Article
Polymer Science
Andrew Selkirk, Nadezda Prochukhan, Ross Lundy, Cian Cummins, Riley Gatensby, Rachel Kilbride, Andrew Parnell, Jhonattan Baez Vasquez, Michael Morris, Parvaneh Mokarian-Tabari
Summary: This study overcomes the kinetic challenges in the self-assembly of UHMW BCPs through precision solvent annealing, resulting in highly ordered large-period lamellar domains. The research reveals that film thickness and solvent concentration significantly affect the domain morphology.
Article
Nanoscience & Nanotechnology
Kshitij Sharma, Aman Agrawal, Ali Masud, Sushil K. Satija, John F. Ankner, Jack F. Douglas, Alamgir Karim
Summary: The kinetics and morphology of block copolymer films are influenced by the processing pathway, which affects the enthalpic and entropic forces driving the ordering processes. Understanding the free energy landscape and how processing procedures can move the system through this landscape is important for controlling the variability of block copolymer morphology. The authors demonstrate a method where a target low-energy structure can be quickly achieved by subjecting as-cast films to initial solvent annealing followed by a short period of thermal annealing.
ACS APPLIED MATERIALS & INTERFACES
(2023)
Article
Chemistry, Physical
Xi Mao, Hao Li, Jinwoo Kim, Shuai Deng, Renhua Deng, Bumjoon J. Kim, Jintao Zhu
Summary: A solvent annealing-induced structural reengineering approach transforms polystyrene-b-poly(4-vinyl pyridine) into polymersomes, allowing for effective encapsulation/loading of cargoes such as fluorescent dyes and metal nanoparticles for various applications.
Article
Materials Science, Multidisciplinary
Sajan Singh, Tandra Ghoshal, Nadezda Prochukhan, Alberto Alvarez Fernandez, Jhonattan Frank Baez Vasquez, Pravind Yadav, Sibu C. Padmanabhan, Michael A. Morris
Summary: In this study, we demonstrated the formation of oxide porous and nanodot structures from the same block copolymer (BCP) through the phase inversion of a BCP template. The effect of solvent annealing time on the ordering of the BCP was investigated. Metal ions were infiltrated into the BCP templates and oxidized to their oxides. The resulting structures were analyzed through various methods, confirming the complete elimination of the BCP template and the presence of metal oxides.
ACS APPLIED POLYMER MATERIALS
(2023)
Article
Polymer Science
Yu-Hsuan Tseng, Yu-Liang Lin, Jhih-Hao Ho, Chun-Ting Chang, Yi-Chun Fan, Ming-Hui Shen, Jiun-Tai Chen
Summary: This study presents a clever approach to form PS-b-PEO nanorods in nanopores of AAO templates using solvent vapor annealing method, allowing for control over the internal morphologies of the nanorods by changing the annealing solvents. This technique provides a powerful tool for fabricating functional nanomaterials with unique morphologies, showing great potential for various applications.
Article
Polymer Science
Ling-Ying Shi, Zhixiong Fei, Qian Wang, Lin Weng, Chenxiao Yin, Jinrui Sun, Zhihao Shen
Summary: Bottlebrush block copolymers (BBCPs) are intriguing architectural polymers that can produce various anisotropic nanostructures. This study presents a method for creating ordered silicon oxide patterns and particles on substrates using solvent vapor induced thin film self-assembly of BBCPs containing polydimethylsiloxane (PDMS) and polystyrene (PS) side chains. Different morphologies, including cylindrical or stripes-like, spherical, and ordered porous structures, as well as Janus particle-like structures, were achieved through solvent vapor annealing. The Janus particle-like structures were further transformed into meso-to-macroporous silicon oxide bowls after oxygen plasma etching. The study also discussed the effects of solvent vapor and backbone length on the self-assembly behavior of the thin film.
Article
Polymer Science
Karim Aissou, Muhammad Mumtaz, Daniel Hermida-Merino, Eduardo Solano, Didier Cot, Belkacem Tarek Benkhaled, Damien Quemener, Stephanie Roualdes, Guillaume Fleury, Georges Hadziioannou
Summary: Vertically aligned nanoporous cylinders were successfully fabricated in PDMSB-b-PS-b-P2VP layers by combining the NIPS process and the SVA treatment. The blended film exhibited a highly-ordered arrangement of cylindrical nanodomains with exceptional alignment persistence. The water permeance of the solvent-annealed film was comparable to the parent NIPS-made terpolymer film with poorly-ordered nanopores.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Polymer Science
Melisa Trejo-Maldonado, Aisha Womiloju, Steffi Stumpf, Stephanie Hoeppener, Ulrich S. Schubert, Luis E. Elizalde, Carlos Guerrero-Sanchez
Summary: This study reports the synthesis of poly(styrene-block-lactic acid) copolymers with triazole rings as a junction between blocks. The self-assembly behavior and morphological changes induced by different techniques were observed. The synthetic approach showed effectiveness in obtaining copolymer structures with specific self-assembly properties.
Article
Materials Science, Multidisciplinary
Yu-Hsuan Tseng, Yi-Chun Fan, Chun-Ting Chang, Yu-Liang Lin, Chia-Wei Chang, Chih-Wei Liao, Jiun-Tai Chen
Summary: In this study, a facile strategy called photoinduced alignment under solvent vapor annealing (PA-SVA) is proposed to form well-aligned block copolymer thin films without the need for chemically or topographically prepatterned substrates. The light-assisted self-assembly of the block copolymers is achieved by incorporating light-responsive azobenzene molecules into the polymer chains. The alignment of the block copolymer chains is induced through supramolecular interactions between the azobenzene molecules and the polymer chains. This method not only allows for manipulation of the position of light-responsive molecules in block copolymer chains, but also provides an alternative way to obtain well-ordered block copolymer thin films.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Nanoscience & Nanotechnology
Wenjie Wu, Maninderjeet Singh, Yue Zhai, Ali Masud, Wafa Tonny, Chuqing Yuan, Rongguan Yin, Abdullah M. Al-Enizi, Michael R. Bockstaller, Krzysztof Matyjaszewski, Jack F. Douglas, Alamgir Karim
Summary: In this study, a novel solvent vapor annealing soft lithography (SVA-SL) method was developed to overcome the technical difficulties in processing high molecular-mass PGNP blends. The SVA-SL method allows for easy imprint patterning and large-scale organization of PGNPs, even with highly entangled grafted chains, resulting in enhanced thermo-mechanical properties and a wider range of potential nanotech applications.
ACS APPLIED MATERIALS & INTERFACES
(2022)
Article
Energy & Fuels
Richard Sakurovs, Mihaela Grigore, Anna Sokolova, Jitendra Mata
Summary: Small Angle Neutron Scattering and Ultra Small Angle Neutron Scattering were used to investigate the changes in pore size distribution of three cokes prepared from Australian coals after annealing at temperatures of 1400 and 1600 degrees C. The study found that annealing caused substantial changes in pore size distribution, with the greatest percentage increase occurring around 10 nm pore size. The number of open pores increased significantly, while the number of closed pores decreased slightly for pores in the size range of 100 nm to 2 mu m. The effect of annealing on pore numbers decreased with increasing pore size above 100 nm.
Article
Materials Science, Multidisciplinary
Iulia Babutan, Otto Todor-Boer, Leonard Ionut Atanase, Adriana Vulpoi, Ioan Botiz
Summary: In this study, a solvent vapor annealing method was used to swell and promote the crystallization of thin films of polybutadiene-b-poly(2-vinylpyridine)-b-poly(ethylene oxide) triblock copolymers. It was found that thin films with a short poly(ethylene oxide) block were unable to crystallize without swelling, while films with a longer poly(ethylene oxide) block could crystallize both before and after swelling in solvent vapors.
Article
Polymer Science
Athmen Zenati, Ashish Pokhrel
Summary: Two sets of liquid crystalline diblock copolymers (DBCs) and triblock copolymers (TBCs) composed of hard and soft blocks were prepared with high control over their molecular masses, dispersities (M-w/M-n = D <= 1.38), and compositions using reversible addition-fragmentation chain transfer polymerization. The structures and properties of the block copolymers were characterized using various techniques, and their morphologies in a mixed solvent system varied depending on the volume fractions of the blocks and the solvent interactions.
JOURNAL OF POLYMER SCIENCE
(2023)
Article
Polymer Science
Xie-jun Hu, Jin-long Hao, Zheng Wang, Yu-hua Yin, Run Jiang, Bao-hui Li
Summary: Solvent annealing is important in promoting the formation of perpendicularly oriented structures in block copolymer thin films, especially cyclic solvent annealing. Factors such as solvent selectivity, film thickness, and solvent evaporation rate affect the preference window of perpendicular cylinders in the self-assembly process.
ACTA POLYMERICA SINICA
(2021)
Article
Chemistry, Multidisciplinary
Andreas Josef Schmid, Lars Wiehemeier, Sebastian Jaksch, Harald Schneider, Arno Hiess, Torsten Bogershausen, Tobias Widmann, Julija Reitenbach, Lucas P. Kreuzer, Matthias Kuehnhammer, Oliver Lohmann, Georg Brandl, Henrich Frielinghaus, Peter Mueller-Buschbaum, Regine von Klitzing, Thomas Hellweg
Summary: In order to exploit the potential of the new European Spallation Source in Lund, researchers have developed plug and play sample environments for different soft matter samples using a general carrier platform and unified connectors for software integration and control. This allows for reduced downtimes of instruments related to changing sample environments.
APPLIED SCIENCES-BASEL
(2021)
Article
Materials Science, Multidisciplinary
Eric R. Gottlieb, Panagiotis Dimitrakellis, Dionisios G. Vlachos, Thomas H. Epps
Summary: Inline rolling shear alignment (IRSA) is a rapid, single-step technique that can align block polymer thin-film nanostructures at high speeds. It enables high-throughput, large-area manufacturing of high-quality nanostructures with low defect densities.
ACS APPLIED POLYMER MATERIALS
(2022)
Article
Chemistry, Physical
Garrett A. Taggart, Aynur Guliyeva, Kyunghee Kim, Glenn P. A. Yap, Darrin J. Pochan, Thomas H. Epps III, Eric D. Bloch
Summary: Porous coordination cages (PCCs) are a unique class of molecular adsorbents that have gained attention due to their potential solubility and various applications. However, the characterization of PCC behavior in solution has been challenging. In this study, the combination of DOSY NMR, TEM, and cryo-TEM was used to confirm the persistence of soluble PCCs in different solutions.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Chemistry, Multidisciplinary
Kyle C. H. Chin, Jianxun Cui, Robert M. O'Dea, Thomas H. Epps III, Andrew J. Boydston
Summary: By using bioderivable photoresins derived from lignin deconstruction, we successfully manufactured thermoplastic parts with highly tunable thermal and mechanical properties, overcoming the difficulties in traditional vat photopolymerization 3D printing. These bioresins, formulated from two monomers obtainable from lignin, generated printed parts ranging from soft elastomers to rigid plastics. The parts exhibited thermoplastic behavior and were largely soluble in common organic solvents, expanding the application and repurposing of 3D-printed parts.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2023)
Article
Chemistry, Multidisciplinary
Darien K. Nguyen, Panagiotis Dimitrakellis, Michael R. Talley, Robert M. O'Dea, Thomas H. Epps III, Mary P. Watson, Dionisios G. Vlachos
Summary: We introduce a method of oxidizing long aliphatic alkanes using non-thermal, atmospheric plasma processing as an eco-friendly route for organic synthesis. By employing pulsed dielectric barrier discharge in He/O2 gas mixtures, we could convert n-octadecane into C18 secondary alcohols and ketones, with a maximum molar yield of 29.2%. Longer treatment times and higher power inputs resulted in the formation of dialcohols, diketones, and higher molecular weight oxygenates. We also observed the production of lighter hydrocarbon products and decarboxylation to CO2 at longer treatment times and higher power inputs. The highest energy yield of 5.48 x 10-8 mol/J was achieved at short treatment times and high powers, accompanied by higher selectivity to primary oxygenates. We propose direct hydroxylation of alkyl radicals and disproportionation reactions as the main pathways to alcohols and ketones. This study shows the potential of catalyst-free plasma discharges for functionalizing long hydrocarbon molecules at ambient conditions.
ACS SUSTAINABLE CHEMISTRY & ENGINEERING
(2022)
Article
Polymer Science
Priyanka M. Ketkar, Nicholas F. Pietra, Andrew G. Korovich, Louis A. Madsen, Thomas H. Epps III
Summary: This study presents a quantitative framework to describe the local polymer and ion dynamics in nanostructured block polymer electrolytes, which is validated through nuclear magnetic resonance spectroscopy measurements. The framework considers various factors such as polymer architecture, segmental mixing, chain stretching, and confinement to accurately capture the local dynamics. It provides insights into ion diffusion and conductivity at the local level and shows good agreement with experimental results.
Article
Polymer Science
Nicholas F. Pietra, Andrew G. Korovich, Priyanka M. Ketkar, Thomas H. Epps III, Louis A. Madsen
Summary: Block polymers have the potential to be used as solid-state battery electrolytes due to their optimized conductive and mechanical properties. This study investigates the role of molecular structure on ion transport and local ion dynamics in a polystyrene-block-poly(oligo-oxyethylene methacrylate) (PS-b-POEM) electrolyte doped with various lithium salts. The results show that increasing the size of the anion delocalizes the anion charge, reducing the coupling between salt ions while increasing the coupling between ions and polymer chain motions. This creates a more mobile overall environment.
Editorial Material
Polymer Science
Ty Christoff-Tempesta, Thomas H. H. Epps
Summary: Ionic liquids (ILs) have unique physicochemical properties that make them a promising medium for advanced recycling of polymers. They can solubilize plastics waste and biopolymers, deconstruct polymers at reduced temperatures, and minimize unwanted side reactions. The use of ILs in advanced recycling offers potential environmental benefits, such as reduced chemical escape and decreased energy demands.
Review
Chemistry, Multidisciplinary
Tianwei Yan, Alex H. H. Balzer, Katie M. M. Herbert, Thomas H. H. Epps III, LaShanda T. J. Korley
Summary: The circularity of polymeric materials is a global issue that impacts society due to undesirable end-of-life outcomes and waste accumulation. Recycling and repurposing are attractive solutions, but are hindered by poor property retention and heterogeneities in waste streams. Dynamic covalent chemistry allows for tailored reversible bonds to address recycling challenges. This review highlights key features of dynamic covalent chemistries, synthetic progress in new and existing polymers, and the influence of covalent bonds and polymer network structure on thermomechanical properties. It also examines the economic and environmental impacts of dynamic covalent polymeric materials in closed-loop processing.
Article
Chemistry, Physical
Garrett A. Taggart, Aynur Guliyeva, Kyunghee Kim, Glenn P. A. Yap, Darrin J. Pochan, Thomas H. Epps III, Eric D. Bloch
Summary: As a unique class of molecular adsorbents, porous coordination cages (PCCs) have attracted interest due to their solubility, which allows for various applications. The understanding of cage behavior in solution is crucial for expanding the utility of soluble PCCs. However, the characterization of PCCs in solution has been limited, and there is a lack of definitive evidence. In this study, the combined use of DOSY NMR, TEM, and cryo-TEM is explored to confirm the persistence of soluble PCCs in various solutions.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Materials Science, Multidisciplinary
Sampanna V. V. Mhatre, Jignesh S. S. Mahajan, Thomas H. H. Epps, LaShanda T. J. Korley
Summary: This study compares lignin-derivable materials with petroleum-derived materials and identifies biobased alternatives for non-isocyanate polyurethane (NIPU) thermosets. The study shows that variations in methoxy content and bridging-carbon substitution have significant effects on the thermomechanical properties of NIPU networks.
MATERIALS ADVANCES
(2023)
Article
Biochemical Research Methods
Esther H. Roh, Millicent O. Sullivan, Thomas H. Epps
Summary: This article presents a computational modeling protocol that accurately predicts the changes in gene expression levels in response to different siRNA formulations, and provides guidance for the design of therapeutic dosing regimens.
Article
Engineering, Environmental
Yuqing Luo, Robert M. O'Dea, Yagya Gupta, Jeffrey Chang, Sunitha Sadula, Li Pei Soh, Allison M. Robbins, Delphis F. Levia, Dionisios G. Vlachos, Thomas H. Epps, Marianthi Ierapetritou
Summary: This study explores the production of chemicals from a yellow poplar-based integrated biorefinery and evaluates the impact of different proportions of cellulose, hemicellulose, and lignin on the greenhouse gas emissions of the biorefinery.
ENVIRONMENTAL ENGINEERING SCIENCE
(2022)
Article
Chemistry, Multidisciplinary
Zachary R. Hinton, Pavel A. Kots, Mya Soukaseum, Brandon C. Vance, Dionisios G. Vlachos, Thomas H. Epps, LaShanda T. J. Korley
Summary: This study systematically investigates the impact of common plastics additives, particularly phenolic antioxidants, on the deconstruction yields of high-density polyethylene (HDPE) over a hydrocracking catalyst. The results show that the chemical composition and concentration of antioxidants significantly affect the conversion rate and selectivity of products.
Article
Chemistry, Multidisciplinary
Thomas H. Epps, LaShanda T. J. Korley, Tianwei Yan, Kathryn L. Beers, Tiffani M. Burt
Summary: The sustainability of current and future plastic materials is a major focus of research, industry, government, and society. Although plastics have positive impacts, negative consequences around end-of-life outcomes and overall materials circularity need to be addressed. Opportunities provided by conventional and advanced recycling/upgrading routes can lead to the valorization of polymers toward a closed-loop environment.
Article
Chemistry, Multidisciplinary
Alice Amitrano, Jignesh S. Mahajan, LaShanda T. J. Korley, Thomas H. Epps
Summary: This study investigates the difference between lignin-derivable bisphenols and bisphenol A in estrogenic behavior, predicting estrogenic activity through calculating binding affinities of lignin-derivable bisphenols to estrogen receptor alpha. The research found that bioderivable bisphenols with two methoxy groups exhibit lower binding affinity to ER alpha when recognized.