Molecular insight into structures of monocationic and dicationic ionic liquids in mica slits

Structures of ionic liquids (ILs) 1-decyl-3-methylimidazolium bis(trifluoromethanesulfonyl)azanide ([C₁₀mim][TFSA]) and 1-decyl-dimethylimidazolium bis(trifluoromethanesulfonyl)azanide ([C₁₀(mim)₂](TFSA)₂) in different-sized mica slits have been investigated using molecular dynamics simulations. Ion density and angular distributions for monocationic IL [C₁₀mim][TFSA] were analysed to elucidate the IL structures under different surface charges and especially their changes in the direction perpendicular to the surfaces. [C₁₀mim][TFSA] formes in bilayers, compatible with existing models of ILs with long alkyl chains. For dicationic IL [C₁₀(mim)₂](TFSA)₂, cations adjacent to the mica surface tend to stay parallel to the surface with both positively charged rings absorbed. While near the centre of the slit, dications show the weak tendency of orientation distribution, more random than [C₁₀mim]⁺ ions. Structures of [C₁₀(mim)₂](TFSA)₂ cannot be described by bilayer models. Additionally, the in-plane arrangement of [C₁₀mim][TFSA] is more ordered when K⁺ ions completely neutralise the negative charge of the mica surface, and [C₁₀mim]⁺ ions tend to be located in hexagonal mica lattices with two aluminium atoms in replacement of silicon atoms. [TFSA]^? ions are constrained by the neighbouring K⁺ ions absorbed onto mica lattices.     

Synthesis and characterization of iPP‐sPP stereoblock produced by a binary metallocene system

Stereoblock polypropylenes comprising of iPP and sPP segments are synthesized by polymerization of the following binary system of metallocenes: the C_s‐symmetric [2,7‐t‐Bu₂(Flu)₂Ph₂C(Cp)ZrCl₂] and the C₂‐symmetric rac‐Me₂Si(2‐Me‐4‐Ph‐Ind)₂ZrCl₂. Blends of samples made either by each catalyst individually (solution blend) with materials obtained with the mixed catalyst system (reactor blend) are compared. The simultaneous presence of MAO and DEZ, enhancing fast and reversible transfer of the growing chains between the two active centers, leads to the formation of a stereoblock microstructure. In this case, low molecular weight polymers are obtained. The junction between the blocks is qualitatively observed in ¹³C NMR. When made in toluene, the stereoblock material consists of a majority of syndiotactic sequences, whereas the ratio is more equilibrated when the polymerization was conducted in the more polar chlorobenzene. This is confirmed by the results obtained with ¹³C NMR, CRYSTAF, HT HPLC, DSC, SSA, WAXD, and optical microscopy. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 1422–1434     

Solvent‐free inkjet printing process for the fabrication of conductive,transparent, and flexible ionic liquid‐polymer gel structures

A new and solvent‐free process for the fabrication of inkjet printed ionic liquid‐polymer gel microstructures with high‐resolution (line widths of ～40 μm), good electrical conductivity (5–30 mS cm^?1), optical transparency, and mechanical flexibility is presented. Carrying out the printing and polymerization process in nitrogen atmosphere eliminates the inhibiting influence of oxygen and guarantees homogeneously gelled structures. Careful selection and combination of ionic liquids (ILs) and unsaturated monomers makes it possible to achieve low viscosities which are printable with commercially available inkjet printers and printheads without adding extra solvents. By using different types and amounts of ILs and monomers the resulting properties of the printed IL‐polymer gels can be controlled in terms of ionic conductivity, optical transmission, and mechanical flexibility. Higher conductivities are possible by using a bifunctional instead of a monofunctional monomer, which allows one to lower the amount of monomer without loss in mechanical strength. Cast samples make it possible to obtain data of transmission (～90% for 170‐μm thick films) and mechanical flexibility (E = 0.02–0.23 MPa) of bulk material. Comparing electrical conductivity of printed and cast samples, the higher values of printed samples indicate the conductivity enhancing influence of moisture absorbed from the surrounding atmosphere after the fabrication process. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

Aggregation of clay platelets in nematic liquid crystal, 5CB: microstructure,electrical conductivity and rheological investigations

The microstructure, electrical conductivity and rheological properties of a nematic liquid crystal (5CB) doped at concentrations up to 4.5 wt% of montmorillonite (MMT) or organomontmorillonite (OMMT) clay nanoplatelets, were investigated at temperatures between 293 and 310 K. Microscopy and electrical conductivity assessment revealed noticeable differences in aggregation in MMT and OMMT suspensions, MMT nanoplatelets showing a strong tendency to aggregation. The incubation of 5CB in the presence of MMT initially produced loose aggregation, followed by the formation of compact aggregates. The latter had practically no influence on the surrounding inter-aggregate regions. In the case of OMMT, a greater degree of integration of the nanoplatelets was observed within the liquid crystal structure of 5CB, resulting in a noticeable effect on electrical conductivity and activation energy of the composite material. Thixotropy was observed in suspensions of 5CB composites formed with either MMT or OMMT. A composite of 5CB with OMMT also exhibited anomalous viscous thinning at shear rates below 100 s^?1. A structural model is suggested to explain this behaviour.     

Azimuthal orientational correlations due to excluded volume epitaxy in growing anisotropic grains

The microstructure of anisotropically shaped grains can strongly influence a range of material properties, including transport, mechanical and electro-optical. A grain-structure-related phenomenon, known as excluded volume epitaxy (EVE), is reported in this study. EVE is a local, inter-grain orientational correlations effect, which results from a combination of continuous nucleation of anisotropic grains and impingement of growing grains. Due to EVE, anisotropically shaped grains have a tendency to be similarly aligned in a local neighbourhood, despite the absence of any forced global orientation in the sample. The effect has been repeatedly observed by the authors in block copolymers, as illustrated by a representative TEM image. Optical microscopy of anisotropically shaped non-polymeric crystals revealed the generality of this effect. The simulation study revealed a tendency for azimuthal, inter-grain orientational correlation and re-confirmed the experimental observation of EVE.     

Crystallographic and microstructural aspects of the superconductor YBa2Cu3O7-y —an overview

Crystal structures and structural inhomogeneities observed in YBa₂Cu₃O_7-y are reviewed. It is brought out that a proper understanding of the nature of the structural inhomogeneities is essential for exploiting the technological potential of this material. The need for an adequate characterization of specimens used for experiments is emphasized. Practical implications of the ferroelastic nature of the material are discussed.     

Characterization of the Charge Transfer Complex from Furan and Maleic Anhydride and the Alternating Copolymer

A previously unreported copolymer between furan and maleic anhydride was readily obtained by free radical initiation of benzene solutions of the comonomers. The product copolymers exhibit remarkably uniform composition regardless of monomer feed ratios. A donor-acceptor complex was suspected to account for the 1:1 alternating sequence of the monomers in the product. The complex was easily detected and partially characterized, although its exact role in the mechanism is uncertain.     

RADICAL POLYMERIZATION OF METHYL METHACRYLATE WITH DIPHENYL DISELENIDE UNDER THERMAL OR PHOTOIRRADIATIONAL CONDITIONS

Polymerization of methyl methacrylate (MMA) with diphenyl diselenide (DPDSE) in the presence of AIBN at 60°C was investigated. DPDSE was worked as a chain transfer agent (CTA). The chain transfer constant (C_tr) of DPDSE for MMA was estimated to be 1.43. On the other hand, DPDSE was functioned as a photoiniferter for the photopolymerization of MMA. In a limited range of conversion, both the polymer yield and number average of molecular weight ([Mbar]_n) increased with the reaction time, and the [Mbar]_n linearly increased with the yield. The terminal structure of poly(MMA) was investigated by the ⁷⁷Se NMR spectrum based on Methyl α-phenylseleno isobutylate (MSEPI) as model compound of the ω-chain end of poly(MMA). Further, photopolymerization of poly (MMA) containing phenylseleno group at ω-chain end as a polymeric photoiniferter with MMA effectively afforded a poly (MMA) having higher molecular weight.     

Arraying Cell Cultures Using PEG‐DMA Micromolding in Standard Culture Dishes

A robust and effortless procedure is presented, which allows for the microstructuring of standard cell culture dishes. Cell adhesion and proliferation are controlled by three‐dimensional poly(ethylene glycol)‐dimethacrylate (PEG‐DMA) microstructures. The spacing between microwells can be extended to millimeter size in order to enable the combination with robotic workstations. Cell arrays of microcolonies can be studied under boundary‐free growth conditions by lift‐off of the PEG‐DMA layer in which the growth rate is accessible via the evolution of patch areas. Alternatively, PEG‐DMA stencils can be used as templates for plasma‐induced patterning.