Article
Polymer Science
Shuyi Xie, Bo Zhang, Frank S. Bates, Timothy P. Lodge
Summary: Salt-doped A/B/AB ternary polymer blends exhibit a variety of nanostructured morphologies that can be tuned by the composition of homopolymers and diblock copolymers. Studies on phase diagrams of lithium bis(trifluoromethane) sulfonimide (LiTFSI)-doped polymer blends show that the composition of homopolymers can affect the resulting microstructures, leading to the formation of higher curvature phases under certain conditions.
Article
Polymer Science
Yu-Hsuan Lin, Chang-Cheng Shiu, Tien-Lin Chen, Hsin-Lung Chen, Jing-Cherng Tsai
Summary: Blending with homopolymer can tune the microdomain morphology of block copolymers, but under certain conditions, the addition of homopolymer may lead to anomalous phenomena such as excessive swelling of junction point separation and decreased interdomain distance.
Article
Polymer Science
Kristof Toth, Suwon Bae, Chinedum O. Osuji, Kevin G. Yager, Gregory S. Doerk
Summary: The study investigates the dependence of domain spacing in thin film blends of a lamellar polystyrene-block-poly(methyl methacrylate) diblock copolymer on thickness and homopolymer molar mass variations. The addition of homopolymers influences domain spacings, with thicker films and different homopolymer compositions leading to changes in lamellae orientation. Molecular simulations suggest that these effects are driven by homopolymer segregation to film surfaces.
Article
Engineering, Chemical
Shu Kikuchi, Ryoka Shoji, Shinji Kanehashi, Guanghui Ma, Kenji Ogino
Summary: Hierarchical nanostructures in polymer blends consisting of PBTPA, PMMA, and PBTPA-b-PMMA were fabricated using a solvent evaporation method. The morphology was influenced by the molecular weight and chemical composition of PBTPA-b-PMMA, molecular weights of homopolymers, and blend composition. The addition of PBTPA-b-PMMA caused a transition from core-shell to Janus or inversed core-shell structures, depending on the molecular weight of PBTPA segment. Watermelon-like particles were observed when the molecular weight of the PMMA segment was higher than that of the PMMA homopolymer. The interfacial tension between PBTPA and the aqueous phase was reduced by PBTPA-b-PMMA.
Article
Polymer Science
Hiroki Hamamoto, Hideaki Takagi, Isamu Akiba, Katsuhiro Yamamoto
Summary: Anomalous grazing incidence small-angle X-ray scattering (AGISAXS) was used to analyze the dispersion state of brominated homopolymer in PS-PHS/Br-PHS blend thin films. The results showed that Br-PHS segregated to the PS-PHS interface to reduce the interfacial energy.
Article
Chemistry, Multidisciplinary
Daniel Sharon, Peter Bennington, Michael A. Webb, Chuting Deng, Juan J. de Pablo, Shrayesh N. Patel, Paul F. Nealey
Summary: Block copolymer electrolytes blending with lithium bis(trifluoromethanesulfonyl)imide show promising potential for solid-state Li batteries. When the Li/EO ratio reaches 1/5, the conductivity of PEO-LiTFSI drops significantly while that of SEO-LiTFSI remains constant, revealing differences in their behavior at higher salt concentrations.
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
(2021)
Article
Materials Science, Multidisciplinary
Ze Ye, Ze-Kun Zhang, Shi-Peng Ding, Ding-Li Xia, Jun-Ting Xu
Summary: In this study, a block copolymer was used to fabricate electrolytes containing double conductive nanophases. The distribution of lithium salt in the two phases was quantitatively characterized, and it was found that the salt content in the PEO phase is relatively higher. The hybrids with lower doping ratios showed larger grain sizes and smaller interphase thickness, and were more sensitive to temperature changes.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Polymer Science
Tong Wu, Hui Sun, Jinhui Jiang, Sha Lin, Liujie Fan, Kai Hong, Qingmei Sun, Yong Hu, Yunqing Zhu, Jianzhong Du
Summary: This study presents a strategy to prepare homopolymer nanobowls with controlled size and denting degree through self-assembly. By tuning the initial concentration, self-assembly temperature, solution pH, and Fe2+ to BPy molar ratio, the size and denting degree of the nanobowls can be controlled. The study provides new insights for preparing nanobowls with controlled size and denting degree.
Article
Polymer Science
Xian Kong, Jian Qin
Summary: Microphase separation is a bottom-up strategy for fabricating nanostructures in polymeric systems. Usually, block copolymers or polyelectrolytes are used for microphase separation. However, recent research shows that neutral homopolymer blends can also undergo microphase separation with the addition of a small amount of salt and sufficient dielectric contrast. This discovery suggests a cost-effective and easy alternative for producing microphase separation, which could be useful in advanced material design and preparation.
Article
Polymer Science
Yi-Fang Chen, Jia-Wen Hong, Jung-Hong Chang, Belda Amelia Junisu, Ya-Sen Sun
Summary: The study focused on the influence of osmotic pressure on nanostructures in thin films, particularly the impact of UV-light exposure and acetic acid rinsing on lamellae orientation and surface wrinkling. It was found that the content of added PS chains affected the formation of lamellae and perforated layers in the films. The combination of UV-light exposure and acetic acid rinsing could produce different surface morphologies and mechanical properties in the films. The use of high-molecular-weight P(S-b-MMA) BCPs could help suppress surface wrinkling in the films.
Article
Polymer Science
Pengyu Chen, Frank S. Bates, Kevin D. Dorfman
Summary: In this study, the feasibility of adding ABC triblock copolymers into a polymer system was investigated using self-consistent field theory. The results showed that the addition of a small amount of ISO could stabilize the GA morphology, but the phase window was relatively narrow. Designing the system to have comparable domain sizes enhanced the stability of GA against competing lamellae.
Article
Engineering, Environmental
Qing-Bao Zheng, Yan-Cheng Lin, Yen-Ting Lin, Yun Chang, Wei-Ni Wu, Jhih-Min Lin, Shih-Huang Tung, Wen-Chang Chen, Cheng-Liang Liu
Summary: Organic-based thermoelectric materials are popular for their waste heat-to-electricity conversion ability, low processing costs, mechanical flexibility, and non-toxicity, which makes them an attractive option for wearable electronics. However, there is a lack of direct integration of stretchable semiconducting polymers in wearable thermoelectric devices. This study explores the potential of using doped P3HT-b-PBA copolymers to develop stretchable thermoelectric devices and presents a promising approach for creating these devices by combining the thermoelectric properties of P3HT and the intrinsic softness of PBA.
CHEMICAL ENGINEERING JOURNAL
(2023)
Article
Chemistry, Multidisciplinary
Han Yi, Yuesheng Li, Dong-Po Song
Summary: The organized spontaneous emulsification (OSE) produces ordered water-in-oil-in-water (W/O/W) multiple emulsion droplets stabilized by bottlebrush block copolymer (BBCP) surfactants, templating ordered porous particles with visible structural colors. The use of homopolymer polystyrenes (hPS) to swell the PS domain effectively increases the W/O interfacial curvature of the internal droplets, allowing for tunable pore diameter and photonic bandgaps in the visible spectrum.
CHINESE JOURNAL OF CHEMISTRY
(2023)
Article
Physics, Fluids & Plasmas
Zhen Xu, Yucen Han, Jianyuan Yin, Bing Yu, Yasumasa Nishiura, Lei Zhang
Summary: The solution landscapes of confined diblock copolymer and homopolymer in two-dimensional domain were investigated using the extended Ohta-Kawasaki model. A projection saddle dynamics method was developed to compute saddle points with mass conservation and construct the solution landscape. Various stationary solutions were identified and classified, showing relationships between different stable states and symmetry-breaking phenomena in the solution landscapes.
Article
Nanoscience & Nanotechnology
Jian Wang, Lang Liu, Guilong Yan, Yanchun Li, Yang Gao, Ye Tian, Lei Jiang
Summary: This study utilizes a new pH-responsive polymer self-assembly method to regulate ion transport inside artificial nanochannels. The designed system shows good switching properties and gating ability, with the ability to recover during repetitive experiments. This work provides a novel and robust strategy for the regulation of ion transport in synthetic nanochannels.
ACS APPLIED MATERIALS & INTERFACES
(2021)
Article
Polymer Science
Michael B. Sims, Bo Zhang, Zachary M. Gdowski, Timothy P. Lodge, Frank S. Bates
Summary: The effect of long-wavelength ultraviolet photo-cross-linking on microphase-separated coumarin-containing blockpolymers was investigated, revealing the ability to control the mechanical properties and preserve the ordered structure of the material. The cross-linking reaction showed high spatiotemporal control and stability in the ordered state.
Article
Chemistry, Medicinal
Sichen Song, Chenguang Wang, Bo Zhang, Changquan Calvin Sun, Timothy P. Lodge, Ronald A. Siegel
Summary: This study reports a method of miscibility determination based on the overlap concentration, c*, which can be conveniently determined from the viscosity-composition diagram. The determined c* values strongly correlate with the physical stability of amorphous solid dispersions (ASDs) of two model drugs, celecoxib and loratadine, with four different grades of polyvinylpyrrolidone (PVP). This suggests the potential application of the c* concept in designing stable high drug loaded ASD formulations and provides a procedure for broader adoption of this methodology, which is easy to apply and widely applicable for thermally stable binary drug/polymer combinations.
JOURNAL OF PHARMACEUTICAL SCIENCES
(2023)
Review
Polymer Science
Saptasree Bose, Victoria Padilla, Alexandra Salinas, Fariha Ahmad, Timothy P. Lodge, Christopher J. Ellison, Karen Lozano
Summary: Nanofibers have unique properties that have attracted significant interest, such as high specific surface area, high aspect ratio, and spatial interconnectivity. Design strategies, including core-sheath, concentric layers, and particle distribution, are being used to prescribe the internal structure of nanofibers. This review provides a comprehensive overview of the design strategies being used to produce the next generation of nanofiber systems, discussing processing methods and their effects on the nano- and microstructure, as well as physico-chemical effects on fiber morphology.
Article
Polymer Science
Claire L. Seitzinger, Timothy P. Lodge
Summary: By incorporating a photoactive moiety into a block polymer, the phase behavior of the polymer can be controlled with light. The positioning of pendant azobenzene groups along the polymer backbone significantly affects the phase transition temperature and the ability to control the behavior with light and temperature. By adjusting the location of the azobenzene units within the polymer solution, the overall behavior of the solution can be changed.
Article
Nanoscience & Nanotechnology
Timothy P. Lodge, Frank S. Bates, Michael B. Sims, Joshua W. Goetze, Gabriela Diaz Gorbea, Zachary M. Gdowski
Summary: We propose an approach to photocrosslink bicontinuous microemulsions derived from ternary blends, enabling detailed structural characterization. This strategy utilizes a photodimerization reaction to covalently crosslink blends, preserving the intricate network structure. The resulting crosslinked microemulsions exhibit rubbery behavior at elevated temperatures and can be imaged by microscopy techniques. The versatile nature of this strategy is demonstrated by achieving a heterogeneous solid electrolyte with high conductivity.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Multidisciplinary
Nicholas J. Van Zee, Amanda S. Peroutka, Marc A. Hillmyer, Timothy P. Lodge
Summary: Poloxamers, also known as Pluronics, have been found to alleviate cellular membrane damage, but the underlying protection mechanism is still unclear. This study investigated the impact of poloxamer molar mass, hydrophobicity, and concentration on the mechanical properties of lipid vesicles, revealing that poloxamers tend to decrease the stretching modulus. The study provides important insights into how poloxamers interact with lipid membranes and protect cells from various stresses.
Article
Polymer Science
Supriya Gupta, Lucy Liberman, Timothy P. Lodge
Summary: The fragmentation kinetics of 1,2-polybutadiene-bpoly(ethylene oxide) block copolymer micelles was investigated, with a focus on the role of driving force for micellar fragmentation. Large micelles were formed in an ionic liquid by the direct dissolution method, and a broad range of micelle sizes was obtained by altering the solvent quality. The rate of fragmentation was found to be significantly influenced by the driving force, leading to a systematic acceleration of the kinetics.
Article
Polymer Science
Supriya Gupta, Timothy P. Lodge
Summary: This study investigates the fragmentation mechanism of block copolymer micelles in ionic liquids. It is found that the driving force for micelle fragmentation can be enhanced by controlling the amount of low interfacial tension solvent, leading to faster fragmentation.
Article
Polymer Science
Bo Zhang, Shuquan Cui, Timothy P. Lodge, Frank S. Bates
Summary: In this study, the structure and phase behavior of ternary mixtures containing AB bottlebrush diblock copolymer and A and B linear homopolymers were systematically investigated using small-angle X-ray scattering and cloud point measurements. The overall phase behavior of these mixtures closely resembles the linear counterparts, but with a significantly weaker increase in lamellar and microemulsion domain spacing as the homopolymer content increases. This behavior is attributed to an unconventional spatial distribution of the homopolymer within the bottlebrush architecture of the diblock copolymer. These ternary mixtures offer a promising platform for designing cocontinuous materials with an expanded parameter space using bottlebrush polymers.
Article
Materials Science, Multidisciplinary
Bo Zhang, Caini Zheng, Frank S. Bates, Timothy P. Lodge
Summary: Charged block copolymers have potential as next generation battery electrolytes due to their ability to self-assemble into various nanostructures with high ionic conductivity and mechanical strength. This study investigates the impact of ions on the self-assembly of charged block copolymers by employing a nonpolar matrix to enhance electrostatic interactions. The phase behavior was analyzed using small-angle X-ray scattering (SAXS), revealing an asymmetric shape of the phase boundary and comparable composition windows of ordered phases to neutral diblock copolymers. These findings provide insight into the design of nanostructured polymer electrolytes and the influence of ions on charged block copolymer self-assembly.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Chemistry, Multidisciplinary
Joseph F. Hassler, Megan Lawson, Erika Cerna Arroyo, Frank S. Bates, Benjamin J. Hackel, Timothy P. Lodge
Summary: Poloxamers, composed of PEO and PPO blocks, interact with phospholipid bilayers and alter their mechanical and surface properties. This study used NMR spectroscopy to measure the binding affinity of Poloxamers to liposomes at different temperatures and found a significant increase in binding affinity at higher temperatures. Moreover, the polymer chains can penetrate the bilayer and access the interior of liposomes at elevated temperatures, which is not possible at lower temperatures. This research reveals the molecular mechanism of Poloxamer-lipid bilayer interactions and has important implications for modulating the properties of liposomes and cell membranes.
Article
Polymer Science
Timothy P. Lodge, En Wang, Jiahao Zhu, Frank S. Bates
Summary: The self-assembly behavior of four polystyrene and poly(ethylene-alt-propylene) block copolymers in a selective solvent was studied. Spherical micelles were formed by all four polymers, with the symmetric triblock copolymer having the smallest micelle size. However, the asymmetric triblock copolymers did not form any specific packing arrangement. This result suggests that the two-layer corona of the asymmetric triblock copolymers may play a role in their self-assembly behavior. At higher concentrations, all four polymers adopted hexagonal packings before transitioning to lamellar structures.
Article
Chemistry, Physical
Caini Zheng, Bo Zhang, Frank S. Bates, Timothy P. Lodge
Summary: The self-assembly behavior of ternary blends of polystyrene (PS) and poly[oligo(ethylene glycol) methyl ether methacrylate] (POEGMA(n)) with different lengths of oligo(ethylene glycol) side chains n was investigated in this study. Small-angle X-ray scattering was used to examine the phase behavior at different compositions and temperatures. The results showed that the side chain length impacted the order-to-disorder transition temperature and longer side chains resulted in poorer miscibility of homopolymers in the corresponding block, leading to a more dry-brush like swelling behavior.
Article
Polymer Science
Timothy P. Lodge, Claire L. Seitzinger
Summary: By incorporating a photoactive moiety into a block polymer, the phase behavior of the polymer solution can be controlled with light. The positioning of the pendant azobenzene groups along the polymer backbone significantly affects the order-disorder transition of the polymer in the ionic liquid. Adjusting the location of the azobenzene units within the thermo-and photoresponsive polymer solution changes the overall behavior of the solutions and the ability to control that behavior with light and temperature.
Article
Polymer Science
Glenn H. Fredrickson, Shuyi Xie, Jerrick Edmund, My Linh Le, Dan Sun, Douglas J. Grzetic, Daniel L. Vigil, Kris T. Delaney, Michael L. Chabinyc, Rachel A. Segalman
Summary: The small specific entropy of mixing of high molecular weight polymers results in immiscibility and poor physical properties. To address this issue, various compatibilization strategies have been explored, including the use of copolymers, emulsifiers, and reactive groups to facilitate the formation of block or graft copolymers. This article argues that ionic bonds and electrostatic correlations are an underutilized tool for polymer compatibilization, and discusses their potential applications in sustainable polymer alloys, organic electronics, and solid polymer electrolytes. Theoretical basis, experimental literature, and emerging functional polymer materials are examined, and the potential of electrostatic interactions in plastic waste upcycling is also discussed.