Microphase-separated Structure Research Articles

Self-consistent field theory for loop-containing polymers: A general algorithm for path-determination

An algorithm was developed for self-consistent field theory (SCFT) simulations of loop-containing polymers (LCPs), where the total number of independent loops (fundamental cycles in the polymer structure) is characterized by the “cycle rank.” Although various multi-ring and cage-like polymers have been reported, there is no explicit SCFT scheme for LCPs with multiple loops. An LCP was cut to open its fundamental cycles to form a pseudo-tree-like polymer. Conventional SCFT calculations for pseudo-tree-like polymers require extra spatial constraints on the pseudo-free endpoints generated by opening the fundamental cycle, which increases the computational cost. A reduction in the computational cost was observed, and the algorithm was applied to microphase-separated structures of small LCPs.

Tailoring physicochemical properties of quaternized polystyrene-ethylene/butylene-styrene membrane for enhanced pervaporation desalination

Pervaporation offers unique advantages for desalination of hypersaline water using highly hydrophilic and selective membrane. Positively charged membrane is superior in repelling cations and preventing scaling through electrostatic repulsion. This study investigates the quaternization and crosslinking of block copolymer styrene-ethylene-butylene-styrene (SEBS) membrane and explores the potential of quaternized membrane for pervaporation desalination. A one-step immersion process was proposed to easily adjust the physicochemical properties of membrane using trimethylamine (TMA) and N,N,N′,N′-tetramethyl-1,6-hexanediamine (TMHDA) for ammonium grafting and crosslinking. Compared to the quaternization with TMA or TMHDA alone, the combination of TMA and TMHDA produces a synergistic effect, improving crosslinking efficiency and facilitating the grafting reaction. This results in high ion exchange capacity (IEC) values and a transformation of microphase separation structure with more interconnected hydrophilic domains. An ultrahigh water permeability coefficient of 0.6 × 106–1.2 × 106 Barrer and highly intrinsic salt rejection were obtained in treating 3.5–20 wt% NaCl solution. The thin film composite QEBS/nylon membranes showed a superior water flux of 116.5 kg·m−2·h−1 and salt rejection of >99.99 % in desalinating 5 wt% NaCl solution at 85 °C. Additionally, the membrane exhibited excellent long-term performance stability and resistance to acid and alkali environment, showing great potential for desalination of hypersaline water.

Poly(p-terphenyl-piperidine-bromoacetophenone) anion exchange membranes with pendant N-spirocyclic cations: Cations synergistic build efficient ion transport networks

The establishment of well-developed ionic conduction channels and the preparation of excellent chemical stability are urgent needs for anion exchange membranes. In this study, we successfully prepared poly (p-terphenyl-piperidine-bromoacetophenone) polymers using superacid catalysis. Then a series of QPTPP-N-ASU-x AEMs were prepared by introducing N-spirocyclic side chain cations (N-ASU) with different grafting rates. The introduction of N-spirocyclic cations with better alkali resistance increases multiple OH− transport sites, contributes to the microphase separation structure, and is synergistic with piperidine cations to rapidly construct ion transport networks, giving the membranes good conductivity and alkali resistance stability. The AFM showed that QPTPP-N-ASU-5% AEM had a remarkable microstructure and formed large ionic domains, the conductivity of the membrane was 121.2 mS cm−1, corresponding to a peak power density of 477.25 mW cm−2. The conductivity residual of QPTPP-N-ASU-5% AEM was 94.15 % and 87.71 % after immersion in 2 M and 4 M NaOH at 80 °C for 1440 h. It shows that membrane has good potential for application.

Effect of carbon black on the liquidity and compression performance of Polyurethane-Based tunnel isolation materials

Cross-sea engineering plays a vital role in the development of human society. However, due to geological constraints, cross-sea tunnels, as the main form of cross-sea engineering structures, are susceptible to instability and safety risks under strong seismic forces. Therefore, the development of tunnel isolation materials with strong elasticity and toughness is of great significance. In this study, a polyurethane-based tunnel isolation material was developed, and its liquidity, compression performance, and microstructure were investigated. The results show that, due to the improvement of the polyurethane microphase separation structure by carbon black, the compression performance of the material can be effectively enhanced, with a compressive strength of up to 1.88 MPa. Additionally, the material’s liquidity meets construction requirements, and its elastic modulus is relatively low, around 15 MPa, which meets the requirements for isolation.

Disclosing Topographical and Chemical Patterns in Confined Films of High-Molecular-Weight Block Copolymers under Controlled Solvothermal Annealing.

The microphase separation of high-molecular-weight block copolymers into nanostructured films is strongly dependent on the surface fields. Both, the chain mobility and the effective interaction parameters can lead to deviations from the bulk morphologies in the structures adjacent to the substrate. Resolving frustrated morphologies with domain period L0 above 100 nm is an experimental challenge. Here, solvothermal annealing was used to assess the contribution of elevated temperatures of the vapor Tv and of the substrate Ts on the evolution of the microphase-separated structures in thin films symmetric of polystyrene-b-poly(2vinylpyridine) block copolymer (PS-PVP) with L0 about 120 nm. Pronounced topographic mesh-like and stripe patterns develop on a time scale of min and are attributed to the perforated lamella (PL) and up-standing lamella phases. By setting Tv/Ts combinations it is possible to tune the sizes of the resulting PL patterns by almost 10%. Resolving chemical periodicity using selective metallization of the structures revealed multiplication of the topographic stripes, i.e., complex segregation of the component within the topographic pattern, presumably as a result of morphological phase transition from initial non-equilibrium spherical morphology. Reported results reveal approaches to tune the topographical and chemical periodicity of microphase separation of high-molecular-weight block copolymers under strong confinement, which is essential for exploiting these structures as functional templates.

Disclosing Topographical and Chemical Patterns in Confined Films of High-Molecular-Weight Block Copolymers under Controlled Solvothermal Annealing

The microphase separation of high-molecular-weight block copolymers into nanostructured films is strongly dependent on the surface fields. Both, the chain mobility and the effective interaction parameters can lead to deviations from the bulk morphologies in the structures adjacent to the substrate. Resolving frustrated morphologies with domain period L0 above 100 nm is an experimental challenge. Here, solvothermal annealing was used to assess the contribution of elevated temperatures of the vapor Tv and of the substrate Ts on the evolution of the microphase-separated structures in thin films symmetric of polystyrene-b-poly(2vinylpyridine) block copolymer (PS-PVP) with L0 about 120 nm. Pronounced topographic mesh-like and stripe patterns develop on a time scale of min and are attributed to the perforated lamella (PL) and up-standing lamella phases. By setting Tv/Ts combinations it is possible to tune the sizes of the resulting PL patterns by almost 10%. Resolving chemical periodicity using selective metallization of the structures revealed multiplication of the topographic stripes, i.e., complex segregation of the component within the topographic pattern, presumably as a result of morphological phase transition from initial non-equilibrium spherical morphology. Reported results reveal approaches to tune the topographical and chemical periodicity of microphase separation of high-molecular-weight block copolymers under strong confinement, which is essential for exploiting these structures as functional templates.

A soluble highly-sulfonated polybenzimidazole with high molecular weight as membrane for vanadium flow battery with enhanced performance and long-term stability

A series of novel sulfonated polybenzimidazole (SPBI) membranes containing flexible double ether segments, having high ion exchange capacity (IEC), good solubility as well as high molecular weight, are designed for vanadium flow batteries (VFBs). The bis-ether structure of self-synthesized sulfonic acid monomer, 4,4'-((2-sulfo-1,4-phenylene)bis(oxy))dibenzoic acid, improves the solubility of produced SPBI and the microphase separation structure of prepared membrane by disrupting the regularity of the backbone through a non-planar structure and attenuating the interchain stacking effect of the polymer backbone. Such a highly reactive bis-ether monomer also leads to high molecular weights (2.37−2.82 dL g−1). The copolymerization using another sulfonic acid monomer, Monosodium-5-Sulfoisophthalate monomer, leads to a high IEC of up to 2.08 mmol g−1. As a result, the SPBI membrane shows a low area resistance of 0.21 Ω cm2 and a low vanadium ion permeability of 3.36 × 10−9 cm2 s−1. The VFB cell employing SPBI membrane achieves a very high energy efficiency exceeding 82% at 200 mA cm−2. In addition, an ultra-long lifetime of over 3400 cycles is accomplished.

High conductivity and dimensional stability brominated poly (aryl piperidinium) anion exchange membranes: Synergistic interaction of hydrophilic and superhydrophobic fluorinated side chains

Anion-exchange membrane fuel cells (AEMFCs) is a promising renewable energy device for hydrogen production. Anion exchange membranes (AEMs), the key component of AEMFCs, is generally needed for excellent dimensional stability and conductivity. Here, we synthesised a variety of AEMs with different number of C–F bonds to enhance the hydrophilic/hydrophobic micro-phase separation structure while maintaining dimensional stability. At 80 °C, the QPBTTP-PEG-10-F9 shows high OH− conductivity (∼179.02 mS cm−1), excellent dimensional stability (swelling ratio <19 %), and mechanical properties (elongation at break: 37 %, tensile strength: 71 MPa). In addition, QPBTTP-PEG-10-F9 shows good alkaline stability (conductivity remaining of 92.52 %) in 3 M NaOH solution for 1800 h. The peak power density (PPD) of a single cell assembled with QPBTTP-PEG-10-F9 can reach 534.79 mW cm−2 with a current density of 951 mA cm−2.

Thermal stimuli response diphenylmethane diisocyanate‐based polyurethane elastomer via adjustable silicon‐induced distinctive microstructure

AbstractThe segment character of polyurethanes (PUs) determines the micromorphology and properties. The effective segment regulation can customize the favorable performance of PUs. Herein, silicon covalent‐modified polyurethanes (MPUs) were prepared by incorporating diphenylmethane diisocyanate (MDI) and diphenyl silanediol (DPSD) into PU molecules as hard segments via a two‐step method. Distinctive microphase separation structures from sheet morphology to radial sheet or withered flower‐like microdomain were formed by adjusting hydrogen bonding of hard segments and post‐treatment techniques. Thus, with the addition of DPSD in hard segments, the thermo‐optic responses for MPUs occurred due to the different microphase evolution under thermal effect. And with the further addition of DPSD, the effect of thermal stimuli on the transmittance gradually weakened. It was very clear that with increasing the temperature, the transmittance of MPUs showed a gradual increase owing to melting the microcrystals or destroying the ordered accumulation of hard segments. Meanwhile, the high mechanical properties were obtained, higher 15 times tensile strength and more than 100 times elastic modulus than those of pure PU as well as the excellent thermal stability. In sum, this study was of great significance for developing new functionalized PU materials.Highlights Polyurethanes were prepared by inducing modified silicon functionality. The distinctive microphase separation evolution of MPUs was found. Thermal stimuli responses showed a gradual decrease due to different structure. High mechanical properties and thermal stability were also obtained.

A Novel Side‐Chain Type Double‐Cation Grafted Poly (Binaphthyl Triphenyl Piperidine) Membranes for Anion Exchange Membrane Fuel Cells

AbstractRecent advancements in anion exchange membrane fuel cells (AEMFCs) have been primarily driven by improvements in anion exchange membranes (AEMs). Aryl ether bond‐free membranes have emerged as a promising avenue for enhancing the overall performance of AEMs. In this study, poly (binaphthyl triphenyl piperidine) with different side‐chain degree (PBTP‐s‐x), possesses double cationic groups, aiming at further enhancing overall performance for AEMs. The use of a twisted stereospecific backbone structure of polymerized binaphthyl and triple biphenyl monomer and grafted side chains of piperidine cationic groups not only improves the microphase separation structure of the membrane, but also improves the alkali resistance. Notably, the PBTP‐s‐100 AEMs exhibit exceptional OH− conductivity, reaching up to 138.21 mS cm−1, and show outstanding mechanical properties with a tensile strength of up to 28 MPa. Additionally, PBTP‐s‐100 displays excellent durability, proved by the NMR spectral consistency and over 80 % ion conductivity retention in 1 M NaOH at 60 °C for 4 weeks. And PBTP‐s‐100 exhibits a higher Lowest Unoccupied Molecular Orbital (LUMO) and a larger energy gap for LUMO and Highest Occupied Molecular Orbital (HOMO) by density functional theory calculation, which indicates it possesses sterling alkaline stability. These findings highlight the potential of PBTP‐s‐100 as a highly performing polymer structure suitable for anion exchange membranes, which is capable of significantly enhancing the performance of fuel cells.

Highly Potent Transparent Passive Cooling Coating via Microphase-Separated Hydrogel Combining Radiative and Evaporative Cooling.

Transparent passive cooling materials can cool targets environmentally without interfering with light transmission or visual information reception. They play a prominent role in solar cells and flexible display cooling. However, achieving potent transparent cooling remains challenging, because light transmission is accompanied by thermal energy. Here we propose to realize effective passive cooling in transparent materials via a microscale phase separation hydrogel film. The poly(N-isopropylacrylamide-co-acrylamide) hydrogel presents light transmittance of >96% and infrared emissivity as high as 95%. The microphase-separated structure affords a higher enthalpy of evaporation. The film is highly adhesive. In field applications, it reduces temperatures by 9.14 °C compared to those with uncovered photovoltaic panels and 7.68 °C compared to those for bare flexible light-emitting diode screens. Simulations indicate that energy savings of 32.76-51.65 MJ m-2 year-1 can be achieved in typical tropical monsoon climates and temperate continental climates. We expect this work to contribute to energy-efficient materials and a carbon-neutral society.

Self-Healing Polyurethane Elastomers with Superior Tensile Strength and Elastic Recovery Based on Dynamic Oxime-Carbamate and Hydrogen Bond Interactions.

The preparation of self-healing polyurethane elastomers (PUEs) incorporating dynamic bonds is of considerable practical significance. However, developing a PUE with outstanding mechanical properties and high self-healing efficiency poses a significant challenge. Herein, this work has successfully developed a series of self-healing PUEs with various outstanding properties through rational molecular design. These PUEs incorporate m-xylylene diisocyanate and reversible dimethylglyoxime as hard segment, along with polytetramethylene ether glycol as soft segment. A significant amount of dynamic oxime-carbamate and hydrogen bonds are formed in hard segment. The microphase separated structure of the PUEs enables them to be colorless with a transparency of >90%. Owing to the chemical composition and multiple dynamic interactions, the PUEs are endowed with ultra-high tensile strength of 34.5MPa, satisfactory toughness of 53.9MJ m-3, and great elastic recovery both at low and high strains. The movement of polymer molecular chains and the dynamic reversible interactions render a self-healing efficiency of 101% at 70°C. In addition, this self-healing polyurethane could still maintain high mechanical properties after recycling. This study provides a design strategy for the preparation of a comprehensive polyurethane with superior overall performance, which holds wide application prospects in the fields of flexible displays and solar cells.

Tetramethyl poly(aryl ether ketone) modified by DABCO cationic polymer for high temperature proton exchange membrane fuel cells

Rationally constructing proton transport channel within high temperature proton exchange membranes (HT-PEMs) plays a critical role in lowering the mass transfer resistance and thus improving the performance of HT-PEM fuel cells (HT-PEMFCs). We herein designed a microphase-separated structure to promote proton transmitting by incorporating 1,4-Diazabicyclo[2.2.2]octane (DABCO) cationic polymer into tetramethyl poly(aryl ether ketone) (TMPAEK). The flexible and cationic segments afforded a polarity difference from TMPAEK, resulting in easier phosphoric acid adsorption. High proton conductivity of 135 mS cm−1 was obtained under anhydrous conditions at 150 °C. Besides, the hydrophilic domains that containing N-heterocycle could stabilize phosphoric acid through hydrogen bonding interactions, resulting in high phosphoric acid retention of ∼80 % after 288 h test. A Peak power density of 496 mW cm−2 was achieved in non-humidified H2/O2 without back pressure at 140 °C, which was higher than that of m-PBI under the same conditions. This work not only paved a way to tailor the ion conductivity of membrane, but also provided a highly competitive membrane for HT-PEMFCs.

The effect of polymer with tunable alkyl spacers on the microstructure of amphoteric membrane for vanadium redox flow battery (VRB)

Amphoteric membranes, as promising candidates for VRBs, have attracted more attention. The side-chain-type polymers go far towards improving ion exchange capacity and further enhancing ion conductivity. A kind of Amphoteric ion exchange membranes (AIEMs) with different alkyl chain lengths (C2, C6, and C12 spacers) were synthesized by using ring-opening metathesis polymerization (ROMP). In addition, the interactions between N-containing groups with positively charged and -SO3- groups prevent swelling and vanadium crossover. The microphase separation structure through side chain induction was regulated, to respond to the ionic mobility of the membrane. The effect of the spacer lengths on the ion selectivity of AIEMs is investigated. In addition, the size and matrix of the constructed ion channel were calculated by using coarse-grained molecular dynamics (CGMD) simulation, which further verified the experiment.

Core-Shell Double Gyroids Directed by Selective Solvation for ABC Triblock Terpolymers.

The formation of ABC triblock terpolymers through solution casting is still challenging. In this study, core-shell double gyroid network structures are fabricated via solution casting using poly(2,2,2-trifluoroethyl methacrylate) (PTFEMA) (F)-b-[poly(4-vinylpyridine) (P4VP) (P)]-b-[polystyrene (PS) (S)] (FPS) triblock terpolymers in N,N-dimethylformamide (DMF). Upon heat treatment, the polymer tends to form a sphere-in-lamellar structure at the F/S interface. Given the solubility properties of each component in DMF, it is anticipated that the effective volume fraction of F relative to P would increase in concentrated solutions and the effective volume fraction of S would decrease. The microphase-separated structure derived from the DMF solution consistently results in the formation of a network structure composed of a core-shell double gyroid, with F as the matrix, P as the shell, and S as the core, and their periodic lengths gradually increase to 110.8, 131.8, and 162.7nm as increase molecular weights of PS blocks to 13.8, 20.7, and 28.8kg mol-1. Based on the solubility properties of the polymer components highlighted in this study, the solvent selection strategy is broadly applicable to ABC triblock terpolymers featuring various polymer components, offering a more efficient avenue for fabricating core-shell double gyroid structures.

Mechanically Ultra-Robust Fluorescent Elastomer for Elaborating Auxetic Composite.

Fluorescent elastomers are predominantly fabricated through doping fluorescent components or conjugating chromophores into polymer networks, which often involves detrimental effects on mechanical performance and also makes large-scale production difficult. Inspired by the heteroatom-rich microphase separation structures assisted by intensive hydrogen bonds in natural organisms, an ultra-robust fluorescent polyurethane elastomer is reported, which features a remarkable fracture strength of 87.2MPa with an elongation of 1797%, exceptional toughness of 678.4MJm-3 and intrinsic cyan fluorescence at 445nm. Moreover, the reversible fluorescence variation with temperature could in situ reveal the microphase separation of the elastomer in real time. By taking advantage of mechanical properties, intrinsic fluorescence and hydrogen bonds-promoted interfacial bonding ability, this fluorescent elastomer can be utilized as an auxetic skeleton for the elaboration of an integrated auxetic composite. Compared with the auxetic skeleton alone, the integrated composite shows an improved mechanical performance while maintaining auxetic deformation in a large strain below 185%, and its auxetic process can be visually detected under ultraviolet light by the fluorescence of the auxetic skeleton. The concept of introducing hydrogen-bonded heteroatom-rich microphase separation structures into polymer networks in this work provides a promising approach to developing fluorescent elastomers with exceptional mechanical properties.

Incomplete ionic interactions and hydrogen bonds constructing elastomers with water accelerated Self-Healing and self-healing strengthening capacities

Self-healing polymers with microphase separation structure typically require external stimuli to achieve self-healing, and their performance often degrades. To solve these issues, we introduce tertiary amine and carboxyl groups into polymer. The intermolecular ionic interactions and H-bonds contribute to the formation of microphase separation structures, endowing polyurethane elastomers (PU-n) outstanding mechanical properties with a maximum tensile strength and toughness of 20.61 MPa and 59.02 MJ/m3, respectively. The self-healing of the prepared PU-n can be achieved at room temperature and accelerated significantly by water because hard phases can be dissociated, resulting in enhanced molecular movement. After self-healing with water, the enhanced molecular movement and further ionization of ionic groups lead to stronger H-bonds and ionic interactions, promoting more distinct microphase separation. Thus, the mechanical strength is strengthened and the self-healing efficiency can reach 104.72 %. The enhanced molecular movement and strengthened intermolecular interactions when self-healing with water can also be verified through in-depth analysis of molecular dynamics (MD) simulations of the self-healing process. Furthermore, PU-n display remarkable shape memory and can be recycled through exposure to solvents and hot water. This study provides a novel and general method for preparing materials that can self-heal with water and self-strengthen after self-healing.

Multi-cation alkoxy chains with high ion conductivity and durability in cross-linked poly (aryl piperidinium) anion exchange membranes

AEMs with high ionic conductivity and excellent alkali stability are one of the cores to ensure that AEMWE achieves high performance. For the current problems of AEMs, multi-cation side chain crosslinkers present a mitigation strategy for the inherent “trade-off” between ion conductivity and mechanical strength and ensure exceptional alkali resistance. Herein, we introduced the first report on cross-linked AEMs with several hydrophilic multi-cation alkoxy chains, featuring ethylene oxide (EO). The differentiation in the hydrophilic/hydrophobic microphase separation structures, characterized by varying positions of the alkoxy chains within the three-stage multi-cation crosslinker, was explored by experiments and simulation, as well as bearing on the comprehensive performance of AEMs. Notably, EO located in the middle of multi-cations crosslinker was found to establish a coherent and ordered ion channel. QPTP-NOBN15 AEM exhibited the highest OH− conductivity (166.6 mS cm−1) and demonstrated lower water uptake (44.4 %) and swelling ratio (14.5 %) at 80°C. And meticulously designed cross-linked structures, along with ether-free backbones, bestowed upon QPTP-NOBN15 impressive alkali stability. After being retained in 1 M KOH solutions for 1200 h, ion conductivity of QPTP-NOBN15 remained largely unaffected. Furthermore, QPTP-NOBN15-MEA was evaluated by water electrolysis in 1 M KOH solutions at 60°C and found that the current density reached 1.8 A cm−2 at 2.99 V.

Highly Durable Silicone-Based Elastomers Achieved Through the Synergy of Bi-Incompatible Soft Segments and Multi-Scale Hydrogen Bonds.

Developing a silicone elastomer with high strength, exceptional toughness, good crack tolerance, healability, and recyclability, poses significant challenges due to the inherent trade-offs between these properties. Herein, the design of silicone-based elastomers with a nanoscopic microphase separation structure and comprehensive mechanical properties is achieved by combining bi-incompatible soft segments and multi-scale hydrogen bonds. The formation of multi-scale hydrogen bonds involving urethane, urea, and 2-ureido-4[1H]-pyrimidinone (UPy) facilitates efficient reversible crosslinking of the synthesized polymer containing thermodynamically incompatible poly(dimethylsiloxane) (PDMS) and poly(propylene glycol) (PPG). The dynamic dissociation and recombination of hydrogen bonds, coupled with the forced compatibility and spontaneous separation of bi-incompatible soft segments, can effectively dissipate energy, particularly in the crack region during the stretching process. The obtained silicone-based elastomer exhibits a high break strength of 8.0 MPa, good elongation at break of 1910%, ultrahigh toughness of 67.8 MJ m-3, and unprecedented fracture energy of 31.8 kJ m-2 while maintaining their thermal stability, hydrophobicity, healability, and recyclability. This resilient and long-lasting silicone-based elastomer exhibits significant potential for use in flexible electronic devices.

Fluorinated semi-interpenetrating polymer networks for enhancing the mechanical performance and storage stability of polymer-bonded explosives by controlling curing and phase separation rates

Herein, the effect of fluoropolymer binders on the properties of polymer-bonded explosives (PBXs) was comprehensively investigated. To this end, fluorinated semi-interpenetrating polymer networks (semi-IPNs) were prepared using different catalyst amounts (denoted as F23-CLF-30-D). The involved curing and phase separation processes were monitored using Fourier-transform infrared spectroscopy, differential scanning calorimetry, a haze meter and a rheometer. Curing rate constant and activation energy were calculated using a theoretical model and numerical method, respectively. Results revealed that owing to its co-continuous micro-phase separation structure, the F23-CLF-30-D3 semi-IPN exhibited considerably higher tensile strength and elongation at break than pure fluororubber F2314 and the F23-CLF-30-D0 semi-IPN because the phase separation and curing rates matched in the initial stage of curing. An arc Brazilian test revealed that F23-CLF-30-D-based composites used as mock materials for PBXs exhibited excellent mechanical performance and storage stability. Thus, the matched curing and phase separation rates play a crucial role during the fabrication of high-performance semi-IPNs; these factors can be feasibly controlled using an appropriate catalyst amount.