Polymer Electrolyte Membrane Fuel Cells (PEMFC) in Automotive Applications: Environmental Relevance of the Manufacturing Stage

This study presents a state of the art of several studies dealing with the environmental impact assessment of fuel cell (FC) vehicles and the comparison with their conventional fossil-fuelled counterparts, by means of the Life Cycle As-sessment (LCA) methodology. Results declare that, depending on the systems characteristics, there are numerous envi-ronmental advantages, but also some disadvantages can be expected. In addition, the significance of the manufac-turing process of the FC, more specifically the Polymer Electrolyte Membrane Fuel Cell (PEMFC) type, in terms of environmental impact is presented. Finally, CIEMAT’s role in HYCHAIN European project, consisting of supporting early adopters for hydrogen FCs in the transport sector, is

New conception in continuum theory of constitutive equation for anisotropic crystalline polymer liquids

A new continuum theory of the constitutive equation of co-rotational derivative type is developed for anisotropic viscoelastic fluid—liquid crystalline (LC) polymers. A new concept of simple anisotropic fluid is introduced. On the basis of principles of anisotropic simple fluid, stress behaviour is described by velocity gradient tensor and spin tensor instead of the velocity gradient tensor in the classic Leslie—Ericksen continuum theory. Analyzing rheological nature of the fluid and using tensor analysis a general form of the constitutive equ- ation of co-rotational type is established for the fluid. A special term of high order in the equation is introduced by author to describe the sp- ecial change of the normal stress differences which is considered as a result of director tumbling by Larson et al. Analyzing the experimental results by Larson et al., a principle of Non- oscillatory normal stress is introduced which leads to simplification of the problem with relaxation times. The special behaviour of non- symmetry of the shear stress is predicted by using the present model for LC polymer liquids. Two shear stresses in shear flow of LC polymer liquids may lead to vortex and rotation flow, i.e. director tumbling in the flow. The first and second normal stress differences are calculated by the model special behaviour of which is in agree- ment with experiments. In the research, the com- putational symbolic manipulation such as computer software Maple is used. For the anisotropic viscoelastic fluid the constitutive equation theory is of important fundamental significance.

Rheological property of low-damage,ideal packing,film-forming amphoteric/sulfonation polymer drilling fluids

Low-permeability dense reservoirs,including micro-fractured reservoirs,are commonly characterized by high content of clay substances,high original water saturation,high sensitivity to invasive fluids,high capillary pressure,complicated structure and anisotropic,high flow-resistance and micro pore throats etc,.Generally they also have lots of natural micro fractures,probably leading to stress sensibility.Main damaging factors in such reservoirs are water-sensibility and water-blocking caused by invasive fluids during drilling and production operations.Once damaged,formation permeability can rarely recovered.Numerous studies have shown that damaging extent of water-blocking ranges from 70% to 90%.Main damaging mechanisms and influencing factors of water-blocking were systematically analyzed.Also some feasible precaution or treating approaches of water-blocking were put forward.In a laboratory setting,a new multi-functional drilling fluid composed mainly of amphion polymer,sulfonation polymer,high effectively preventive water-blocking surfactants,ideal packing temporary bridging agents(TBA) and film-forming agents,etc.,were developed.New low-damage drilling fluids has many advantages,such as good rheological properties,excellent effectiveness of water-blocking prevention,good temporary plugging effect,low filtration and ultra-low permeability(API filtration≤5 mL,HTHP filtration≤10 mL,mud cake frictional coefficient≤0.14,permeability recovery>81%),can efficiently prevent or minimize damage,preserve natural formation and enhance comprehensive development-investment effect in TUHA Jurassic dense sandstone reservoir formation with low-permeability,the only one developing integrated condense gas field.Some references can be provided to similar reservoir formations.

A new constitutive theory for extrusion-extensional flow of anisotropic liquid crystalline polymer fluid

A new continuum theory of the constitutive equation of co-rotational derivative type was developed by the author for anisotropic viscoelastic fluid-liquid crystalline (LC) polymers (S.F. Han, 2008, 2010) . This paper is a continuation of the recent publication [1] to study extrusion-extensional flow of the fluid. A new concept of simple anisotropic fluid is introduced. On the basis of anisotropic simple fluid, stress behavior is described by velocity gradient tensor F and spin tensor W instead of the velocity gradient tensor D in the classic Leslie?Ericksen continuum theory. A special form of the constitutive equation of the co-rotational type is established for the fluid. Using the special form of the constitutive equation in components a computational analytical theory of the extrusion-extensional flow is developed for the LC polymer liquids - anisotropic viscoelastic fluid. Application of the constitutive theory to the flow is successful in predicting bifurcation of elongational viscosity and contraction of extrudate for LC polymer liquids–anisotropic viscoelastic fluid. The contraction of extrudate of LC polymer liquids may be associated with the stored elastic energy conversion into that necessary for bifurcation of elongational viscosity in extrusion extensional flow of the fluid.

Preparation of Fluoroalkyl End-Capped Oligomer/Cyclodextrin Polymer Composites: Development of Fluorinated Composite Material Having a Higher Adsorption Ability toward Organic Molecules

Fluoroalkyl end-capped vinyltrimethoxysilane oligomer [RF-(CH2CHSi(OMe)3)n-RF;RF = CF(CF3)OCF7, n = 2, 3;RF-(VM)n-RF] was applied to the preparation of fluoroalkyl end-capped vinyltrimethoxysilane oligomer/α-, β-, γ-cyclodextrin polymers (α-, β-, γ-CDPs) composites [RF-(VM-SiO2)n-RF/α-, β-, γ-CDPs] by the sol-gel reaction of the corresponding oligomer in the presence of the α-, β-, γ-CDPs under alkaline conditions. The RF-(VM-SiO2)n-RF/α-, β-, γ-CDPs composites thus obtained were found to give a good dispersibility toward the traditional organic media except for water, and were applied to the surface modification of glass to provide a sueperoleophilic/superhydrophobic characteristic on the modified surface, although the corresponding RF-(VM-SiO2)n-RF nanocomposites can give a usual oleophobic/superhydrophobic property on the surface. These composites powders were also found to be applicable to the packing material for the column chromatography to separate the mixture of oil/water and the water in oil (W/O) emulsions. More interestingly, these composite powders were found to have a higher adsorption ability toward not only low-molecular weight aromatic compounds such as bisphenol A and bisphenol AF but also volatile organic compounds, compared to that of the pristine α-, β-, γ-CDPs.

一维链状2-氧-1(4H)-吡啶乙酸桥联钙配位聚合物[Ca(2-OPA)_2(H_2O)_2]_n的合成、晶体结构及热稳定性研究

A novel coordination polymer of [Ca(2-OPA)2(H2O)2]n (2-OPA-=2-oxo-1(4H)-pyridineacetate anion) was synthesized and characterized by elemental analysis, IR, TG and single crystal X-ray diffraction. The title complex crystallizes in orthorhombic with space group Pna21, a=0.799 96(16) nm, b=0.823 77(16) nm, c=2.415 3(5) nm, V=1.591 6(6) nm3, Z=4, R=0.030 3, wR=0.070 0. The Ca atom is eight-coordinated by six O atoms of four 2-OPA- ligands and two water molecules, and displays a dodecahedron coordination geometry. Each 2-OPA- ligand bridges two adjacent Ca atoms, forming a infinite chain along the a direction. The Ca...Ca distance is 0.4102 2(8)nm. A two-dimensional supramolecular framework is further constructed by the hydrogen bonds and the weak π-π interactions. The results of TG analysis show the chain structure of the title complex was stable under 297.5 ℃. CCDC: 251669.

配位聚合物｛[Zn(CF_3COO)_2(C_5H_5ON)·]H_2O｝_n的合成、晶体结构及表征

new coordination polymer {[Zn(CF3COO)2(C5H5ON)]·H2O}n was synthesized based on the reaction of zinc(Ⅱ) trifluoroacetate and 3-hydroxypyridine(C5H5ON) in methanol medium for the first time. The structure of the coordination polymer was confirmed by IR, 1H NMR, elemental analysis and thermal analysis. The crystal structure of the coordination polymer was also determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group P21/m, and crystallographic data of the coordination polymer are: a= 0.863 1(4) nm, b=0.717 7(3) nm, c=1.116 4(5) nm, α=γ=90°, β=107.542(6)°, V=0.659 4(5) nm3; Dc=2.037 g·cm-3; Z=2; F(000)=400; μ=1.969 mm-1. Zinc(Ⅱ) atom lies at the center of an octahedron formed by the coordination of zinc atom and six O atoms which come from four different trifluoroacetate ions and two different 3-hydroxypyridine molecules where each trifluoroacetate ion and 3-hydroxypyridine are coordinated to two different zinc ions to form coordination polymer. CCDC: 253909.

Poly(Acrylamide-Co-Acrylic Acid)-Zinc Acetate Polymer Electrolytes: Studies Based on Structural and Morphology and Electrical Spectroscopy

Solid polymer electrolytes (SPEs) of polyacrylamide-co-acrylic acid (PAA) as the polymer host and zinc acetate (ZnA) as an ionic dopant were prepared using a single solvent by the solution casting technique. The amorphous and crystalline structures of film were investigated by X-ray diffraction (XRD). The surface morphology of samples was examined by scanning electron microscopy (SEM). The composition and complex formation of films were characterized by Fourier transform infrared (FTIR) spectroscopy. The conductivity of the PAA-ZnA films was determined by electrochemical impedance spectroscopy. According to the XRD and FTIR analyses, all electrolyte films were in amorphous state and the existence of interaction between Zn2+ cations and the PAA structure confirms that the film was successfully prepared. The SEM observations reveal that the electrolyte films appeared to be rough and flat with irregularly shaped surfaces. The highest ionic conductivity (σ) of 1.82 × 10-5 Scm-1 was achieved at room temperature (303 K) for the sample containing 10 wt % ZnA.

孤岛中一区注聚井二氧化氯解堵技术

胜利孤岛油田中一区一部分注聚井地层堵塞严重,常规酸化解堵效果不好,为此开发了二氧化氯解堵技术。室内实验结果表明:1%CMC和0 5%HPAM溶液与等体积0 4%ClO2溶液的混合液在60℃放置3小时后,粘度较空白混合液下降95%和87%;HPAM/Cr3+强凝胶在0 4%ClO2溶液中于80℃放置12h后解体,产生少量絮状沉淀;ClO2在加量30～200mg/L时在30～90min内基本上杀灭全部SRB菌(初始菌数2 5×104～≥1 1×108个/mL),在加量5～100mg/L时在5～60min内基本上杀灭全部TGB菌(初始菌数≥1 1×107个/mL);0 2%～0 8%ClO2溶液对FeS的溶蚀率为16 8%～23 1%,远高于15%盐酸液的5 3%;常温下ClO2对N80钢的腐蚀率符合现场施工要求。在4口注聚后恢复注水的井实施0 4%ClO2解堵,使平均注水压力由13 3MPa降至10 1MPa,注水量达到配注量,有效期79～325天,平均192天;10口对应采油井原油增产,其中7口油井增产显著,有效期107～301天,平均178 4天。表5参2。

Modeling size-dependent thermo-mechanical behaviors of shape memory polymer Bernoulli-Euler microbeam

The objective of this paper is to model the size-dependent thermo-mechanical behaviors of a shape memory polymer (SMP) microbeam.Size-dependent constitutive equations,which can capture the size effect of the SMP,are proposed based on the modified couple stress theory (MCST).The deformation energy expression of the SMP microbeam is obtained by employing the proposed size-dependent constitutive equation and Bernoulli-Euler beam theory.An SMP microbeam model,which includes the formulations of deflection,strain,curvature,stress and couple stress,is developed by using the principle of minimum potential energy and the separation of variables together.The sizedependent thermo-mechanical and shape memory behaviors of the SMP microbeam and the influence of the Poisson ratio are numerically investigated according to the developed SMP microbeam model.Results show that the size effects of the SMP microbeam are significant when the dimensionless height is small enough.However,they are too slight to be necessarily considered when the dimensionless height is large enough.The bending flexibility and stress level of the SMP microbeam rise with the increasing dimensionless height,while the couple stress level declines with the increasing dimensionless height.The larger the dimensionless height is,the more obvious the viscous property and shape memory effect of the SMP microbeam are.The Poisson ratio has obvious influence on the size-dependent behaviors of the SMP microbeam.The paper provides a theoretical basis and a quantitatively analyzing tool for the design and analysis of SMP micro-structures in the field of biological medicine,microelectronic devices and micro-electro-mechanical system (MEMS) self-assembling.

Experimental study on surface-active polymer flooding for enhanced oil recovery: A case study of Daqing placanticline oilfield, NE China

Experiments on surface-active polymer flooding for enhanced oil recovery were carried out by detection analysis and modern physical simulation technique based on reservoirs and fluids in Daqing placanticline oilfield.The experimental results show that the surface-active polymer is different from other common polymers and polymer-surfactant systems in molecular aggregation,viscosity and flow capacity,and it has larger molecular coil size,higher viscosity and viscosifying capacity,and poorer mobility.The surface-active polymer solution has good performance of viscosity-increasing and viscosity retention,and has good performance of viscoelasticity and deformability to exert positive effects of viscosifying and viscoelastic properties.Surface-active polymer can change the chemical property of interface and reduce interfacial tension,making the reservoir rock turn water-wet,also it can emulsify the oil into relatively stable oil-in-water emulsion,and emulsification capacity is an important property to enhance oil washing efficiency under non-ultralow interfacial tension.The surface-active polymer flooding enlarges swept volume in two ways:Microscopically,the surface-active polymer has mobility control effect and can enter oil-bearing pores not swept by water to drive residual oil,and its mobility control effect has more contribution than oil washing capacity in enhancing oil recovery.Macroscopically,it has plugging capacity,and can emulsify and plug the dominant channels in layers with high permeability,forcing the injected fluid to enter the layer with medium or low permeability and low flow resistance,and thus enlarging swept volume.

Role of Flexible Macro Fibre Composite (MFC) Actuator on Bragg Wavelength Tuning in Microstructure Polymer Optical Fibre Long Period Grating for Strain Sensing Applications

The microstructure polymer optical fibre (mPOF) inscribed long period grating (LPG) offers a wide field of application in strain sensors arena within the materials elastic limit. Flexible innovative macro fibre composite (MFC) actuator generates electromechanical force under DC driving voltage. We propose a novel method for Bragg wavelength blue shifting through stretch tuning of mPOF LPG in axial direction under applied DC voltage on attached MFC with LPG. The grating period of mPOF LPG changes refractive index and causes blue shift of Bragg grating fibre wavelength. The shifting governs on the values of generated electromechanically strain transfer from flexible MFC to mPOF LPG and they have potential applications in strain sensor.

家H2分支水平井钻井液技术

家H2井是大港油田第一口分支水平井,位于沈家铺油田官107×1断块,目的层为孔二油组上砂体。该井为三开井,由一个主井眼和两个分支井眼构成,完钻垂深为2211.65m,斜深为2658m,井底水平位移为521m,最大井斜为92.87°;一分支水平段段长为119.12m,最大井斜为92.19°;二分支水平段段长为25m,最大井斜为92°。该井二开井段使用聚合物钻井液,三开井段使用无固相KCl聚合物钻井液,采用无固相超低渗透技术保护油层,满足了筛管完井对油层保护技术的要求。在施工过程中无固相KCl聚合物钻井液性能稳定,携砂冼井能力强,滤失量小,能有效地稳定井壁,保护油气层,大大提高了原油产量。

地下聚合交联成胶的耐酸耐高温凝胶堵剂

研制了用于注蒸汽油藏堵水酸化联合作业的两种地下聚合、交联、成胶的凝胶类堵剂。筛选出的最佳配方如下。①丙烯酰胺体系AM 1:5 0%AM+0 035%引发剂PP+0 02%苯酚+1 0%甲醛液+0 05%稳定剂SS;②疏水缔合共聚体系AM 2:AM 1+1 0%AA+0 06%阳离子疏水缔合单体NA。250℃下的成胶时间,AM 1约为12小时,AM 2约为25小时,可通过配方调整在4～38小时范围改变。生成的凝胶按Sydansk提出的目测相对强度等级为J级,即高刚性凝胶,可抗高温,在250℃至少15天内不变化。表面浸泡在土酸液中的凝胶在250℃下可稳定存在9～10天(15%HCl+5%HF)或16～17天(5%HCl+1%HF)。AM 1的耐温耐酸性好于AM 2;AM 2的耐高温性好于AM 1。在人造岩心中AM 2凝胶堵塞物的突破压力为85 3MPa/m。两种堵剂还可用于封堵蒸汽窜流及高温油藏堵水调剖。图1表1参4。

污水配制的Al^(3+)交联聚合物凝胶性能特征

用大庆采油二厂的污水(矿化度4013mg/L)配制不同HPAM浓度的Al3+交联聚合物凝胶,在气测渗透率1 25μm2的人造岩心上,按清水(矿化度729mg/L)—凝胶—污水或清水的注入程序,注入量>5PV,测得凝胶中HPAM浓度为0 6、0 5、0 4g/L时,残余阻力系数FRR(368 6～277 4)大于阻力系数FR(266 7～246 0),二者均随HPAM浓度减小而减小;后续注入清水时FRR较低;凝胶中HPAM浓度为0 3g/L时FRR<RR;注入用25%、50%污水稀释的0 6g/LHPAM的凝胶时,FRR略有下降而FR不变。在二维纵向非均质人造岩心上,注凝胶(0 5g/LHPAM)、注水、再注凝胶过程中,入口压力升高而中间点压力基本不变,20天后再注水时两测点压力急剧上升,两测点压力差逐渐减小,与注聚合物溶液时两测点压力升高、注水时又降低的现象形成鲜明对比。初始粘度8 8mPa·s的Al3+交联聚合物凝胶,2天时粘度最高(10 2mPa·s),60天时下降至8 4mPa·s,FR和FRR则随凝胶放置时间加长而增大,由1天时的4 92和3 32增加到10天时的192 4和271 2,FRR>FR;聚合物溶液的粘度略低,在放置过程中FR和FRR大体不变,FR和FRR值很小且FRR<FR。实验温度45℃。图2表7参6。

耐温抗盐聚合物TS-45流变性及驱油效率研究

在45℃(大庆主力油藏温度)下,以超高分子量(2 8×107)HPAM为对比,实验考察了耐温抗盐聚合物TS 45溶液的流变性能和驱油能力。TS 45为丙烯酰胺、强极性(含—SO3H)支链单体及少量疏水缔合单体的共聚物。实验聚合物溶液含盐(NaCl)5g/L,含聚合物1g/L。两种聚合物溶液在0 02～600s-1范围均为假塑性流体,TS 45溶液的粘度大于HPAM溶液。溶液的G′和G″随振荡频率增加(0 1～50Hz)而增大;TS 45的G′(和G″)大于HPAM的相应值;G′和G″曲线的交点,TS 45为0 1Hz,此时G′=G″=0 078Pa,HPAM为0 147Hz,此时G′=G″=0 0088Pa,表明TS 45溶液的弹性大于HPAM溶液。与NaCl浓度1g/L的聚合物溶液相比,实验溶液的G′和G″均下降,在2 81Hz下的保留率对于TS 45分别为48 2%和38 3%,对于HPAM分别为24 1%和17 2%,说明TS 45的耐盐性较好。TS 45在岩心中的阻力系数和残余阻力系数(38 6和9 6)大于HPAM的相应值(25 4和5 7)。在岩心驱油实验中,注入0 38PV聚合物溶液提高采收率的幅度,1g/L的TS 45污水溶液、HPAM清水和污水溶液分别为12 6%、10 5%、8 9%,0 8g/L的TS 45污水溶液为10 7%;在注入量0 2～2 0PV范围内提高采收率的幅度,1g/L的TS 45污水溶液恒大于HPAM污水溶液。图6表2参5。

扩散致相转化法制备结晶性聚合物多孔膜

介绍了扩散致相转化法制备结晶性聚合物多孔膜的研究现状。其三元等温成膜体系的相图包含液液分相和固液分相两种相分离方式,是理解成膜过程的重要工具,总结了成膜机理和膜的结构形貌:单纯S L相分离生成粒子状对称膜结构;单纯L L相分离生成蜂窝状非对称膜结构;两种相分离方式竞争发生将生成多样的混合膜结构。铸膜液浓度、非溶剂种类、铸膜溶剂组成、凝胶浴组成、制膜温度是影响膜结构形貌的主要因素。

Solidification/Stabilization of Chromium in Red Mud-based Geopolymer

Up to 1.5wt%of Cr(Ⅲ)salts(CrCl_(3),and Cr_(2)O_(3))and Cr(Ⅵ)salts(Na_(2)CrO_(4),and CaCr_(2)O_(7))were incorporated into red mud-based geopolymers,respectively.The solidification/stabilization,compressive strength,and durability of the Cr-containing geopolymers were investigated.The experimental results indicate that the red mud-based geopolymer could effectively solidify/stabilize different types of Cr salts with solidification/stabilization rates of above 99.61%.Geopolymers are environmentally safe when the dosage of CaCr_(2)O_(7)is≤1.0wt%,or the dosage of CrCl_(3),Cr_(2)O_(3),and Na_(2)CrO_(4)is≤1.5wt%,respectively.The effects of Cr salts on the compressive strength varies with the type and content of Cr salts.The freeze-thaw cycle is more destructive to geopolymer properties than sulfate attack or acid rain erosion.The solidification/stabilization of Cr is mainly attributed to the following reasons:a)The chemical binding of Cr is related to the formation of Cr-containing hydrates(eg,magnesiochromite((Mg,Fe)(Cr,Al)_(2)O_(4)))and doping into N-A-S-H gel and C-A-S-H gel framework;b)The physical effect is related to the encapsulation by the hydration products(e g,N-A-S-H gel and C-A-S-H gel).This study provides a reference for the treatment of hazardous Cr-containing wastes by solid waste-based geopolymers.

高炉水淬矿渣固井液配方与性能研究

用乌鲁木齐钢厂的高炉水淬矿渣(BFS),MTC激活剂BAS 1和分散剂MT 1,吐哈油田5口井使用的聚合物钻井液配制了一系列高(1 81～1 84g/cm3)、低(1 56～1 66g/cm3)密度高炉水淬矿渣固井液(BFSCF)并在不同温度下(65℃,85℃,93℃)对其性能进行了评定。列表给出了BFS的组成,钻井液的性能,各BFSCF的配方与性能(包括稠化时间,24小时强度,流动度及API滤失量)。实验结果表明,温度较高时BAS 1的加量应减小;在高密度BFSCF中BAS 1加量为3%～4%,低密度BFSCF中BAS 1加量大于4%;增大MT 1加量使高温(93℃)下BFSCF稠化时间延长;加入少量水泥可改善低温(65℃)下BFSCF的早期强度;高温(93℃)BFSCF的强度可达到30MPa以上。加入水泥的一种BFSCF的强度随65℃下养护龄期的延长而提高。BFSCF具有良好的沉降稳定性。表6参2。