New dynamic axial compression columns with means for monitoring floating adapter position. Column design and utilisation in low pressure LC on soft packings

Summary The design of new dynamic, axial-compression columns with a system for continous packed bed adjustment and monitoring of the floating adapter position is described. The columns are meant for liquid chromatography at low pressures (up to 8 bar) in aqueous and organic media with stationary phases of all types. The columns have adapter position pickups for continuous automatic monitoring of the bed height (original “swellographic” monitoring). The column described with gas pressurisation was tested with soft Sephadex G-10 and G-25. In spite of the reduction in external porosity there was no dramatic increase in back-pressure. The column proved to provide long-term stability of the packed bed and improvement in resolution. Presented at the 21^st ISC held in Stuttgart, Germany, 15^th–20^th September, 1996     

DETERMINATION OF DEGREE OF CRYSTALLINITY OF NYLON 1212 BY WIDE-ANGLE X-RAY DIFFRACTION

Based on the X-ray scattering intensity theory and using the approximate expression for the atomic scattering factor, the correction factors for three crystalline peaks and an amorphous peak of Nylon 1212 were calculated and the formula of degree of crystallinity of Nylon 1212 was derived by a graphic multipeak resolution method. The degree of crystallinity calculated from the WAXD method is compatible with those obtained by density and calorimetry methods.     

A density-functional calculation of dynamic dipole polarizabilities of noble gas atoms

Using a very simple trial function and unperturbed electron densities calculated by a new procedure, the frequency-dependent dipole polarizability () of Ne, Ar, Kr and Xe has been calculated in the range 0 0.45 a.u., by a Karplus-Kolker-type variation-perturbation method. Results progressively worsen for larger systems so that, for Xe, (0) is only 75% of the experimental value. Probable reasons for this are discussed.     

The relationship between the linear (oscillatory) and nonlinear (steady-state) flow properties of a series of polymer and colloidal systems

The Cox-Merz empirical relationship between the linear (oscillatory) and nonlinear (steady-state) viscosities has been shown to be valid for many polymeric systems. Here, we present an equivalent expression to relate the linear (G) and nonlinear (N ₁) elastic properties of viscoelastic systems. Like the Cox-Merz relationship, it uses a combination of elastic and viscous parameters. The modified form of the storage modulus is then equivalent to the Cox-Merz complex viscosity. It can be used to correlate with (half) the normal force at numerically equal circular frequency and shear rate, respectively.This new expression and the Cox-Merz rule are tested for a range of polymeric and colloidal systems. It is found that both expression work for the polymeric systems considered, but fail for the colloidal systems. In the latter, the steady state values of viscosity and elasticity are consistently low, and replacing them by the complex viscosity and our new elastic expression only makes matters worse.For polymer systems, we suggest this is a general but not universal observation, since we are aware of exceptions to the rule that polymeric systems obey the Cox-Merz rule for viscosity and our rule for elasticity. For colloidal systems we find that neither rule is obeyed for any of our systems.     

MCM-41分子筛负载钼钴系催化剂的噻吩HDS研究

通过氧吸附量、噻吩吸附热及反应速率常数的测定，研究了MoO3/MCM-41、MoO3-CoO(NiO)/MCM-41系列催化剂，发现，对于MoO3/MCM-41催化剂，当MoO3的质量分数（以MCM－41为底数，即MCM－41＝1g时，MoO3含量为0．15g，下同）从15％增加到20％时，其噻吩的加氢硫（HDS）活性增大，至25％时活性下降，所对应的氧吸附量（mL/g催化剂）也是先增大后减少，并且两者有很好的线性对应关系，而且噻吩吸附热则基本保持不变，采用不同的MoO3-CoO(NiO)浸渍顺序制备的MoO3-CoO(NiO)/MCM-41催化剂中，先浸渍CoO(NiO）再浸渍MoO3的催化剂，其噻吩HDS活性明显优于对其它浸渍顺序制备的催化剂，同时催化剂的氧吸附量和噻吩吸附热也最大。     

Observations on the swelling characteristics of the zwitterionic hydrogel of poly(1-3-sulfopropyl)-2-vinyl-pyridinium-betaine hydrogel

Samples of poly[1-(3-sulfopropyl)-2-vinyl-pyridinium-betaine] (PSPV) have been synthesized to high conversion by free radical polymerization in aqueous solution of the zwitterionic monomer SPV with several concentrations of the crosslinker N,N′-methylene-bis-acrylamide (MBA). The densities of the resultant xerogels increased regularly with the content of MBA. Hydrogels obtained by swelling them in water and aqueous KSCN solution were examined by gravimetric and dimensional analysis. The water contents increased with decreasing content of MBA, the value of 92.7 wt% at the lowest MBA content being higher than that for other zwitterionic hydrogels. Enhanced swelling occurred in 1 M aq. KSCN at each MBA content, the total swelling being 98.1 wt% at the lowest crosslinker content. Swelling increased with increasing temperature. An approximate procedure to formulating swelling equilibrium in term of the volume fraction of water in hydrogel, in conjunction with the van’t Hoff equation, yields a small positive value for the enthalpy of swelling. This is compared with values derived similarly for other hydrogels.     

Polymeric positive-temperature-coefficient materials: dynamic curing effect

The object of this work was to prepare high-density polyethylene (HDPE)/ethylene–propylene–diene terpolymer (EPDM)/conductive carbon black (CB) composites by dynamic curing and to characterize the positive-temperature-coefficient (PTC) performances of the composites.EPDM and dicumyl peroxide were preblended in a research mill. The roll-milled strands were blended with HDPE and CB in a Haake mixer. The sheet resistivity and morphology of the HDPE/EPDM/CB composites with or without the dynamic curing process were investigated. It was concluded that the dynamically cured blends exhibit better PTC performance than the simple blends without dynamic curing. The effects of shear intensity and dicumyl peroxide content during the dynamic curing process were discussed for the PTC characteristics of the HDPE/EPDM/CB composites.     

Study of poly(bisphenol A carbonate) relaxation kinetics at the glass transition temperature

In this work, the variations of the relaxation times are investigated above and below the glass transition temperature of a model amorphous polymer, the polycarbonate. Three different techniques (calorimetric, dielectric and thermostimulated currents) are used to achieve this goal. The relaxation time at the glass transition temperature was determined at the temperature dependence convergence of the relaxation times calculated with dynamic dielectric spectroscopy (DDS) for the liquid state and thermostimulated depolarisation currents (TSDC) for the vitreous state. We find a value of τ(T_g) = 110 s for PC samples. The knowledge of the temperature dependence, τ(T), and the value τ(T_g) enables to determine the glass-forming liquid fragility index, m. We find m = 178 ± 5.     

Dynamic kinetic resolution of secondary alcohols with a readily available ruthenium-based racemization catalyst

An easy to handle and stable racemization catalyst for secondary alcohols is obtained by an in situ mixture of readily available [Ru(cymene)Cl₂]₂ with chelating aliphatic diamines. Optimization of the reaction revealed that N,N,N′,N′-tetramethyl-1,3-propanediamine as ligand racemizes aromatic alcohols completely within 5 h. This easy to handle and stable catalytic system is combined with a lipase-catalyzed resolution to provide an efficient dynamic kinetic resolution of secondary alcohols.     

Application of a dynamic method of minimisation in the study of reaction surfaces

This paper describes the application of Snyman's dynamic minimisation method to a fitted potential surface of H₃. Comparisons are made with conventional algorithms. A method is described to extend Snyman's method so that it will find only a particular kind of stationary point. It is emphasized that this method enables saddle points to be found without having to resort to approaches based on trial and error.