Nanophase Separation Research Articles

Phosphorylated poly(ethylene-co-vinyl alcohol) doping for enhanced proton conductivity and mechanical properties of side chain–type sulfonated poly(aryl ether ketone) proton-exchange membranes

Phosphorylated poly (ethylene-co-vinyl alcohol) (PEVOH) was synthesized and blended with side chain–type sulfonated poly (aryl ether ketone) (SPAEK) to prepare SPAEK proton-exchange membranes with improved physicochemical and electrochemical properties. The results indicate that PEVOH doping helps improve the mechanical properties and proton conductivity of the membranes. The addition of PEVOH not only enhances proton transport but also provides proton transport channels for the membranes at a high temperature and low humidity, leading to excellent fuel cell performance and low ohmic resistance. The interaction between sulfonic acid and phosphonic acid side chain groups leads to the excellent nano-phase separation under microscopic morphology. This forms a large hydrogen bonding network between the acidic and amphoteric groups, which facilitates proton transport at low relative humidities.

Amphibious Polymer Materials with High Strength and Superb Toughness in Various Aquatic and Atmospheric Environments.

Herein, the fabrication of amphibious polymer materials with outstanding mechanical performances, both underwater and in the air is reported. A polyvinyl alcohol/poly(2-methoxyethylacrylate) (PVA/PMEA) composite with multiscale nanostructures is prepared by combining solvent exchange and thermal annealing strategies, which contributes to nanophase separation with rigid PVA-rich and soft PMEA-rich phases and high-density crystalline domains of PVA chains, respectively. Benefiting from the multiscale nanostructure, the PVA/PMEA hydrogel demonstrates excellent stability in harsh (such as acidic, alkaline, and saline) aqueous solutions, as well as superior mechanical behavior with a breaking strength of up to 34.8MPa and toughness of up to 214.2MJm-3 . Dehydrating the PVA/PMEA hydrogel results in an extremely robust plastic with a breaking strength of 65.4MPa and toughness of 430.9MJm-3 . This study provides a promising phase-structure engineering route for constructing high-performance polymer materials for complex load-bearing environments.

Microscopic Evidence for the Topological Transition in Model Vitrimers.

In addition to the glass transition, vitrimers undergo a topological transition from viscoelastic liquid to viscoelastic solid behavior when the network rearrangements facilitated by dynamic bond exchange reactions freeze. The microscopic observation of this transition is elusive. Model polyisoprene vitrimers based on imine dynamic covalent bonds were synthesized by reaction of α,ω-dialdehyde-functionalized polyisoprenes and a tris(2-aminoethyl)amine. In these dynamic networks nanophase separation of polymer and reactive groups leads to the emergence of a relevant length scale characteristic for the network structure. We exploited the scattering sensitivity to structural features at different length scales to determine how dynamical and topological arrests affect correlations at segmental and network levels. Chains expand obeying the same expansion coefficient throughout the entire viscoelastic region, i.e., both in the elastomeric regime and in the liquid regime. The onset of liquid-like behavior is only apparent at the mesoscale, where the scattering reveals the reorganization of the network triggered by bond exchange events. The such determined "microscopic" topological transition temperature is compared with the outcome of "conventional" methods, namely viscosimetry and differential scanning calorimetry. We show that using proper thermal (aging-like) protocols, this transition is also nicely revealed by the latter.

A Limit to Accelerated Free-Sintering: Nano-Phase Separation Interferes With Organic Debinding

Nano-phase separating Ni–12 at. pct Ag powders are processed via high-energy ball milling and brought into a supersaturated state with a reduction of the grain size to the nanocrystalline scale, a combination that is designed to encourage rapid densification by phase separation upon heating. This unstable powder is then characterized by dilatometry, in-situ x-ray diffraction, thermogravimetry and microstructure analysis for sintering cycles up to 940 °C. However, these powder compacts exhibit excessive pore evolution and significant macroscopic swelling caused by removal of the organic process additives. This competition of organic removal with densification is known in nanocrystalline metals, but the present study adds an additional dimension of phase separation, which shifts the dominant swelling mechanism as the formation of the second phase traps the volatilizing organics and hinders the debinding process. The creep swelling and overall loss in relative density is then dominated by the creep deformation of the second Ag phase. The interference between organic removal and low-temperature onset of consolidation represents a new challenge to efforts aimed at rapid free sintering and should guide the design of rapidly sintering alloys; specifically, the present work emphasizes the need to select alloys that have their sintering-accelerating phase separation temperature above the range where gases are evolved.

Nanophase separated, grafted alternate copolymer styrene-maleic anhydride as an efficient room temperature solid state lithium ion conductor

All solid-state lithium metal batteries (ASSLMBs) based on polymer solid electrolyte and lithium metal anode have attracted much attention due to their high energy density and intrinsic safety. However, the low ionic conductivity at room temperature and poor mechanical properties of the solid polymer electrolyte result in increased polarization and poor cycling stability of the Li metal batteries. In order to improve the ionic conductivity at room temperature while maintaining mechanical strength, we combine the conductivity of short chain polyethylene oxide (PEO) and strength of styrene-maleic anhydride copolymer (SMA) to obtain a grafted block copolymer with nanophase separation structure, which has room temperature ionic conductivity up to 1.14 × 10−4 S/cm and tensile strength up to 1.4 MPa. Li||Li symmetric cell can work stably for more than 1500 h under the condition of 0.1 mA/cm2. Li||LiFePO4 full cells can deliver a high capacity of 151.4 mAh/g at 25 °C and 0.2 C/0.2 C charge/discharge conditions, showing 85.6% capacity retention after 400 cycles. Importantly, the all solid state Li||LiFePO4 pouch cell shows excellent safety performance under different abuse conditions. These results demonstrate that the nanophase separated, grafted alternate copolymer electrolyte has huge potential for application in Li metal batteries.

Proton transport through interfaces in nanophase-separation of hydrated aquivion membrane: Molecular dynamics simulation approach

We investigate the effect of temperature and hydration on the nanophase-separated structure and proton conductivity in Aquivion and Nafion membranes using molecular dynamics simulation method. By considering two different temperatures (298 and 353 K) and water contents (10 and 20 wt%), our study reveals that Nafion exhibits better nanophase separation and a more mature internal structure of the water phase compared to Aquivion, leading to facilitated proton dissociation and improved proton conduction through vehicular and hopping mechanisms. This study also identifies the formation of a hydronium-mediated bridge configuration that restricts vehicular mobility at low hydration, resulting in a decrease of the vehicular contribution to proton conduction. From quantitative evaluation of the extent of nanophase-separation using structure factor analysis, we find that Nafion has a shorter correlation length with greater concentration contrast in comparison to Aquivion. At high hydration conditions, the hopping mechanism dominates at low temperature while the vehicular mechanism is dominant at high temperature. At low hydration, the vehicular mechanism is significantly decreased due to hydronium-mediated bridge configurations. It is interesting to note that the proton conductivity in the Aquivion membrane is higher despite the Nafion membrane having a higher proton diffusion. We discover that the greater proton conductivity of Aquivion membrane is caused by its higher proton concentration. In general, our findings offer a fundamental knowledge of the connection between nanophase-separated structure and proton transport characteristics in Nafion and Aquivion systems under a range of temperature and hydration circumstances.

Conductivity of Ionic Liquids In the Bulk and during Infiltration in Nanopores.

The conductivity of ionic liquids (ILs) in nanopores is essential when considering their application as materials for energy. However, no consensus has been reached about the influence of confinement on the mobility of the ions. A series of ILs bearing the same cation, 1-butyl-3-methylimidazolium ([BMIM]+), and six different anions ([Cl]-, [Br]-, [I]-, [BF4]-, [PF6]-, and [TFSI]-) with radii from 0.168 to 0.326 nm were investigated with respect to their self-assembly, the thermodynamics, and the ionic conductivity in the bulk, during flow and under confinement in cylindrical nanopores with sizes in the range from 400 to 25 nm. In the bulk, the [BMIM]+[X]- exhibits weak ordering as a result of cation-anion correlations (charge alteration peak), and nanophase separation of polar/apolar groups. Liquid-to-glass temperatures were found to differ by ∼50 K, their viscosities by a factor of ∼270, and their conductivities by a factor of 24 (all at a temperature of 303 K). Electrostatic interactions were largely responsible for variations in the glass temperature, the viscosity, and the conductivity. Confined ILs behave differently from the bulk. The majority of ILs in the bulk were prone to crystallization during heating but were unable to crystallize in the smaller pores. Changes in dc-conductivity were used as markers of the phase state. This allowed the construction of the effective phase diagrams under confinement. The ILs penetrate the pores with an effective viscosity of the order of their viscosity in their bulk state. However, within the pores the dc-conductivity was reduced relative to bulk, indicating the immobilization of ions at the pore walls. Hydrophobization of the pore walls by hexamethyldisilazane could partially restore the conductivity. ILs are model systems where the phase state and ion mobility can be controlled by confinement.

Multiblock copolymers with disulfonated bis(phenylsulfonylphenyl) sulfone group for polymer electrolyte membrane water electrolysis

Hydrogen, a zero-emissions fuel, is increasingly being targeted as a source of renewable energy. However, hydrogen production by electrolysis is limited by the characteristics of the hydrogen-separating membrane. Here, a series of multiblock copolymers composed of a hydrophilic block based on disulfonated bis(phenyulfonylphenyl) sulfone groups, and a hydrophobic block based on bis(p-phenoxyphenyl) ether groups is developed for application as a proton exchange membrane for water electrolysis. The multiblock copolymers combining stiff hydrophilic block and flexible hydrophobic block are expected to have reduced water swelling and low hydrogen permeability even under full-wet and high-temperature conditions in water electrolysis. Microscopy and X-ray scattering analyses of the multiblock copolymer-based membranes reveal strong nanophase separation and well-developed ion transport channels. The as-synthesized membranes exhibit advantages including low swelling, high proton conductivity, good mechanical and thermal properties, high oxidative stability, and reduced hydrogen permeability. A membrane electrode assembly employing the multiblock copolymer membrane achieved a current density above 3 A cm−2 at 1.8 V, far surpassing that of Nafion 212, and a long-term operating stability exceeding 500 h, demonstrating the suitability of the membrane for practical water electrolysis.

Unexpected Kinetic Solvent Effects Enhance Activity and Selectivity in Biphasic Systems

Biphasic dehydration of fructose to 5-hydroxymethylfurfural (HMF) has shown unprecedented increases in productivity, but a mechanistic understanding is lacking. Herein, we couple fast experimental reaction kinetics, multiscale modeling (phase behavior, classical molecular dynamics(MD), and quantum mechanics/molecular mechanics MD), in situ sampling, and IR and 13C-NMR spectroscopy to elucidate the complex effects of nonpolar extracting organic solvents on the kinetics of fructose dehydration. We show that these organic solvents can reach significant mutual solubility with water at reaction temperatures, enabling the partition of the sugar and catalyst into the extracting phase. In the organic-rich environment, the dehydration of fructose proceeds faster and more selectively than in water due to increased relative abundance of the reactive furanose isomer, enhanced water–catalyst–substrate interactions driven by nanophase separation, and higher product stability stemming from preferential solvation. We demonstrate that these solvent effects impact other critical biphasic reactions in biomass upgrading and provide qualitative principles for solvent selection.

Nanophase-Separated Copper–Zirconia Composites for Bifunctional Electrochemical CO2 Conversion to Formic Acid

A copper-zirconia composite having an evenly distributed lamellar texture, Cu#ZrO2, was synthesized by promoting nanophase separation of the Cu51Zr14 alloy precursor in a mixture of carbon monoxide (CO) and oxygen (O2). High-resolution electron microscopy revealed that the material consists of interchangeable Cu and t-ZrO2 phases with an average thickness of 5 nm. Cu#ZrO2 exhibited enhanced selectivity toward the generation of formic acid (HCOOH) by electrochemical reduction of carbon dioxide (CO2) in aqueous media at a Faradaic efficiency of 83.5% at -0.9 V versus the reversible hydrogen electrode. In situ Raman spectroscopy has revealed that a bifunctional interplay between the Zr4+ sites and the Cu boundary leads to amended reaction selectivity along with a large number of catalytic sites.

Pure Blue Perovskites Nanocrystals in Glass: Ultrafast Laser Direct Writing and Bandgap Tuning (Laser Photonics Rev. 17(5)/2023)

Perovskites Nanocrystals In article number 2200902, Dexhi Tan, Jianrong Qiu, and colleagues demonstrate that by manipulating ultrafast laser-induced liquid nanophase separation, the Cd/Pb cation concentration can be controlled at the nanoscale, and the emission wavelength of CsCdxPb1−xBr3 perovskites nanocrystals (PNCs) can be tuned within the range of 461–520 nm. The high stability and bandgap tenability of PNCs in one single glass can be applied for the encryption and decryption of crucial information.

Tailoring the microphase separation structure of poly(crown ether) anion exchange membranes by introducing aliphatic chains

Energy conversion devices such as alkaline fuel cells (AFCs) rely critically on anion exchange membranes (AEMs) with high hydroxide conductivity as well as good chemical stability. Poly (crown ether) (PCE) based AEMs with different aliphatic chain lengths in polymer backbone are successfully designed and prepared in this study. The longer hydrophobic aliphatic chain segments can promote the formation of nanophase separation and ionic clusters. As examined by morphology observation such as atomic force microscopy (AFM), small angle X-ray scattering (SAXS) and transmission electron microscopy (TEM), the QAPCE-16C AEMs which the carbon number of aliphatic chains is sixteen show a well-connected ion cluster region and a distinct micromorphology separation. QAPCE-16C with an IEC of 1.43 meq g−1 shows a hydroxide conductivity of 125 mS cm−1 at 80 °C. After immersing in a 1 M sodium hydroxide solution at 80 °C for 960 h, QAPCE-16C presents good alkaline resistance with the ionic conductivity retention of 95.77%. Besides this, the peak power density of QAPCE-16C can reach to 653.8 mW cm−2 in H2/O2 as well as 458.8 mW cm−2 in H2/Air (CO2-free) at 80 °C.

13% Single-Component Organic Solar Cells based on Double-Cable Conjugated Polymers with Pendent Y-Series Acceptors.

Double-cable conjugated polymers with pendent electron acceptors, including fullerene, rylene diimides, and nonfused acceptors, have been developed for application in single-component organic solar cells (SCOSCs) with efficiencies approaching 10%. In this work, Y-series electron acceptors have been firstly incorporated into double-cable polymers in order to further improve the efficiencies of SCOSCs. A highly crystalline Y-series acceptor based on quinoxaline core and the random copolymerized strategy are used to optimize the ambipolar charge transportand the nanophase separation of the double-cable polymers. As a result, an efficiency of 13.02% is obtained in the random double-cable polymer, representing the highest performance in SCOSCs, while the regular double-cable polymer only provides a low efficiency of 2.75%. The significantly enhanced efficiencies are attributed to higher charge carrier mobilities, better ordering conjugated backbones and Y-series acceptors in random double-cable polymers.

Synthesis of poly(n-alkyl acrylamides) and evaluation of nanophase separation effects by temperature-dependent infrared spectroscopy

Common linear polymers are known to undergo phase changes at the glass-transition temperature (Tg) and the melting point (Tm). In recent years, it has also been shown that molecules with long aliphatic side chains can give rise to a backbone-independent melting phenomenon, known as nanophase separation. This effect describes the self-assembly — independent of the polymer backbone — of alkyl side chains into semi-crystalline nanostructures. This work presents optimized, gram scale synthesis routes for dodecyl and octadecyl acrylamide and their respective homopolymers. Differential scanning calorimetry (DSC) experiments detected a broad endothermal signal for poly(n-dodecyl acrylamide) at − 29 °C and a narrower, more intense signal for poly(n-octadecyl acrylamide) at 34 °C. These signals indicate the nanophase separation TM of the alkyl side chains. We undertook the first temperature-controlled infrared spectroscopy investigations of these materials revealing a clear hypsochromic shift of the C–H stretching signals above TM and the amide I signal shifts that occurred only above and below Tg. These results provide further evidence, that the side chains act independently of the polymer backbone and show that infrared spectroscopy is a powerful tool for monitoring conformational changes in polymer side chains.Graphical abstract

Carbonized Polymer Dots Assemble in Proton-Conducting Channels to Enhance the Conductivity and Selectivity Simultaneously for High-Performance Fuel Cells.

Fabricating polymer electrolyte membranes (PEMs) simultaneously with high ion conductivity and selectivity has always been an ultimate goal in many membrane-integrated systems for energy conversion and storage. Constructing broader ion-conducting channels usually enables high-efficient ion conductivity while often bringing increased crossover of other ions or molecules simultaneously, resulting in decreased selectivity. Here, the ultra-small carbon dots (CDs) with the selective barriers are self-assembled within proton-conducting channels of PEMs through electrostatic interaction to enhance the proton conductivity and selectivity simultaneously. The functional CDs regulate the nanophase separation of PEMs and optimize the hydration proton network enabling higher-efficient proton transport. Meanwhile, the CDs within proton-conducting channels prevent fuel from permeating selectively due to their repelling and spatial hindrance against fuel molecules, resulting in highly enhanced selectivity. Benefiting from the improved conductivity and selectivity, the open-circuit voltage and maximum power density of the direct methanol fuel cell (DMFC) equipped with the hybrid membranes raised by 23% and 93%, respectively. This work brings new insight to optimize polymer membranes for efficient and selective transport of ions or small molecules, solving the trade-off of conductivity and selectivity.

Composite elastomers with on-demand convertible phase separations achieve large and healable electro-actuation.

Phase separation has been widely exploited for fabricating structured functional materials. Generally, after being fabricated, the phase structure in a hybrid material system has been set at a specific length scale and remains unchanged during the lifespan of the material. Herein, we report a strategy to construct on-demand and reversible phase switches among homogenous, nano- and macro-phase separation states in a composite elastomer during its lifespan. We trigger the nanophase separation by super-saturating an elastomer matrix with a carefully selected small-molecule organic compound (SMOC). The nanoparticles of SMOC that precipitate out upon quenching will stretch the elastomer network, yet remain stably arrested in the elastomer matrix at low temperatures for a long time. However, at elevated temperatures, the nano-phase separation will transform into the macro-one. The elastic recovery will drive the SMOC onto the elastomer surface. The phase-separated structures can be reconfigured through the homogeneous solution state at a further elevated temperature. Taking advantage of the reversible phase switches leads to a novel strategy for designing high-performance dielectric elastomers. The in situ formed nanoparticles can boost the electro-actuation performance by eliminating electro-mechanical instability and lead to a very large actuation strain (∼146%). Once the actuator broke down, SMOC could on-demand be driven to the breakdown holes and heal the actuator.

Extremely strengthening fatigue resistance, elastic restorability and thermodynamic stability of a soft transparent self-healing network based on a dynamic molecular confinement-induced bioinspired nanostructure.

Soft self-healing materials are crucial for the development of next-generation wearable electronics that could function in dynamic environments and resist mechanical damage. However, several challenges remain, including fatigue fracture, poor elasticity, and thermodynamic lability, which significantly limit their practical applications. Here, with a model system of soft self-healing polyurea, we propose a molecular engineering strategy of transforming inherently fragile materials with an island-like structure into resilient ones with a bicontinuous nanophase separation structure using 2-ureido-4-pyrimidinone (UPy) supramolecular motifs as structural regulators. The dynamic and continuous hard domains modified by UPy formed a repairable bicontinuous network similar to those of the reticular layer in animal dermis. This design allows for a simultaneous and tremendous improvement in the fatigue threshold (34.8-fold increase), elastic restorability (the maximum elongation for full dimensional recovery increasing from 6 times to 13 times), and thermodynamic stability (4 orders of magnitude improvement in the characteristic flow transition relaxation time), without significantly compromising the compliance, autonomous self-healing, and optical transparency. These mechanical and thermodynamic improvements address current limitations in unfilled soft self-healing materials as reliable substrates for transparent strain-electronics.

Blending to Make Nonhealable Polymers Healable: Nanophase Separation Observed by CP/MAS 13C NMR Analysis

AbstractCan commodity polymers are made to be healable just by blending with self‐healable polymers? Here we report the first study on the fundamental aspect of this practically challenging issue. Poly(ether thiourea) (PTUEG3; Tg=27 °C) reported in 2018 is extraordinary in that it is mechanically robust but can self‐heal even at 12 °C. In contrast, poly(octamethylene thiourea) (PTUC8; Tg=50 °C), an analogue of PTUEG3, cannot heal below 92 °C. We found that their polymer blend self‐healed in a temperature range above 32 °C even when its PTUEG3 content was only 20 mol %. Unlike PTUEG3 alone, this polymer blend, upon exposure to high humidity, barely plasticized, keeping its excellent mechanical properties due to the non‐hygroscopic nature of the PTUC8 component. CP/MAS 13C NMR analysis revealed that the polymer blend was nanophase‐separated, which possibly accounts for why such a small amount of PTUEG3 provided the polymer blend with humidity‐tolerant self‐healable properties.

Blending to Make Nonhealable Polymers Healable: Nanophase Separation Observed by CP/MAS 13 C NMR Analysis.

Can commodity polymers are made to be healable just by blending with self-healable polymers? Here we report the first study on the fundamental aspect of this practically challenging issue. Poly(ether thiourea) (PTUEG3 ; Tg =27 °C) reported in 2018 is extraordinary in that it is mechanically robust but can self-heal even at 12 °C. In contrast, poly(octamethylene thiourea) (PTUC8 ; Tg =50 °C), an analogue of PTUEG3 , cannot heal below 92 °C. We found that their polymer blend self-healed in a temperature range above 32 °C even when its PTUEG3 content was only 20 mol %. Unlike PTUEG3 alone, this polymer blend, upon exposure to high humidity, barely plasticized, keeping its excellent mechanical properties due to the non-hygroscopic nature of the PTUC8 component. CP/MAS 13 C NMR analysis revealed that the polymer blend was nanophase-separated, which possibly accounts for why such a small amount of PTUEG3 provided the polymer blend with humidity-tolerant self-healable properties.

Design of a rapidly sintering Mo-W-Cr alloy

Mo-W based materials have excellent mechanical and thermal properties, but are difficult to produce and require either very high temperatures or complicated sintering procedures, and typically have coarse structures. Here the nanophase separation sintering (NPSS) design criteria are used to develop a rapidly sintering ternary Mo-W based alloy. A composition of Mo-25 W-15Cr is chosen and shown to exhibit the critical features of NPSS. The relevant sintering temperatures are shown to be much lower than for comparable refractory alloys. The kinetic mechanisms that facilitate the enhanced sintering are verified, and these involve the transient precipitation and redissolution of a second phase that accelerates sintering. That second phase is fully eliminated at the end of sintering, permitting potential usage of the alloy at temperatures above the sintering range. Finally, the resulting hardness of the material is compared to that of Mo-W alloys produced through other methods, showing a significant strength boost due to the rapid low-temperature sintering and its attendant fine microstructure.