Membrane Design for Direct Ethanol Fuel Cells: A Hybrid Proton‐Conducting Interpenetrating Polymer Network

A series of hybrid proton‐conducting membranes with an interpenetrating polymer network (IPN) structure was designed with the direct ethanol fuel cell (DEFC) application in mind. In these membranes, glutaraldehyde crosslinked poly(vinyl alcohol) (PVA) were interpenetrated with the copolymer of 2‐acrylamido‐2‐methyl‐propanesulphonic acid (AMPS) and 2‐hydroxyethyl methacrylate (HEMA) crosslinked by poly(ethylene glycol) dimethacrylate (PEGDMA). Silica from the in situ sol–gel hydrolysis of tetraethyl orthosilicate (TEOS) was uniformly dispersed in the polymer matrix. The membranes fabricated as such had ion exchange capacities of 0.84–1.43 meq g^–1 and proton conductivities of 0.02–0.11 S cm^–1. The membranes exhibited significantly lower fuel permeabilities than that of Nafion. In a manner totally unlike Nafion, fuel permeabilities were lower at higher fuel concentrations, and were lower in ethanol than methanol solutions. These behaviours are all relatable to the unique swelling characteristics of PVA (no swelling in ethanol, partial swelling in methanol and extensive swelling in water) and to the fuel blocking and swelling suppression properties of silica particles. The membranes are promising for DEFC applications since a high concentration of fuel may be used to reduce fuel crossover and to improve the anode kinetics for a resultant increase in both the energy and power densities of the fuel cell.     

聚乙烯醇/聚丙烯酸钠/Zn0.2Fe2.8O4复合水凝胶的制备及其溶胀行为

将水溶性纳米Zn0.2Fe2.8O4(ZFO)粒子、用氢氧化钠(NaOH)中和的丙烯酸(PAAS)加入一定量的聚乙烯醇(PVA)水溶液中分散均匀,再加入引发剂过硫酸钾、交联剂N,N’-亚甲基双丙烯酰胺引发聚合,制备了PVA/PAAS/ZFO水凝胶。采用傅里叶红外光谱仪(FTIR)、透射电子显微镜(TEM)对其组成和结构进行表征,并系统研究了复合水凝胶在不同溶剂中的溶胀性能。结果表明,纳米ZFO粒子均匀分散在PVA/PAAS凝胶网络中,纳米ZFO粒子的加入使水凝胶的溶胀速率和平衡溶胀度先增加后减小,在纳米ZFO含量为1%时达到最大;在不同浓度的电解质溶液和不同pH值的溶液中进行溶胀时,水凝胶表现出良好的离子浓度和p H刺激响应性。     

Influence of microstructure on dynamic mechanical behaviour of polymeric composites with complex inclusions

The dynamic mechanical properties of polymeric composites composed of crosslinked poly(n-butyl methacrylate) continuous-phase and crosslinked polystyrene dispersed phase with poly(n-butyl methacrylate) occlusion have been examined. The composite samples were prepared by mixing and swelling of the crosslinked polystyrene particles obtained by emulsifier-free emulsion polymerization, with n-butyl methacrylate and crosslinker, then photopolymerizing at the desired temperature. The composite microstructure was varied by either changing the crosslink density of polystyrene, and temperature of swelling and polymerization, or using different sizes and contents of polystyrene particles. The tan δ peak positions of composite samples are found to be dependent on morphological characteristics as well as the properties of the dispersed phase while the peak height seems to be dependent on the effective volume of dispersed phase composed of polystyrene and poly(n-butyl methacrylate) occlusions. Special attention has been paid to the comparison among composite, homonetworks, and bulk IPN samples that are expected to have the identical structure with the complex dispersed phase of the composite samples. © 1993 John Wiley & Sons, Inc.     

Comparison of fuel properties and emission characteristics of two- and three-phase emulsions prepared by ultrasonically vibrating and mechanically homogenizing emulsification methods

Emulsions have long been considered as an alternative fuel for combustion equipment in order to achieve better fuel economy and pollution reduction. While a mechanical homogenizing method is frequently used to prepare emulsions, the use of an ultrasonic emulsification method to do so is still rather limited, and is mostly applied to two-phase emulsions only. Hence, two-phase W/O and three-phase O/W/O emulsions, prepared by a mechanical homogenizer and an ultrasonic vibrator, respectively, were prepared and used as engine fuel. The emulsion properties, engine performance, and engine emission characteristics between these two emulsification methods were measured and compared. The potential of the ultrasonic emulsification method was also evaluated. The experimental results show that the emulsions prepared by the ultrasonic vibrator appeared to have more favorable emulsification characteristics such as smaller dispersed water droplets that were distributed more uniformly in the continuous oil phase, lower separation rate of water droplets from the continuous phase of diesel fuel and thus a lower separating rate of the dispersed water droplets from the emulsion, larger emulsion stability, and larger emulsion viscosity than the emulsions produced using a mechanical homogenizer. In addition, a larger content of water was emulsified when the emulsion was prepared using the ultrasonic vibrator than the mechanical homogenizer. The emulsions prepared by the ultrasonic vibrator also had a lower fuel consumption rate, lower bsfc, and significantly lower CO emission while at the same time having a larger black smoke opacity. When comparing the two-phase W/O and the three-phase O/W/O emulsions prepared by either the ultrasonic vibrator or the mechanical homogenizer, the two-phase W/O emulsions appeared to have a lower fuel consumption rate, bsfc, CO, and a lower black smoke opacity than the three-phase O/W/O emulsions, regardless of whether they were prepared by ultrasonic vibrator or mechanical homogenizer.     

Effects of NOx-inhibitor agent on fuel properties of three-phase biodiesel emulsions

Biodiesel is one of the more promising alternative clean fuels to fossil fuel, which can reduce the emissions of fossil fuel burning, and possibly resolve the energy crisis caused by the exhaustion of petroleum resources in the near future. The burning of biodiesel emits much less gaseous emissions and particulate matter primarily because of its dominant combustion efficiency. However, the high oxygen content in biodiesel not only promotes the burning process but also enhances NO_x formation when biodiesel is used as fuel. Biodiesel emulsion and the additive of NO_x-inhibitor agent are considered to reduce levels of NO_x emissions in this experimental study. The biodiesel was produced by transesterification reaction accompanied with peroxidation process. A three-phase biodiesel emulsion of oil-in water drops-in oil (O/W/O) and an O/W/O biodiesel emulsion containing aqueous ammonia were prepared afterwards. The effect of the existence of NO_x-inhibitor agent on the fuel properties and the emulsion characteristics of the O/W/O biodiesel emulsions were investigated. The experimental results show that the burning of the O/W/O biodiesel emulsion and the O/W/O biodiesel emulsion containing aqueous ammonia had larger fraction of fuel burnt and thus larger heat release than the neat biodiesel if water content is not considered for the calculation of heating value. The addition of aqueous ammonia within the dispersed phase of the O/W/O biodiesel emulsion appeared to deteriorate the emulsification characteristics. A smaller quantity of emulsion and greater kinematic viscosity were formed while a larger carbon residue and actual reaction-heat release also appeared for this O/W/O biodiesel emulsion. Aqueous ammonia in the O/W/O biodiesel emulsion produces a higher pH value as well. In addition, the number as well as the volumetric fraction of the dispersed water droplets is reduced for the O/W/O biodiesel emulsion that contains aqueous ammonia.     

Effects of pre-treatment in air microwave plasma on the structure of CNTs and the activity of Ru/CNTs catalysts for ammonia decomposition

Carbon nanotubes (CNTs) were treated in air microwave plasma at three different microwave powers 80, 100 and 150 W. The effects of the treatment on the structure of CNTs and the dispersion of Ru particles supported on CNTs were evaluated using XRD, N₂ physisorption, FTIR, TPD, XPS, TEM and CO chemisorptions. The results show that the bulk structure and the texture of the CNTs were unchanged, but phenolic hydroxyls and carboxyls appeared on the surface. The total concentration of these groups increases with the microwave power to 100 W, then decreases. The phenolic hydroxyls and carboxyls on the CNTs interact with Ru ions during the preparation of Ru/CNTs resulting in highly dispersed Ru particles. The activity of Ru/CNTs for ammonia decomposition depends on the dispersion of Ru particles, but is negatively affected by any remaining oxygen-containing groups on the surface.     

水凝胶-水凝胶复合材料的制备与表征

将聚乙二醇400(PEG400)溶胀的交联N-乙烯吡咯烷酮(NVP)水凝胶微粒浸渍在含有引发剂过氧化苯甲酰(BPO)的甲基丙烯酸-2-羟基乙酯(HEMA)单体中并加热引发聚合反应,制备水凝胶-水凝胶复合材料,研究了产物的溶胀行为,并采用SEM、DSC对产物进行了表征。结果表明,水凝胶-水凝胶复合材料的饱和含水量随交联NVP水凝胶颗粒的含量及饱和含水量增大而增大,两种水凝胶之间的界面结构可分为包埋、部分互穿网络以及完全部分互穿网络等三种,其原因在于HEMA单体部分进入交联NVP水凝胶微粒并进行原位聚合的程度不同;处于分散相的水凝胶与处于连续相的水凝胶的吸水倍率不同,导致水凝胶-水凝胶复合材料吸水溶胀时不同相结构之间互相制约,处于分散相的水凝胶的大分子链不能充分伸展,非冻结水的熔融峰被自由水的熔融峰掩盖,表现为DSC谱图上非冻结水的熔融峰被自由水的熔融峰掩盖。     

Preparation of submicron-sized porous titanium oxide particles by the swelling process

A method to prepare submicron-sized porous titanium oxide (TiO₂) particles is studied in this work. Polystyrene (PS) template particles were prepared by emulsifier-free emulsion polymerization. The polymer templates dispersed in the aqueous solution have been used for entrapping titanium(IV) isopropoxide (TTIP), by the swelling process in a suitable solvent mixture containing a swelling solvent (good solvent or poor solvent), a TiO₂ precursor (TTIP), and a chelating agent (AcAc), within the polymer templates, followed by hydrolysis/condensation reaction of TTIP confined in PS template particles by the addition of the chelating agent. The influence of various reaction parameters, such as mixtures of different weight ratios between the PS particles and desiccative TTIP, AcAc amounts, and the swelling solvent amounts and type, on the size, bulk, and composition of the particles was investigated. Porous TiO₂ particles have been prepared by thermal decomposition of the PS templates at 500 °C.     

Electrically conductive hydrogel composites made of polyaniline nanoparticles and poly(N-vinyl-2-pyrrolidone)

A novel electrically conductive composite material, consisting of polyaniline (PANI) nanoparticles dispersed in a polyvinyl pyrrolidone (PVP) hydrogel, was prepared ‘in situ’ by water dispersion polymerisation (DP) of aniline using PVP as steric stabiliser, followed by γ-irradiation induced crosslinking of the PVP component. Conversion yield of aniline into PANI particles was determined via HPLC and gas chromatography, while structural confirmation of the synthesised polymer was sought by FTIR. Morphology and dimensions of PANI particles into the coloured, optically transparent hydrogel was determined by electronic microscopy; moreover, swelling behaviour of composite hydrogels in different buffer solutions was investigated by gravimetric measurements and compared to that of pure PVP hydrogels.Cyclic voltammetry experiments were carried out both on these hydrogels and on the parent aqueous dispersions, at different pH values of the suspending/swelling medium, while conductivity of the composite hydrogels was derived from Impedance Spectroscopy; in both cases results were compared to those relative to hydrogels containing commercial-grade PANI particles.     

Synthesis of polyacrylonitrile/polystyrene latex particles that contain platinum

Studies on the incorporation of highly dispersed platinum (Pt) nanoparticles into proton‐exchange membrane fuel cells (PEMFC) as a possible catalyst have gained tremendous attention in the past decade. The major obstacle to fully commercialize PEMFCs is the high cost of Pt as the catalyst. In this study, the incorporation of highly dispersed platinum molecules into poly(acrylonitrile) (PAN) or polystyrene (PS)/PAN latex particles was carried out to form a possible a catalyst precursor for fuel‐cell applications. Pt‐containing PAN/PS particles were prepared using miniemulsion polymerization. Both transmission electron microscopy (TEM) and induction coupled plasma (ICP) measurements indicated that Pt salt was encapsulated into PAN/PS copolymer latex particles. In addition, the encapsulation percentages of Pt salt are all above 90% for different PAN/PS ratios. Additional experiments have been carried out to convert these Pt molecules into nanoparticles and will be elaborated upon subsequent studies. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41933     

Water-Swellable Thermoplastic Vulcanizates Based on Ethylene-vinyl Acetate Copolymer/Cross-linked Sodium Polyacrylate/Chlorinated Polyethylene

A novel water-swellable rubber (WSR) was prepared by dynamically vulcanizing ethylene-vinyl acetate copolymer (EVA)/chlorinated polyethylene (CPE) blends where the cross-linked poly (sodium acrylate) (CPNaAA) was used as a super water-absorbent resin and dispersed in the CPE rubber. Experimental results showed that the mechanical properties of TPVs decreased while the water-swelling ratio increased significantly with increasing of CPNaAA dosages, the swelling ratio of 60 phr CPNaAA TPVs reaching 746.1% at 93 h. Morphological study showed that the CPNaAA particles were dispersed randomly in the TPVs; Some significant gaps and large cavities could be found in the surface of dried TPVs.     

分散颗粒和超声场对鼓泡塔内传质性能的影响

用双电导探针气泡特征参数测量系统实时测定超声场与分散颗粒(活性炭)对鼓泡塔水+CO₂体系气泡Sauter直径和体积传质系数影响的变化规律。实验结果表明:无活性炭颗粒添加时,多频超声场比单频超声场更有利于提高体积传质系数,输入功率为100 W、组合超声频率为20-50-100 kHz时,体积传质系数增幅达40%~64%;加入活性炭颗粒后,体积传质系数随加入活性炭固含量的增大呈现先增大后逐渐减少的趋势,气泡Sauter直径变化规律相反,当体系中活性炭固含量为1.0 kg·m^-3时,传质增强最明显。体积传质系数随加入活性炭粒径的减小呈现增大的趋势。与无活性炭颗粒(d_s=0)比较,活性炭(固含率1.0 kg·m^-3)粒径d_s=38 μm时,液相体积传质系数在扣除吸附传质效果后仍增大1.58倍,同时引入超声场后,当组合超声频率为20-50-100 kHz,超声功率100 W时,液相体积传质系数增大2.02倍,可见超声场和分散颗粒对气液传质有显著的协同强化作用。     

Solvent swelling behavior of Permian-aged South African vitrinite-rich and inertinite-rich coals

Two South African coals similar in rank and age, but different in maceral composition, were studied using solvent swelling. Inertinite-rich Highveld coal (dominated by semifusinite) and vitrinite-rich Waterberg coal were evaluated for swelling extent and swelling rate using N-methylpyrrolidone (NMP) and CS₂/NMP. A stop-motion videography method was developed to study individual particle swelling behavior. This method allowed observation of overshoot and climbing-type swelling, as well as swelling kinetics. Single-particle swelling experiments showed that both coals exhibited overshoot-type and climbing-type swelling. The inertinite-rich coal swelled much faster (in both solvents) than the vitrinite-rich coal. The swelling in CS₂/NMP was faster for both coals. Kinetic parameters showed that solvent swelling was governed by relaxation (super-Case II relaxation) of the coal structure. X-ray computed tomography was conducted over a 50 h swelling period in NMP for single particles of each coal. Anisotropic swelling was observed in all the particles (swelling greater perpendicular to the bedding plane than parallel to it). The subtle changes in molecular structure, fine structural and physical differences resulted in significant differences in solvent swelling behavior.     

Novel one‐step synthesis of acrylonitrile butadiene rubber/bentonite nanocomposites with (3‐Mercaptopropyl)trimethoxysilane as a compatilizer

Acrylonitrile butadiene rubber (NBR)/bentonite (Bt) nanocomposites were synthesized by an one‐step method in NBR latex with (3‐Mercaptopropyl)trimethoxysilane (MPTMS) as a compatilizer. The nanocomposites were compounded with curing additives and then vulcanized. The prepared vulcanizates were characterized by Fourier transform infrared spectroscopy (FTIR) and X‐ray diffraction (XRD). The curing properties and mechanical properties were also investigated. The thermal properties were studied with thermal gravimetric analysis (TGA) and differential scanning calorimetry (DSC). The morphology was investigated by field emission‐scanning electron microscopy (FE‐SEM). By swelling test, the swelling ratio and the crosslinking density were achieved. The hydrolyzation and condensation of MPTMS was identified by FTIR while the intercalated/exfoliated structure of Bt was determined by XRD. It was evident that the mechanical properties of the nanocomposites were significantly improved compared with the neat NBR. The well‐dispersed bentonite particles and effects of MPTMS were supported by the images from FE‐SEM. The results of TGA showed that the fastest weight‐loss temperature (T_max) was elevated by over 10°C for the nanocomposites compared with the neat NBR, indicating an enhanced thermal stability. By swelling test, the swelling ratio was determined, decreased to 139% for the optimized NBR/MPTMS/Bt nanocomposites compared with 210% for neat NBR. POLYM. COMPOS., 36:1693–1702, 2015. © 2014 Society of Plastics Engineers     

Thermal degradation of the support in carbon-supported platinum electrocatalysts for PEM fuel cells

The cathode catalyst layer in proton exchange membrane (PEM) fuel cells can contain nanometer-sized platinum particles dispersed on a high surface area carbon. In order to assess support stability, samples of carbon-supported catalysts were held at elevated temperatures under dry air conditions. The samples were weighed at regular intervals. These tests showed that the platinum particles were able to catalyze the combustion of the carbon support at moderate temperatures (125-195 °C). As the temperature increased, the rate of carbon combustion increased. The amount of carbon that was lost after extended oven exposure at a constant temperature was shown to depend on both the temperature and platinum loading. A simple first-order kinetic model was able to describe the results. With further work on a range of different carbon supports, this work is expected to help develop more stable catalyst supports for PEM fuel cells.     

Preparation of composite particles made from solid powders and wasted plastics by semichemical recycle method

Composite particles composed of solid powders and polymer were prepared by semichemical recycle of wasted plastics. Waste expanded polystyrene was used as raw materials of polymer matrix of composite particles. Both magnetite and silicon carbide powders were used as solid powders to give thermal and electric conductivity and magnetization, respectively. In the experiment, the oil‐phase dissolving expanded polystyrene was dispersed in fine droplets into the continuous water phase. Two kinds of powders were added at the same time or separately in the O/W dispersion. Composite particles were found to have the structure that polymer particle was covered with two kinds of solid powders. The mean diameter of composite particles and the content of each solid powder were strongly affected by the addition time when silicon carbide powder was added into the dispersion. Furthermore, it was found that the gradient adhesion layer due to two solid powders was able to be formed on the surface of polymer particle. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 483–488, 2003     

The quantitative analysis of nano-clay dispersion in polymer nanocomposites by small angle X-ray scattering combined with electron microscopy

The main objective of this work is to propose a new approach for the quantitative analysis of the degree of dispersion of clay particles in the polymer matrix by small angle X-ray scattering (SAXS) combined with electron microscopy. Due to the low temperature processibility and good thermal stability, poly[(butylene succinate)-co-adipate] (PBSA) was chosen as a model polymer matrix for this study. The nanocomposites of PBSA with four different weight percentages of organically modified montmorillonite (OMMT) loadings were prepared via melt-blending method. The dispersed structure of the clay particles in the PBSA matrix was studied by SAXS. Results show that the clay particles are nicely dispersed in the case of all nanocomposites. However, with a systematic increase in clay loading, the dispersed clay structure of the nanocomposites changes from a highly delaminated to a flocculated and then to a stacked intercalated one. The probability of finding neighboring clay particles in the PBSA matrix as well as their thickness was calculated using the Generalized Indirect Fourier Transformation technique developed by Glatter and the modified Caillé theory proposed by Zhang. The morphology of the nanocomposites was also extensively studied by scanning transmission electron microscopy (STEM). In the case of all nanocomposites, SAXS results were in good agreement with STEM observations. Finally, a correlation between the predicted morphology of nanocomposites and their melt-state rheological properties is reported.     

超高固含量水基聚氨酯分散体的合成理论与实践

综述了超高固含量聚氨酯分散体合成的理论和实践,以球状物体堆积密度数学模型分析了高分子乳液和分散体的极限浓度,以高分子分散体粒子存在水溶胀层的实验分析了分散体体积浓度和固含量的区别,从理论的角度分析了合成超高固含量聚氨酯分散体采用内乳化结合外乳化及采用连续瞬间分散工艺的必需性,简单介绍了国外超高固含量聚氨酯分散体的合成工艺。     

Application of Amorphous Boron Granulated With Hydroxyl‐ Terminated Polybutadiene in Fuel‐Rich Solid Propellant

Amorphous boron powder granulated with HTPB, whose particle diameter could be controlled, was prepared by mechanical mill method. It was found that amorphous boron powder could be granulated with HTPB binder to form B‐HTPB particles, whose median particle diameter (d₅₀) and specific surface area are in the range of 125.0–431.0 µm and 0.02–0.1 m² g⁻¹, respectively. The B‐HTPB particles could be dispersed in the HTPB binder with relatively low viscosity compared with direct addition of amorphous boron powder to the HTPB binder. The experimental results showed that the content of boron particles in a fuel‐rich propellant could be increased by addition of B‐HTPB particles and the combustion characteristics of the fuel‐rich solid propellant could be improved.     

Effects of emulsification variables on fuel properties of two- and three-phase biodiesel emulsions

Biodiesel has attractive fuel properties such as excellent biodegradability and lubricity, almost no emissions of sulfur oxides, PAH and n-PAH, reduced CO₂, PM and CO emission, superior combustion efficiency, etc. However, burning of biodiesel generally produces higher levels of NO_x emissions, primarily due to its high oxygen content. In this study, the emulsification technology has been considered to reduce the NO_x emission level of fossil fuel. Biodiesel, produced by means of transesterification reaction accompanied with a peroxidation process, was emulsified to form two-phase W/O and three-phase O/W/O emulsions. The effects of the emulsification variables such as hydrophilic lipophilic balance (HLB), and water content on the fuel properties and emulsion characteristics of W/O and O/W/O emulsions were investigated in this study. The experimental results show that the surfactant mixture with HLB = 13 produced the highest emulsification stability while HLB = 6 produced the lowest emulsification stability and the most significant extent of water–oil separation among the various HLB values for O/W/O biodiesel emulsion. The kinematic viscosity, specific gravity and carbon residual of the biodiesel emulsions were larger than those of the neat biodiesel. In addition, the W/O biodiesel emulsion was found to have a smaller mean droplet size, lower volumetric fraction of the dispersed phase than the O/W/O biodiesel emulsion, and the highest heating value among the test fuels, if the water content is deducted from the calculation of the heating value.