MACROMOLECULAR RAPID COMMUNICATIONS
·
2024
·Vol. 45
·期 19
·2400259
·
IF 4.2
Zhihao Niu,Yimin Wang,Xin Wang,Dexian Yin,Tao Shou,Pengfei Cao,Xiuying Zhao,Shikai Hu,Liqun Zhang
The thermodynamic incompatibility between the soft and hard segments of thermoplastic polyurethane (TPU) results in a microphase-separated behavior and excellent mechanical properties. However, the effect of the chain extender on the degree of microphase separation (DMS) and the resultant mechanical properties of TPU have not been well studied because of the complex interactions between the soft and hard segments. Herein, hydroxyl-terminated polybutadiene-based TPUs(HTPB-TPUs) without hydrogen bonding between the soft and hard segments are synthesized using hydroxyl-terminated polybutadiene, toluene diisocyanate, and four different chain extenders, and the effect of the chain extender structure on DMS is analyzed experimentally using a combination of analytical techniques. Furthermore, the solubility parameters of the soft and hard segments, glass transition temperatures, and hydrogen-bond density of the HTPB-TPUs, are computed using all-atom molecular dynamics simulations. The results clearly reveal that the chain extender significantly affects the DMS and thus the mechanical properties of HTPB-TPUs. This study paves the way for studying the relationship between the structure and properties of TPU.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
PubMed
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2025
·
IF 9
Yufeng Liang,Ziqiang Liu,Kejing Lin,Weimin Yin,Yuanqin Zhu
Aromatic hydrocarbon proton exchange membranes (PEMs) hold promises as alternatives to Nafion membranes. Here we report on the design and preparation of graft-type PEMs based on poly ( m -terphenyl fluorenyl)s (TSPHFTP-x) with a featured structure of rigid all-carbon aromatic backbones and long flexible side chains with dual 1,2,3-triazole and disulfonated units. Benefiting from the well-designed structure, the TSPHFTP-x membranes exhibit a well-defined bicontinuous microphase separation structure, thus achieving high proton conductivities up to 175.6 mS cm −1 (25 °C) and 303.0 mS cm −1 (80 °C) under 100 % relative humidity, and excellent dimensional stability with swelling ratio below 24 %. Meanwhile, these membranes show good oxidative stability and mechanical properties. In addition, the H 2 –O 2 fuel cell assembled with the TSPHFTP-50 PEM shows a peak power density of 1013 mW cm −2 at 60 °C. This study provides a valuable insight into the design of polymer architectures for high-performance hydrocarbon PEMs.
研究领域:
材料科学
·
化学工程
·
能源技术
✓ 已验证
产品关联
DOI
高影响因子
ADVANCED FUNCTIONAL MATERIALS
·
2025
·
IF 19
Guo-Rui Zhu,Qin Zhang,Ying-Ying Zhang,Xiu-Li Wang,Gang Wu,Yu-Zhong Wang
Robust structures are essential for extending the application of shapeless soft polymer electrolytes and maintaining the self-supporting of solid-state all-polymer electrolytes (SPEs) at elevated temperatures. Common strategies of introducing additional separators or cross-linking can significantly increase the manufacturing complexity of SPEs, thus limiting their commercialization. Herein, inspired by the musculoskeletal structure, a “soft-hard synergy” enhanced SPE (named PPH-SPE) is successfully designed and manufactured by a simple one-step in situ microphase separation strategy for high-temperature lithium–metal batteries. In the bicontinuous PPH-SPE, the “soft” polyphosphazene liquid polymer electrolyte (PPZ-LPE) phase provides excellent electrochemical properties, interfacial compatibility, and high-temperature stable Li 3 N/Li 3 PO 4 -rich hybrid interfaces. PVDF-HFP crystals are skillfully used to build a 3D continuous, high-strength (0.32 ± 0.02 MPa at 90 °C), thermotolerant “hard” skeleton. In the synergy of two phases, Li//Li cell can maintain continuous electrodeposition over 4500 h of the plating/stripping process at 0.25 mA cm −2 and 0.25 mAh cm −2 . Furthermore, LiFePO 4 //Li coin and pouch cells achieve an ultra-long lifetime of over 1000 (1 C) and 1800 (0.5 C) cycles at 90 °C, respectively. This strategy provides new ideas for large-scale fabrication and enhancement of solid all-polymer electrolytes.
研究领域:
材料科学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
Polymer Chemistry
·
2017
·Vol. 9
·期 6
·699-711
·
IF 5.375
Xueliang Zhang,Qian Shi,Pei Chen,Jinfang Zhou,Songsong Li,Hua Xu,Xinbing Chen,Zhongwei An
A series of poly(arylene ether sulfone) block copolymer ionomers have been synthesized through pre-polycondensation, block copolycondensation, bromomethylation and the Menshutkin reaction, where benzyl-quaternary ammonium groups are tethered to the side chains of hydrophilic blocks. Atomic force microscopy (AFM) results indicate the formation of a well-defined microphase-separated morphology in ionomer-based membranes, which is attributed to its well-controlled block copolymer as well as aromatic side-chain structures. The prepared side-chain block anion exchange membranes (bQPAES) with IECs of 0.79–1.15 mequiv g−1 have isotropic membrane swelling and high hydroxide conductivity (54.8–86.3 mS cm−1). Compared to random copolymer ionomer membranes, the present block anion exchange membranes exhibit acceptable high hydroxide conductivity, which is ascribed to well-connected ionic nano-channels resulting from the better microphase separation induced by block copolymer structures. Besides this, the side-chain block bQPAES membranes display reasonably high alkaline stability with good chemical stability of both quaternary ammonium ionic groups and block copolymer backbones considering the harsh aging conditions (4 M NaOH at 80 °C).
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
POLYMER
·
2018
·
IF 3.483
Yaqian Guo,Ruoyu Zhang,Qiang Xiao,Hongxia Guo,Zongbao Wang,Xing Li,Jing Chen,Jin Zhu
Four chain extenders, 1,3-propanediol (PDO), 2-methyl-1,3-propanediol (MPO), 2,2-dimethyl-1,3-propanediol (NPG) and 2,2,4,4-tetramethyl-1,3-cyclobutanedio (CBDO) are chosen to synthesize model polyurethanes , respectively. Although with similar oxygen distance between the two hydroxyl groups , their volumes increase gradually according to computer simulation. As expected, the degree of microphase separation decreases with the increasing chain extender volume. Except for CBDO based polyurethane, the other three samples show systematic variations in mechanical properties . Various techniques including single-molecule force spectroscopy (SMFS), small-angle X-ray scattering (SAXS) and Fourier transform infrared spectroscopy (FTIR) are employed to investigate the structural changes after tensile break in different length scales. A picture of asynchronous fracture of microstructures during the tensile break of thermoplastic polyurethane elastomers can be obtained by the combination of different analytical methods. It is interesting to note that the macroscopic break may not affect the state of hydrogen bonding or the hard phase network. Sometimes, the hydrogen bonding state changes a lot while the phase network keeps almost the same, or vice versa.
研究领域:
材料科学
·
化学
✓ 已验证
产品关联
DOI
高影响因子
INTERNATIONAL JOURNAL OF HYDROGEN ENERGY
·
2020
·
IF 4.939
Yongheng Yin,Hongbo Li,Hong Wu,Wei Wang,Zhongyi Jiang
Designing polymer chains which contain building blocks with well-defined dimension is an efficient method to induce microphase separation and regulate the ionic channels of polymer electrolyte membranes (PEMs). In this study, a Wells-Dawson-type polyoxometalate (POM) is synthesized and chemically bonded to a norbornene derivative to prepare poly (POM) blocks. Then the block copolymer poly (POM) 10 - b -poly (COOH) 300 is fabricated using poly (POM) and poly (COOH) blocks. Finally, the block copolymer is blended with sulfonated polysulfone (SPS). The electrostatic interactions between the block copolymer and SPS confer the blend membrane with enhanced mechanical and dimensional stabilities. Due to the homogenous distribution of POM clusters and the hydrophilic-hydrophobic interactions between POMs and polymer backbones , the adjacent hydrophilic domains are connected and continuous proton-transfer channels are induced. As a result, the blend membrane displays proton conductivity of 0.053 S cm −1 (25 °C, 100% RH) and 1.5 × 10 −2 S cm −1 (80 °C, 40% RH), which are 2.52 and 6.25 times higher than those of the plain SPS membrane. Furthermore, SPS/POM-BC-30 shows a maximum power density of 164.9 mW cm −2 , which is 54.7% higher than SPS.
研究领域:
材料科学
·
化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF MEMBRANE SCIENCE
·
2020
·
IF 7.183
Zihan Qu,Rui Zhao,Hong Wu,Yanxiong Ren,Yutao Liu,Zheyuan Guo,Yingzhen Wu,Leixin Yang,Xu Liang,Zhongyi Jiang
High-performance membrane materials are urgently demanded for efficient membrane-based biogas upgrading. Polyelectrolytes with convertible ionic groups, spontaneously forming interconnected facilitated transport pathways for gas molecules via microphase separation , exhibit promising potential in membrane-based separation. However, there is a great challenge to further enhance the gas permeability and selectivity simultaneously due to the limited microphase separation and low free volume generated by the strong interaction between ionic groups. Herein, we demonstrate a novel strategy to construct the tunable hollow quaternary ammonium (-N + (CH 2 CH 3 ) 3 ) clusters with good CO 2 affinity via sacrificial template method in quaternized polysulfone (QAPSf) membranes for achieving the fast transport of CO 2 . The templates (POSS) induce the formation of –N + (CH 2 CH 3 ) 3 clusters through forced microphase separation in the membranes and then are etched away to generate hollow CO 2 -philic clusters to increase the fractional free volume in membranes and thus improve CO 2 diffusion. After that, the B(OH) 4 - as counterions by ion exchange endow the hollow CO 2 -philic clusters with high CO 2 -facilitating ability, which simultaneously enhance the CO 2 permeability and CO 2 /CH 4 selectivity. The resultant QAPSf-B(POSS-2) membrane exhibits superior separation performance with an optimal permeability of 1113 Barrer and a CO 2 /CH 4 gas selectivity of ~45, i.e. 334% and 73% higher than the pristine QAPSf membrane, respectively, breaking the trade-off between permeability and selectivity and surpassing the Robeson 2008 upper-bound.
研究领域:
材料科学
·
环境工程
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Energy Materials
·
2021
·
IF 6.024
Wanxia Li,Xinlin Zhu,Ning Zhou,Yong Yang,Ruijing Li,Cheng Wang,Zhao Fang,Xinyan Ma,Wentian Zhao,Xiaolong Fu,Wuwei Yan
Poly(ethylene oxide) (PEO) with excellent solvating capacity toward lithium salts and easy processable feature is considered as the promising polymer electrolyte matrix for energy storage devices. However, the poor capacity and cycling performances of PEO-based batteries resulted from weak mechanical strength and electrochemical properties greatly limit its development. Herein, chiral polyurethane (HPU) with a unique helical configuration is integrated into PEO, and a well-defined microphase separation architecture is induced in the resulted PEO@HPU hybrid. Besides the decreased crystallinity of PEO, the well-organized ordered and disordered microphase structure provides a “green channel” for Li+ transfer, contributing to a record lithium ion transference number of 0.43 for PEO-based dual-ion conductors. The mechanical strength and dimensional stability of PEO are significantly improved by the introduction of rigid helical segments and intermolecular hydrogen bondings. The electrochemical window and the ionic conductivity of the PEO@HPU hybrid are 5.0 V (vs Li+/Li) and 4.92 × 10–5 S cm–1 (60 °C), respectively. By synergism of the decreased crystallinity and microphase separation, the LiFePO4/Li cell assembled with the optimized PEO@HPU presents a high discharge capacity of 153 mA h g–1 at 0.1 C, and the capacity retention ratio is 83.6% after the 80th cycle with a Coulombic efficiency of approximately 99%. The growth of lithium dendrites is effectively inhibited, and the improved interfacial compatibility between PEO@HPU and the Li metal electrode also plays a crucial role. The introduction of a helical structure and the induced microphase separation may provide a new strategy for developing advanced solid-state polymer electrolytes for practical applications.
研究领域:
材料科学
·
能源存储
✓ 已验证
产品关联
DOI
高影响因子
MACROMOLECULES
·
2018
·
IF 5.914
Dong Xiang,Jingjing He,Tongtong Cui,Li Liu,Qi Song Shi,Lan Chao Ma,Yongri Liang
Understanding the relationship between multiphase structure and electromechanical property of thermoplastic dielectric elastomers is significantly important in the developments of high-performance and novel dielectric elastomers. In this work, we fabricated a series of aliphatic polyurethane elastomers (PUEs) based on hydroxyl-terminated butadiene-acrylonitrile copolymer (HTBN), hexamethylene diisocyanate (HDI), and various lengths of linear aliphatic diols and investigated effect of their microstructure and morphology on dielectric and electromechanical properties. The FTIR, WAXS, SAXS, and viscoelastic AFM results showed that the PUEs existed in crystalline phase, hard domain (HD) and soft domain (SD) phases composed HD-rich region and few HDs and SD composted SD-rich region by crystallization and microphase separation. Also, the crystal morphology and crystallinity of PUEs are strongly influenced by the length of chain extender due to the chain extender adopting various conformations by hydrogen bonding. The mechanical and electric fields induced responses of segment motions in PUEs at below room temperature were relative to the constrained SS motions from HD-rich and SD-rich regions. The electric field induced strain of PUEs was actuated by both Maxwell stress and electrostriction effect, of which contribution of electrostriction effect was above 64% in total actuation strain. In addition, we found that the effect of electrostriction on the actuation strain played an important role in improving the actuation strain of PUEs at lower electric field. Our results showed that the dielectric and electromechanical properties of PUEs can be adjusted by controlling the crystallization and microphase separation.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF DRUG DELIVERY SCIENCE AND TECHNOLOGY
·
2016
·
IF 0.62
Zheng-Bai Zhao,Hai-Jiao Xie,Yan-Li Li,Yong Jiang
In this article, the multicomponent hydrogel was prepared by the copolymerization of the hydrophobic silicon-containing monomer tris(trimethylsiloxy)-3-methacryloxypropyl-sliane (TRIS) with the hydrophilic monomers 2-hydroxyethyl methacrylate (HEMA) and N-vinyl pyrrolidone (NVP). The ethanol extraction experiments as well as the FTIR, DSC results showed that the copolymerization was effective. The silicone hydrogel that had hydrophilic and hydrophobic phases could be loaded with hydrophilic drug (FITC) and hydrophobic drug (Nile Red) simultaneously. The drug release properties of the hydrogel were studied by taking advantage of its innate stimuli-responsiveness to solvent and pH. The release behaviors of hydrophilic and hydrophobic drugs were found to be solvent dependent. And the release behavior of hydrophilic drug was also pH sensitive. With the characteristics above, the silicone hydrogels can be good candidates for specified materials and may have broad applications in responsiveness, drug release, contact lens, etc.
研究领域:
材料科学
·
药学
·
生物医学工程
✓ 已验证
产品关联
DOI
高影响因子
Materials Research Express
·
2019
·Vol. 6
·期 5
·055321
·
IF 1.449
Ruo-Can Liu,Ke Liu,Yong Du,Xiao-Wei Xu,Run-Ping Jia
The thermoplastic polyurethane/Nd2O3 (TPU/Nd2O3) nanocomposites with different content of Nd2O3 nanoparticles are synthesized via an in situ bulk polymerization technique. The results of x-ray Diffraction and Scanning Electron Microscopy show that Nd2O3 nanoparticles with size of 40 nm are uniformly dispersed in TPU matrix. Furthermore, the degrees of microphase separation of the nanocomposites are evaluated by Fourier Transform Infrared Spectroscopy and Dynamic Mechanical Analysis, and the effect of different Nd2O3 nanoparticle contents on the properties of TPU/Nd2O3 nanocomposites is investigated. When the content of Nd2O3 nanoparticles is 0.5 wt%, the nanocomposites has the highest degree of microphase separation, and the corresponding melting temperature, decomposition temperature, tensile strength, and elongation at break of TPU/Nd2O3 nanocomposites reach their maximum values of 196.5 °C, 352.7 °C, 53.9 MPa, and 703%, which are higher by 17.9%, 13.5%, 89.1% and 32.4% than pure TPU, respectively. Meanwhile, the TPU/Nd2O3 nanocomposites also illustrate better chemical resistance characteristics compared with pure TPU. Finally, the interaction mechanism between Nd2O3 and TPU is investigated by x-ray Photoelectron Spectroscopy, which confirms that the coordination bonds between Nd2O3 and carbamate groups of TPU are existed in the nanocomposites.
研究领域:
材料科学
·
高分子化学
✓ 已验证
产品关联
DOI
高影响因子
INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH
·
2020
·
IF 3.573
Fei Shi,Qianqian Tian,Jingtao Wang,Qi Wang,Feng Shi,Yifan Li,Suzana P. Nunes
In this study, molecular-level mixed matrix membranes are prepared by incorporating two types of carbon quantum dots (QDs), polymer-like QDs (PQD) and graphene oxide QDs (GQD) into Pebax, a poly(ether-b-amide) copolymer. PQD is shown to destroy part of the intrinsic crystalline structure of Pebax as typical fillers do. By comparison, GQD has fewer functional groups and causes an interesting enhancement of the microphase separation of Pebax. The polyether domains become more segregated and more available for the selective CO2 permeation. As a result, the gas separation performance of the membranes is evidently enhanced. GQD outperforms PQD as a filler, and encouraging enhancement occurs at lower loading. The membrane with 0.05 wt % GQD loading shows the optimal gas separation property, while it is 1 wt % for PQD-doped membranes. A possible mechanism is tentatively proposed based on the findings of this study.
研究领域:
材料科学
·
化学工程
·
环境科学
✓ 已验证
产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）