Search Results (83)

Achieving a synergistic improvement in flame retardancy and mechanical performance remains a persistent challenge in intumescent flame-retardant (IFR) polypropylene (PP) systems. Previous studies have predominantly focused on optimizing flame retardant formulations while largely overlooking the critical role of polymer matrix chain architecture in determining the overall composite performance. In this work, three PP matrices with distinct chain architectures—homopolymer (hPP), random copolymer (rPP), and block copolymer (bPP)—were systematically investigated within an identical IFR formulation. The results reveal a dominant role of chain architecture in differentiating flame retardancy and mechanical performance, which are governed by distinct structural factors, namely melt rheological behavior and phase morphology. Specifically, bPP exhibits superior flame retardancy, as evidenced by a higher limiting oxygen index (LOI) and improved UL 94 rating, which may be associated with its higher melt viscosity and resistance to dripping during combustion. In contrast, rPP shows significantly improved mechanical performance, owing to its more homogeneous phase structure and enhanced chain mobility. These findings demonstrate that flame retardancy and mechanical properties can be effectively tuned through different structural pathways, providing a viable strategy to mitigate the conventional trade-off in IFR systems. This work highlights the importance of polymer chain architecture as a complementary design parameter alongside flame retardant additives for developing high-performance PP composites. Full article

Concerns about the environmental and health impacts of plasticized poly (vinyl chloride) (PVC), from plasticizer loss to microplastic formation, have created a clear demand to find alternative packaging materials for medical and pharmaceutical use. As a possible polyolefin-based alternative, we blended polypropylene–ethylene copolymers with different ethylene content-controlled phase structures with styrene–ethylene/butylene–styrene block copolymer (SEBS), as modifier. SEBS is elastomeric and performs mechanically like a cross-linked rubber due to its unique microphase-separated morphology of hard spherical polystyrene (PS) domains dispersed in the soft elastomeric ethylene-butylene copolymer (EB) phase. Tests with injection-molded samples and cast films demonstrated promising combinations of flexibility, durability, and transparency—qualities essential for soft medical packaging like infusion pouches and blow–fill–seal bottles. For the desired level of flexibility (reflected by a flexural modulus of 150–250 MPa), blends with two random-heterophasic (RAHECO) copolymers achieved the lower limit with only 15–25 wt.-% SEBS, compared to the 37 wt.-% needed for a single-phase random copolymer (RACO). These blends also exhibited greater toughness and excellent transparency. In contrast, a standard impact copolymer (HECO), with its more crystalline matrix, required a higher modifier content of 45 wt.-% SEBS. Film morphology analysis indicated a gradual shift in disperse phase structure and orientation, leading to phase inversion at the highest SEBS content without negatively affecting transparency. Full article

Chain topology offers a chemistry-preserving route to tune block copolymer (BCP) self-assembly by modifying intrachain correlations and relaxation pathways without changing monomer interactions. Here, we perform a unit-matched comparison of four lamella-forming AB architectures reconstructed from an identical constitutive diblock unit ($N_0$): a linear diblock (DB), a linear multiblock (MB), a comb-like architecture (CB), and a star-like architecture (SB). Using dynamical density functional theory (DDFT), we quantify topology-dependent bulk ordering thresholds and show that architectural reconfiguration systematically stabilizes the ordered phase, reducing the order–disorder transition relative to DB (MB/CB/SB $\approx 0.793/0.762/0.752$ of the diblock value), in semi-quantitative agreement with random phase approximation (RPA) spinodal trends. We also compare topology-dependent directed self-assembly in a common trench geometry under matched reduced quench depth $\Delta \left(\chi N_0\right)=\chi N_0-{\left(\chi N_0\right)}_{\mathrm{ODT}}$, thereby isolating kinetic differences at comparable thermodynamic distance from bulk ordering. A Fourier-based alignment order parameter $\alpha \left(t\right)$ reveals sigmoidal alignment kinetics over decades in time and is well captured by a logistic form in $lnt$, enabling compact descriptors ($t_{50}$, $t_{90}$, and a steepness parameter k) that separate alignment onset from late-stage defect annihilation, while selective sidewalls robustly template sidewall-parallel lamellae across all topologies, the late-stage kinetics remain strongly connectivity dependent and can exhibit long-tailed completion associated with slow late-stage defect annihilation. These results demonstrate a dual role of topology in DSA: lowering the segregation strength required for bulk ordering while reshaping defect-mediated alignment pathways under confinement. Full article

Amphiphilic copolymers based on polystyrene and polyglycidol combine the chemical inertness of polystyrene with the biocompatibility of polyglycidol, making them attractive materials for polymeric micelles. While comb-like architectures have been explored to control micellization behavior and biological response, a direct comparison between comb-like and coil-comb topologies in polystyrene–polyglycidol copolymers at identical polyglycidol content remains insufficiently investigated. In this work, amphiphilic comb-like and coil-comb polystyrene–polyglycidol copolymers were synthesized via copper-catalyzed azide–alkyne click chemistry by grafting a monoalkyne-terminated polyglycidol precursor onto azide-functionalized random and block styrene copolymers. The copolymers were characterized by size exclusion chromatography and nuclear magnetic resonance. Polymeric micelles were prepared by nanoprecipitation, and their self-assembly in aqueous solution was investigated by critical micelle concentration determination, dynamic and electrophoretic light scattering, and atomic force microscopy. Both copolymers formed stable aqueous dispersions and exhibited comparable critical micelle concentrations. At identical polyglycidol content, the random copolymer formed a uniform, monomodal micellar population, whereas the block-based coil-comb architecture led to bimodal size distributions, indicating the coexistence of two distinct micellar populations. The investigated systems showed low cytotoxicity and did not induce significant oxidative stress within the studied concentration range. On isolated rat brain sub-cellular fractions (synaptosomes, mitochondria and microsomes), administered alone, the comb-like and coil-comb polystyrene-polyglycidol copolymers did not reveal statistically significant neurotoxic effects. The results demonstrate that macromolecular architecture plays a key role in governing micellar organization and in vitro biological response in polystyrene–polyglycidol copolymers, highlighting their potential as architecture-controlled polymer-based nanocarriers. Full article

In recent years, the unsustainable consumption of fossil resources has been causing major ecological concerns, especially for the production of polymeric materials. 2,5-furandicarboxylic acid (FDCA) is one of the most appealing biobased chemical building blocks, because of its potential to replace the industrially widespread petrochemical, terephthalic acid. Camphoric acid (CA) is also an interesting biobased chemical derived from camphor, one of the most widespread fragrances. This work had the objective of combining CA, FDCA and biobased 1,6-hexanediol to synthesize random copolymers for sustainable food packaging applications by means of a solvent-free polycondensation process, obtaining poly(hexamethylene furanoate-co-camphorate)s (PHFC). The optimization of the synthesis made it possible to obtain high molecular weight polyesters with a percentage of camphoric acid up to 17 mol%, which could be compression-molded into films. They were subjected to molecular, structural, thermal and functional characterization via NMR, GPC, WAXS, DSC, and TGA analyses, as well as mechanical and gas permeability tests. Compared to the homopolymer of reference, it was possible to obtain higher flexibility, 430% higher elongation at break, and 223% higher toughness, with comparable, excellent gas permeability properties. Calorimetric evidence suggested that camphoric acid might have enhanced the formation of a partially ordered mesomorph phase in the copolymers under study. Full article

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