Influence of plasticizer content on the transition of electromechanical behavior of PVC gel actuator

The actuation performance of plasticized poly(vinyl chloride) (PVC) gel actuators in an electric field depends on their chemical composition and electrical and mechanical properties. The influence of plasticizer (dibutyl adipate) content on electromechanical behavior of PVC gels was investigated by impedance spectroscopy and space charge measurement. By plasticizing the PVC, the dielectric constant and space charge density of PVC gel were drastically increased at 1:2 w/w ratio of PVC to plasticizer. To apply the results obtained from the impedance spectroscopy and space charge measurement, electrostatic adhesive forces generated between the PVC gel and the anode were measured. The electrostatic adhesive force at the anode was also dramatically increased at the same plasticizer content. All of the results indicated a transition of electromechanical behavior of PVC gel in the electric field, which was considered to originate from the orientation of polarized plasticizer molecules and dipole rotation of PVC chains. By using the electrostatic adhesive force of PVC gel derived from the electromechanical transition, a new electroactive actuator can be developed for novel applications.     

聚皂凝胶对直流电场作用的响应

研究了三种聚皂凝胶在直流电场下的响应．这三种凝胶在直接接触电场下,在阳极端发生消溶涨,而在非直接接触电场下形状发生显著的弯曲这些响应均随电场电压的升高而增强．聚皂凝胶在电场下产生响应的驱动力,除了因离子迁移产生的渗透压差外,疏水相互作用也是驱动力之一.     

Phase Separation in Methylsiloxane Sol-Gel Systems in a Small Confined Space

The organo-siloxane gel with co-continuous structure derived from methyltrimethoxysilane (MTMS) was synthesized in a confined space between parallel plates by inducing spinodal decomposition during sol-gel transition. The resultant gel morphology was 3-dimensionally observed by laser scanning confocal microscopy (LSCM). The sliced LSCM photographs revealed that the confined gels have inhomogeneity perpendicular to the plate, exhibiting a layered structure. The layered structure can be divided into three regions according to their morphology; interface, near-surface layer, bulk phase. The organo-siloxane depletion layer had formed in the vicinity of both hydrophobic and hydrophilic plates, and the bulk phase had formed slight away from the plates exhibited co-continuous structure. In addition, the confined gels exhibited no shrinkage during drying process that resulted in the larger domain size compared to the monolithic gel. The attractive interaction between the plates and the resultant organo-siloxane phase accounts for the inhibition of shrinkage of confined gels.     

Physico-chemical and structural properties of hydrogels formed by chitosan, in the presence and absence of poly(vinylpyrrolidone) and sodium decylsulfate

The structure of chemically-crosslinked chitosan and chitosan-poly(vinylpyrrolidone) (PVP) hydrogels is investigated by means of the combined use of small-angle neutron scattering (SANS), electron paramagnetic resonance spectroscopy (EPR), intradiffusion, and swelling degree measurements. These hydrogels may be described in terms of an inhomogeneous structure composed by polymer-rich and polymer-poor regions. The polymer-rich regions, whose correlation distance zeta is ranged between approximately 600 and approximately 850 A, are, in turn, characterized by the presence of a network formed by the chemical crosslinks, with a mean correlation distance xi approximately 90 A. The structures of chitosan and chitosan-PVP hydrogels have also been analyzed in the presence of sodium decylsulfate micelles that could provide a multidomain system useful, in principle, for drug delivery applications. Both SANS and EPR measurements show that sodium decylsulfate micelles do not significantly interact with both the gels. Finally, intradiffusion and swelling degree measurements show an improved hydrophilicity of chitosan-PVP gels, even further magnified by the presence of C10OS surfactant.     

Effect of salt on the performance of immobilized pH gradient isoelectric focusing gels

The effect of salt and buffer ions in the sample or in an immobilized pH gradient (IPG) on sample entry into the gel and on the final focused pattern are presented. During the initial phase of electrofocusing, ions present in the gel, either as counter ions to the immobilized charge groups of the IPG gel or added to the gel matrix during the rehydration process, are transported toward the electrodes. For ions present at a concentration exceeding approximately 1 mM the transport can be followed by the refractile line marking the trailing edge of an ion-containing zone. Gradual sample entry may be achieved by applying the sample at a site (near the anode or cathode) opposite to that from which the sharpest refractile line, marking the ion present in the highest concentration, approaches the sample. Additionally, lateral band spreading of the sample is avoided. Thus, sample applied at the cathode for IPG gels rehydrated with 1-2 mM Tris base, or at the anode for gels rehydrated with 1-2 mM acetic acid or sodium acetate, enters the gel matrix gradually without lateral band spreading. In contrast, sample applied at the anode, for Tris-containing gels, or at the cathode, for acetate-containing gels, enters rapidly in a sharp zone when the refractile line reaches the sample zone. This results in a high local protein concentration in the zone immediately behind the boundary with lateral band spreading.(ABSTRACT TRUNCATED AT 250 WORDS)     

亲水/疏水半互穿网络凝胶在直流电场作用下的响应

研究了一种亲水 疏水型半互穿网络水凝胶 (PAAc QPVPDgels)对直流电场的刺激应答 .该凝胶中的疏水型N 十二烷基聚 (4 乙烯吡啶 )溴化盐 (QPVPD)高分子链与亲水型聚丙烯酸水凝胶 (PAAc)网络通过物理缠绕复合 .由于疏水力和亲水力的共同作用 ,在接触电场下 ,该凝胶在阳极端发生消溶胀 ,疏水相互作用对消溶胀有一定的影响 ;在非接触电场下 ,该凝胶在弱碱性溶液中迅速向阴极方向弯曲 ,在弱酸性溶液中首先发生消溶胀 ,然后向阳极方向弯曲     

电促灰岩离解动态除氟实验研究

高氟地下水的除氟是保证居民远离氟地方病的有效手段之一。本研究利用新型封闭除氟装置探究电促灰岩动态除氟的化学驱动力、主控因素及稳定除氟能力。结果表明,在电场强化条件下,与灰岩接触的高氟水会形成局部萤石过饱和,可有效去除水中过量的氟。整个反应过程可分为启动阶段与稳定阶段。电压梯度是除氟反应主控因素,当电压梯度大于4. 8V·cm~(-1)时,除氟效果较好。反应过程中阳极附近F-富集高于初始浓度,而阴极附近更易生成CaF_2沉淀,表明阴极除氟效果更优。灰岩固体颗粒表面形态变化巨大,存在明显的腐蚀现象。当两极电压差为24V、极板间距3cm时,阴极附近氟浓度能迅速地由10mg·L~(-1)降低至国家饮用水标准以下。     

Operating characteristics and energy distribution in transferred plasma arc systems

A specially designed plasma chamber was constructed to study the operating characteristics of a dc plasma-transferred arc of argon, struck between a fluid convective cathode and a water-cooled anode. The arc voltage increased markedly with arc length and with an increase in the inlet velocity of the argon flow past the cathode tip, and much less with an increase in current. Radiation from the plasma column to the chamber walls and transfer of energy to the anode were the two principal modes of transfer of the arc energy. The former was dominant in the case of long arcs and at high inlet argon velocities. At the anode, the major contribution was from electron transfer, which occurred on a very small area of the anode (～5 mm in diameter). Convective heat transfer from the plasma was somewhat less. In all cases, the arc energy contributions to cathode cooling and to the exit gas enthalpy were small. From total heat flux and radiative heat transfer measurements, it was estimated that the plasma temperature just above the anode was in the range 10,000–12,000 K. Preliminary experiments with an anode consisting of molten copper showed that the arc root was no longer fixed but moved around continuously. The arc was othwewise quite stable, and its operating characteristics differed little from those reported for solid anodes, in spite of the greater extent of metal vaporization.     

利用铁电薄膜研究体异质结型有机光伏器件的光电流极性

制备了铌镁酸铅-钛酸铅(PMN-PT)铁电薄膜,并通过紫外-可见(UV-Vis)透射光谱、X射线衍射(XRD)和原子力显微镜(AFM)对其进行了表征.为了研究体异质结型有机共混膜的光电流特性,制作了氧化铟锡(ITO)/PMN-PT/有机共混膜/铝(Al)的光伏器件,调制激光照射下外加偏压的极性和大小变化将直接改变瞬态光电流的极性和大小,从而可在实验上证明传统体异质结型有机光伏器件的光电流极性是由器件阴、阳电极的功函数差所导致的内建电场的方向决定.同时也提出了一种利用铁电薄膜来研究体异质结型有机光伏器件光电流特性的新方法.     

Switchable mirrors of chiral liquid crystal gels

Chiral nematic liquid crystal compositions containing mono- and di-acrylates in mixtures with non-reactive liquid crystal molecules were produced. Defect-free planar macroscopic alignment of the molecules was induced between uniaxially rubbed substrates. Polymerization of the acrylate groups was initiated photochemically leading to the formation of a new class of chiral gels consisting of a lightly cross-linked network containing non-reactive molecules. In this way, the chiral pitch and, hence, the reflection colour became permanently fixed. Under the influence of an electric field the gels could be switched to the homeotropic state and reverted to the planar defect-free state upon removal of the electric field. Depending on the composition of the gel, either the position of the reflection band remained the same while its magnitude and/or width decreased, or its position shifted to smaller wavelengths with increasing electric field. Some of the gels showed sharp switching characteristics with a hysteresis making them suitable for passive matrix addressing with a high degree of multiplexability. The gels also showed fast switching times as they reverted to the defect-free optical state upon removal of the electric field. The phase structure of the gels was studied using dielectric spectroscopy which showed that the gels have an inhomogeneous structure.     

Electrical conduction in composites of a TCNQ anion-radical salt in a polymer matrix

The conduction behavior of composites of the anion-radical salt NaTCNQ (sodium 7,7,8,8-tetracyanoquinodimethanide) in poly(vinyl chloride) plasticized by polyurethane has been studied. TCNQ salt-polymer composites that have good moldability and flexibility are characterized by molecular or granular dispersion of the TCNQ salt in a polar polymer matrix. The conduction mode changes from one due to molecularly dispersed sites (CMDS) to one due to granularly dispersed sites (CGDS) with increasing NaTCNQ content. In the CMDS region, the predominant conduction is ionic; TCNQ anion-radicals migrate toward the anode under a dc biasing voltage and a high-resistivity layer is formed near the cathode. The fixation of TCNQ salt at sites in the polymer matrix is believed to be important for the stabilization of electronic conduction under a dc electric field. In the CGDS region, the conduction is electronic and the current-voltage characteristics of the composite are nonohmic, which indicates that carrier generation depends on the Poole-Frenkel effect.     

Morphological characteristics of the lyotropic and gel phases in the cellulose/NH3/NH4SCN system

Solutions of cellulose in the ammonia/ammonium thiocyanate (24.5/75.5 w/w) solvent form several stable phases. Of particular interest in this work are the temperature-dependent liquid crystalline and gel phases which are stable at cellulose concentrations above 6% w/v. While the temperature-composition conditions yielding these phases are reasonably well established, very little is currently known about the morphological characteristics of lyotropic and gelled cellulose. Polarized light microscopy is employed here to demonstrate that solutions at temperatures above the gel melting point are birefringent, composed of liquid crystals. Field-emission scanning electron microscopy has been used to (i) examine the three-dimensional network in cellulose gels, and (ii) correlate network morphology with cellulose molecular weight and solution concentration. Results obtained from two complementary sample preparation techniques (i.e., critical point drying and freeze drying) are compared to identify and minimize artifacts, and reveal that gel formation occurs as the solutions phase-separate into polymer-rich anisotropic and solvent-rich isotropic phases. The polymer-rich phase is highly interconnected and forms a fibrillar network, with fibrils measuring 20–70 nm in diameter. © 1996 John Wiley & Sons, Inc.     

Anisotropic siloxane-based monolith prepared in confined spaces

When bicontinuous gels are prepared via sol-gel method in a 2-dimensionally (2D) confined space, the gel skeletons in the vicinity of interface of a mold are elongated perpendicular to the interface. This phenomenon was attributed to the dynamic wetting of polymerizing siloxane phase onto the interface of the mold under gravity. In this paper, we report the successful preparation of monolithic columns with an oriented pillar structure in a variety of 2D confined spaces. Starting from a solution, which consists of methyltrimethoxysilane (MTMS), the macroporous structure is prepared in situ by a completely spontaneous process. In the oriented pillar structure, bicontinuous siloxane skeletons deformed or disappeared and most pillars are oriented along the direction of gravity. Gel morphologies with the pillar structure were examined by scanning electron microscopy (SEM) and laser scanning confocal microscopy (LSCM). Geometrical information on gel morphologies was numerically derived from the obtained 3D LSCM images.     

Study about thermal runaway behavior of high specific energy density Li-ion batteries in a low state of charge

Lithium-ion batteries are widely used in electric vehicles and electronics, and their thermal safety receives widespread attention from consumers. In our study, thermal runaway testing was conducted on the thermal stability of commercial lithium-ion batteries, and the internal structure of the battery was analyzed with an in-depth focus on the key factors of the thermal runaway. Through the study of the structure and thermal stability of the cathode, anode, and separator, the results showed that the phase transition reaction of the separator was the key factor affecting the thermal runaway of the battery for the condition of a low state of charge.     

Characteristics of charged networks under an electric stimulus

The electrokinetic phenomena of poly(2-acrylamido-2-methyl-1-propane sulfonic acid-co-n-butylmethacrylate) were examined to investigate physical changes of the gel under an applied electric current. When an electrical stimulus was applied to a piece of the gel, without being in contact with an electrode, reversible gel bending was observed. The bending degree was directly proportional to the intensity of the applied electric stimulus. This was explained by ‘depletion polarization’ of ionic species under the stimulus. The swelling of the gel surface facing the anode increased, due to the decreased ionic strength of the boundary layer upon electric stimulation, while gel shrinking occurred at the cathode. When the gel is in direct contact with electrodes, deswelling of the gel was observed at the anode side, while water seepage occurred at the cathode side. This observation was attributed to the electro-osmosis inside the gel, combined with local pH changes around the electrodes resulting from electrochemical reactions, particularly water electrolysis. © 1994 John Wiley & Sons, Inc.     

A High‐Energy‐Density Potassium Battery with a Polymer‐Gel Electrolyte and a Polyaniline Cathode

A safe, rechargeable potassium battery of high energy density and excellent cycling stability has been developed. The anion component of the electrolyte salt is inserted into a polyaniline cathode upon charging and extracted from it during discharging while the K⁺ ion of the KPF₆ salt is plated/stripped on the potassium‐metal anode. The use of a p‐type polymer cathode increases the cell voltage. By replacing the organic‐liquid electrolyte in a glass‐fiber separator with a polymer‐gel electrolyte of cross‐linked poly(methyl methacrylate), a dendrite‐free potassium anode can be plated/stripped, and the electrode/electrolyte interface is stabilized. The potassium anode wets the polymer, and the cross‐linked architecture provides small pores of adjustable sizes to stabilize a solid‐electrolyte interphase formed at the anode/electrolyte interface. This alternative electrolyte/cathode strategy offers a promising new approach to low‐cost potassium batteries for the stationary storage of electric power.     

Surface phase transitions in athermal mixtures of hard rods and excluded volume polymers investigated using a density functional approach

Using fundamental measures' density functional framework based on Wertheim's first order perturbation theory [J. Chem. Phys. 87, 7323 (1987)] we study the surface phase transitions in athermal polymer-needle mixtures, which demix in bulk into the isotropic polymer-rich (rod-poor) and polymer-poor (rod-rich) phases. We find that the polymer-rich (rod-poor) phase wets the hard wall at coexistence and the wetting transition is of first order. In the partial wetting regime we find a sequence of layerings but these transitions are gradually suppressed as the chain length increases. For long enough chains we detect the prewetting line. Rods exhibit pronounced ordering at the wall in the polymer-rich phases. Our results imply that experiments on the (isotropic) wetting transition for colloidal rod-polymer mixtures should be easier to carry out than those for the colloidal rod-sphere mixtures because the wetting transition occurs at lower rod densities. On the other hand, layerings in sphere-needle mixtures may turn out to be difficult to observe experimentally because some of them will be metastable with respect to the freezing transition, whereas the remaining ones are located very close to the binodal.     

Drying dissipative patterns of the colloidal crystals of silica spheres in an dc-electric field

Drying dissipative structural patterns of the colloidal crystals of silica spheres were studied under an dc-electric field. Platinum plate electrodes of anode and cathode were set on a cover glass. The broad hills accumulated with the spheres were observed at the outer edges of the dried film without and also with the electric fields. The column-like structures were formed by the electric flux, and movement of the spheres took place toward anode. The dried film kept colloidal crystal structure, where the nearest-neighbored spheres contact each other more compactly in the areas closer to the anode. Drying times needed for the complete dryness of the suspensions decreased as the strength of the electric field increased. Addition of sodium chloride to the suspensions retarded the movement of spheres toward the anode substantially.     

Self-diffusion study of poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) block copolymers in aqueous solution

The self-diffusion of poly (ethylene oxide)-poly (propylene oxide)-poly (ethylene oxide) block copolymers dissolved in deuterated water was investigated by means of pulsed field gradient NMR (PFG-NMR). The polymer forms micelles in the solution and, with increasing temperature, clouding and phase demixing occurs. The self-diffusion coefficient indicates the association of the polymer molecules in the vicinity of the cloud point because of its maximum with increasing temperature. Above the cloud point, two kinds of diffusing species are observed due to phase separation. The faster diffusing species is attributed to the polymer-poor phase. The self-diffusion coefficient of the polymer-rich phase species decreases with increasing temperature above the cloud point due to further association and dehydration. The correlation length of the diffusing associates, calculated from the self-diffusion coefficient and the viscosity by means of the Stokes-Einstein equation is nearly independent of temperature and concentration up to 30 wt-% polymer concentration. The correlation length is about 1.4 nm. It shows a slight maximum at the cloud point.     

Effect of Temperature on Dynamic Physical Behavior of Poly(vinyl chloride) Gel Structure with Ester Plasticizers

Dynamic viscoelastic properties of poly(vinyl chloride) (PVC)/bis(2-ethylhexyl) phthalate (DOP) and PVC/di-n-butyl sebacate (DBS) gels with molecular weight distribution (M_w/M_n), of 2.16 and various polymer concentrations c, have been studied as a function of temperature. These PVC gels exhibited an elastic solid at room temperature T, and gradually became liquid (sol) with increasing temperature. The sol-gel transition took place at a critical gel temperature at which the scaling law of G′(ω) ∼ G″(ω) ∝ ωⁿ held, allowing an accurate determination of the critical gel temperature by means of the frequency ω independence of the loss tangent. In this study the scaling exponent n, was 0.75–0.77. This is in good agreement with the previous results observed at different temperatures and suggests the formation of a similar fractal structure of the PVC gels. The gel strength S_g, at the gel point increased with increasing PVC concentration. These results suggest a unique character and structure for the gel points of PVC-plasticizers.