聚邻苯二胺/蒙脱土纳米复合材料的合成及其电流变效应

用乳液共混插层法制备了聚邻苯二胺/蒙脱土纳米复合材料微粒,通过IR、XRD及TEM对其结构进行了表征。 结果发现,邻苯二胺插入蒙脱土层间聚合后,导致蒙脱土片层之间的剥离,形成纳米复合材料。 将其分散在甲基硅油中(体积分数,22%)配制成无水电流变液,该复合材料表现出较大的协同效应,具有较好的电流变行为。实验结果表明在外加电场下,其电流变效应比聚邻苯二胺、蒙脱土均有显著提高。 在3 kV/mm(DC, 74.5 s-1)时,剪切强度达8.27 kPa;同时抗沉降性极好,静置60 d沉淀率小于3%。介电性能测试表明,聚邻苯二胺/蒙脱土纳米颗粒的介电常数和介电损耗较蒙脱土和聚邻苯二胺均有一定提高,电导率也达到了最佳范围。     

Synthesis and electrorheological performance of nanosized composite with polar inorganic compounds

To obtain an economical and applicable electrorheological (ER) material, a novel nanocomposite composed of polar inorganic compounds, NH₄Al(OH)₂CO₃, AlO(OH) and (NH₄)₂SO₄, has been synthesized using low-toxic and economical and facile starting materials by a simple chemical reaction process. The experimental result shows that this material has better ER performance. The static yield stress (τ_y) of the suspension (50 wt%) of the material in silicone oil reached 22.8 kPa at a DC electric field of 4 kV/mm, and the relative yield stress (τ_r) (the ratio of the yield stresses with to without an electric field) is also higher (12.7-33.3 for different concentration suspensions). The composition, grain size, dielectric and surface properties of the material have been studied by the elemental analyses, X-ray diffraction (XRD), infrared spectroscopy (IR), transmission electron microscopy (TEM), dielectric spectroscopy and determinations of the surface area and surface energy of the material. The influences of the grain size, dielectric and surface properties on ER performance of the material have been discussed.     

稀土改性二氧化钛电流变液的剪切强度随温度变化关系

用溶胶-凝胶法制备了系列锐钛矿型掺杂稀土元素二氧化钛粉粒,在干态下对其所配制的电流变液进行了力学性能测试及其温度效应研究。结果表明,掺杂后的电流变液性能远优于同条件下所制纯二氧化钛电流变液。温度效应明显优化,在10 ℃~100 ℃均有较强的电流变活性,使用温度范围比纯二氧化钛电流变液大幅度加宽,80℃剪切应力达到最大。材料中的RE/Ti摩尔比对电流变效应影响显著,不同温度下RE/Ti=0.07~0.11之间电流变液呈现最佳的电流变效应,RE/Ti摩尔比引起电流变液介电性质的改变是电流变效应增强和不同的起因。     

The giant electrorheological effect in suspensions of nanoparticles

Electrorheology (ER) denotes the control of a material's flow properties (rheology) through an electric field. We have fabricated electrorheological suspensions of coated nanoparticles that show electrically controllable liquid-solid transitions. The solid state can reach a yield strength of 130 kPa, breaking the theoretical upper bound on conventional ER static yield stress that is derived on the general assumption that the dielectric and conductive responses of the component materials are linear. In this giant electrorheological (GER) effect, the static yield stress displays near-linear dependence on the electric field, in contrast to the quadratic variation usually observed. Our GER suspensions show low current density over a wide temperature range of 10-120 degrees C, with a reversible response time of <10 ms. Finite-element simulations, based on the model of saturation surface polarization in the contact regions of neighbouring particles, yield predictions in excellent agreement with experiment.     

电场作用下电流变液的拉伸、压缩和剪切特性

对外加直流电场作用下电流变液的拉伸、压缩和剪切特性进行了实验研究。实验结果表明,在外电场作用下,电流变液的压缩强度比剪切强度约高一个数量级,压缩强度是拉伸强度的2~3倍。压缩弹性模量约与压缩过程中电场强度的三次方成正比。压缩应力与电流变液本身性能、外加电压大小和压缩应变都有密切关系。拉伸屈服应力为剪切屈服应力的拉伸屈服应力和剪切屈服应力的3~4倍,据此计算得到剪切屈服应变角度在15°~18.5°之间。     

Preparation,microstructure and electrorheological property of nano-sized TiO<Subscript>2</Subscript> particle materials doped with metal oxides

New nano-sized TiO₂ electrorheological (ER) materials doped with different metal (M = Na, Zr, Ce, Al, Ca, Zn) oxides have been prepared. Relationships between the composition, microstructure, conductivity, dielectric property and ER effect of these materials have been studied. The results show that doping Na₂O, ZrO₂, Al₂O₃ or CeO₂ can enhance the ER performance of the TiO₂ material, whereas, doping CaO or ZnO would decrease the ER activity of the material. The shear stress (τ_E) of the suspension (25 wt%) of Na-doped TiO₂ in dimethyl silicone oil reaches 1.6 kPa at the electric field strength E = 4.2 kV/mm and shear rate γ = 300 s⁻¹, and its τ_r value of 54.6 (τ_r = τ_E/τ₀, where τ₀ is the shear stress at no electric field) is seven times higher than that of pure TiO₂ suspension. This high τ_r value is very advantageous to the use. The dielectric loss tangent (tanδ) plays a dominant role in influencing the ER performance of a particle material, and the effect of the surface area (pore volume, especially) and grain size should be taken into account.     

丙三醇/羧甲基淀粉/改性氧化钛复合颗粒的电流变性能

结合改进的水解法和溶胶-凝胶法,制备了丙三醇/羧甲基淀粉/改性纳米氧化钛复合颗粒,分析表明羧甲基淀粉和纳米氧化钛之间存在有相互作用;同时,介电测试表明此颗粒配制的电流变液的介电极化特性有很大改善.经流变学测试,此复合颗粒电流变液的动态剪切应力在颗粒质量分数为25%,剪切速率为100s-1,3kV/mm DC下为960Pa,剪切增幅比为35.同时,此电流变液的静态屈服应力在更高浓度,5kV/mm DC下可达到18kPa,比同等条件下改性氧化钛和CMS电流变液的静态屈服应力均有所提高.此外,这种电流变液还表现出较好的抗沉降性能.     

新型聚合物电流变材料的合成及性能

以间苯二胺,2,5-二氧环己二甲酸二甲酯为原料,经缩合、闭环、氧化等反应,制得了聚喹吖(2,3b)啶-12,14(5,7)二酮(PQA)并进行了表征;并以PQA为基础粒子制备了无水型电流变流体(ERF),研究了其电流变性能。考察了溴代二苯甲烷(BDPM)-PQA体系中粒子浓度、电场强度、剪切速率等对电流变流体性能的影响,并从聚合物粒子的分子结构特点出发,对该体系的电流变效应进行了解释;对比了不同分散介质(BDPM及硅油)对电流变效应的影响。结果表明,PQA在BDPM中具有较佳的电流变效应,当粒子的质量分数为30%,外加电场为3 kV/mm时,屈服应力达4.0 kPa。     

Influence of liquid phase on nanoparticle-based giant electrorheological fluid

We show that the chemical structures of silicone oils can have an important role in the giant electrorheological (GER) effect. The interaction between silicone oils and solid nanoparticles is found to significantly influence the ER effect. By increasing the kinematic viscosity of silicone oils, which is a function of siloxane chain length, sol-like, gel-like and clay-like appearances of the constituted ER fluids were observed. Different functional-group-terminated silicone oils were also employed as the dispersing media. Significant differences of yield stress were found. We systematically study the effect of siloxane chain lengths on the permeability of oils traveling through the porous spaces between the particles (using the Washburn method), oils adsorbed on the particles' surface (using FT-IR spectra), as well as their particle size distribution (using dynamic light scattering). Our results indicate the hydrogen bonds are instrumental in linking the silicone oil to GER solid particles, and long chain lengths can enhance the agglomeration of the GER nanoparticles to form large clusters. An optimal oil structure, with hydroxyl-terminated silicone oil and a suitable viscosity, was chosen which can create the highest yield stress of ～300?kPa under a 5?kV?mm(-1) DC electric field.     

Electrorheological fluids containing Ce-doped titania

A new type of water-free electrorheological (ER) material of anatase titania doped with Ce has been synthesized by a sol-gel technique. The thermal character and crystal structure of doped titania are characterized with FT-IR, DSC-TG and XRD. The ER behaviors of the suspension made of such particles dispersed in silicone oil at a volume fraction of 18% are investigated in a DC electric field. The results show that the doped titania ER suspension has a much increased shear stress compared with the pure titania one. The shear stresses of 1.7 kPa at 3 kV/mm and 2.6 kPa at 4 kV/mm can be induced in a 8.5 mol% cerium-doped titania ER suspension, which is 5~times higher than that of the pure titania one. Moreover, the induced shear stress has a significant dependence on the Ce/Ti molar ratio and the maximum shear stress can be obtained when Ce/Ti molar ratio is about 0.1. In addition, significant differences in the temperature dependence of shear stress between the pure and doped titania ER suspensions are found. The working temperature range is extended by Ce doping. The obvious improvement in the ER effect resulting from Ce doping can be explained in terms of the dielectric and conduction properties of the ER suspensions.     

稀土铈改性二氧化钛微粉的制备及其介电性质

用Sol-gel法制备了掺杂稀土元素铈的二氧化钛微粉,测试了它的介电常数和电导率,由该材料作分散相与甲基硅油配制了无水电流变液,对其电常数和电导率增加,材料的电流变性能也发生很大的改变,存在一个稀土含是珠最佳浓度范围,在此区域介电常数取得最大值,电流变液的剪切强度也取得极大值,比纯二氧化钛电流变液的流变性能提高5倍以上。     

Gelation of chitin and chitosan dispersed suspensions under electric field: effect of degree of deacetylation

Herein, the effect of the degree of deacetylation (DD) on the gelation of the chitosan dispersed suspension as an electrorheological (ER) fluid under an electric field is presented. The fluids were prepared by dispersing the chitin and the chitosan particles having various DDs into silicone oil, and they were evaluated under various electric fields. The alignment of chitosan particles in the fluid was also observed using an optical microscope under the electric field. The formed fibrous structure between electrodes are though to continue to the viscosity increase, because an attempt to move one electrode relative to the order would be hindered by the drag of the dangling fibrils. A noteworthy result is that the region of the frequency for gel state of the ER fluids increased in the order of chitosan DD 99.3, 93.4, 73.2, 83.8, and 87.3% under electric fields while the modulus of the fluids increased in the reverse order. This order was well-matched with the result of dielectric constants and yield stresses of ER fluids. The study of influence of DD on the gelation of the chitosan dispersed suspension under an electric field shows the relevance of the chemical composition of the heteropolysaccharide (chitin-chitosan copolymer) to the rheological and electric properties of ER suspensions.     

Study on electrorheological properties of novel polymer-Ce4+ complex

A new polymer containing bithiazole ring and p-aminobenzoic acid was first synthesized using 2,2′-diamino-4,4′- bithiazole with paraformaldehyde and p-aminobenzoic acid. The polymer ‒Ce⁴⁺ complex was prepared from the polymer and CeCl₄ in DMSO. The electrorheological suspensions were prepared by the polymer-Ce⁴⁺ powder and bromodiphenylmethane. Under external electric field, the yield stress and dielectric constant of ER fluid were measured. The results showed that the polymer-Ce⁴⁺ complex ER fluid has higher dielectric properties, exhibits much stronger ER effect than pure the polymer under our experimental conditions.     

A High‐Performance Top‐Gated Graphene Field‐Effect Transistor with Excellent Flexibility Enabled by an iCVD Copolymer Gate Dielectric

A high‐performance top‐gated graphene field‐effect transistor (FET) with excellent mechanical flexibility is demonstrated by implementing a surface‐energy‐engineered copolymer gate dielectric via a solvent‐free process called initiated chemical vapor deposition. The ultrathin, flexible copolymer dielectric is synthesized from two monomers composed of 1,3,5‐trimethyl‐1,3,5‐trivinyl cyclotrisiloxane and 1‐vinylimidazole (VIDZ). The copolymer dielectric enables the graphene device to exhibit excellent dielectric performance and substantially enhanced mechanical flexibility. The p‐doping level of the graphene can be tuned by varying the polar VIDZ fraction in the copolymer dielectric, and the Dirac voltage (V_Dirac) of the graphene FET can thus be systematically controlled. In particular, the V_Dirac approaches neutrality with higher VIDZ concentrations in the copolymer dielectric, which minimizes the carrier scattering and thereby improves the charge transport of the graphene device. As a result, the graphene FET with 20 nm thick copolymer dielectrics exhibits field‐effect hole and electron mobility values of over 7200 and 3800 cm² V^?1 s^?1, respectively, at room temperature. These electrical characteristics remain unchanged even at the 1 mm bending radius, corresponding to a tensile strain of 1.28%. The formed gate stack with the copolymer gate dielectric is further investigated for high‐frequency flexible device applications.     

Electrorheology of undoped poly(p-phenylene) particle-based suspension

Electrorheological (ER) properties of synthesized, pristine poly(p-phenylene) (PPP) particles without any dopant treatment was investigated via flow curves including shear viscosity and yield stress. The ER characteristics were examined as functions of both particle concentration and applied electric field strengths. This undoped, PPP based suspension exhibited normal ER characteristics displayed by conventional semi-conducting polymeric ER materials with doping. The yield stress, which is an important design parameter for ER fluids, satisfied a universal scaling function. We found that the critical electric field strength for the undoped PPP suspension was much higher than the doped PPP suspension. These undoped particles can be used as a model system to test the doped system at low concentration via a universal scaling function.     

A Fluid Liquid‐Crystal Material with Highly Polar Order

An anomalously large dielectric permittivity of ≈10⁴ is found in the mesophase temperature range (MP phase) wherein high fluidity is observed for a liquid‐crystal compound having a 1,3‐dioxane unit in the mesogenic core (DIO). In this temperature range, no sharp X‐ray diffraction peak is observed at both small and wide Bragg angles, similar to that for a nematic phase; however, an inhomogeneous sandy texture or broken Schlieren one is observed via polarizing optical microscopy, unlike that for a conventional nematic phase. DIO exhibits polarization switching with a large polarization value, i.e., P = 4.4 µC cm^?2, and a parallelogram‐shaped polarization–electric field hysteresis loop in the MP phase. The inhomogeneously aligned DIO in the absence of an electric field adopts a uniform orientation along an applied electric field when field‐induced polarization switching occurs. Furthermore, sufficiently larger second‐harmonic generation is observed for DIO in the MP phase. Second‐harmonic‐generation interferometry clearly shows that the sense of polarization is inverted when the +/? sign of the applied electric field in MP is reversed. These results suggest that a unidirectional, ferroelectric‐like parallel polar arrangement of the molecules is generated along the director in the MP phase.     

Sol-Gel Preparation of Graphite/TiO2 Composite Particles and Their Electrorheological Effect

Graphite/TiO2 composite particles were obtained by sol-gel technique in this paper. The structure and characteristic of the composite particles are analyzed by XRD, SEM and TG-DTA. The electrorheological properties of the ER fluid containing the particles were measured by a Couette-type rheometer under shear rates of 1～136 s-1 and AC electric fields of 0～3 kV/mm. The experimental results show that the leaking current density of the ER fluid is higher than that of pure titanium dioxide particles dispersed in damping oil. The shear yield stress of the ER fluid increases with increasing electric field and exhibits a typical Bingham flow behavior. The suspension demonstrates an excellent ER performance (τ/τ0=1200) compared with conventional ER fluids (τ/τ0 ≤500). The sedimentation of the ER fluid is improved obviously due to the coating effect of the particles.     

A new class of electrorheological material: synthesis and electrorheological performance of rare earth complexes of phosphate cellulose

A new class of electrorheological (ER) material, rare earth (RE = Ce, Gd, Er and Y) complexes of phosphate cellulose, has been synthesized using microcrystalline cellulose, phosphoric acid, urea and RE(NO₃)₃ solutions as starting materials. The ER properties of suspensions of microcrystalline cellulose, phosphate cellulose [cellulose-P-ONH₄] and the [cellulose(-P-O)₃RE] complex particle materials in silicon oil have been investigated under DC electric field. The formation of rare earth complexes helps to decrease the shear stress and viscosity at zero electric field, and to enhance the ER effect of the materials. The shear stress (τ_E) of the ER fluid (20% weight fraction) of a typical yttrium complex [cellulose(-P-O)₃Y], the yttrium content of which is 0.04 mol/100 g, is 2.3 kPa at 4.2 kV/mm and 300 s⁻¹ with a τ_r value (τ_r = τ_E/τ₀, where τ₀ is the shear stress at no electric field and 300 s⁻¹) of 34.3, which is 18 times higher than that of pure microcrystalline cellulose suspensions. The improvement of dielectric loss tangent of the material, due solely to the formation of rare earth complexes, resulted in an enhancement in the ER effect of the material. In addition, the cellulose(-P-O)₃RE materials possess better thermal stability, and their suspensions are more stable in the anti-sedimentation than that of the cellulose-P-ONH₄ material.     

硫酸改性TiO2粒子的表征与电流变性能研究

采用硫酸溶液浸渍TiO₂干凝胶的方法制备了硫酸改性的TiO₂粒子, 并组成了具有显著电流变性能的电流变材料. 用FT-IR、XRD、比表面积分析仪等表征了样品结构, 并测试了其电流变性能. 结果表明：由于硫酸根对晶粒生长的阻碍作用, 与纯TiO₂粒子相比, 硫酸改性的TiO₂粒子的晶粒尺寸降低, 比表面积提高, 并含有大量的强极性键SO. 当电场强度为3kV/mm时, 纯TiO₂粒子电流变液的场致剪切应力与零场剪切应力之比（τ_E/τ₀）仅为80, 而硫酸改性TiO₂电流变液的τ_E/τ₀高达500. 产生这些现象可归因于硫酸改性TiO₂粒子带来的结构改变赋予其明显的界面极化能力.     

Electrocaloric Materials for Solid‐State Refrigeration

The electrocaloric effect (ECE) in dielectric materials has great potential in realizing solid‐state cooling devices with compact size and high efficiency, which are highly desirable for a broad range of applications. This paper presents the general considerations for dielectric materials to achieve large ECE and reviews the experimental efforts investigating ECE in various polar dielectrics. For practical cooling devices, an ECE material must possess a large isothermal entropy change besides a large adiabatic temperature change. We show that polar dielectrics operated at temperatures near order–disorder transition have potential to achieve large ECE due to the possibility of large change in polarization induced by electric field and large entropy change associated with the polarization change. We further show that indeed the ferroelectric poly(vinylidene fluoride–trifluoroethylene)‐based polymers display a large ECE, i.e., an isothermal entropy change of more than 55 J (kgK)^?1 and an adiabatic temperature change of more than 12 °C, at temperatures above the order–disorder transition.