Silicone‐urethane membranes for lithium batteries. Part 1. Moisture‐cured poly(siloxane‐urethane‐urea) elastomers containing polyethylene oxide (PEO) segments – synthesis and characterization as potential membrane materials

Poly(siloxane‐urethane‐urea) elastomers containing both polysiloxane and polyethylene oxide (PEO) segments in the polymer chain were obtained by moisture‐curing of NCO‐terminated poly(siloxane‐urethane) prepolymers synthesized from isophorone diisocyanate and mixtures of polyoxyethylene diols and polysiloxane diols with various molecular weights. Mechanical properties of the moisture‐cured films and their swelling ability in solvent mixtures commonly used in lithium batteries were investigated, and it was found that they were greatly influenced by PEO content in the polymer. PEO content in the polymer was also found to affect very much the electric conductivity of the films after immersion in lithium salt solution in ethylene carbonate–dimethyl carbonate solvent mixture. At high contents of PEO in the polymer chain specific conductivities of the films in a range of 10^?3, Scm^?1 could be achieved at room temperature. Based on the results of Scanning Electron Microscopy with X‐ray Analysis (SEM/EDS) investigations and wide‐angle X‐ray scattering and small‐angle X‐ray scattering studies, it could be anticipated that the reason for good conductivity of the films might be their specific supramolecular structure that potentially facilitated lithium ion mobility. Copyright © 2015 John Wiley & Sons, Ltd.     

Solute redistribution profiles during rapid solidification of undercooled ternary Co-Cu-Pb alloy

The solute redistribution and phase separation of liquid ternary Co-35%Cu-32.5%Pb immiscible alloy have been investigated using glass fluxing method. A bulk undercooling of 125 K was achieved and the macrosegregation pattern was characterized by a top Co-rich zone and a bottom Cu-rich zone. The average solute contents of the two separated zones decreased with the increase of undercooling, except for the solute Pb in Cu-rich zone. With the enhancement of undercooling, a morphological transition from dendrites into equaxied grains occurred to the primary α(Co) phase in Co-rich zone. The solute redistribution of Cu in primary α(Co) phase was found to depend upon both the undercooling and composition of Co-rich zone. Stokes migration is shown to be the main dynamic mechanism of droplet movement during liquid phase separation.     

基于可调负载重分配的无标度网络连锁效应分析

为了深入研究复杂网络抵制连锁故障的全局鲁棒性,针对现实网络上的负载重分配规则常常是介于全局分配与最近邻分配、均匀分配与非均匀分配的特点,围绕负荷这一影响连锁故障发生和传播最重要的物理量以及节点崩溃后的动力学过程,提出了一种可调负载重分配范围与负载重分配异质性的复杂网络连锁故障模型,并分析了该模型在无标度网络上的连锁故障条件.数值模拟获得了复杂网络抵制连锁故障的鲁棒性与模型中参数的关系.此外,基于网络负载分配规则的分析以及理论解析的推导,验证了数值模拟结论,也证明在最近邻与全局分配两种规则下都存在负载分配均匀性参数等于初始负荷强度参数即β=τ使得网络抵御连锁故障的能力最强.     

强外电场作用下二甲基硅酮的分子结构和激发态

The ground states of dimethyl siloxane under different intense electric fields ranging from - 0. 04 to 0. 04 a. u. are optimized using density functional theory DFT / B3P86 at 6-311 ++ G（d,p）level. The excitation energies and oscillator strengths under the same intense applied electric fields are calculated employing the revised hybrid CIS-DFT method. The result shows that the electronic state,molecular geometry,total energy,dipole moment and excitation energy are strongly dependent on the field strength and behave asymmetry to the direction of the applied electric field. As the electric field changes from - 0. 04 to 0. 04 a. u. ,the bond length of Si-O increases whereas the bond length of Si-C decreases because of the charge transfer induced by the applied electric field. The dipole moment of the ground state decreases linearly with the applied field strength. However,the dipole moment of molecule changes from positive to negative as the inverse electric field increase to - 0. 03 a. u. Further increase of the inverse electric field results in an increase of the total energy of the molecule. The dependence of the calculated excitation energies on the applied electric field strength is fitting well to the relationship proposed by Grozema. The excitation energies of the first five excited states of dimethyl siloxane decrease as the applied electric filed increases because the energy gap between the HOMO and LUMO become close with the field,which shows that the molecule is easy to be excited under electric field and hence can be easily dissociated.     

Liquid‐Crystalline Soft Actuators with Switchable Thermal Reprogrammability

Thermal reprogrammability is essential for new‐generation large dry soft actuators, but the realization sacrifices the favored actuation performance. The contradiction between thermal reprogrammability and stability hampers efforts to design high‐performance soft actuators to be robust and thermally adaptable. Now, a strategy has been developed that relies on repeatedly switching on/off thermal reprogrammability in liquid‐crystalline elastomer (LCE) actuators to resolve this problem. By post‐synthesis swelling, a latent siloxane exchange reaction can be induced in the common siloxane LCEs (switching on), enabling reprogramming into on‐demand 3D‐shaped actuators; by switching off the dynamic network by heating, actuation stability is guaranteed even at high temperature (180 °C). Using partially black‐ink‐patterned LCEs, selectively switching off reprogrammability allows integration of completely different actuation modes in one monolithic actuator for more delicate and elaborate tasks.     

Synthesis and characterization of siloxane resins derived from silphenylene‐siloxane copolymers bearing benzocyclobutene pendant groups

Two bis(dimethylamimo)silanes with benzocyclobutene (BCB) groups, bis(dimethylamino)methyl(4′‐benzocyclobutenyl)silane ( 2 ) and bis(dimethylamino)methyl [2′‐(4′‐benzocyclobutenyl)vinyl]silane ( 4 ), were synthesized from different synthetic routes, which were then employed to prepare two novel silphenylene‐siloxane copolymers (SiBu and SiViBu) bearing latent reactive BCB groups by polycondensation procedure with 1,4‐bis(hydroxydimethylsilyl)benzene. At elevated temperatures these copolymers were readily converted to highly crosslinked films and molding disks with network structures by polymer chain crosslinking, which followed the first‐order kinetic reaction model. The final resins of SiBu and SiViBu demonstrated excellent thermal stability with high glass transition temperatures (218 and 256 °C) and high temperatures at 5% weight loss (553 and 526 °C in N₂, 530 and 508 °C in air). After aging at 300 °C in air for 100 h, the cured resins showed weight loss lower than 4%. The films of cured SiBu and SiViBu also exhibited relatively low dielectric constants of 2.66 and 2.64, low dissipation factors of 2.23 and 2.12 × 10^?3, low water absorptions (≤0.28%), and high transparence in the visible region with cutoff wavelengths of 321 and 314 nm. Moreover, the aged films exhibited good dielectric properties and low water absorptions. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 7868–7881, 2008     

An analytical study on the bond behaviour between an externally bonded FRP and concrete in the case of continuous beams

One of the greatest challenges in structural engineering nowadays is the strengthening, upgrading, and retrofitting of existing structures. The use of fibre-reinforced polymers (FRPs) bonded to the tension face of a structural member is an attractive technique in this field of application. The strengthening of reinforced concrete structures by means of an externally bonded reinforcement (EBR) is achieved by gluing a FRP laminate to the concrete substrate. For an efficient utilization of the FRP EBR systems, an effective stress transfer is required between the FRP and concrete. The paper discusses the bond behaviour between a FRP and concrete in the case of flexural strengthening of continuous beams. With respect to this type of beams, only a few studies have been reported, though continuous members often occur in concrete constructions. The structural behaviour of statically indeterminate elements is typically characterized by redistributions of the internal forces. These distributions are related to the nonlinear deformations of the beams and has also a distinct influence on the bond behaviour between the FRP and concrete. Russian translation published in Mekhanika Kompozitnykh Materialov, Vol. 44, No. 3, pp. 389–402, May–June, 2008.