Double metal cyanide catalyst prepared using H3Co(CN)6 for high carbonate fraction and molecular weight control in carbon dioxide/propylene oxide copolymerization

Simple mixing of H₃Co(CN)₆ and ZnCl₂ in methanol resulted in precipitates of [ZnCl]⁺₂[HCo(CN)₆]^2?, constituting a new type of double metal cyanide (DMC) catalyst exhibiting a high performance in carbon dioxide (CO₂)/propylene oxide (PO) copolymerization. High‐molecular‐weight poly(propylene carbonate‐co‐propylene oxide)s [poly(PC‐co‐PO)s] (M_n～40,000) were consistently obtained with high carbonate fractions (～60 mol %) and a high selectivity (>95%) with the new type of DMC catalyst. Conventional preparation of the DMC catalyst using K₃Co(CN)₆ and ZnCl₂ required removing KCl through thorough washing and resulted in lower carbonate fractions (10–40 mol %), which depended on the washing conditions. Feeding hydrophobic diols such as 1,10‐decanediol as chain transfer agent preserved the high carbonate fraction (～60%) and enabled precise control of the molecular weight, including preparation of a low‐molecular‐weight poly(PC‐co‐PO)‐diol (M_n ～2000), which was a flowing viscous liquid with a low T_g (?30 °C) suitable for polyurethane applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4811–4818     

Generalized incomplete Trojan-type designs

Generalized incomplete Trojan-type designs are defined to be row–column designs in which each cell, corresponding to the intersection of row and column, contains more than one treatment and the rows are incomplete. A method of constructing generalized incomplete Trojan-type design has been developed and some properties of this class of designs are discussed.     

Polydimethylsiloxane–cristobalite composite adhesive system for aerospace applications

The effect of phase‐pure cristobalite (a high temperature crystalline polymorph of silica) on the adhesive characteristics of hydroxyl terminated polydimethylsiloxane (PDMS) was studied. The potential advantages of PDMS/cristobalite composite system as an adhesive for aerospace applications are also discussed. A PDMS/cristobalite composite adhesive system containing different filler contents (0–46 volume percentage, vol%) was prepared. The filler material, phase‐pure cristobalite, was synthesized by the pyrolysis of fused silica at 1400°C. The mechanical, rheological, and thermal characteristics of the composites were studied. A high yield stress (0.151 Pa), shear‐thinning index (1.051), and fast recovery rate were observed for ～34 vol% cristobalite loading, which indicate that PDMS retains its excellent adhesive and flow characteristics even at high filler loading with enhanced mechanical characteristics. Thermal analysis shows the onset of degradation of PDMS shifts to higher temperatures, 372–438°C and 317–417°C in nitrogen and air atmosphere respectively, which shows excellent thermal stability. The residual component yields after thermal degradation of PDMS/cristobalite composite system in nitrogen and air atmosphere show different degradation mechanisms. Copyright © 2008 John Wiley & Sons, Ltd.     

Spectroscopic properties of guanidinium zinc sulphate [C(NH2)3]2Zn(SO4)2 and ab initio calculations of [C(NH2)3]2 and HC(NH2)3

Raman and FTIR spectra of guanidinium zinc sulphate [C(NH₂)₃]₂Zn(SO₄)₂ are recorded and the spectral bands assignment is carried out in terms of the fundamental modes of vibration of the guanidinium cations and sulphate anions. The analysis of the spectrum reveals distorted SO₄²⁻ tetrahedra with distinct S–O bonds. The distortion of the sulphate tetrahedra is attributed to Zn–O–S–O–Zn bridging in the structure as well as hydrogen bonding. The CN₃ group is planar which is expressed in the twofold symmetry along the C–N (1) vector. Spectral studies also reveal the presence of hydrogen bonds in the sample. The vibrational frequencies of [C(NH₂)₃]₂ and HC(NH₂)₃ are computed using Gaussian 03 with HF/6-31G* as basis set.     

Size selective assembly of colloidal particles on a template by directed self-assembly technique

We report a simple and effective approach to organize micron- and submicron-sized particles in a size selective manner. This approach utilizes the template assisted directed self-assembly technique. A topographically patterned photoresist surface is fabricated and used to create an ordered array of colloidal particles from their aqueous suspensions. Assembly of particles on this template is then achieved by using a conventional spin coating technique. Feasibility of this technique to form a large area of patterned particle assemblies has been investigated. To arrange the particles on the template, the physical confinement offered by the surface topography must overcome a joint effect of centrifugal force and the hydrophobic nature of the photoresist surface. This concept has been extended to the size selective sorting of colloidal particles. The capability of this technique for sorting and organizing colloidal particles of a particular diameter from a mixture of microspheres is demonstrated.