their ENDF/B-VIII.0 TSL evaluations, though some discrepancies were noticed. In the case of the yttrium hydride, the high energy oscillations in the hydrogen cross section and the low energy Bragg edges in the yttrium cross section were clearly seen. These measurements represent the first total cross section measurements that encompass the entire thermal region from 0.0005 – 1 eV for polystyrene and yttrium hydride.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Thermal cross section measurements at the RPI LINAC [Abstract]
Recently, a cold moderator was designed and developed for use at the RPI LINAC. This cold moderator proved to easily and safely couple to an existing neutron producing target, while enhancing neutron flux below 0.02 eV by cooling polyethylene down to 29 K. This cold moderator capability allowed for significantly improved counting statistics below 0.02 eV not previously possible due to a poor signal to background ratio. Additionally, testing was performed to characterize the energy resolution of the new cold moderator system and found the system easily capable of resolving resonances in Ta-181 at 4 and 10 eV, while also clearly resolving the Bragg edges found in Be metal below 0.01 eV. Following the design and development of a cold polyethylene moderator, a series of thermal total cross section measurements were performed for polyethylene, polystyrene, Plexiglas and yttrium hydride in the thermal region. These measurements serve to help validate thermal scattering law (TSL) evaluations in the 0.0006 – 20 eV energy range. For polyethylene and polystyrene, two sets of experiments were performed – one with the Enhanced Thermal Target (ETT) and another with the ETT plus the new cold moderator capability (ETTC). The yttrium hydride and Plexiglas measurements were only performed with the ETTC. The measurements for polyethylene help to validate the data processing methodology when using the ETTC, while extending the measured range of polyethylene down to 0.0007 eV. Two different Plexiglas, Plexiglas G and Plexiglas G-UVT, and two different concentrations of yttrium hydride, H/Y = 1.85 and 1.68, were measured. Overall, all materials had generally good agreement with their ENDF/B-VIII.0 TSL evaluations, though some discrepancies were noticed. In the case of the yttrium hydride, the high energy oscillations in the hydrogen cross section and the low energy Bragg edges in the yttrium cross section were clearly seen. These measurements represent the first total cross section measurements that encompass the entire thermal region from 0.0006 – 3 eV for polystyrene and yttrium hydride.
46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
Effect of Molecular Weight on the Morphology of a Polymer Semiconductor–Thermoplastic Elastomer Blend
Abstract Polymer semiconductors (PSCs) are essential active materials in mechanically stretchable electronic devices. However, many exhibit low fracture strain due to their rigid chain conformation and the presence of large crystalline domains. Here, a PSC/elastomer blend, poly[((2,6‐bis(thiophen‐2‐yl)‐3,7‐bis(9‐octylnonadecyl)thieno[3,2‐b]thieno[2′,3′:4,5]thieno[2,3‐d]thiophene)‐5,5′‐diyl)(2,5‐bis(8‐octyloctadecyl)‐3,6‐di(thiophen‐2‐yl)pyrrolo[3,4‐c]pyrrole‐1,4‐dione)‐5,5′‐diyl]] (P2TDPP2TFT4) and polystyrene‐ block ‐poly(ethylene‐ran‐butylene)‐ block ‐polystyrene (SEBS) are systematically investigated. Specifically, the effects of molecular weight of both SEBS and P2TDPP2TFT4 on the resulting blend morphology, mechanical, and electrical properties are explored. In addition to commonly used techniques, atomic force microscopy‐based nanomechanical images are used to provide additional insights into the blend film morphology. Opposing trends in SEBS‐induced aggregation are observed for the different P2TDPP2TFT4 molecular weights upon increasing the SEBS molecular weight from 87 to 276 kDa. Furthermore, these trends are seen in device performance trends for both molecular weights of P2TDPP2TFT4. SEBS molecular weight also has a substantial influence on the mesoscale phase separation. Strain at fracture increases dramatically upon blending, reaching a maximum value of 640% ± 20% in the blended films measured with film‐on‐water method. These results highlight the importance of molecular weight for electronic devices. In addition, this study provides valuable insights into appropriate polymer selections for stretchable semiconducting thin films that simultaneously possess excellent mechanical and electrical properties.
36 MATERIALS SCIENCE↗
Surfactant-Induced Interfacial Aggregation of Porphyrins for Structuring Color-Tunable Liquids
Locking nonequilibrium shapes of liquids into targeted architectures by interfacial jamming of nanoparticles is an emerging area in material science. 5,10,15,20-tetrakis(4-sulfonatophenyl) porphyrin (H 6 TPPS) shows three different aggregation states that present an absorption imaging platform to monitor the assembly and jamming of supramolecular polymer surfactants (SPSs) at the liquid/liquid interface. The interfacial interconversion of H 6 TPPS, specifically H 4 TPPS 2- dissolved in water, from J- to an H-aggregation was induced by strong electrostatic interactions with amine-terminated polystyrene dissolved in toluene at the water/toluene interface. We find that this resulted in color-tunable liquids due to interfacial jamming of the SPSs formed between H 4 TPPS 2- and amine-terminated polystyrene. However, the formed SPSs cannot lock in nonequilibrium shapes of liquids. In addition, a self-wrinkling behavior was observed when amphiphilic triblock copolymers of PS-block-poly(2-vinylpyridine)-block-poly(ethylene oxide) were used to interact with H 4 TPPS 2- . Subsequently, the SPSs formed can lock in nonequilibrium shapes of liquids.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Alignment frustration in block copolymer films with block copolymer grafted TiO 2 nanoparticles under soft-shear cold zone annealing
Block copolymers (BCPs) have received significant attention as promising candidates for sequestering nanoparticles and fabrication of aligned nanostructures with optimal optical or electrical properties. We investigate the influence of static and dynamic thermal field on the alignment of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) BCP morphology with the loading of novel poly(methyl methacrylate-block-Polystyrene) (PMMA-b-PS)-grafted-TiO 2 nanoparticles (BCP-g-TiO 2 ). Observation of characteristics IR peaks for PMMA and PS in BCP-g-TiO 2 nanoparticles and Transmission Electron Microscopy (TEM) results of the outer coating of core nanoparticle, validate the grafting to approach in synthesizing BCP-g-TiO 2 . In this work, we report that under the sharp dynamic thermal field, at low loading of BCP-g-TiO 2 , there is good dispersion of nanoparticles in unidirectionally aligned BCP matrix in film interior probed by GISAXS, while, at high nanoparticle loading (~10 wt%), there is local frustration in the unidirectional alignment of the BCP matrix due to aggregation of BCP-g-TiO 2 nanoparticles. However, Grazing incidence small angle X-ray scattering (GISAXS) shows clearly that the BCP films remain largely locally ordered at the domain scale, despite these large perturbations to long-range ordering even at high loading level, while bringing in new TiO 2 functionality to the BCP films, such as UVO absorptivity or biofouling prevention, important to potential new applications of such membranes.
77 NANOSCIENCE AND NANOTECHNOLOGY↗
Degradation in Photovoltaic Encapsulant Transmittance: Results of the Second PVQAT TG5 Artificial Weathering Study
The optical degradation of encapsulants from ultraviolet (UV) radiation has historically resulted in a significant loss in performance throughout the life of a photovoltaic (PV) module. International Electrotechnical Commission (IEC) test methods have recently been developed to screen for PV encapsulants prone to loss in optical performance. The present study was performed to benchmark polymeric packaging materials relative to IEC 62788-1-4 (covering the measurement of optical transmittance) and IEC 62788-1-7 (on the durability of transmittance), provide feedback toward improvement of the methods, and develop insight regarding optical degradation. Contemporary materials were examined, including poly(ethylene-co-vinyl acetate) (EVA), thermoplastic polyolefin (TPO), polyolefin elastomer (POE), and polyvinyl butyral (PVB) encapsulants; a poly(ethene-co-tetrafluoroethene)/poly(ethylene terephthalate) (ETFE/PET) transparent backsheet; and a polystyrene (PS) working reference material. The use of silica-, specialty-, and rolled-glass was also compared in laminated coupons. Specimen size was separately examined from 2.5 to 12.5 cm. Weathering was performed with a xenon source, using IEC TS 62788-7-2 methods A2, A3, A4, and A5 (chamber temperature of 55 degrees C, 65 degrees C, 75 degrees C, or 85 degrees C), respectively. Characterizations were made using a UV-visible-near-infrared (UV-VIS-NIR) spectrophotometer (transmittance and reflectance, with and without an integrating sphere), a UV-VIS fluorescence spectrophotometer, a camera, and an optical microscope. Performance was analyzed, including solar weighted transmittance, yellowness index, UV cut-off wavelength, and haze (scattering). Separate Arrhenius analyses were performed to assess retention of transmittance and changes in yellowness index. The activation energy for both characteristics was found to range from 15-80 kJ mol-1, with an average of 48 kJ mol-1, similar to the average of 45 kJ mol-1 identified in the previous international PV Quality Assurance Task Force (PVQAT) Task Group 5 (TG5) study of more traditional encapsulants. The separate degradation modes of discoloration and scattering were distinguished in the encapsulants using a comprehensive spectral characterization. Based on these results, the IEC 62788-1-7 pass/fail criteria of 5% change in transmittance was confirmed to identify a known bad encapsulant.
durability↗
Molecular dynamics simulations of energy accommodation between gases and polymers for ultra-low thermal conductivity insulation
Determining the energy accommodation between gases and solids is essential to developing porous thermal insulation materials with ultra-low effective thermal conductivity that reduce energy use, greenhouse gas emissions, and fossil fuel consumption. The energy accommodation coefficients of most gases, however, have been rarely studied, especially with respect to solids that have relatively high thermal resistivity, e.g., polymers. Here, by using all-atom nonequilibrium molecular dynamics simulations, we reveal the accommodation coefficients of He, Ar, N 2 , and O 2 with polymers, mainly polystyrene. We find that their values are around 0.51, 0.72, 0.79, and 0.90, respectively, suggesting a critical reexamination of the commonly used theoretical maximum value of 1. We have also conducted experiments and validated the value for air, which is about 0.81. Such a change in accommodation coefficients can lead to a reduction of about 70%, 50%, 35%, and 20% in the thermal conductivity of He, Ar, N 2 , and O 2 gases in nano pores (below 100 nm) or at low pressures (below 1 millibar). With these new accommodation coefficients, we find that in a 10 nm pore with ambient pressure at 300 K, the gas thermal conductivity of He, Ar, N 2 , and O 2 in porous polystyrene can be as low as 9.7 × 10 –4 , 3.4 × 10 –4 , 7.3 × 10 –4 , and 8.5 × 10 –4 W·m –1 ·K –1 , respectively, which are two to three orders of magnitude lower than their bulk values, promising higher thermal resistivity of insulation materials. This work reveals the fundamental energy exchange between gases and polymers, providing important guidance for designing high-performance thermal insulation materials for various applications.
36 MATERIALS SCIENCE↗
Quantifying the Influence of Size, Shape, and Density of Microplastics on Their Transport Modes: A Modeling Approach
Microplastics (MPs) pose significant risks to marine ecosystems and human health, necessitating accurate predictions of their distributions in aquatic environments for effective risk mitigation. However, understanding MP transport dynamics is challenging because of the inadequate representation of MP characteristics such as size, shape, and density in numerical models. Further, the accuracy of the MP vertical profiles in existing models has not been thoroughly validated. Thus, we developed an MP transport model within the Finite Volume Community Ocean Model framework (FVCOM-MP) by integrating MP characteristics. We validated FVCOM-MP against experimental and analytical data, focusing on various MP transport modes and transitions. FVCOM-MP successfully replicates MP profiles in different transport modes, including the bedload, surface-load, suspended-load, and mixed-load modes. Additionally, we introduce phase diagrams for classifying MP transport modes based on particle characteristics, enhancing our understanding of MP dynamics in aquatic systems. The transport modes for a number of real-world MP particles, including fishing line, plastic bag/bottle fragments, synthetic fibers, tire wear particles, polyvinyl chloride and expanded polystyrene pellets, were analyzed with these phase diagrams.
Microplastic transport, Settling velocity, Rising ↗
Polymeric Microcapsules as Robust Mimics of Emulsion Liquid Membranes for Selective Ion Separations
Selective ion separations are increasingly needed to combat water scarcity, recover resources from wastewater, and enable the efficient recycling of electronics waste. Emulsion liquid membranes (ELMs) have received interest due to rapid kinetics, high selectivities, and low solvent requirements but are too unstable for industrial usage. Here, we demonstrate that polymeric microcapsules can serve as robust, solvent-free mimics of ELMs. As a proof of concept, we incorporated the copper-selective ligand Lix 84-I in the walls of microcapsules formed from a commercial polystyrene-b-polybutadiene-b-polystyrene triblock polymer. The microcapsules were formed from a double-emulsion template, resulting in particles typically 20–120 μm in diameter that encapsulated even smaller droplets of a dilute (≤0.5 M) H 2 SO 4 solution. Batch experiments demonstrated facilitated-transport behavior, with equilibrium reached in as little as 10 min for microcapsules with 1% ligand, and with ~15-fold selectivity for Cu 2+ over Ni 2+ . Furthermore, the microcapsules could be packed readily in columns for flow-through operation, thus enabling near-complete Cu 2+ removal in ~2 min under certain conditions, recovery of Cu 2+ by flowing through fresh dilute H 2 SO 4 , and reuse for at least 10 cycles. The approach in this work can serve as a template for using selective ligands to enable robust and simple flow-through processes for a variety of selective ion separations.
54 ENVIRONMENTAL SCIENCES↗