Distinguishing the parallel and vertical orientations and optic axis characteristics determination of azobenzene mesogen by conoscopic polarized microscopy

Orientational behaviours under the action of linearly polarized light and circularly polarized light of a side-chain azobenzene containing polymer were studied by conoscopic polarized microscopy. The results suggest that the linearly polarized light (473 nm, 20 mW cm(-2)) results in an in-plane orientation of the azobenzene groups. The irradiation with circularly polarized light (473 nm, 20 mW cm(-2)) leads to a tilt orientation (out-of-plane) of the azobenzene groups with the long axis of mesogens aligned along the propagation direction of the actinic light. Characteristic features of the in-plane and out-of-plane orientated films were obtained from their interference figures. The in-plane orientated film shows an interference cross consisting of a broad fuzzy bar, and the cross-centre lies in the centre of view field. In-plane orientated film also yields a flash figure upon a less than 10° rotation of the sample under polarized microscopy. The interference figures yielded from the out-of-plane orientated films consist of narrow bar cross. The locations of those interference figures depend on the oblique angle of the irradiation light. A method for distinguishing the in-plane orientation of the mesogens from the vertically out-of-plane orientation is demonstrated, which is based on comparing the bar width of their interference figures, and by whether they can produce a flash figure upon a small angle rotation of the film. The liquid crystalline film is identified as positive and uniaxial anisotropy after annealing of the perpendicularly irradiated film.     

聚砜/聚碳酸酯/热致液晶聚合物共混体系的流变性及形态

对聚砜（ＰＳＵ）／聚碳酸酯（ＰＣ）／热致液晶聚合物（ＴＬＣＰ）共混体系的流变性及形态进行了研究。结果表明，ＰＳＵ／ＴＬＣＰ＝９５／５、ＰＳＵ／ＰＣ＝７０／３０、ＰＳＵ／ＰＣ／ＴＬＣＰ＝６６．５／２８．５／５三种共混物的表观粘度均比ＰＳＵ的表观粘度低很多，且ＰＳＵ／ＰＣ／ＴＬＣＰ共混物的表观粘度也较ＰＳＵ／ＰＣ的有所下降。形态研究表明，ＰＳＵ与ＰＣ、ＴＬＣＰ具有部分相容性，ＴＬＣＰ以不规则的颗粒状分散在ＰＳＵ／ＰＣ基质中。     

Polymer surface properties and their effect on the adhesion of Proteus mirabilis

A problem encountered in patients undergoing long-term catheterization of the urinary tract is that of encrustation and blockage of the catheter by crystalline bacterial biofilms. This is principally caused by the action of the urease-producing pathogen Proteus mirabilis. A major aim of this work is to develop materials resistant to encrustation. Here, the effects of polymer surface properties on the adhesion of P. mirabilis are examined. Spin-coated polymer films were characterized through contact angle measurements to give the Lifschitz-van der Waals, electron acceptor and electron donor terms of the surface free energy, gamma(s)LW, gamma(s)+ and gamma(s)- respectively. A parallel-plate flow cell was used to assess adhesion to these polymer films of P. mirabilis suspended in an aqueous phosphate buffer, pH 7.4, ionic strength 0.26 mol/kg. P. mirabilis was found to adhere significantly less (p < 0.02) to films of agarose, poly(2-hydroxyethylmethacrylate) and cross-linked poly(vinyl alcohol) than to more hydrophobic materials. These polymer films were found to be strongly electron donating, i.e. possessing large gamma(s)-. Films examined using scanning electron microscopy mostly showed no evidence of roughness down to a scale of 1-10 microm. The better performance is thought to be due to a repulsive interaction with the bacterial surface caused by acid/base-type interactions.     

Structure and morphology of the in situ composites of a liquid crystalline polymer and polycarbonate

In situ composites were prepared via melt blending of a liquid crystalline polymer (LCP) and polycarbonate using a twin screw extruder. The structure and morphology of these composites were analysed using both transmission electron microscopy (TEM) and scanning electron microscopy. The LCP phases were able to orientate and form in situ submicrometre fibres during the extrusion and post-extrusion drawing. TEM images as well as selected-area diffraction patterns were obtained from the materials. The effects of both composition, i.e. LCP content, and post-extrusion draw-down ratio on the development of the in situ formed LCP fibres were studied in detail. A skin–core morphological differentiation is observed in these materials where well-defined LCP fibres of higher aspect ratios were formed in the skin region. However, a significant amount of unelongated LCP particles were found coexisting with the less well-defined fibres in the core region of the extrudates. This skin–core differentiation was found to be dependent on the composition and the processing conditions, e.g. draw ratio. In this instance, electron microscopy is proven to be a powerful technique not only for direct observation of the formation, dimensions and morphology of the in situ LCP fibres, but also for the qualitative and quantitative characterization of the molecular orientation and crystalline structures in these fibres using selected-area electron diffraction. It is observed that the skin–core differentiation becomes more distinct in the in situ composites containing a higher percentage of LCP but diminishes when the material is processed at higher post-extrusion draw ratio.     

半灵活主链型液晶聚合物的结构特性

采用分子动力学(MD)模拟方法研究了半灵活主链型液晶聚合物(LCPs)的结构特性,其中分子链通过最新定义的模型——Solo-LJ-SP-GB模型来描述。该模型已被证实所需计算时间不到传统GB/LJ模型的十分之一,可大大地提高计算效率。通过模拟半灵活主链型LCPs 的液晶形成过程,研究了LCP分子中不同个数的间隔体对该材料热力学特性的影响。研究发现其热力学特性呈现出与间隔体个数相关的奇偶效应,这与现有试验结果相当吻合。通过对半灵活主链型LCPs的局域空间方位时间相关函数及平移灵活性的测量,并与传统GB/LJ模型的模拟结果相比较,发现两种模型显示出相似的各向异性及灵活性。     

非对称锚定制备均匀单畴排列铁电液晶器件

为了消除chiral nematic-chiral smectic C(N*-SmC*)相序铁电液晶从N*相降温到SmC*相时形成的两畴织构缺陷,提高液晶的响应速度,选用铁电液晶R-2301以及两种取向剂SE-410和RN-1199制备了5种铁电液晶样品器件。实验后,对5种器件的排列织构的正交偏光显微镜照片进行对比,得出通过非对称边界锚定作用可以得到均匀单畴排列的铁电液晶器件的结论。实验结果表明:经过非对称边界锚定作用可以得到电光曲线为半"V"字型且静态对比度为300:1的均匀单畴排列铁电液晶器件。这一结论和理论近似计算结果相吻合,为N*-SmC*相序铁电液晶器件实现单畴排列制备提供了新的方法和途径。     

聚砜/半芳族热致液晶聚合物原位复合材料的形态及性能

向聚砜 (PSF)中加入 5 %可原位成纤的半芳族热致液晶聚合物 (TL CP1) ,原位复合材料的表观粘度同PSF相比有明显降低 ,聚砜的加工性得到明显改进 ,同时复合材料的拉伸强度、弯曲强度、拉伸模量、弯曲模量均有所提高。形态研究表明 :在 TL CP含量为 5 %～30 %范围内 TL CP1均可在基体中分散并形成具有一定长径比的微纤。当 TL CP1用量高于 10 %时 ,原位复合体系呈现明显的皮 -芯形态 ,抗拉及抗弯曲性能发生劣化 ,但模量显著增加     

Towards self-lubricated nanocoatings

The microtribological performance of molecularly thick (<10 nm) thermoplastic elastomeric films grafted to a silicon surface was enhanced by adding a minute amount of paraffinic oil, which was adsorbed from vapor phase and held by the rubber matrix. We studied the kinetics of polymer swelling in oil and the formation of polymer gels. We observed that a vast majority of adsorbed oil evaporated from the ultrathin polymer coating leaving a minute amount of oil trapped within the rubber phase. This resulted in a dramatic enhancement of the microtribological performance of the grafted polymer gel layers. These polymer gel layers exhibited a very steady friction response and a small value of the coefficient of friction as well as greater wear-resistance as compared to the initial polymer coating. The performance of polymer gel coatings was much better than the performance of a classic ‘boundary lubricant’ for silicon surfaces, an alkylsilane self-assembled monolayer. The approach proposed demonstrated a new efficient route towards enhanced tribological performance of ultrathin polymer coatings.     

Exploring dynamic surface processes during silicate mineral (wollastonite) dissolution with liquid cell TEM

Most liquid cell transmission electron microscopy (LC TEM) studies focus on nanoparticles or nanowires, in large part because the preparation and study of materials in this size range is straightforward. By contrast, this is not true for samples in the micrometre size range, in large part because of the difficulties associated with sample preparation starting from a ‘bulk’ material. There are also many advantages inherent to the study of micrometre‐sized samples compared to their nanometre‐sized counterparts. Here, we present a liquid cell transmission electron study that employed an innovative sample preparation technique using focused ion beam (FIB) milling to fabricate micrometre‐sized electron transparent lamellae that were then welded to the liquid cell substrate. This technique, for which we have described in detail all of the fabrication steps, allows for samples having dimensions of several square micrometres to be observed by TEM in situ in a liquid. We applied this technique to test whether we could observe and measure in situ dissolution of a crystalline material called wollastonite, a calcium silicate mineral. More specifically, this study was used to observe and record surface dynamics associated with step and terrace edge movement, which are ultimately linked to the overall rate of dissolution. The wollastonite lamella underwent chemical reactions in pure deionized water at ambient temperature in a liquid cell with a 5‐m‐spacer thickness. The movement of surface steps and terraces was measured periodically over a period of almost 5 h. Quite unexpectedly, the one‐dimensional rates of retreat of these surface features were not constant, but changed over time. In addition, there were noticeable quantitative differences in retreat rates as a function crystallographic orientation, indicating that surface retreat is anisotropic. Several bulk rates of dissolution were also determined (1.6–4.2 ? 10^?7 mol m^?2 s^?1) using the rates of retreat of representative terraces and steps, and were found to be within one order of magnitude of dissolution rates in the literature based on aqueous chemistry data.     

Tribological Behavior of Grafted Polymer Gel Nanocoatings

A robust molecular lubrication layer on a silicon surface has been fabricated from a grafted polymer gel with thickness below 10 nm. A functionalized rubber-glassy block-copolymer was chemically grafted to a silicon oxide surface and its tribological performance was enhanced by vapor saturation with a minute amount of alkyl-based paraffinic oil. A combination of tribological measurements and Auger electron spectroscopy was used to monitor the polymer layer wearing behavior. We observed that unlike a dry polymer layer and a classic boundary lubricant, an alkylsilane self-assembled monolayer, the polymer gel coating exhibited a steady friction response, a very low value of the coefficient of friction, and possessed much higher wear-resistance.     

蛋白质组学研究中的多维液相分离系统

在后基因组时代,蛋白质组学成为新的研究热点。多维液相分离系统具有分离样品动态范围宽、分辨率高、峰容量大、分析速度快、自动化程度高等优点,因而近年来在蛋白质组学的研究中受到了越来越多的关注。本文根据目前已发表的文章,对二维液相色谱(2D-LC)、二维液相色谱-毛细管电泳(2D-LC-CE)、二维毛细管电泳(2D-CE)以及它们在蛋白质组学中的应用进行了系统的综述。     

用溶胶—凝胶方法制备磁光记录用的铋代钇铁石榴石薄膜

研究了在ＧＧＧ基底上用溶胶—凝胶方法制备的铋代钇铁石榴石单晶薄膜的磁光法拉弟效应与铋的替代量之间的关系。该膜层是以低于液相外延３００℃左右的６６０℃在大气中退火４ 小时制得的。最大的铋的置换量为ｘ＝ ２．７,实验发现石榴石相的晶化温度随ｘ 的增大而降低。且薄膜有很强的法拉弟效应,在λ＝ ０．６３３μｍ 的波长,可达－ ８．１×１０４ｄｅｇ／ｃｍ 。     

Microstructure of PTFE-Based Polymer Blends and Their Tribological Behaviors Under Aqueous Environment

Four polytetrafluoroethylene-based polymer blends (PTFE blends) with polyimide (PI), polyether ether ketone (PEEK), poly(phenyl p-hydroxybenzoate) (PHBA), and perfluoroethylene propylene copolymer (FEP) were prepared by compression molding and follow-up sintering. Their microstructure was observed by scanning electron microscope. And the tribological behaviors of PTFE blends sliding against 316 steel under pure water and sea water lubrication were comparatively evaluated using block-on-ring tribology test rig. The worn surface of counterpart was examined by X-ray photoelectron spectroscopy. The results showed that by blending with the four polymers, PTFE exhibited the transformed microstructure and improved wear resistance. Compared with FEP, rigid polymers PI, PHBA, and PEEK can enhance the wear resistance of PTFE greatly because they can effectively improve the load-carrying capacity of PTFE matrix and can more efficiently prevent the crystalline bands of PTFE from being pulled out. However, because of the weak inhibition on the pulling out of PTFE crystalline bands, FEP cannot enhance the wear resistance of PTFE as significantly as other polymers. In addition, the friction coefficients and wear rates of PTFE and its blends were lower under the lubrication of sea water than under the lubrication of pure water, which was ascribed to more excellent lubricating effect of sea water originating from the deposition of CaCO₃ and Mg(OH)₂ onto the sliding surfaces.     

Studying local liquid velocity in liquid–solid packed bed using the newly developed X-ray DIR technique

Combination of X-ray Digital Industrial Radiography (DIR) and Particle Tracking Velocimetry (PTV) techniques for local liquid velocity measurement (V_LL) has been newly developed and successfully applied for trickle bed reactor (TBR). The technique was validated against newly developed fiber optical probe technique. This work attempts to highlight the applicability of this newly developed technique on a liquid–solid packed bed reactor. In this work, liquid was represented by water and solids were represented by EPS beads. The EPS beads were chosen because of its low density property. Three superficial liquid velocities (V_SL) were applied to the system. The experiment was replicated four times. The digital industrial radiography (DIR) consists of a complementary metal oxide semiconductor (CMOS) digital detector and X-ray source. Results of this work suggest that the technique has been successfully applied and comparable with previous work that has been done in the literature. It also suggests that there will be a maximum measurable interstitial liquid velocity when it travel inside the packed bed. The measured V_LL can have a maximum range that is between 4 and 4.7 times that of its V_SL. For V_SL=0.42±±2%, the V_LL-Max is in between 1.7 cm/s and 1.9 cm/s, V_SL=0.84±±2%, the V_LL-Max is in between 3.6 cm/s and 4.0 cm/s, and for V_SL=1.11±±2%, the V_LL-Max is in between 4.3 cm/s and 4.8 cm/s.     

Study on carrier mobility measurement using electroluminescence in frequency domain and electrochemical impedance spectroscopy

In this paper, the two methods, electroluminescence in frequency domain and electrochemical impedance spectroscopy, have been applied to investigate the carrier mobility in single layer polymer light-emitting diode employing the polymer MEH-PPV (Poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene]) as the light-emitting layer. The carrier mobility μ is 1.64 × 10⁻⁶ cm²/V s under the electric field 8.3 × 10⁵ V/cm measured by the method of electroluminescence in frequency domain. The electrochemical impedance spectroscopy results indicate that the carrier mobility μ is 1.08 × 10⁻⁶ cm²/V s under the electric field 7.5 × 10⁵ V/cm. A significant advantage of the two methods is that both of them can be applied to measure the carrier mobility in the thin film.     

Shearing microscopy using polarized optical microscope with shear stage and spectral analyser to study liquid crystalline polymers

In‐situ polarized optical microscopy using a shear stage and a spectral analyser as well as a CCD camera were applied to study the phase transition under shear flow for a thermotropic and side‐chain‐type liquid crystalline polysiloxane. The onset of the appearance of anisotropic texture of the polysiloxane was observed under shear flow using the CCD camera at temperatures much higher than the isotropic‐liquid crystalline phase transition temperature if the polysiloxane was cooled from the isotropic phase in the quiescent state. Both the onset temperature and the temperature for full development of the anisotropic texture across the field of view became higher as the shear rate increased. The transmitted light intensity was also measured using a spectral analyser with crossed polarisers at wavelengths from 300 nm to 800 nm, and the integrated intensity of the spectrum was calculated. Changes in the spectrum and the integrated intensity against temperature in the cooling process were compared with observation using the CCD camera. Temperature dependence of the integrated intensity showed that the onset of the appearance of the anisotropic texture under high shear rates was detected at temperatures slightly higher than that observed using the CCD camera.     

Instability of Electrically Driven Polymer Liquid Jets

Polymer nanofibers can be generated by a electrospinning process. The process involves electrically charged jet of polymer solutions evolving from a droplet. The jet stretches in vertical direction due to the difference between charged particle and constant current located at the collector, while the Coulomb and viscoelastic forces start to contribute to radial and azimuthal (torsional) stretching. In this paper, the unstable dynamics of the liquid polymer jet is examined experimentally and theoretically. A complex viscoelastic rheological model has been adopted to analyze the behavior of a charged liquid jet. The model includes complex phenomena of stress relaxation of the liquid jet resulting from the competing force components. The experimental data of the jet paths captured by high-speed videocamera also confirm the similar behavior with the predictions.     

Design of Low Wear Polymer Composites

Multifunctional tribological coatings rely on combinations of materials to improve properties, such as lubricity and wear resistance. For example, some polymer composites exhibit favorable tribological performance as solid lubricants. Here, classical molecular dynamics simulations are used to investigate the tribological behaviors of a mixed system of polyethylene (PE) sliding over polytetrafluoroethylene (PTFE) with the results compared with the sliding of the relevant homogeneous systems. In particular, oriented cross-linked PTFE and PE surfaces are slid in several relative sliding directions such that the surface chains are in-registry or out-of-registry and at various applied normal loads. The simulation results quantify the ways in which the mixed PTFE–PE system behaves differently than either of the homogeneous systems due to the lack of interlocking phases at the interface. These findings are compared with experimental production of polyetheretherketone (PEEK)–PTFE composites that have unusually low wear rates of 7.0 × 10⁻⁸ mm³/Nm, coupled with a steady, low friction coefficient of μ = 0.11 for over two million sliding cycles. The simulation results explain the atomic-scale origins of the frictional properties of this composite.     

应用组合型四极杆-静电轨道阱质谱研究一种新合成二肽聚合物对糖肽的富集效果

采用高分辨和高质量精度的组合型四极杆-静电轨道阱质谱（hybrid quadrupole orbitrap mass spectrometer）全面分析一种新合成的二肽聚合物对糖肽的富集效果,并由此建立一种评价材料对糖肽富集效果的方法。实验配制了一系列不同质量浓度比的牛胎球蛋白（bovine fetuin,糖蛋白）与牛血清蛋白（BSA,干扰蛋白）的混合干扰模型,先用胰蛋白酶酶解处理混合蛋白样品,再经合成的二肽聚合物富集样品中的糖肽。通过优化糖肽富集步骤和质谱分析条件,新合成的二肽聚合物可以从干扰蛋白浓度达目标蛋白100倍的样品中成功富集糖肽。与亲水性相互作用色谱（hydrophilic interaction liquid chromatography, HILIC）相比,该材料的富集性能远高于HILIC小柱。因此,该二肽聚合物能够提供更有效的糖肽富集,可为糖蛋白/糖肽的分离富集提供新途径。     

Ultrastructure of Tracheal Surface Liquid: Low-Temperature Scanning Electron Microscopy

A layer of liquid lines the airways in the lung. Previous microscopic studies have suggested that it is in two phases, with a mucous gel lying above a periciliary sol. However, shrinkage artifacts due to chemical fixation, dehydration, and drying have prevented reliable estimates of the depth of these layers. To avoid such problems, we have studied the surface liquid of bovine trachea by low-temperature scanning electron microscopy (LTSEM). A polished copper probe cooled to liquid nitrogen temperature was applied to the mucosal surface of sheets of excised tracheal epithelium to effect rapid freezing of surface liquid. Tissue sheets were then mounted in an LTSEM (AMRay 1000A with Biochamber) which maintains samples at -180°C with a Joule-Thompson refrigerator built into the stage. Tissues were fractured at right angles to the epithelial surface, coated with gold, and viewed, all at 10^?5 to 10^?6 torr without transfer through air. The sample was stable under the electron beam at accelerating voltages up to 20 kV. Epithelial features (nuclei, cilia, microvilli, mucous granules) were well preserved. The mucosal surface of the cells was covered with material on the order of 8 μm in depth. The mucous gel and periciliary sol could be seen as distinct layers and could be distinguished by the size and pattern of ice crystal voids generated by radiant-etching of the fractured surface of the sample.