Recombinant cellulose crosslinking protein: a novel paper-modification biomaterial

Cellulose-binding domains have been isolated from various cellulases, and proteins, which lack hydrolytic activity. The hypothesis that a cellulose-binding domain can be used to alter surface and mechanical properties of paper was tested. Two cellulose-binding domains from Clostriium cellulovorans were fused to form a cellulose crosslinking protein (CCP). The recombinant bifunctional cellulose-binding protein was expressed in E. coli, appliedby immersion onto Whatman cellulose filter paper, and its mechanical properties were tested. The purified protein improved the treated paper's mechanical properties (tensile strength, brittleness, Young's modulus and energy to break). In addition, cellulose crosslinking protein treatment was shown to transform filter paper into a more water-repellent paper. The binding of cellulose-binding domains to cellulose under a wide range of envi-ronmentalconditions, without the need for chemical reactions, and its biodegradability make them attractive moieties for the design of a new class of paper-modification materials.p>     

燃料电池聚合物电解质膜的研究进展

本文根据聚合物电解质膜燃料电池操作温度、使用的电解质和燃料的不同,将其分为高温质子交换膜燃料电池、低温质子换膜燃料电池、直接甲醇燃料电池和阴离子交换膜燃料电池,综述了它们所用电解质膜的最新进展.第一部分简要介绍了这4种燃料电池的优点和不足.第二部分首先介绍了Nafion膜的结构模型,并对平行柱状纳米水通道模型在介观尺度上进行了修正;接着分别对应用于不同燃料电池的改性膜的改性思路作了分析;最后讨论了用于不同燃料电池的新型质子交换膜的研究,同时列举了性能突出的改性膜和新型质子交换膜.第三部分介绍了阴离子交换膜的研究现状.第四部分对未来聚合物电解质膜的研究作了展望.     

Investigation of mechanical properties of polyvinyl chloride-polyethylene oxide (PVC-PEO) based polymer electrolytes for lithium polymer cells

Polymer electrolytes composed of a blend of polyvinyl chloride-polyethylene oxide (PVC-PEO) as a host polymer, lithium triflate (LiCF₃SO₃) as a salt, mixture of ethylene carbonate (EC) and dibuthyl phthalate (DBP) as plasticizers and silica (SiO₂) as the nanocomposite filler were studied. Results suggest that PVC-PEO blending exhibits improved mechanical strength compared to that of pure PEO. The introduction of LiCF₃SO₃ changes the mechanical properties of PVC-PEO blends from hard and brittle to soft and tough. In PVC-PEO:LiCF₃SO₃ (70:30) system, the Young’s modulus value decreases from 5.30 × 10⁻¹ MPa to 4.78 × 10⁻⁴ MPa and the elongation at peak value increases from 3.71 mm to 32.09 mm with the incorporation of DBP and EC. The deteriorated mechanical properties with the addition of plasticizers are overcome with the addition of SiO₂ as nanocomposite filler. In PVC-PEO-LiCF₃SO₃-DBP-EC system, the addition of 5% SiO₂ increases the Young’s modulus value from 4.78 × 10⁻⁴ MPa to 1.51 × 10⁻³ MPa. The improvement of the mechanical properties reveals greater dispersion of SiO₂ particles in PVC-PEO blend based polymer electrolytes. In practical lithium polymer cells, inorganic fillers are frequently added to improve the mechanical strength of the electrolyte films.     

Improving protonic conduction of membranes for polymer electrolyte fuel cells

Method for the modification of proton-conducting Nafion membranes by using a zirconium citrate one-substituted salt, aimed at the improving of characteristics of membranes for polymer-electrolyte-based fuel cells, is suggested. In the method, the membrane is impregnated first with zirconyl chloride and then with citric acid; an insoluble sol is thus formed in the membrane pores. The impregnation is carried out in ultrasound bath, using an isopropyl alcohol-water solvent, to make it more rapid and uniform. It is shown that the impregnation lowers the real component of the membrane impedance. The discharge characteristics of the impregnated and nonimpregnated membranes are compared.     

Experimental and molecular simulating study on promoting electrolyte-immersed mechanical properties of cellulose/lignin separator for lithium-ion battery

Lithium-ion batteries have been developing intensively and earn an unprecedented reputation, yet advanced performance and safety issue still require considerable investigation. Separator is vital to comprehensive properties of batteries, where the mechanical properties are key to breaking through of new-type separator. Unfortunately, electrolyte submersion has caused damage to strength of cellulose separator. Whereupon, in this work, cellulose separator is optimized by introducing lignin particles to promote electrolyte-immersed mechanical strength. Experiments are conducted concerning surface morphology, contact angle, porosity, electrolyte uptake, mechanical properties and electrochemical performance. Molecular simulation is implemented to explore the mechanism of tensile behavior of cellulose and lignin subjected to electrolyte solvents. Experimental results confirm positive effect of lignin addition in improving mechanical properties and simultaneously maintaining impressive electrochemical performance of the cellulose/lignin composites separators. Besides, lignin addition amount of 2.5% and 5% is recommended to achieve promising overall properties. Molecular simulation has successfully unveiled that weakening of cellulose separator submerged in electrolyte is resulted by the deformed cellulose amorphous region and the promoting effect of adding lignin is contributed from the new hydrogen bonds generated between cellulose and lignin molecules. Hopefully, this work provides novel insight on preparing remarkable separator and mechanism of materials behavior.     

Chitosan‐based composite membranes containing chitosan‐coated carbon nanotubes for polymer electrolyte membranes

Considering the poor dispersion and inert ionic conduction ability of carbon nanotubes (CNTs), functionalization of CNTs is a critical issue for their application in polymer electrolyte membranes. Herein, CNTs were functionalized by the polyelectrolyte, chitosan (CS), via a facile noncovalent surface‐deposition method. The obtained CS‐coated CNTs (CS@CNTs) were then incorporated into the CS matrix and fabricated composite membranes. The CS coating can enhance the compatibility between CNTs and the matrix, thus ensuring the homogenous dispersion of CS@CNTs and effectively improved the mechanical properties of the composites. Moreover, the CS coating can make CS@CNTs act as an additional proton‐conducting pathway through the membranes. The CS/CS@CNTs‐1 composite shows the highest proton conductivity of 3.46 × 10⁻² S cm⁻¹ at 80°C, which is about 1.5‐fold of the conductivity of pure CS membrane. Consequently, the single cell equipped with CS/CS@CNTs‐1 membrane exhibits a peak power density of 47.5 mW cm⁻², which is higher than that of pure CS (36.1 mW cm⁻²).     

Effects of polymer concentration and coagulation temperature on the properties of regenerated cellulose films prepared from LiOH/urea solution

Aqueous 5 wt% LiOH/12 wt% urea solution pre-cooled to −12 °C has a more powerful ability to dissolve cellulose compared to that of NaOH/urea and NaOH/thiourea solution system. The influences of the cellulose concentration and coagulation temperature on the structure, pore size and mechanical properties of the cellulose films prepared from LiOH/urea system were investigated. The cellulose films exhibited good mechanical properties either at wet or dry state and their pore size and water permeability at wet state can be controlled by changing the cellulose concentration or coagulation temperature. With a decrease of the coagulation temperature, the mechanical properties and optical transmittance of the cellulose films enhanced, as a result of the formation of relative smaller pore size and denser structures. This work provided a promising way to prepare cellulose films with different pore sizes at wet state and good physical properties at dry state.     

Alkaline Zn-air and Al-air cells based on novel solid PVA/PAA polymer electrolyte membranes

High ionic conducting solid polymer electrolyte membranes (SPEM) had been successfully prepared from poly(vinyl alcohol) (PVA) and poly(acrylic acid) (PAA). The solution casting method yielded highly hydrophilic membranes with uniform structure that were suitable for electrochemical applications. The room temperature ionic conductivity of the alkaline PVA/PAA polymer electrolyte membranes was in the range of 0.142–0.301 S cm⁻¹ depending on the composition. The cyclic voltammetry analysis was carried out using Zn|SPEM|Zn and Al|SPEM|Al cells. The analysis results revealed the excellent electrochemical stability of these newly developed alkaline solid PVA/PAA polymer electrolyte membranes. Metal-air fuel cells were also prepared from the alkaline solid PVA/PAA polymer electrolyte membranes. The electrochemical cell performance was evaluated based on Zn-air and Al-air cells at C/10 and C/5 discharge rates. The experimental results exhibited high percent of utilization for metal powders at room temperature. It was up to 90% for Zn-air cell when assembled with PVA:PAA = 10:7.5 polymer electrolyte membrane and discharged at C/10 rate. The power density could be as high as 50 mW cm⁻² at room temperature. However, the cell percent utilization was reduced to 73% with the same composition electrolyte membrane when C/5 discharge rate was tested.     

A novel sandwiched membrane as polymer electrolyte for application in lithium-ion battery

A novel kind of sandwiched polymer membrane was prepared, which consists of two outer layers of electrospun poly(vinyl difluoride) (PVDF) fibrous films and one inner layer of poly(methyl methacrylate) (PMMA) film. Its characteristics were investigated by scanning electron microscopy and X-ray diffraction. The membrane can easily absorb non-aqueous electrolyte to form gelled polymer electrolytes (GPEs). The resulting gelled polymer electrolytes had a high ionic conductivity up to 1.93 × 10⁻³ S cm⁻¹ at room temperature, and exhibited a high electrochemical stability potential of 4.5 V (vs. Li/Li⁺). It is of great potential application in polymer lithium-ion batteries.     

Mechanical properties of Nafion and titania/Nafion composite membranes for polymer electrolyte membrane fuel cells

Measurements of the mechanical and electrical properties of Nafion and Nafion/titania composite membranes in constrained environments are reported. The elastic and plastic deformation of Nafion‐based materials decreases with both the temperature and water content. Nafion/titania composites have slightly higher elastic moduli. Thecomposite membranes exhibit less strain hardening than Nafion. Composite membranes also show a reduction in the long‐time creep of ～40% in comparison with Nafion. Water uptake is faster in Nafion membranes recast from solution in comparison with extruded Nafion. The addition of 3–20 wt % titania particles has minimal effect on the rate of water uptake. Water sorption by Nafion membranes generates a swelling pressure of ～0.55 MPa in 125‐μm membranes. The resistivity of Nafion increases when the membrane is placed under a load. At 23 °C and 100% relative humidity, the resistivity of Nafion increases by ～15% under an applied stress of 7.5 MPa. There is a substantial hysteresis in the membrane resistivity as a function of the applied stress depending on whether the pressure is increasing or decreasing. The results demonstrate how the dynamics of water uptake and loss from membranes are dependent on physical constraints, and these constraints can impact fuel cell performance. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2327–2345, 2006     

Monitoring the mechanical properties of the solid electrolyte interphase(SEI) using electrochemical quartz crystal microbalance with dissipation

Stable solid electrolyte interphase(SEI) has been well established to be critical for the reversible operation of Li(ion) batteries,yet our understanding of its mechanical properties currently remains incomplete.Here,we used an electrochemical quartz crystal microbalance combined with dissipation monitoring(EQCM-D) to investigate SEI formation.By quantitatively estimating in-situ,the change in mass,shear modulus,and viscosity of the SEI,we show that the SEI formation in propylene carbonate(PC)-and ethylene carbonate/diethyl carbonate(EC/DEC)-based electrolytes involves the growth of a rigid laye r followed by a viscoelastic layer,whereas a distinct "one-layer" rigid model is applicable to the SEI formulated in tetraethylene glycol dimethyl ether(TEGDME)-based electrolyte.With the continuous formation of the SEI,its shear modulus decreases accompanied by an increase in viscosity.In TEGDME,the lightest/thinnest SEI(mass lower than in PC by a factor of nine) yet having the greatest stiffness(more than five times that in PC) is obtained.We attribute this behavior to differences in the chemical composition of the SEIs,which have been revealed by tracking the mass-change-per-mole-of-electrontransferred using EQCM-D and further confirmed by X-ray photoelectron spectroscopy.     

Influence of grafting solvents on the properties of polymer electrolyte membranes prepared by γ-ray preirradiation method

The effect of grafting solvents, such as isopropanol (iPrOH), tetrachloroethane (TCE), tetrahydrofuran (THF), and toluene, on the preparation of poly(ethylene-co-tetrafluoroethylene)-graft-poly(styrene sulfonic acid) (ETFE-g-PSSA) electrolyte membranes by the γ-ray preirradiation grafting method was investigated. It was found that the iPrOH can drastically accelerate the grafting, resulting in a higher degree of grafting. However, for an appropriate degree of grafting of about 50%, the sulfonic acid groups in the ETFE-g-PSSA membrane prepared with the iPrOH were mainly distributed near the membrane surface, as shown by low proton conductivity in the membrane thickness direction. In contrast to this result, the ETFE-g-PSSA membranes prepared with the THF, toluene and TCE exhibited uniform distribution of the sulfonic acid groups in the membrane. Especially, in the case of the TCE grafting solvent, the chemical stability of the resultant electrolyte membrane was clearly higher than those prepared with the other grafting solvents.     

Isomeric effect of sulfonated poly(arylene ether)s comprising dihydroxynaphthalene on properties for polymer electrolyte membranes

Polymer electrolyte membranes (PEMs) made of sulfonated poly(arylene ether)s consisted of 3,3′‐disulfo‐4,4′‐dichlorodiphenylsulfone disodium salt, 2,6‐dichlorobenzonitrile, and one of three dihydroxynaphthalene isomers (2,6‐, 2,7‐, and 1,5‐dihydroxynaphthalene, abbreviated as 2,6‐N, 2,7‐N, and 1,5‐N, respectively) were prepared with similar level of inherent viscosity and ion exchange capacity, and structural effect of the catenation in dihydroxynaphthalene isomers on membrane properties was compared. In the case of membranes for PEM fuel cell application with relatively high ion exchange capacity around 2.1 mequiv/g, three copolymers showed almost the same proton conductivity; however, swelling in water increased with the following order: 1,5‐N < 2,6‐N < 2,7N. In the case of direct methanol fuel cell membranes with lower ion exchange capacity around 1.5 mequiv/g, no remarkable difference in proton conductivity was also observed in three isomeric copolymers and swelling property and methanol permeability were lower in 1,5‐N and 2,6‐N copolymers than 2,7‐N copolymer. These tendencies show that higher rigidity or energy barrier for conformational change of polymer chain gives better performance of PEM for fuel cells with superior dimensional stability. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Enhanced electrochemical properties of a novel polyvinyl formal membrane supporting gel polymer electrolyte by Al2O3 modification

Polyvinyl formal (PVFM)‐based dense polymer membranes with nano‐Al₂O₃ doping are prepared via phase inversion method. The membranes and also their performances as gel polymer electrolytes (GPEs) for lithium ion battery are studied by field emission scanning electron microscope, X‐ray diffraction, differential scanning calorimetry, mechanical strength test, electrolyte uptake test, electrochemical impedance spectroscopy, cyclic voltammetry, and charge–discharge test. The polymer membrane with 3 wt % nano‐Al₂O₃ doping shows the improved mechanical strength of 12.16 MPa and electrolyte uptake of 431.25% compared with 10.47 MPa and 310.59% of the undoped sample, respectively. The membrane absorbs and swells liquid electrolyte to form stable GPE with ionic conductivity of 4.92 × 10^?4 S cm^?1 at room temperature, which is higher than 1.77 × 10^?4 S cm^?1 of GPE from the undoped membrane. Moreover, the Al₂O₃‐modified membrane supporting GPE exhibits wide electrochemical stability window of 1.2–4.8 V (vs. Li/Li⁺) and good compatibility with LiFePO₄ electrode, which implies Al₂O₃‐modified PVFM‐based GPE to be a promising candidate for lithium ion batteries. © 2014 Wiley Periodicals, Inc. J. Polym. Sci. Part B: Polym. Phys. 2014 , 52, 572–577     

Structure and properties of composites of highly crystalline cellulose with polypropylene: Effects of polypropylene molecular weight

Composite of highly crystalline fibrous cellulose (CE) and polypropylene (PP) of different molecular weights () was prepared via melting-mixing, maleic anhydride grafted polypropylene (MAPP) was used as a compatibilizer. And the effects of molecular weight of PP on the properties of the composites were investigated. Through the studying of mechanical properties, dynamic mechanical properties, melting and crystallization behaviors, thermo-oxidative properties, water absorption behaviors, and the morphology of the composites, it was found that PP with higher molecular weight revealed stronger interfacial interaction with cellulose in the composites. Compared with the lower molecular weight, the composites derived from higher molecular weight of PP exhibited stronger tensile strength at the same cellulose content.     

Self-reinforced composites obtained by the partial oxypropylation of cellulose fibers. 2. Effect of catalyst on the mechanical and dynamic mechanical properties

This work describes the partial oxypropylation of filter paper cellulose fibers, employing two different basic catalyst, viz., potassium hydroxide and 1,4-diazabicyclo [2.2.2] octane, to activate the hydroxyl groups of the polysaccharide and thus provide the anionic initiation sites for the “grafting-from” polymerization of propylene oxide. The success of this chemical modification was assessed by FTIR spectroscopy, X-ray diffraction, scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis and contact angle measurements. The study of the role of the catalyst employed on the extent of the modification and on the mechanical properties of the ensuing composites, after hot pressing, showed that both the Brønsted and the Lewis base gave satisfactory results, without any marked difference.     

Synthesis of sulfonated poly(imidoaryl ether sulfone) membranes for polymer electrolyte membrane fuel cells

New sulfonated poly(imidoaryl ether sulfone) copolymers derived from sulfonated 4,4′‐dichlorodiphenyl sulfone, 4,4′‐dichlorodiphenyl sulfone, and imidoaryl biphenol were evaluated as polymer electrolyte membranes for direct methanol fuel cells. The sulfonated membranes were characterized with Fourier transform infrared spectroscopy, thermogravimetric analysis, and proton nuclear magnetic resonance spectra. The state of water in the membranes was measured with differential scanning calorimetry, and the existence of free water and bound water was discussed in terms of the sulfonation level. The 10 wt % weight loss temperatures of these copolymers were above 470 °C, indicating excellent thermooxidative stability to meet the severe criteria of harsh fuel‐cell conditions. The proton conductivities of the membranes ranged from 3.8 × 10^?2 to 5 × 10^?2 S/cm at 90 °C, depending on the degree of sulfonation. The sulfonated membranes maintained the original proton conductivity even after a boiling water test, and this indicated the excellent hydrolytic stability of the membranes. The methanol permeabilities ranged from 1.65 × 10^?8 to 5.14 × 10^?8 cm²/s and were lower than those of other conventional sulfonated ionomer membranes, particularly commercial perfluorinated sulfonated ionomer (Nafion). The properties of proton and methanol transport were discussed with respect to the state of water in the membranes. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5620–5631, 2005