Microphase-separated Morphology Research Articles

Engineering Biodegradable Polyurethanes with Precisely Controlled Hierarchical Structures to Access Shape Memory Effect and Enhanced Bioactivities.

Biodegradable polymers with shape memory effects (SMEs) offer promising solutions for short-term medical interventions, facilitating minimally invasive procedures and subsequent degradation without requiring secondary surgeries. However, achieving a good balance among desirable SMEs, mechanical performance, degradation rate, and bioactivities remains a significant challenge. To address this issue, we established a strategy to develop a versatile biodegradable polyurethane (PPDO-PLC) with tunable hierarchical structures via precise chain segment control. Initial copolymerization of l-lactide and ε-caprolactone sets a tunable Tg close to body temperature, followed by block copolymerization with poly(p-dioxanone) to form a hard domain. This yields a uniform microphase-separation morphology, ensuring robust SME and facilitating the development of roughly porous surface structures in alkaline environments. Cell experiments indicate that these rough surfaces significantly enhance cellular activities, such as adhesion, proliferation, and osteogenic differentiation. Our approach provides a methodology for balancing biodegradability, SMEs, three-dimensional (3D) printability, and bioactivity in materials through hierarchical structure regulation.

Exploring the effects of flexibility of monomers on poly (isatin monomer-co-biphenyl) anion exchange membranes

To investigate the effect of the monomer with different flexibility and rigidity on the random copolymer, we prepare anion exchange membranes (AEMs) with a similar copolymerization ratio containing different monomers. The results show that the introduction of rigid dibenzofuran, moderately flexible diphenyl ether and flexible bibenzyl affects the conformation and morphology of the polymers, further tuning the overall performance of the AEMs. The three random copolymers exhibit better microphase-separated morphology and conductivity than the homopolymer owing to their more twisted conformation. It is found that the incorporation of flexible monomers has an advantage in holding size consistence and flexibility. Overall, the integration of bibenzyl monomer has the most positive impact on the membrane characteristics, the QPIBBP-40 AEM with flexible units possesses the highest OH− conductivity (80 °C, 159.6 mS cm−1) and an excellent mechanical stability (elongation at break: 48.2 %, tensile strength: 15.6 MPa). The wet-stated QPIBBP-40 AEM maintains an inferior swelling ratio (80 °C, 10.8 %), indicating that it possesses good size consistence and ionic conductivity simultaneously. The highest output power density of the QPIBBP-40 AEM based fuel cell is 655 mW cm−2.

Mechanically Robust, Durable, and Multifunctional Hyper-Crosslinked Elastomer Based on Metal-Organic-Cluster Crosslinker: The Role of Topological Structure.

Polymer materials formed by conventional metal-ligand bonds have very low branch functionality, the crosslinker of such polymer usually consists of 2-4 polymer chains and a single metal ion. Thus, these materials are weak, soft, humidity-sensitive, and unable to withstand their shape under long-term service. In this work, a new hyperbranched metal-organic cluster (MOC) crosslinker containing up to 16 vinyl groups is prepared by a straightforward coordination reaction. Compared with the current typical synthesis of metal-organic cages (MOCs) or metal-organic-polyhedra (MOP) crosslinkers with complex operations and low yield, the preparation of the MOC is simple and gram-scale. Thus, MOC can serve as a high-connectivity crosslinker to construct hyper-crosslinked polymer networks. The as-prepared elastomer exhibits mechanical robustness, creep-resistance, and humidity-stability. Besides, the elastomer possesses self-healing and recyclability at mild condition as well as fluorescence stability. These impressive comprehensive properties are proven to originate from the hyper-crosslinked topological structure and microphase-separated morphology. The MOC-driven hyper-crosslinked elastomers provide a new solution for the construction of mechanically robust, durable, and multifunctional polymers.

High conductive and dimensional stability proton exchange membranes with an all-carbon main chain and densely sulfonated structure

Sulfonated polyarylene membranes are demonstrated to be efficient as proton exchange membranes (PEMs) for proton exchange membrane fuel cells (PEMFCs) in clean energy conversion systems. In this study, we design and synthesize a series of sulfonated polyarylene with all-carbon backbones and densely sulfonated pendant groups, which can be prepared by copolymerization of 1,3-Disulfonic acid benzaldehyde, 1,1,1-trifluoroacetone and biphenyl under superacid-catalyzed conditions. Rigid, hydrophobic backbone and hydrophilic side chains make the membrane form good microphase separation morphology. The PEMs exhibit high proton conductivity (404 mS cm−1) and excellent dimensional stability (swelling ratio lower than 24% and water uptake lower than 40%) at 80 °C. Moreover, the PEMs show good oxidization stability (the retaining weight rate of membrane up to 99.2% for 1 h oxidative treatment), and the oxidization stability and degradation mechanism of Ar3CH in polymer backbone are also studied. The H2/O2 fuel cell assembled with PEMs exhibited a maximum peak power density of 560 mW cm−2. It indicates that all-carbon main chain and densely sulfonated structure show great potential for improving the performance of PEMs.

Facilitated belt for ion transport by comb-shape Poly(terphenyl piperidone) carried with macrocyclic crown ether as anchor in anion exchange membrane

To ensure efficient ion transport in anion exchange membranes (AEMs) for hydrogen production, it is essential to develop efficient ion transport pathways. Utilization of intermolecular interactions induced by embedded macrocycles is an attemptable approach. Self-aggregated channels can be constructed with this force serving as a driving force for stepped-up ion transport. Herein, we present a delicate strategy to polymerize the macro crown ether in the backbone and graft flexible alkyl long chains to prepare comb-type copolymers as AEMs. The macrocycle dynamically traps ammonium ions as an anchor which accelerates the aggregation of ionic phases. The resulting AEMs show favorable membrane-forming ability and tensile strength. As the side chain length increases, the microphase-separated morphology develops well and formed ‘belt’-like channels in the poly(terphenyl piperidone)-5-bis-quaternary ammonium (PTCP-5-bisQA) membrane, exhibiting a hydroxide conductivity of 78.1 mS/cm at 80 °C. The alkaline durability of PTCP-5-bisQA AEM is explored by nuclear magnetic hydrogen spectrum (1H NMR) investigation at 80 °C for 720 h. Furthermore, the PTCP-5-bisQA based electrolyzer reaches a current density of 330 mA/cm2 at 1.85V by 1 wt% potassium hydroxide solution circulation. A life endurance observation is carried out on this electrolyzer for a 100h operation with performance degradation rate of 40.1 mV/h.

Design and Synthesis of Comb‐Like Bisulfonic Acid Proton Exchange Membrane with Regulated Microstructure

AbstractThe design and synthesis of proton exchange membranes (PEMs) with controllable microstructure and sulfonation degree play a crucial role in enhancing their performance and expanding their application. In this study, the disulfonic acid monomer is designed and prepared to synthesize the comb‐like disulfonic PEMs with controllable ion exchange capacity. The results show that the side chain structure and more concentrated sulfonic acid groups facilitate the aggregation of sulfonic acid groups in the polymer, improve the microphase separation morphology of PEMs, and increase the ionic conductivity. The proton conductivity of the DS‐PXIDI‐60 membrane is approximately 300 mS cm−1. The PEMs with controllable microstructure are prepared by introducing comonomers, including 9,9‐dimethylxanthrene, biphenyl, and p‐terphenyl, with different reactivity, spatial structure, and solubility. Biphenyl is copolymerized to form a copolymer with an alternating structure, and 9, 9‐dimethylxanthrene is copolymerized to form a random copolymer. In addition, it is worth noting that p‐terphenyl is copolymerized to form a microblock structure of the copolymer, with more excellent comprehensive properties. DS‐PXITp‐60 exhibits better performance than Nafion 212 in redox­flow batteries and fuel cells. Therefore, such molecular design and synthesis strategies provide a reference guide for the development of high‐performance PEMs.

Novel Fluorinated Anion Exchange Membranes Based on Poly(Pentafluorophenyl-Carbazole) with High Ionic Conductivity and Alkaline Stability for Fuel Cell Applications.

Constructing good microphase separation structures by designing different polymer backbones and ion-conducting groups is an effective strategy for improving the ionic conductivity and chemical stability of anion exchange membranes (AEMs). In this study, a series of AEMs based on the poly(pentafluorophenylcarbazole) backbone grafted with different cationic groups are designed and prepared to construct well-defined microphase separation morphology and improve the trade-off between the properties of AEMs. Highly hydrophobic fluorinated backbone and alkyl spaces enhance phase separation and construct interconnected hydrophilic channels for anion transport. The ionic conductivity of the PC-PF-QA membrane is 123 mS cm-1 at 80°C, and the ionic conductivity of the PC-PF-QA membrane decreased by only 6% after 960h of immersion at 60°C in 1M NaOH aqueous solution. The maximum peak power density of the single cell based on PC-PF-QA is 214mW cm-2 at 60°C.

Advancing Ion Selective Membranes with Micropore Ion Channels in the Interaction Confinement Regime.

Ion exchange membranes allowing the passage of charge-carrying ions have established their critical role in water, environmental, and energy-relevant applications. The design strategies for high-performance ion exchange membranes have evolved beyond creating microphase-separated membrane morphologies, which include advanced ion exchange membranes to ion-selective membranes. The properties and functions of ion-selective membranes have been repeatedly updated by the emergence of materials with subnanometer-sized pores and the understanding of ion movement under confined micropore ion channels. These research progresses have motivated researchers to consider even greater aims in the field, i.e., replicating the functions of ion channels in living cells with exotic materials or at least targeting fast and ion-specific transmembrane conduction. To help realize such goals, we briefly outline and comment on the fundamentals of rationally designing membrane pore channels for ultrafast and specific ion conduction, pore architecture/chemistry, and membrane materials. Challenges are discussed, and perspectives and outlooks are given.

Oligo (ethylene glycol)-grafted poly(terphenyl indole piperidinium) with high water diffusivity for anion exchange membrane fuel cells

The water diffusivity of polymeric anion exchange membranes (AEMs) plays a critical role in determining the AEM fuel cells (AEMFCs) performance because it generates an imbalance in the amount of water at the anode and cathode. However, the correlation between water diffusivity and the chemical structure of AEMs remains unclear. This study focuses on a series of oligo(ethylene glycol) (OEG) functionalized poly(arylene indole piperidinium) AEMs, in which OEG grafts are directly attached onto the polymer backbones. The polar and flexible OEG side chains afford a microphase-separated morphology, close polymer-chain packing, and extra sites for water–ion transport, resulting in high ion-exchange-capacity (IEC)-normalized conductivity, improved water diffusivity, and dimensional stability. Moreover, these side chains provide excellent ex-situ stability in a 1 M NaOH solution (80 °C) for 1080 h, surpassing the stability of its alkyl side chain counterpart (PITP-C10Q85) by a significant margin. The resultant PITP-OEG-85 with the highest water diffusivity exhibits a highest peak power density of 1.23 W cm−2 at 80 °C despite its low IEC value and conductivity. In-situ durability tests of this membrane at 0.2 A cm−2 for 24 h revealed the degradation of piperidinium under harsh conditions (70 % anode relative humidity at 60 °C). This work opens a new avenue for designing highly conductive and alkali-stable AEM materials with high water diffusivity to realize high-performance AEMFCs.

Dimensionally Stable Anion Exchange Membranes Based on Macromolecular-Cross-Linked Poly(arylene piperidinium) for Water Electrolysis.

The advancement of anion exchange membranes (AEMs) with superior ionic conductivity has been greatly hindered due to the inherent "trade-off" between membrane swelling and ionic conductivity. To resolve this dilemma, macromolecular covalently cross-linked C-FPVBC-x AEMs were fabricated by combining partially functionalized ether-bond-free polystyrene (FPVBC) with poly(arylene piperidinium). The results from atomic force microscopy reveal that an increase in the ratio of FPVBC promotes the fabrication of microphase separation morphology, resulting in a high ionic conductivity of 40.15 mS cm-1 (30 °C) for the C-FPVBC-1.7 membrane. Molecular dynamics simulations further examine the ionic conduction effect of cross-linked AEMs. Besides, the unique cross-linking structure significantly improves mechanical and alkaline stability. After treatment in 1 M KOH at 50 °C for 1200 h, the C-FPVBC-1.7 membrane shows only a 6.9% decrease in conductivity. The C-FPVBC-1.7 AEM-based water electrolyzer achieves a high current density of 890 mA cm-2 at 2.4 V (80 °C) and maintains good stability, enduring over 100 h at 100 mA cm-2 (50 °C). These results demonstrate the significant potential of macromolecularly cross-linked AEMs for practical applications in water electrolysis.

The permeability of diamond and other microphase-separated morphologies in copolymer films.

A method is proposed for the theoretical assessment of potential membrane properties in materials based on microphase-separated block copolymer films subjected to the etching of one of the components. The concepts of topological permeability and connectivity contrast introduced by the authors are used to compare the percolation characteristics of simple cubic, diamond, and diamond-like morphologies compatible with the slit geometry and specified by a given distribution of the order parameter. The diamond-like morphology, which has the most promising transport characteristics, can be formed in a thin film of diblock copolymer AB placed on a chemically structured substrate. For this case, the quantitative analysis of permeability for certain parameters of the model system is carried out using the local distribution of A and B units calculated with the self-consistent field theory of microphase separation. The results obtained may be useful for the design of isoporous membranes based on block copolymers.

High performance quaternary ammonium-functionalized polybenzoxazine-based anion exchange membranes

Two kinds of benzoxazine monomers were synthesized by Mannich reaction with N,N-dimethyl-p-phenylenediamine and N,N-dimethylethylenediamine using polyformaldehyde, 4,4′-dihydroxydiphenylmethane as raw materials. Subsequently, quaternary ammonium functionalization was realized by Menshutkin reaction. The aromatic amine-based quaternary ammonium-functionalized polybenzoxazine (AQPBZ) and aliphatic amine-based quaternary ammonium-functionalized polybenzoxazine (LQPBZ) were synthesized by ring-opening polymerization. Polybenzoxazine anion exchange membrane (AEM) was prepared by solution casting method. The AQPBZ and LQPBZ AEMs exhibit micro-phase separated morphology clearly. LQPBZ AEM displays more large ion clusters and ion conductive channels due to the flexible alkyl connection between QA group and polybenzoxazine skeleton. AQPBZ and LQPBZ AEMs have the ionic conductivity of 75.5 mS/cm and 86.3 mS/cm at 80 °C and 100% relative humidity, respectively. AQPBZ and LQPBZ AEMs show excellent alkaline stability. After treated with 6 M sodium hydroxide solution at 80 °C for 240 h, they manitained the 49.8 mS/cm and 50.2 mS/cm, respectively. They also exhibit good oxidation stability and thermal stability. Their oxidation weight losses are 4.1% and 7.2% through Fenton test, respectively. Their Td5s are 325 °C and 289 °C, respectively.

Alkali-resistant poly (vinyl benzyl chloride) based anion exchange membranes with outstanding flexibility and high hydroxide ion conductivity

Preparing AEMs with robust mechanical properties, high ionic conductivity and excellent chemical stability is challenging. Here, cross-linked/aggregated AEMs are prepared by incorporating hydrophilic Jeffamine cross-linkers and hydrophobic side chains into the rigid quaternized poly (vinyl benzyl chloride). Jeffamine's flexibility ensures high elongation at break of the cross-linked/aggregated membranes (125.0–199.8%). The hydrophobic side chain limits excessive water absorption and facilitates self-aggregation of hydrophilic and hydrophobic domains, enhancing tensile strength (5.08–7.40 Mpa in wet state) and improving ionic conductivity of the AEMs (73.8–110.4 mS cm−1 at 80 °C). Alkali-resistant PVB, restricted dimensionality, and ordered micro-phase separation morphology contribute to outstanding chemical stability of the AEMs. Degradation of both backbones and cations is <20% after treatment in 1 M NaOH solution at 80 °C for 30 days. Based on the membrane, a peak power density of 354.4 mW cm−2 at 60 °C is yielded.

High‐Efficiency Organic Solar Cells Enabled by Non‐Fullerene Acceptors with Benzimidazole as the Central Core

AbstractElectron‐deficient central core plays a crucial role in the construction of efficient Y‐series non‐fullerene acceptors (NFAs). Here, fused‐ring benzimidazole (BIm) served as a central core for the first time to yield a new NFA named MZ‐1 and its structural analogue named MZ‐2, which is obtained by replacing the methyl group on the 2C position of BIm in MZ‐1 with trifluoromethyl group. Compared with MZ‐1, MZ‐2 shows obviously blue‐shifted absorption and lowers the highest occupied molecular orbital (HOMO) energy level that is more matched to that of polymer donor PM6. Benefiting from the more efficient charge transport and favorable microphase separation morphology of the active layer, the acceptor MZ‐2‐based device affords an excellent power conversion efficiency (PCE) of 17.31% along with a high open‐circuit voltage (Voc) of 0.903 V, a short‐circuit current density (Jsc) of 26.32 mA cm−2 and a fill factor (FF) of 72.83%, which is remarkably superior to that of MZ‐1‐based devices with PCE of 10.70%. This study offers valuable insight into the design of acceptors to enrich Y series NFAs for high‐performance organic solar cells (OSCs).

Nanostructures, Linear Rheological Responses, and Tunable Mechanical Properties of Microphase-Separated Cellulose-graft-Diblock Bottlebrush Copolymer Elastomers.

A series of cellulose-graft-diblock bottlebrush copolymer elastomers (cellulose-graft-poly(n-butyl acrylate)-block-poly(methyl methacrylate) (Cell-g-PBA-b-PMMA)) with short side chains were synthesized via successive atom transfer radical polymerization (ATRP) to study the influence of varying compositions and lengths of the graft diblock side chains on microphase morphologies and properties. The microphase-separated morphologies from misaligned spheres to cylinders were observed by atomic force microscopy (AFM) and small-angle X-ray scattering (SAXS) measurements. These bottlebrush copolymer elastomers possessed thermal stability and enhanced mechanical properties because the PMMA outer block could self-assemble into hard microdomains, which served as physical cross-links. The viscoelastic responses of these bottlebrush copolymers within the linear viscoelastic (LVE) regime were carried out by the oscillatory shear rheology. The time-temperature superposition (tTs) principle was applied to construct the master curves of the dynamic moduli, and the sequential relaxation of dense bottlebrush copolymers with different PMMA hard outer block lengths was analyzed. The rheological behaviors in this work could be utilized to build up the connection of microstructures and properties for the application of these bottlebrush copolymers as high-performance thermoplastic elastomers.

Effects of molecular weight of polyethylene glycol on the moisture-absorption capacity and morphology of the channeling structure in desiccant composite

Moisture removal inside the packaging of food and pharmaceutical products prevents their deterioration during storage. Therefore, the preparation of desiccants derived from moisture-absorbing materials is important. Herein, desiccant composites with channeling morphologies in the polypropylene (PP) matrix are prepared using polyethylene glycol (PEG) with different molecular weights (Mw) and molecular sieves (MS). The effects of the Mw on the formation, morphology, and stability of the channeling structure are investigated. All composites exhibit microphase separation morphology caused by the channeling structure. Accordingly, the PEG with an Mw of 8000 allows uniform microphase separation in the composite matrix owing to the higher chemical compatibility with MS in the formation of the channeling structure, thus inducing significant moisture absorption. Therefore, these composites can be used to introduce novel desiccant packaging in the food and pharmaceutical industries.

Semi-crystalline sulfonated poly(ether ketone) proton exchange membranes: The trade-off of facile synthesis and performance

Improving the performance of proton exchange membranes (PEMs) through the synthesis of sulfonated polymers with elaborate molecular structures has received extensive approval. However, the tedious synthetic process and consequently high costs restrain their possible substitution for Nafion, a classic PEM material. Herein, a series of semi-crystalline sulfonated poly(ether ketone)s with fluorene-based units were prepared via direct copolymerization of commercially available monomers and followed post-sulfonation, namely SPEK-FD-x, where × represents the molar ratio of the fluorene-containing monomer to the employed bisphenol monomers. The entire synthetic pathway was facile without involving hardly accessible materials. Subsequently, various properties of SPEK-FD-x membranes were investigated and further compared with Nafion 117. Due to the formation of the well-defined hydrophilic-hydrophobic microphase separation morphology and the reinforcement of the PEK crystalline regions, the SPEK-FD-x membranes exhibited outstanding proton conductivity, resistance for methanol permeation, as well as dimensional, thermal, oxidative, and mechanical stability. Among them, the overall behavior of the SPEK-FD-25 membrane was comparable to or even greater than that of Nafion 117, most importantly, it also performed decently in both H2/air fuel cells and direct methanol fuel cells. Therefore, with the straightforward synthesis and superior performance, the SPEK-FD-x membranes may serve as a promising alternative to Nafion.

Block copolymer interfaces investigated by means of NMR, atomic force microscopy and dielectric spectroscopy

Self-assembly of block copolymers (BC) is a key feature for bottom-up patterning that is applied in the fabrication of templates for nanostructured membranes, photonic nanodevices, or solar cells. The wide range of possible BC applications is because the dissimilar blocks can be appropriately selected to form distinct domains with controllable dimensions and functionalities. An important representative of these materials is polystyrene-b-poly(ethylene oxide) (PS-b-PEO) diblock copolymer. This copolymer is of considerable academic interest and therefore it is examined by a plethora of experimental techniques to elucidate its structure and molecular dynamics. Particularly worth investigating is the interphase, consisting of polymer chains located at the interface of crystallite-amorphous and inter-domain regions, which codetermines the properties of such a system. It is shown that below the melting point of the PEO, the majority of the amorphous PEO are occupying interfacial sites and are represented by the rigid amorphous fraction (RAF) which can be monitored by dielectric and nuclear magnetic resonance spectroscopies. Moreover, two independent NMR spin-diffusion experiments reveal the asymmetrical nature of PS-PEO interface indicating a significant fraction of the PEO phase under the influence of stiff, adjacent polystyrene. An analysis of complementary thermal calorimetry and X-ray scattering data confirms the presence of microphase-separated morphology as well as the semicrystalline nature of PEO component. Lamelar domain architecture was confirmed by atomic force microscopy data acquired in the case of thin copolymer film.

“Thiol-ene” crosslinked polybenzimidazoles anion exchange membrane with enhanced performance and durability

To address the “trade-off” between conductivity and stability of anion exchange membranes (AEMs), we developed a series of crosslinked AEMs by using polybenzimidazole with norbornene (cPBI-Nb) as backbone and the crosslinked structure was fabricated by adopting click chemical between thiol and vinyl-group. Meanwhile, the hydrophilic properties of the dithiol cross-linker were regulated to explore the effect for micro-phase separation morphology and hydroxide ion conductivity. As result, the AEMs with hydrophilic crosslinked structure (PcPBI-Nb-C2) not only had apparent micro-phase separation morphology and high OH− conductivity of 105.54 mS/cm at 80 °C, but also exhibited improved mechanical properties, dimensional stability (swelling ratio < 15%) and chemical stability (90.22 % mass maintaining in Fenton’s reagent at 80 °C for 24 h, 78.30 % conductivity keeping in 2 M NaOH at 80 °C for 2016 h). In addition, the anion exchange membranes water electrolysis (AEMWEs) using PcPBI-Nb-C2 as AEMs achieved the current density of 368 mA/cm2 at 2.1 V and the durability over 500 min operated at 150 mA/cm2 under 60 °C. Therefore, this work paves the way for constructing AEMs by introduction of norbornene into polybenzimidazole and formation of hydrophilic crosslinked structure based on “thiol-ene”.

Synthesis and characterization of UV curable biocompatible hydrophilic copolymers containing siloxane units

Tissues are highly three-dimensional structure complexes composed of different cell types and their interactions. One of the main challenges in tissue engineering is the inability to produce large, highly perfused scaffolds in which cells can grow at a high cell density and viability. Poly(dimethyl siloxane) (PDMS) is used as a flexible, biocompatible cell culture substrate with tunable mechanical properties. However, its fragility and hydrophobicity still pose a challenge. Here, we present a new strategy for the three-step one-pot synthesis of novel biocompatible hydrophilic copolymers containing siloxane units. In the first step, free radical copolymerization of acrylic acid (AA), butyl methacrylate (BMA), and 2-hydroxyethyl methacrylate (HEMA) was carried out in dioxane (DO) solution in the presence of 2,2′-azodiisobutyronitrile (AIBN). In the second step, the copolymers were modified with diepoxypropoxypropyl-terminated polydimethylsiloxane (DE-PDMS), and in the third step, the copolymers were additionally modified with glycidyl methacrylate (GMA). The modified copolymers were characterized by FTIR, NMR spectroscopy and elemental analysis. Films of modified copolymers were prepared by UV curing. SEM studies revealed microphase separated morphology with distribution of PDMS domains. The mechanical properties of the films depended on the amount of incorporated silicone modifier. The films were more hydrophilic than PDMS films. All novel copolymers showed high biocompatibility.