Synthesis and tailoring phase behavior of mesogen jacketed liquid crystalline copolymers based on 2, 5‐bis[(4‐alkoxyphenyl)oxycarbonyl]styrenes

Based on 2, 5‐bis[(4‐alkoxyphenyl)oxycarbonyl]styrenes (M‐OCm, m is the number of the carbons of alkyl tails, m = 1, 4, and 18), three series of binary copolymers with high‐molecular weights, {poly(M‐OC1‐co‐M‐OC4), poly(M‐OC1‐co‐M‐OC18), and poly(M‐OC4‐co‐M‐OC18)} have been prepared via free‐radical polymerization. The random nature of the copolymers was expected on the basis of the assumed similar reactivities because of the analogous monomers. The phase behaviors of copolymers were studied by DSC, POM, and one‐dimensional wide‐angle X‐ray diffraction. The results showed that liquid crystalline (LC) phase structures of copolymers, containing smectic phase, reentrant isotropic phase, columnar phase. and isotropic phase, were strongly depended on the composition and the alkyl length due to the competing among the steric effect, the microphase separation and the driving force of the entropy. When one of them occupied a dominant position, the LC phase structure can be presented for the copolymers. Otherwise, the LC phase structure is lost despite the pair of corresponding homopolymers forming mesogenic structure. Therefore, through copolymerization, LC behavior of the mesogen‐jacketed liquid crystalline polymers can be greatly varied. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 2804–2816     

Synthesis and Characterization of the Titanium Containing Mesoporous Molecular Sieve MCM-48

Ti-MCM-48 mesoporous materials have been synthesized by sequential addition of alkoxides. The atomic ratio of Si and Ti in the synthesis gel was 40 and 5, respectively. The materials were characterized by means of powder XRD, N₂ adsorption-desorption measurements. HREM, ²⁹Si MAS NMR, diffuse reflectance FT-IR spectroscopy, electrophoretic mobility measurements and electron probe microanalysis.     

Solution‐processable colorless polyimides derived from hydrogenated pyromellitic dianhydride with controlled steric structure

This work presents novel colorless polyimides (PIs) derived from 1R,2S,4S,5R‐cyclohexanetetracarboxylic dianhydride (H″‐PMDA). Isomer effects were also discussed by comparing with PI systems derived from conventional hydrogenated pyromellitic dianhydride, that is, 1S,2R,4S,5R‐cyclohexanetetracarboxylic dianhydride (H‐PMDA). H″‐PMDA was much more reactive with various diamines than H‐PMDA, and the former led to PI precursors with much higher molecular weights. The results can be explained from the quite different steric structures of these isomers. The thermally imidized H″‐PMDA‐based films were colorless regardless of diamines because of inhibited charge‐transfer interaction. In particular, the H″‐PMDA/4,4′‐oxydianiline system simultaneously achieved a very high T_g exceeding 300 °C, high toughness (elongation at break > 70%), and good solution processability. In contrast, the H‐PMDA‐based counterparts were essentially insoluble. The outstanding solubility of the former probably results from disturbed chain stacking by its nonplanar steric structure. An advantage of chemical imidization process is also proposed. In some cases, a copolymerization approach with an aromatic tetracarboxylic dianhydride was effective to improve the thermal expansion property. The results suggest that the H″‐PMDA‐based PI systems can be promising candidates for novel high‐temperature plastic substrate materials in electronic paper displays. A potential application as optical compensation film materials in liquid crystal displays (LCD) is also proposed in this work. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Thermoresponsive brush copolymers with poly(propylene oxide‐ran‐ethylene oxide) side chains via metal‐free anionic polymerization “grafting from” technique

Thermoresponsive brush copolymers with poly(propylene oxide‐ran‐ethylene oxide) side chains were synthesized via a “grafting from” technique. Poly(p‐hydroxystyrene) was used as the backbone, and the brush copolymers were prepared by random copolymerization of mixtures of oxyalkylene monomers, using metal‐free anionic ring‐opening polymerization, with the phosphazene base (t‐BuP₄) being the polymerization promoter. By controlling the monomer feed ratios in the graft copolymerization, two samples with the same side‐chain length and different compositions were prepared, both of which possessed high molecular weights and low molecular weight distributions. The results from light scattering and fluorescence spectroscopy indicated that the brush copolymers in their dilute aqueous solutions were near completely solvated at low temperature and underwent slight intramolecular chain contraction/association and much more profound intermolecular aggregation at different stages of the step‐by‐step heating process. Above 50 °C, very turbid solutions, followed by macrophase separation, were observed for both of the samples, which implied that it was difficult for the brush copolymers to form stable nanoscopic aggregates at high temperature. All these observations were attributed, at least partly, to the distribution of the oxyalkylene monomers along the side chains and the overall brush‐like molecular architecture. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2320–2328, 2010     

Optical characterization of polycarbonate: Influence of additives on optical properties

In laser transmission welding of thermoplastics the optical properties of the joining parts determine the quality of the welding result. Especially, the scattering of laser radiation in the transparent welding part has an impact on weld seam properties. This scattering is caused by additives. For polycarbonate (PC) with different additives the transmittance, the reflectance and the collimated transmittance are measured with a UV‐VIS‐NIR spectrometer. From this data, the optical properties, such as scattering coefficient, absorption coefficient, and anisotropy factor are calculated. The calculations are made with the aid of the four‐flux model of radiation transport in the diffusive approximation. The results show that the additives have a significant influence on the scattering coefficient. For most additives under consideration the scattering is forward directed, which means that most of the radiation is transmitted into the absorbing welding part. However, the power density distribution of the transmitted radiation may differ significantly from PC without additives. So, the weld seam may also differ due to different additives. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 451–455, 2010     

Electro-osmotic flow of a viscoelastic fluid in a channel : Applications to physiological fluid mechanics

The paper presents a comprehensive theoretical study on the electro-osmotic flow of a viscoelastic fluid past a channel having stretching walls. An attempt has been made to investigate the effect of rheological and electro-osmotic parameters on the kinematics of the fluid. Results presented here pertain to the case where the channel height is much greater than the thickness of electrical double layer comprising the Stern and diffuse layers. The study reveals that an increase in electro-osmotic parameter leads to an increase in the axial velocity throughout the channel for a fluid having viscoelastic coefficient equal to that of blood. This aspect provides a source of novel insight into the process of designing bio-sensing and micro-fluidic devices.     

Rich-club and page-club coefficients for directed graphs

Rich-club and page-club coefficients and their null models are introduced for directed graphs. Null models allow for a quantitative discussion of the rich-club and page-club phenomena. These coefficients are computed for four directed real-world networks: Arxiv High Energy Physics paper citation network, Web network (released from Google), Citation network among US Patents, and email network from a EU research institution. The results show a high correlation between rich-club and page-club ordering. For journal paper citation network, we identify both rich-club and page-club ordering, showing that “elite” papers are cited by other “elite” papers. Google web network shows partial rich-club and page-club ordering up to some point and then a narrow declining of the corresponding normalized coefficients, indicating the lack of rich-club ordering and the lack of page-club ordering, i.e. high in-degree (PageRank) pages purposely avoid sharing links with other high in-degree (PageRank) pages. For UC patents citation network, we identify page-club and rich-club ordering providing a conclusion that “elite” patents are cited by other “elite” patents. Finally, for email communication network we show lack of both rich-club and page-club ordering. We construct an example of synthetic network showing page-club ordering and the lack of rich-club ordering.     

Improvement in estimating the population mean in simple random sampling using information on auxiliary attribute

This paper proposes some estimators for the population mean by adapting the estimator in Singh et al. (2008) [5] to the ratio estimators presented in Kadilar and Cingi 2006 [2]. We obtain mean square error (MSE) equation for all proposed estimators, and show that all proposed estimators are always more efficient than ratio estimator in Naik and Gupta (1996) [3], and Singh et al. (2008) [5]. The results have been illustrated numerically by taking some empirical population considered in the literature.     

Effective responses of nonlinear elliptic cylindrical composites

The higher-order dielectric responses of composites composed of weakly nonlinear elliptic cylindrical inclusions randomly embedded in linear media are investigated. The general formulae for effective DC coefficients are newly derived by the average field method up to the ninth order and then applied to analyze the effects of inclusion shapes on the effective response. The results are directly transformed to the quasi-static AC response of the composites under the sinusoidal external electric field with fundamental and third harmonic frequencies. The more general relationships between the effective DC and AC coefficients are established up to the seventh order and third harmonic, which are applicable to all weakly nonlinear isotropic composites.