Post‐polymerization modification of bio‐based polymers: maximizing the high functionality of polymers derived from biomass

The renaissance of the bio‐based chemical industry over the last 20 years has seen an ever growing interest in the synthesis of new bio‐based polymers. The building blocks of these new polymers, so called platform molecules, contain significantly more chemical functionality than their petrochemical counterparts (such as ethene, propene and para‐xylene). As a result bio‐based polymers often contain greater residual chemical functionality in their chains, with groups such as alkenes and hydroxyls commonly observed. These functional groups can act as sites for post‐polymerization modification (PPM), thus further extending the range of applications for bio‐based polymers by tailoring the polymers' final properties. This mini‐review highlights some of the most recent and compelling examples of how to make use of bio‐based polymers with residual functional groups for PPM. It also looks at how the emerging interdisciplinary field of enzymatic polymer synthesis allows for increased functionality in polymers by avoiding side‐reactions as a result of milder reaction conditions, and additionally offers an alternative means of polymer surface modification. © 2018 Society of Chemical Industry     

Large Area Self-Assembled Ultrathin Polyimine Nanofilms Formed at the Liquid–Liquid Interface Used for Molecular Separation

Separation membranes with higher molecular weight cut-offs are needed to separate ions and small molecules from a mixed feed. The molecular sieving phenomenon can be utilized to separate smaller species with well-defined dimensions from a mixture. Here, the formation of freestanding polyimine nanofilms with thicknesses down to ≈14 nm synthesized via self-assembly of pre-synthesized imine oligomers is reported. Nanofilms are fabricated at the water–xylene interface followed by reversible condensation of polymerization according to the Pieranski theory. Polyimine nanofilm composite membranes are made via transferring the freestanding nanofilm onto ultrafiltration supports. High water permeance of 49.5 L m^-2 h⁻¹ bar⁻¹ is achieved with a complete rejection of brilliant blue-R (BBR; molecular weight = 825 g mol⁻¹) and no more than 10% rejection of monovalent and divalent salts. However, for a mixed feed of BBR dye and monovalent salt, the salt rejection is increased to ≈18%. Membranes are also capable of separating small dyes (e.g., methyl orange; MO; molecular weight = 327 g mol⁻¹) from a mixed feed of BBR and MO. Considering a thickness of ≈14 nm and its separation efficiency, the present membrane has significance in separation processes.     

New approaches to determine the interface height of fire smoke based on a three-layer zone model and its verification in large confined space

Large confined space has high incidence of fires, which seriously threatens the safety of people working there. Understanding the distribution of smoke in such large space is critical to fire development prediction and smoke control. Three improved methods for the stratification interface prediction of fire smoke are developed, including of improved intra-variance, integral ratio and N-percentage methods. In these methods, the interface height is determined by the vertical temperature distribution based on a three-layer smoke zone model, which is an improvement of a two-layer zone model. Thereafter, the three improved methods are applied to several typical fire cases simulated CFD to predict the smoke interface, and their applicability and reliability are verified by comparison of the smoke stratification results with the filed simulation results. Results show that the three improved methods can effectively determine the location of the three-layer zone model's interface, and they have the ability to predict smoke interface for fires with different fire source types and ventilation conditions.     

Research on hydrophobicity of electrospun Fe3O4/PVDF nanofiber membranes under different preparation conditions

Abstract

Preparation condition can affect the structure and the properties of nanofiber membrane. In order to explore suitable conditions to prepare the Fe₃O₄/PVDF nanofiber membrane with good hydrophobicity, the hydrophobicity of Fe₃O₄/PVDF nanofiber membranes obtained by electrospinning was investigated by changing preparation conditions like weight percentage of Fe₃O₄ nanoparticles, blending quality concentration of poly (vinylidene fluoride) (PVDF) and Fe₃O₄ nanoparticles, and positive voltage. And the variations of hydrophobicity of Fe₃O₄/PVDF nanofiber membranes modified by 1H, 1H, 2H, 2H-perfluorodecyl trimethoxysilane were studied. The results show that the hydrophobicity of Fe₃O₄/PVDF nanofiber membranes has changed under different preparation conditions. The contact angles of samples increased after a modification by 1H, 1H, 2H, 2H-perfluorodecyl trimethoxysilane, which indicates that the hydrophobicity of Fe₃O₄/PVDF nanofiber membranes has been enhanced.     

Preparation and mechanism of active Mo–Mn metallization on ZTA particles surface and interfacial bonding of reinforced iron matrix composite

ZrO₂ toughened Al₂O₃ particles (ZTAp) have poor wettability with iron, and therefore some defects are easily formed at the interface between ZTAp and iron matrix, which may lead to material failure. This paper illustrates that the ZTAp were modified on the surface by the active Mo–Mn metallization, and thus, they were used as the reinforcing phases to prepare the iron-matrix composite (ZTAp/Fe composite). It is concluded that the sponge-like skeleton structure was formed on the surface of ZTAp after the metallization. The interface of ZTAp/Fe composite, which has been proved to have bearing and transitional capacity by scratch test, was formed by chemical bonding with elemental diffusion, besides mechanical bonding. The metallization mechanism of elemental diffusion can be explained by the migration of glass phase, and the elements diffusion between the interface and iron matrix is to form solid solution.     

GO@TA-Fe/PVDF纳米复合材料制备与介电性能

为降低氧化石墨烯（GO）/聚偏氟乙烯（PVDF）体系的介电损耗，本文采用单宁酸-铁配合物（TA-Fe）修饰GO表面，将改性GO和PVDF复合后制得了GO@TA-Fe/PVDF纳米复合电介质材料，研究了GO@TA-Fe对PVDF复合材料的微观形貌及介电性能影响。研究结果表明，TA-Fe包覆层强化了GO与PVDF基体间界面相容性及界面作用力，促进了GO在基体中均匀分散；TA-Fe界面层的存在显著降低了GO/PVDF漏导电流及损耗，归因于绝缘界面层有效阻止了GO之间直接接触，抑制漏导电流；TA-Fe用量对体系介电性能有明显影响，随TA-Fe用量增大，体系的介电损耗和电导率显著降低。与GO/PVDF相比，质量分数2%的GO@TA-Fe/PVDF在100Hz下介电常数为1000，而介电损耗由19.8降低为0.08。本研究制备的高介电常数及低损耗的柔性GO@TA-Fe/PVDF纳米电介质材料在电子器件及电力设备领域具有潜在应用。     

机械涂覆技术在光催化材料制备中的应用进展

机械球磨技术因工艺简单、成本低廉而受到广泛关注,特别在粉体材料的混合、细化及合金化等领域有着广阔的应用前景。综述了由机械球磨原理发展而成机械涂覆技术的应用现状,包括用于材料表面改性的功能涂层和光催化降解的薄膜材料制备。分析了工艺参数、涂覆材料及涂覆基底等因素对涂覆效果（厚度）的影响规律,并对该技术在薄膜制备中表现出的简便、廉价且可在球形等形状复杂基底上成膜的独特优势做了讨论。基于当前机械涂覆技术制备的薄膜形貌、厚度不可控且成膜基底材质受限等现状,指出今后应该向拓展成膜基底材料类型和加快推进光催化薄膜材料的实际应用方向发展。     

Co-based zeolitic imidazolate framework ZIF-9 membranes prepared on α-Al2O3 tubes through covalent modification for hydrogen separation

Hydrogen has been regarded as the most promising clean and renewable energy. Beside the production of the hydrogen, the separation of hydrogen is also an import issue before it can be used in fuel cells. Membrane-based separation technologies have gained considerable attentions due to its high efficiency and low energy consumption. Zeolite imidazolate framework (ZIF) membranes have drawn intense interest due to their zeolite-like properties such as permanent porosity, uniform pore size and exceptional thermal and chemical stability. It is rather challenged to prepare well-intergrown Co-based zeolitic imidazolate frameworks (ZIFs) membranes on porous α-Al₂O₃ tubes since Co-based ZIFs prefer to form crystals in the synthesis solution rather than grow as membrane layer on the support surface. In this work, we report the preparation of high-quality ZIF-9 membrane with high H₂/CO₂ selectivity and excellent thermal stability by using 3-aminopropyltriethoxysilane (APTES) as a covalent linker to modify the α-Al₂O₃ tube. Due to the formation of covalent bonds between APTES and ZIF-9, ZIF-9 nutrients are bound to the support surface, thus promoting the growth of dense and phase-pure ZIF-9 membrane with a thin thickness of about 4.0 μm. The gas separation performances of the ZIF-9 membrane were evaluated by single gas permeation and mixture gas separation of H₂/CO₂, H₂/N₂ and H₂/CH₄, respectively. The mixture separation factors of H₂/CO₂, H₂/CH₄, and H₂/N₂ of the ZIF-9 membrane are 21.5, 8.2 and 14.7, respectively, which by far exceeds corresponding Knudsen coefficients. Moreover, the as-prepared ZIF-9 membrane exhibits excellent stability at a relatively broad range of operating temperature, which is beneficial for the industrial application of hydrogen separation or further membrane reactor.     

The role of viscoelasticity on heterogeneous stress fields at frictional interfaces

We investigate the evolution of heterogeneous stress states along frictional interfaces. Using finite-element simulations, we model the occurrence of precursory slip sequences on a deformable-deformable as well as a deformable–rigid interface between two solids. Every interface rupture creates a stress concentration at its arrest position and erases the stress concentrations produced by previous slip events. While the interface is sticking perfectly between two slip events, erased stress concentrations reappear and survive several cycles of ruptures. Such reestablished stress concentrations are smaller than they were before the rupture. We show that the decrease rate of these stress concentrations is exponential with respect to the number of subsequent events and that the bulk viscoelasticity is at the origin of this history effect. During a slip event, the friction tractions at the interface change almost instantaneously, which leads, between two ruptures, to a relaxation-resembling viscous effect that restores the stress concentration. We describe the decrease rate analytically and highlight that it is proportional to the ratio of the viscous over the instantaneous Young’s moduli, and illustrate it by varying the material properties in our simulations.     

Surface energy and separation mechanics of droplet interface phospholipid bilayers

Droplet interface bilayers are a convenient model system to study the physio-chemical properties of phospholipid bilayers, the major component of the cell membrane. The mechanical response of these bilayers to various external mechanical stimuli is an active area of research because of its implications for cellular viability and the development of artificial cells. In this article, we characterize the separation mechanics of droplet interface bilayers under step strain using a combination of experiments and numerical modelling. Initially, we show that the bilayer surface energy can be obtained using principles of energy conservation. Subsequently, we subject the system to a step strain by separating the drops in a step-wise manner, and track the evolution of the bilayer contact angle and radius. The relaxation time of the bilayer contact angle and radius along with the decay magnitude of the bilayer radius were observed to increase with each separation step. By analysing the forces acting on the bilayer and the rate of separation, we show that the bilayer separates primarily through the peeling process with the dominant resistance to separation coming from viscous dissipation associated with corner flows. Finally, we explain the intrinsic features of the observed bilayer separation by means of a mathematical model comprising the Young–Laplace equation and an evolution equation. We believe that the reported experimental and numerical results extend the scientific understanding of lipid bilayer mechanics, and that the developed experimental and numerical tools offer a convenient platform to study the mechanics of other types of bilayers.