Volumetric and infrared measurements on amorphous ice structure

We have simultaneously used adsorption isotherm volumetry and Fourier transform infrared spectroscopy in order to take the investigations on amorphous ice structure a step further, especially concerning porosity and annealing-induced modifications. We have studied surface reorganization during annealing and found that the number of surface sites decreases before crystallization, their relative ratios being different for amorphous and crystalline ice. We also present results confirming that ice can have a large specific surface area and nevertheless be non-microporous.     

Studies on calcium‐containing poly(urethane ether)s

The calcium salt of mono(hydroxyethoxyethyl)phthalate [Ca(HEEP)₂] was synthesized by the reaction of diethylene glycol, phthalic anhydride, and calcium acetate. Calcium‐containing poly(urethane ether)s (PUEs) were synthesized by the reaction of hexamethylene diisocyanate (HMDI) or tolylene 2,4‐diisocyanate (TDI) with a mixture of Ca(HEEP)₂ and poly(ethylene glycol) (PEG₃₀₀ or PEG₄₀₀) with di‐n‐butyltin dilaurate as a catalyst. A series of calcium‐containing PUEs of different compositions were synthesized with Ca(HEEP)₂/PEG₃₀₀ (or PEG₄₀₀)/diisocyanate (HMDI or TDI) molar ratios of 2:2:4, 3:1:4, and 1:3:4 so that the coating properties of the PUEs could be studied. Blank PUEs without calcium‐containing ionic diols were also prepared by the reaction of PEG₃₀₀ or PEG₄₀₀ with HMDI or TDI. The PUEs were well characterized by Fourier transform infrared, ¹H and ¹³C NMR, solid‐state cross‐polarity/magic‐angle‐spinning ¹³C NMR, viscosity, solubility, and X‐ray diffraction studies. The thermal properties of the polymers were also studied with thermogravimetric analysis and differential scanning calorimetry. The PUEs were applied as top coats on acrylic‐coated leather, and their physicomechanical properties were also studied. The coating properties of PUEs, such as the tensile strength, elongation at break, tear strength, water vapor permeability, flexing endurance, cold crack resistance, abrasion resistance, color fastness, and adhesive strength, were better than the standard values. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2865–2878, 2003     

Kinetics and mechanism of the formation of poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene] and poly(methyldecylsiloxane) by hydrosilylation

The kinetics of the formation of poly(carbosiloxane), as well as of alkyl-substituted poly(siloxane), by Karstedt's catalyst catalyzed hydrosilylation were investigated. Linear poly(carbosiloxane), poly[(1,1,3,3-tetramethyldisiloxanyl)ethylene], (PTMDSE), was obtained by hydrosilylation of 1,3-divinyltetramethyldisiloxane (DVTMDS) and 1,1,3,3-tetramethyldisiloxane (TMDS), while alkyl-substituted poly(siloxane), poly(methyldecylsiloxane), (PMDS), was synthesized by hydrosilylation of poly(methylhydrosiloxane) (PMHS) and 1-decene. To investigate the kinetics of PTMDSE formation, two series of experiments were performed at reaction temperatures ranging from 25 to 56 °C and with catalyst concentrations ranging from 7.0 × 10⁻⁶ to 3.1 × 10⁻⁵ mol Pt/mol CHCH₂. A series of experiments was performed at reaction temperatures ranging from 28 to 48 °C, with catalyst concentrations of 7.0 ×10⁻⁶ mol of Pt per mol of CHCH₂, when kinetics of PMDS formation was investigated. All reactions were carried out in bulk, with equimolar amounts of the reacting Si H and CHCH₂ groups. The course of the reactions was monitored by following the disappearance of the Si H bands using quantitative infrared spectroscopy. The results obtained showed typical first order kinetics for the PTMDSE formation, consistent with the proposed reaction mechanism. In the case of PMDS an induction period occurred at lower reaction temperatures, but disappeared at 44 °C and the rate of Si H conversion also started to follow the first-order kinetics. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 2246–2258, 2007     

Coupled lubrication and Stokes flow finite elements

A method is developed for performing a local reduction of the governing physics for fluid problems with domains that contain a combination of narrow and non‐narrow regions, and the computational accuracy and performance of the method are measured. In the narrow regions of the domain, where the fluid is assumed to have no inertia and the domain height and curvature are assumed small, lubrication, or Reynolds, theory is used locally to reduce the two‐dimensional Navier–Stokes equations to the one‐dimensional Reynolds equation while retaining a high degree of accuracy in the overall solution. The Reynolds equation is coupled to the governing momentum and mass equations of the non‐narrow region with boundary conditions on the mass and momentum flux. The localized reduction technique, termed ‘stitching,’ is demonstrated on Stokes flow for various geometries of the hydrodynamic journal bearing—a non‐trivial test problem for which a known analytical solution is available. The computational advantage of the coupled Stokes–Reynolds method is illustrated on an industrially applicable fully‐flooded deformable‐roll coating example. The examples in this paper are limited to two‐dimensional Stokes flow, but extension to three‐dimensional and Navier–Stokes flow is possible. Copyright © 2003 John Wiley & Sons, Ltd.     

等厚双层涂层材料受集中力作用的平面问题理论解

界面应力的正确评价是分析薄膜涂层材料力学特性的难题之一。利用镜像点法和Dirichlet等值性原理，本文推导了等厚双层薄膜涂层材料受表面集中力作用的平面问题理论解。该显式理论解是以固定在各镜像点上的局部坐标系下的Goursat应力函数的形式给出的。对应于高阶镜像点的应力函数，可通过递推的方法，从对应于低阶镜像点的应力函数求得，而且也易于计算机编程。随着镜像点阶数的增大，它与界面的距离也越来越大，因而相对应的应力函数对界面应力的影响越来越小。最后的算例表明，只需考虑前面有限个镜像点，便可获得足够精度的解。该理论解可作为格林函数，以求解复杂问题的理论解，也可用作边界元法的基本解，提高数值计算的精度和效率。     

Cationic poly(methacryl oxyethyl trimethylammonium) and its poly(ethylene glycol)‐grafted analogue as capillary coating materials in electrophoresis

Cationic polyelectrolytes were synthesized and used as semipermanent coating materials for capillaries in electrophoresis. The polyelectrolytes used were a homopolymer of poly(methacryl oxyethyl trimethylammonium chloride) (PMOTAC) and its poly(ethylene glycol) (PEG)‐grafted analogue. Two PMOTAC polyelectrolytes, with molar masses of 85,000 and 300,000 g/mol, and PEG‐grafted PMOTAC with a molar mass of 280,000 g/mol were synthesized and then characterized by size exclusion chromatography (SEC) and nuclear magnetic resonance (NMR) spectroscopy. Attachment of the polyelectrolytes to the wall of the fused silica capillary for electrophoresis caused the electroosmotic flow (EOF) to reverse. The polyelectrolyte coatings were tested over the pH range 2–11 at different buffer ionic strengths, and the most stable and strongest anodic EOFs were obtained at acidic pH values with low ionic strength buffers. Between runs the capillary is merely rinsed for 2 or 3 min with the background electrolyte solution. With the PMOTAC coatings at pH values ≤5, the RSDs of the EOFs were less than 2.9% after 60 injections. The effects of the molar mass of the polycation and of PEGylation of PMOTAC on the interactions between the polycations and basic proteins were studied at acidic pH values. The differences in the effective electrophoretic mobilities, resolution values, and plate numbers of the proteins with the different coatings were due to the EOF, as demonstrated through calculations of reduced mobilities, relative resolution values, and relative plate numbers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 2655–2663, 2007     

Vacuum Ultraviolet Photolysis of Polyethylene,Polypropylene, and Polystyrene

Using infrared reflection absorption spectroscopy (IRRAS), quartz crystal microbalance (QMB) measurements, and X-ray photoelectron spectroscopy (XPS) in combination with chemical derivatization techniques the VUV photolysis of polyethylene (PE), polypropylene (PP), and polystyrene (PS) was investigated. A mass balance obtained from the quantification of the data was used to suggest reaction path ways. Although PE and PP behave similar, the mass loss is about 8 times higher in the case of PP. These differences originate from the higher disproportionation to recombination ratio for the branched polymer. Both polymers form double bonds and at extended treatment times they tend to crosslink. PS is rather stable due to the possibility of the energy dissipation by fluorescence.     

Acetylenic/cyanoacetylenic complexes: simulation of the Titan’s atmosphere chemistry

The structures and energies of the 1:1 acetylene/cyanoacetylene, acetylene/dicyanoacetylene and cyanoacetylene/dicyanoacetylene complexes in solid argon matrices have been investigated using FT-IR spectroscopy and ab initio calculations, at the B3LYP/6-31G** level of theory. For the three complexes, predicted frequency shifts for the L shaped structures, characterized by a hydrogen bond between the nitrogen of the cyano group and the acetylenic proton, were found to be in good agreement with those experimental. Only in the case of acetylene/cyanoacetylene complex, we obtained a second minimum with a T shaped structure characterized by an interaction between the proton of cyanoacetylene and the Π system of acetylene. It appears clearly that HC₃N acts as an electrophile or as a nucleophile in these complexes.     

Vibrational frequencies and structural determination of phosphirane

The normal mode frequencies and corresponding vibrational assignments of phosphirane in are examined theoretically using the GAUSSIAN 98 set of quantum chemistry codes. All normal modes were successfully assigned to one of nine types of motion (C–C stretch, P–C stretch C–H stretch, P–H stretch, CH₂ scissors, CH₂ wag, CH₂ rock, CH₂ twist, and P–H wag) predicted by a group theoretical analysis. Comparing the vibrational frequencies with IR and Raman spectra available in the literature, a set of scaling factors are derived. Predicted infrared and Raman intensities are reported.     

Chiral stationary phases for LC and SFC obtained by “Polymer coating”

Summary Chirally substituted Si–H-containing polysiloxanes were synthesized, which can be immobilized on small particle silica gel as well as on the smooth surfaces of fused silica capillaries. Immobilization is achieved either by crosslinking or by chemical bonding to the surfaces via silanol groups; both reactions can only be performed by addition of H₂PtCl₆, which acts as catalyst for hydrosilylation and as stoichiometric reagent for crosslinking. Chiral substituents of systematically varied chemical structure were introduced into the polysiloxanes by hydrosilylation. The mechanism of immobilization was investigated by spectroscopic methods, notably²⁹Si-NMR. Homogenous stationary-phase coatings of variable film thickness and corresponding retentivity can easily be achieved. The enantioselectivity of the phase systems was characterized in dependency on the chemical structure of the chiral selectors attached to the polysiloxane chain of the chiral stationary phases and also in terms of the functional groups introduced into the solutes by derivatisation.