Membrane decoration by amphiphilic block copolymers in bicontinuous microemulsions

The effect of various amphiphilic block copolymers of different molar masses on the structure and phase behavior of ternary amphiphilic systems (water, oil, and nonionic surfactant) is investigated. Small amounts of PEP-PEO block copolymer lead to a dramatic increase in the volumes of oil and water, which can be solubilized in a bicontinuous microemulsion. High-precision neutron scattering experiments with a sophisticated contrast variation technique demonstrate that the polymers form uniformly distributed mushroom conformations on the surfactant membrane. Based on these observations, we propose a universal mechanism for the swelling behavior, which is due to the variation of the membrane curvature elasticity.     

Globules of annealed amphiphilic copolymers: Surface structure and interactions

A mean-field theory of globules of random amphiphilic copolymers in selective solvents is developed for the case of an annealed copolymer sequence: each unit can be in one of two states, H (insoluble) or P (soluble or less insoluble). The study is focussed on the regime when H and P units tend to form long blocks, and when P units dominate in the dilute phase, but are rare in the globule core. A first-order coil-to-globule transition is predicted at some T = T _cg. The globule core density at the transition point increases as the affinity of P units to the solvent, ˜, is increased. Two collapse transitions, coil → “loose” globule and “loose” globule → “dense” globule, are predicted if ˜ is high enough and P units are marginally soluble or weakly insoluble. H and P concentration profiles near the globule surface are obtained and analyzed in detail. It is shown that the surface excess of P units rises as ˜ is increased. The surface tension decreases in parallel. Considering the interaction between close enough surfaces of two globules, we show that they always attract each other at a complete equilibrium. It is pointed out, however, that such equilibrium may be difficult to reach, so that partially equilibrium structures (defined by the condition that a chain forming one globule does not penetrate into the core of the other globule) are relevant. It is shown that at such partial equilibrium the interaction is repulsive, so the globules may be stabilized from aggregation. The strongest repulsion is predicted at the coil-to-globule transition point T _cg: the repulsion force decreases with the distance between the surfaces according to a power law. In the general case (apart from T _cg) the force vs. distance decay becomes exponential; the decay length ξ diverges as T → T _cg. The developed theory explains certain anomalous properties observed for globules of amphiphilic homopolymers.     

An approach to hybrid inorganic nanoparticles in reactive PS-b-PMSMA amphiphilic copolymers

A series of well-defined amphiphilic poly(styrene)-block-poly 3-(trimethoxysilyl) propyl methacrylate (PS-b-PMSMA) copolymers with controlled molecular weight and block length were prepared by the atom transfer free radical polymerization. The cadmium sulfide (CdS) nanoparticles were fabricated in the spherical micelles self-assembled from these prepared PS-b-PMSMA copolymers. Then, the CdS/PS-b-PMSMA films were obtained by spin coating the CdS/PS-b-PMSMA solution on silicon wafer. The experimental results showed the addition of Cu(II) could decrease the value of polydispersity index for the prepared copolymers. Nuclear magnetic resonance and Fourier transform infrared spectra showed the synthesis of PS-b-PMSMA copolymer. The average roughness and mean square roughness of the prepared CdS/PS-b-PMSMA films obtained from the atomic force microscopy analysis were 3.0–3.4 nm and 1.7–2.0 nm, respectively, indicating the excellent surface planarity. On the other hand, the ratio of block length between PS and PMSMA had a great influence on the micelle size. The larger ratio of PS to PMSMA block length resulted in the larger size of micelles and CdS nanoparticles that caused a red-shift of ultraviolet–visible and photoluminescence spectra. The red-shift of spectra was explained by the quantum confinement effect associated with the tiny size of the CdS nanoparticles.     

Confinement-induced novel morphologies of block copolymers

Self-assembly of block copolymers confined in cylindrical nanopores is studied systematically using a simulated annealing technique. For diblock copolymers which form two-dimensional hexagonally packed cylinders with period L0 in the bulk, novel structures such as helices and stacked toroids spontaneously form inside the cylindrical pores. These confinement-induced morphologies have no counterpart in the bulk system and they depend on the pore diameter (D) and the surface-polymer interactions, reflecting the importance of structural frustration and interfacial interactions. On tightening the degree of confinement, transitions from helices to toroids to spheres are observed. Mechanisms of the morphological transitions can be understood based on the degree of structural frustration parametrized by the ratio D/L0.     

两亲性嵌段聚合物的同步辐射小角x射线散射研究

应用同步辐射小角x射线散射(SAXS)方法研究了不同聚合条件下苯乙烯对乙烯基苯甲酸两亲性嵌段聚合物的聚集行为,结果发现该聚合物在选择性溶液中自组装形成胶束.胶束的形态和结构取决于嵌段聚合物的组成、浓度以及溶剂的性质等因素 关键词： 小角x射线散射 两亲性嵌段聚合物 分形维数 粒径     

A novel method for the synthesis of polystyrene-graft-silica particles using random copolymers based on styrene and triethoxyvinylsilane

In the present research, random copolymers based on triethoxyvinylsilane (TEVS) and styrene (St) are synthesized and structurally characterized. According to the reactivity ratios of the monomers determined by infrared analysis; St tends to form blocks whilst TEVS is expected to be incorporated as isolated units. A sample of poly(styrene-co-triethoxyvinylsilane) synthesized at low conversion using a monomer feeding ratio St:TEVS of 2:3 was used as macrosilane in the synthesis of polystyrene-g-silica particles. The grafting reaction was confirmed by infrared spectroscopy, thermogravimetric analysis and by the evaluation of the morphological characteristics of the hybrid particles.     

The surface properties of ionomers based on styrene-co-acrylic acid copolymers

The surface properties of styrene-co-acrylic acid copolymers and of the obtained ionomers containing alkali metal ions, before and after UV-irradiation, were investigated by the measurements of water contact angles and ATR-FTIR spectroscopy.It was examined, how the content and nature of the alkali metal introduced into the initial copolymer influences the water contact angle, surface free energy and its components, polar and dispersive.It was ascertained that the water contact angle, surface free energy and its components depend on the content of introduced acid or salt. These values were practically independent of the nature of the alkali metal introduced into the copolymer. However, more considerable changes were observed for the ionomers containing sodium ions.The research has indicated that UV-irradiation causes the increase in surface hydrophilicity of the investigated ionomers.     

Polymer electrolytes based on ethylene oxide–epichlorohydrin copolymers

In this work we studied the ionic conductivity for three copolymers of the title co-monomers as a function of LiClO₄ content, temperature and ambient relative humidity. We also investigated the interactions between the salt and the co-monomer blocks in the copolymers and its effect on the morphology and thermal properties of the copolymer/salt complexes. Our data indicate that the Li⁺ ion predominantly interacts with the ethylene oxide repeating units of the copolymers. The copolymer with the highest ionic conductivity was obtained with an ethylene oxide/epichlorohydrin ratio of 84/16 containing 5.5% (w/w) of LiClO₄. It showed a conductivity of 4.1×10⁻⁵ S cm⁻¹ (30°C, humidity< 1 ppm) and 2.6×10⁻⁴ S cm⁻¹ at 84% relative humidity (24°C). The potential stability window of the copolymer/salt complex is 4.0 V, as measured by cyclic voltammetry. For comparison, we also prepared a blend of the corresponding homopolymers containing LiClO₄; it showed higher crystallinity and lower ionic conductivity.     

Collapse of hydrogels based on copolymers of N-isopropylacrylamide and sodium vinylsulfonate

This paper describes the investigation of the behavior of polyelectrolyte thermosensitive hydrogels based on copolymers of N-isopropylacrylamide and sodium vinylsulfonate at different temperatures. The influence of ionogenic groups on the swollen gel-collapsed gel phase transition was studied by means of highly sensitive differential scanning calorimetry. It was demonstrated that the presence of ionogenic groups in the thermosensitive copolymer influences the reversibility and the amplitude of gel collapse, as well as the temperature, enthalpy, and increment of the transition heat capacity.     

Ionic conductivity of polymer electrolytes based on phosphate and polyether copolymers

Linear polyphosphate random copolymers (LPC) composed of phosphate as a linking agent with poly(ethylene glycol) (PEG) and/or poly(tetramethylene glycol) (PTMG) were synthesized to increase local segmental motion for improved ion transport. Ionic conductivity and thermal behavior of LPC series–LiCF₃SO₃ complexes were investigated with various compositions, salt concentrations and temperatures. The PEG(70)/PTMG(30)/LiCF₃SO₃ electrolyte exhibited ionic conductivity of 8.04×10⁻⁵ S/cm at 25°C. Salt concentration with the highest ionic conductivity was considerably dependent on EO/TMO compositions in LPC series–salt systems. Relationship between solvating ability and chain flexibility with various compositions and salt concentrations was investigated through theoretical aspects of the Adam–Gibbs configurational entropy model. Temperature dependence on the ionic conductivity in LPC6 series–salt systems suggested the ion conduction follows the Williams–Landel–Ferry (WLF) mechanism, which is confirmed by Vogel–Tamman–Fulcher (VTF) plots. The ionic conductivity was affected by segmental motion of the polymer matrix. VTF parameters and apparent activation energy were evaluated by a non-linear least square minimization method. These results suggested that the solvating ability of the host polymer might be a dominant factor to improve the ionic conductivity rather than chain mobility.     

A novel accelerometer based on microring resonator

A novel microring resonator accelerometer is proposed. It is realized by a suspended straight waveguide coupled with a microring resonator. Under the external acceleration, the coupling coefficient is a function of gap spacing between the two waveguides. The mathematical model of the sensing element is established. Both the finite element method and coupled mode theory are adopted to analyze and optimize the proposed structure. Simulation results show that the mechanical sensitivity is 0.015 μm/g with the working frequency below 500 Hz and cross-axis sensitivity less than 0.001%, which is promising in seismic related applications.     

新型声表面波电流传感器*

将声表面波技术的快速响应特点与磁致伸缩薄膜的高磁敏特点相结合,可实现一种快速、高灵敏、稳定可靠的新型电流检测技术。传感器由双通道差分式振荡器与沉积在传感通道器件表面的声传播路径上的磁致伸缩薄膜组成。该文基于分层介质中声传播理论及磁致伸缩效应,对声表面波电流传感机理进行了分析,以实现对传感器结构的优化设计。实验研制了采用铁钴(FeCo)薄膜的声表面波电流传感器,测试结果表明,该传感器具有快速响应和高灵敏特点。为抑制磁致伸缩薄膜自身的剩磁效应所带来的高磁滞误差,采用的有效途径是将沉积的磁致伸缩薄膜进行图形化设计。实验结果表明,采用栅阵化FeCo薄膜结构的传感器表现出更高检测灵敏度、更好线性及更低的磁滞误差。     

A novel FOCAL technique based on BP-ANN

In this paper, the feed-forward back-propagation artificial neural network (BP-ANN) algorithm is introduced in the traditional Focus Calibration using Alignment procedure (FOCAL) technique, and a novel FOCAL technique based on BP-ANN is proposed. The effects of the parameters, such as the number of neurons on the hidden-layer and the number of training epochs, on the measurement accuracy are analyzed in detail. It is proved that the novel FOCAL technique based on BP-ANN is more reliable and it is a better choice for measurement of the image quality parameters.     

Effect of amphiphilic hyperbranched-star polymer on the structure and properties of PVDF based porous polymer electrolytes

An amphiphilic hyperbranched-star polymer (HPE-g-MPEG) was synthesized by grafting methoxy poly(ethylene glycol) to the end of the hyperbranched polyester (HPE) molecule using terephthaloyl chloride (TPC) as the coupling agent. The synthesized amphiphilic hyperbranched-star polymer was blended with poly(vinylidene fluoride) (PVDF) to fabricate porous membranes via typical phase inversion process, and then the membranes were filled and swollen by a liquid electrolyte solution to form polymer electrolytes. The influences of HPE-g-MPEG on the morphology, crystallinity, liquid electrolyte uptake, mechanical properties of the porous membranes and the electrochemical properties of the activated membranes were investigated. It was found that the addition of HPE-g-MPEG resulted in a significant increase in porosity and a considerable reduction in crystallinity of the blend membranes, which favored the liquid electrolyte uptake and, consequently, led to a remarkable increase in ion conductivity at ambient temperature. The maximum ion conductivity observed in this study was 1.76 × 10^? 3 S/cm at 20 °C for the blend membrane with a HPE-g-MPEG/PVDF ratio of 3/10 (w/w).     

Conductivities of electrolytes based on PEI-b-PEO-b-PEI triblock copolymers with lithium and copper TFSI salts

Tri block-copolymer poly(iminoethylene)-b-poly(oxyethylene)-b-poly(iminoethylene) with a poly(oxyethylene) central block (PEI-b-PEO-b-PEI) were used as a “dual” matrix for polymer electrolytes having selectivity for hard cations (Li⁺/PEO) in one phase and for soft cations (Cu²⁺/PEI) in the other. Conductivity measurements were recorded for 20:1, 12:1 and 8:1 coordinating atom (O or/and N) to cation (Li⁺, Cu²⁺) ratios, for each of the three complexes studied: PEI-b-PEO-LiTFSI-b-PEI, PEI-Cu(TFSI)₂-b-PEO-b-PEI-Cu(TFSI)₂ and PEI-Cu(TFSI)₂-b-PEO-LiTFSI-b-PEI-Cu(TFSI)₂. For either low (20 °C) or high temperature (80 °C) the highest conductivity was given by the polymer electrolyte based on Cu(TFSI)₂ with N/Cu²⁺ = 20:1 (10^− 6, respectively 2 × 10^− 4 S cm^− 1). In the present paper, the conductivity evolution is discussed in relation with the polymer structure, the type and the concentration of the salt and the thermal behavior of our systems.     

Surface properties of ionomers based on styrene-b-acrylic acid copolymers obtained by copolymerization in emulsion

Surface properties of styrene-b-acrylic acid copolymers obtained in emulsion and suitable ionomers before and after UV-irradiation were studied by measurements of contact angles and FTIR-ATR spectroscopy.The research focused on the influence of different content of carboxylic acid groups in copolymers, of various types and contents of alkali metal salts in ionomers and of cesium acrylate or methacrylate in ionomers on hydrophilicity of the surfaces of these samples and the course of photodegradation in them.Hydrophilicity of initial copolymer surfaces was higher than this of polystyrene as a result of presence of carboxylic acid groups, which also made the surfaces of these copolymers more sensitive to UV-irradiation.Hydrophilicity of the surfaces of ionomers containing cesium acrylates depended on the content of cesium salt in the samples. The course of ionomer photooxidation was also dependent on the content of this salt.The surface of ionomer containing cesium methacrylate was more polar than this of ionomer containing cesium acrylate.Styrene-based ionomers containing 3.7 mol% of various alkali metal acrylates had less polar surfaces than initial copolymer and they were also more resistant to UV-irradiation in comparison to the initial copolymer.Copolymers obtained in emulsion and suitable ionomers had more polar surfaces and they were more sensitive to UV-light compared to copolymers obtained in bulk and their ionomers.     

基于模拟电路的新型忆感器等效模型

本文首先利用光敏电阻阻值的可控性, 建立了磁通控制型忆阻器的等效电路模型. 通过对忆感器和忆阻器间转换关系的分析, 采用模拟电子元器件设计了磁通控制型忆感器的实用等效电路模型, 给出了理论分析并结合Pspice软件进行了仿真验证. 忆感器等效电路模型的韦安关系展现出典型的非线性磁滞回线特性. 最后, 运用实验手段研究了正弦波和三角波两种典型电压信号激励下忆感器与RC串联后电路的动态特征, 证明了本文提出忆感器等效电路模型的有效性. 关键词： 忆阻器 忆感器 磁滞回线特性 Pspice     

A novel frequency multiplier based on magnetoelectric laminate

We report a novel frequency multiplier based on the magnetoelectric (ME) effect in a simple multiferroic laminate, made up of an amorphous FeBSiC magnetic layer bonded onto a Pb(Zr,Ti)O₃ plate wrapped with a coil. By applying an input signal with a frequency f to the coil, an output signal with 2f can be generated from the PZT plate due to the ME coupling. This ME laminate-based device can be operated in a broad frequency range and switched by a low bias magnetic field, offering potential opportunities for frequency multipliers in electrical applications.