Search Results (78)

This study explored the formation of soft colloidal particles from a diblock ionomer (DI) with the monomeric composition (acrylonitrile)_x-co-(glycidyl methacrylate)_y-b-(3-sulfopropyl methacrylate potassium)_z—abbreviated as (A_xG_y)S_z, where x >> z > y. A colloidal dispersion was generated by introducing water into the pre-prepared DMSO solutions of DI, which led to micelle formation and subsequent coagulation. The assembly of the hydrophobic (A_xG_y) blocks was influenced by water content and chain conformational flexibility (the ability to adopt various forms of conformation). The resulting microgel structure (in particle form) consists of coagulated micelles characterized by discrete internal hydrophobic gel domains and continuous external hydrophilic gel layers. Characterization methods included light scattering, zeta potential analysis, and particle size distribution measurements. In contrast, the copolymer (A_xG_y) chains form random coil aggregates in DMSO–H₂O mixtures, displaying a chain packing state distinct from the hydrophobic gel domains as aforementioned. Additionally, the amphiphilic glycidyl methacrylate (G) units within the (A_xG_y) block were found to modulate the microgel dimensions. Notably, the nanoscale hydrogel corona exhibits high accessibility to reactive species in aqueous media. The typical microgel has a spherical shape with a diameter ranging from 50 to 120 nm. It exhibits a zeta potential of −65 mV in a neutral aqueous medium; however, it may precipitate if the metastable colloidal dispersion state cannot be maintained. Its properties could be tailored through adjusting the internal chain conformation, highlighting its potential for diverse applications. Full article

Highly symmetric protein cages represent one of the most artistic architectures formed by biomolecules. However, the underlying reasons for the formation of some of these architectures remain unknown. The present study aims to investigate the significance behind their morphological formation by fabricating protein cage-like vesicles using a synthetic polymer. The vesicles were synthesized by combining polymerization-induced self-assembly (PISA) with polymerization-induced microphase separation (PIMS), employing an amphiphilic poly(methacrylic acid)-block-poly(n-butyl methacrylate-random-cyclohexyl methacrylate-random-methacrylic acid) diblock copolymer, PMAA-b-P(BMA-r-CMA-r-MAA). The copolymer, with a 60 mol% molar ratio of CMA to the BMA units, produced clathrin-like vesicles with angular windows in their shell, resulting from the segregation of the hard CMA units from the soft BMA matrix in the hydrophobic phase of the vesicle. These vesicles were highly stable against rising temperatures. In contrast, the vesicles with a 30 mol% CMA ratio dissociated upon heating to 50 °C into triskelion-like segments due to intramolecular microphase separation. These findings indicate that designing synthetic polymers can mimic living organ morphologies, aiding in elucidating their morphological significance and inspiring the development of new materials utilizing these morphologies. Full article

Grazing incidence small- and wide-angle X-ray scattering (GISAXS, GIWAXS) has been widely applied for the study of functional thin films, be it for the characterization of nanostructured morphologies in block copolymers, nanocomposites, and nanoparticle assemblies, or for the packing and orientation of aromatic molecules or conjugated polymers. Solution-processed thin films are typically uniaxial powders, with a specific crystallographic plane oriented parallel to the substrate surface while ordered domains assume random orientations laterally. The convenient GISAXS/GIWAXS scattering geometry facilitates obtaining complete information about thin film structure as well as the ability to study samples in well-defined sample environments, as controlled by temperature, exposure to solvent vapor and drying, or coating processes. Moreover, with suitable X-ray sources and detectors, information about the ordering kinetics and phase transitions can be obtained down to the millisecond scale. The scattering geometry and an interactive graphical tool to index such scattering patterns will be discussed here. Furthermore, it will be demonstrated that proper indexing of the X-ray scattering patterns can provide deep insight into thin film structure–property relationships and the kinetics of structure formation. Recent examples of nanostructures and molecular organization in thin films will be discussed, as well as self-assembly processes leading to such structures. Full article

The role of interfacial effects on an ion-conducting poly(styrene-b-ethylene oxide) (PS-b-PEO or SEO) diblock copolymer doped with lithium bis(trifluoromethanesulfonyl) imide (LiTFSI) was investigated by electrochemical impedance spectroscopy (EIS). Coating the surface of commonly used stainless steel electrodes with a specific random copolymer brush increases the measured ionic conductivity by more than an order of magnitude compared to the uncoated electrodes. The increase in ionic conductivity is related to the interfacial structure of the block copolymer domain morphology on the electrode surface. We show that the impedance associated with the electrode–electrolyte interface can be detected using nonmetallic electrodes, allowing us to distinguish the ionic conductivity behaviors of the bulk electrolyte and the interfacial layers for both as-prepared and annealed samples. Full article

Double hydrophilic, random, hyperbranched copolymers were synthesized via reversible addition–fragmentation chain transfer (RAFT) polymerization of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) utilizing ethylene glycol dimethacrylate (EGDMA) as the branching agent. The resulting copolymers were characterized in terms of their molecular weight and dispersity using size exclusion chromatography (SEC), and their chemical structure was confirmed using FT-IR and ¹H-NMR spectroscopy techniques. The choice of the two hydrophilic blocks and the design of the macromolecular structure allowed the formation of self-assembled nanoparticles, partially due to the pH-responsive character of the DMAEMA segments and their interaction with -COOH end groups remaining from the chain transfer agent. The copolymers showed pH-responsive properties, mainly due to the protonation–deprotonation equilibria of the DMAEMA segments. Subsequently, a nanoscopic polymer–lipid (lipomer) mixed system was formulated by complexing the synthesized copolymers with cosmetic amphiphilic emulsifiers, specifically glyceryl stearate (GS) and glyceryl stearate citrate (GSC). This study aims to show that developing lipid–polymer hybrid nanoparticles can effectively address the limitations of both liposomes and polymeric nanoparticles. The effects of varying the ionic strength and pH on stimuli-sensitive polymeric and mixed polymer–lipid nanostructures were thoroughly investigated. To achieve this, the structural properties of the hybrid nanoparticles were comprehensively characterized using physicochemical techniques providing insights into their size distribution and stability. Full article

Propylene-based elastomers (PBEs) have received widespread attention and research in recent years due to their structural diversity and excellent properties, and are also an important area for leading chemical companies to compete for layout, but efficient synthesis of PBEs remains challenging. In this paper, we review the development of PBEs and categorize them into three types, grounded in their unique chain structures, including homopolymer propylene-based elastomers (hPBEs), random copolymer propylene-based elastomers (rPBEs), and block copolymer propylene-based elastomers (bPBEs). The successful synthesis of these diverse PBEs is largely credited to the relentless innovative advancements in homogeneous catalysts (metallocene catalysts, constrained geometry catalysts, and non-metallocene catalysts). Consequently, we summarize the catalytic performance of various homogeneous catalysts employed in PBE synthesis and delve into their effect on molecular weight, molecular weight distribution, and chain structures of the resulting PBEs. In the end, based on the current academic research and industrialization status of PBEs, an outlook on potential future research directions for PBEs is provided. Full article

For vertical interconnect access (VIA) in three-dimensional (3D) structure chips, including those with high bandwidth memory (HBM), shrinking contact holes (C/Hs) using the resist flow process (RFP) represents the most promising technology for low-${\mathrm{k}}_1 (\mathrm{w}\mathrm{h}\mathrm{e}\mathrm{r}\mathrm{e} \mathrm{C}\mathrm{D}={\mathrm{k}}_1\mathsf{\lambda }/\mathrm{N}\mathrm{A},$$\mathrm{C}\mathrm{D}$ is the critical dimension, $\mathsf{\lambda }$ is wavelength, and $\mathrm{N}\mathrm{A}$ is the numerical aperture). This method offers a way to reduce dimensions without additional complex process steps and is independent of optical technologies. However, most empirical models are heuristic methods and use linear regression to predict the critical dimension of the reflowed structure but do not account for intermediate shapes. In this research, the resist flow process (RFP) was modeled using the evolution method, the finite-element method, machine learning, and deep learning under various reflow conditions to imitate experimental results. Deep learning and machine learning have proven to be useful for physical optimization problems without analytical solutions, particularly for regression and classification tasks. In this application, the self-assembly of cylinder-forming block copolymers (BCPs), confined in prepatterns of the resist reflow process (RFP) to produce small contact hole (C/H) dimensions, was described using the self-consistent field theory (SCFT). This research paves the way for the shrink modeling of the enhanced resist reflow process (RFP) for random contact holes (C/Hs) and the production of smaller contact holes. Full article

Nanopatterning methods utilizing block copolymer (BCP) self-assembly are attractive for semiconductor fabrication due to their molecular precision and high resolution. Grafted polymer brushes play a crucial role in providing a neutral surface conducive for the orientational control of BCPs. These brushes create a non-preferential substrate, allowing wetting of the distinct chemistries from each block of the BCP. This vertically aligns the BCP self-assembled lattice to create patterns that are useful for semiconductor nanofabrication. In this review, we aim to explore various methods used to tune the substrate and BCP interface toward a neutral template. This review takes a historical perspective on the polymer brush methods developed to achieve substrate neutrality. We divide the approaches into copolymer and blended homopolymer methods. Early attempts to obtain neutral substrates utilized end-grafted random copolymers that consisted of monomers from each block. This evolved into side-group-grafted chains, cross-linked mats, and block cooligomer brushes. Amidst the augmentation of the chain architecture, homopolymer blends were developed as a facile method where polymer chains with each chemistry were mixed and grafted onto the substrate. This was largely believed to be challenging due to the macrophase separation of the chemically incompatible chains. However, innovative methods such as sequential grafting and BCP compatibilizers were utilized to circumvent this problem. The advantages and challenges of each method are discussed in the context of neutrality and feasibility. Full article

In this experiment, a series of poly(propylene 2,5-furan dicarboxylate)-b-poly(ethylene glycol) (PPFEG) copolymers with different ratios were synthesized using melt polycondensation of dimethylfuran-2,5-dicarboxylate (DMFD), 1,3-propanediol (PDO) and poly(ethylene glycol) (PEG). The effect of PEG content on the crystallization behavior of the poly(propylene 2,5-furan dicarboxylate) (PPF) copolymers was investigated. For PPF, the nucleation density of the β-crystals was higher than that of α-crystals. As T_c increases, the β crystals are suppressed more, but at T_c = 140 °C, the bulk of PPF has already been converted to α crystals, which crystallize faster at higher nucleation densities, resulting in a difference in polymer properties. For this case, we chose to add a soft segment material, PEG, which led to an early multi–melt crystallization behavior of the PPF. The addition of PEG led to a decrease in the crystallization temperature of PPF, as well as a decrease in the cold crystallization peak of PPF. From the crystalline morphology, it can be seen that the addition of PEG caused the transformation of the PPF crystalline form to occur earlier. From the crystalline morphology of PPF at 155 °C, it can be observed that the ring-banded spherical crystals of the PPF appear slowly with increasing time. With the addition of PEG, spherical crystals of the ring band appeared earlier, and even appeared first, and then disappeared slowly. Full article

The group-transfer polymerization (GTP) of N,N-bis(2-methoxyethyl)acrylamide (MOEAm) initiated by Me₂EtSiH in the hydrosilylation-promoted method and by silylketene acetal (SKA) in the conventional method proceeded in a controlled/living manner to provide poly(N,N-bis(2-methoxyethyl)acrylamide) (PMOEAm) and PMOEAm with the SKA residue at the α-chain end (MCIP-PMOEAm), respectively. PMOEAm-b-poly(N,N-dimethylacrylamide) (PDMAm) and PMOEAm-s-PDMAm and PMOEAm-b-poly(N,N-bis(2-ethoxyethyl)acrylamide) (PEOEAm) and PMOEAm-s-PEOEAm were synthesized by the block and random group-transfer copolymerization of MOEAm and N,N-dimethylacrylamide or N,N-bis(2-ethoxyethyl)acrylamide. The homo- and copolymer structures affected the thermoresponsive properties; the cloud point temperature (T_cp) increasing by decreasing the degree of polymerization (x). The chain-end group in PMOEAm affected the T_cp with PMOEAm_x > MCIP-PMOEAm_x. The T_cp of statistical copolymers was higher than that of block copolymers, with PMOEAm_x-s-PDMAm_y > PMOEAm_x-b-PDMAm_y and PMOEAm_x-s-PEOEAm_y > PMOEAm_x-b-PEOEAm_y. Full article

Polyethylene (PE)-based elastomers are the ideal choice for enhancing the compatibility of polypropylene/polyethylene (PP/PE) blends and improving the mechanical properties of PP-based materials. However, the issue of blend systems lies in the interplay between the crystallization processes. Therefore, we investigated the crystallization behavior during the cooling process of a new generation of PP/PE block copolymers (PP-b-PE) and random polypropylene (PPR, a copolymer of propylene and a small amount of ethylene or an alpha-olefin) blends using in-situ X-ray diffraction/scattering and differential scanning calorimetry (DSC) techniques. We also conducted mechanical performance tests on PPR/PP-b-PE blends at room temperature and low temperature (−5 °C). The results indicate that during the cooling process, the PP phase of PP-b-PE will follow the PPR to crystallize in advance and form a eutectic mixture, thereby enhancing the compatibility of PP/PE. Moreover, the PPR/PP-b-PE blend will form stable β-(300) crystals with excellent mechanical properties. Due to the improved compatibility of PP/PE with PP-b-PE, PE crystals are dispersed within PP crystals, providing bonding that improves the toughness of PPR under the low stiffness failure conditions of PPR/PP-b-PE blends, thereby enhancing their impact performance at low and room temperatures. This research has great significance for both recycling waste plastics and enhancing the low-temperature toughness of PPR. Full article

Block copolymers, known for their capacity to undergo microphase separation, spontaneously yield various periodic nanostructures. These precisely controlled nanostructures have attracted considerable interest due to their potential applications in microfabrication templates, conducting films, filter membranes, and other areas. However, it is crucial to acknowledge that microphase-separated structures typically exhibit random alignment, making alignment control a pivotal factor in functional material development. To address this challenge, researchers have explored the use of block copolymers containing liquid-crystalline (LC) polymers, which offer a promising technique for alignment control. The molecular structure and LC behavior of these polymers significantly impact the morphology and alignment of microphase-separated structures. In this study, we synthesized LC diblock copolymers with cyano-terminated phenyl benzoate moieties and evaluated the microphase-separated structures and molecular alignment behaviors. The LC diblock copolymers with a narrow molecular weight distribution were synthesized by atom transfer radical polymerization. Small angle X-ray scattering measurements revealed that the block copolymers exhibit smectic LC phases and form cylinder structures with a lattice period of about 18 nm by microphase separation. The examination of block copolymer films using polarized optical microscopy and polarized UV-visible absorption spectroscopy corroborated that the LC moieties were uniaxially aligned along the alignment treatment direction. Full article

Despite the considerable research attention paid to block copolymer (BCP)-toughened epoxy resins, the effects of their terminal groups on their phase structure are not thoroughly understood. This study fills this gap by closely examining the effects of amino and carboxyl groups on the fracture toughness of epoxy resins at different temperatures. Through the combination of scanning electron microscopy and digital image correlation (DIC), it was found that the amino-terminated BCP was capable of forming a stress-distributing network in pure epoxy resin, resulting in better toughening effects at room temperature. In a 60 wt.% silica-filled epoxy composite system, the addition of a carboxyl-terminated BCP showed little toughening effect due to the weaker filler/matrix interface caused by the random dispersion of the microphase of BCPs and distributed silica. The fracture toughness of the epoxy system at high temperatures was not affected by the terminal groups, regardless of the addition of silica. Their dynamic mechanical properties and thermal expansion coefficients are also reported in this article. Full article

More than five hundred images of individual macromolecules of random styrene-butadiene copolymers and styrene-isoprene block copolymers dissolved in a polystyrene matrix were analyzed. The presence of density fluctuations inside the macromolecular coil has been established. Within the framework of the model of harmonic oscillations, the radial distribution of such density fluctuations is estimated. Full article

The solid polymer electrolyte is a promising candidate for solid-state lithium battery because of favorable interfacial contact, good processability and economic availability. However, its application is limited because of low ionic conductivity and insufficient mechanical strength. In this study, the delicate molecular structural design was realized via controlled / “living” radical polymerization in order to decouple the trade-off between ionic conductivity and mechanical strength. The random and triblock copolymer electrolytes were designed and synthesized to investigate the influence of molecular structure on ionic conduction, while a chemical cross-linking network was constructed via a semi-spontaneous post-crosslinking reaction. Compared with a random counterpart, the triblock copolymer electrolyte presented stronger chain segment motion and a liquid-like mechanical response due to the independent ion-conducting block, resulting in significantly improved ionic conductivity (from 6.29 ± 1.11 × 10⁻⁵ to 9.57 ± 2.82 × 10⁻⁵ S cm⁻¹ at 60 °C) and cell performance. When assembled with LiFePO₄ and lithium metal electrodes, the cell with triblock copolymer electrolyte showed significantly improved rate performance (150 mAh g⁻¹ at 1 C) and cycling life (200 cycles with 92.8% capacity retention at 1 C). This study demonstrates the advantages of molecular structure regulation on ionic conduction and mechanical support, which may provide new insights for the future design of solid polymer electrolytes. Full article