Evaluation of electron capture cell designs for use in high resolution capillary column gas chromatography

A comparison of the effects on peak shape is made between a 350 and 100 microliter displaced coaxial and a 350 microliter concentric cylinder electron capture cell. Peaks as fast as W_1/2 = 0.5 second were detected using electronics operating in the constant current mode. The measured peak shapes are compared to those obtained by computer simulation assuming either complete mixing or plug-like flow within ECD cell. The advantage of controlling the flow pattern through the cell to obtain plug-like flow is demonstrated. Differences in peak shape between the displaced coaxial and concentric cylinder cells of the same volume are explained in terms of the electrostatic fields within the cells.     

Modeling of RF plasma torch with a metallic tube inserted for reactant injection

Flow, temperature, and electromagnetic (EM) fields in a radio-frequency thermal plasma torch designed for the preparation of superconducting powders or films have been analysed by using a new two-dimensional modeling approach with the electric field intensity as the fundamental EM field variable. The insertion of a stainless steel injection tube into the torch leads to large induction currents in this tube. Although such large induction currents cause pronounced changes of the EM fields near the injection tube, flow and temperature fields are little affected. There exists only one large toroidal vortex in the upper part of the present torch, while the maximum temperature appears at an off-axis location within the coil region.     

Ion trajectories in an electrostatic ion guide for external ion source fourier transform ion cyclotron resonance mass spectrometry

An electrostatic ion guide (EIG) that consists of concentric cylinder and central wire electrodes can transport ions efficiently from an external ion source to an ion cyclotron resonance (ICR) ion trap for mass analysis, with several advantages over current injection methods. Because the electrostatic force of the EIG captures ions in a stable orbit about the wire electrode, ions with initially divergent trajectories may be redirected toward the ICR ion trap for improved ion transmission efficiency. SIMION trajectory calculations (ion kinetic energy, 1–200 eV; elevation angle, 0.30 °; azimuthal angle, 0.360°) predict that ions of m/z 1000 may be transmitted through a strong (0.01 → 3.0-T) magnetic field gradient. Judicious choice of ion source position and EIG potential minimizes the spread in ion axial kinetic energy at the ICR ion trap. Advantages of the EIG include large acceptance angle, even for ions that have large initial kinetic energy and large radial displacement with respect to the central z-axis, low ion extraction voltage (5–20 V), and efficient trapping because ions need not be accelerated to high velocity to pass through the magnetic field gradient.     

Dehydration Efficiency of Water-in-Crude Oil Emulsions in Alternating Current Electrical Fields

The influence of several operational variables on the electrostatic separation of water-in-crude oil emulsions is investigated in a concentric cylinder rheometer equipped with an alternating current (AC) generator. Shear rate, temperature, emulsion water content, electric field strength, and application time are all found to play a role in the process. The droplet size distributions achieved across some of the experiments are acquired to give further support to the conclusions. Finally, the experimental results are compared to the theoretical expression for the electrocoalescence process and discussed.     

Transient Response of Radio Frequency Inductively Coupled Plasma for Pulse Modulation

Properties of an argon/hydrogen (89% molar argon) radio frequency inductivelycoupled plasma subject to a periodic power (or coil current) profile isinvestigated both numerically and experimentally. The model is based on atime-dependent, two-dimensional (2-D), axisymmetric model of the radiofrequency (rf) inductively coupled plasma (ICP) under local thermodynamicequilibrium (LTE). The governing time-dependent equations for theconservation of mass, momentum, and energy, along with Maxwell'sequations are solved numerically. The ICP is operated at 1 MHz inductionfrequency with 55 slpm total gas-flow rate. Spectroscopic measurements ofargon line intensities are also made for a similar plasma setup andpredictions are compared with the measured ArI line intensity at 751 nm. Wefound that the plasma responds quickly to a change in the power (or coilcurrent). Two important parameters responsible for plasma heating (Jouleheating term) and for its constriction (Lorentz force) follow the temporalbehavior of the coil current. The response of the theoretically predictedatomic argon line intensity at 751 nm is slower compared to the experimentalobservations. This is thought to be due to the fast response of the electrongas to a change in the electromagnetic fields, which is not represented inan LTE model.     

Cell model for hydromagnetic axial flow over a cylinder. Part I. transverse magnetic field

Using cell model initiated by Happel, the filtration problem across a membrane composed of an aggregate of parallel circular cylinders subject to a uniform transverse magnetic field is studied. The system is simulated by a single cylinder enveloped by a concentric cylindrical enveloping surface with axial flow. The analysis leads to the evaluation of the permeability parameter. The results are then graphically presented and discussed. The effect of magnetic field is seen to increase the permeability.     

Influence of magnetic forces on electrochemical mass transport

Enhancements of the order of 100% in the mass transport limited current for electrodeposition have been observed in magnetic fields of order 1 T. The effect of the field is to induce convection in the solution and it is equivalent to rotating the electrode or stirring the solution. In this communication, a quantitative comparison is made of the magnitude of various body forces which have been proposed to account for the experimentally observed effects, with a view to identifying the likely source of the field enhancement. When the magnetic field is uniform, the Lorentz force and the electrokinetic force both contribute significantly to the field enhancement.     

New design of a radio-frequency plasma torch

A numerical model has been developed for predicting the two-dimensional flow and temperature fields in a radio-frequency (rf) plasma torch. The method employed here is based on Boulos' model with the exception of the boundary conditions for the electric and magnetic field equations. Calculations have been made for the confirmation of a new sample injection method, which is capable of completely evaporating refractory materials at high feeding rates without interfering with the stability of the plasma. In the newly designed torch, the reagent is radially injected into the hottest part of the plasma through quartz capillary tubes set symmetrically between an inductor coil. Experimental investigations have also been performed for verifying the proper function of the design. These results provide evidence that our radial injection method developed here is more effective in practical processing than the conventional axial injection methods.     

Rapid separation of polysaccharides using a novel spiral coil column by high‐speed countercurrent chromatography

The separation of polysaccharides is time consuming. We developed and optimized a type‐J counter‐current chromatography system with a novel tri‐rotor spiral coil column for the rapid separation of polysaccharides. The optimal composition of an aqueous PEG1000/K₂HPO₄/KH₂PO₄ system was found to be 14:16:14 w/w/w where the lower phase was the mobile phase. Optimal performance was achieved at a column rotational speed, temperature, and flow rate of 1200 rpm, 45°C, and 3.0 mL/min, respectively. The mobile phase was pumped from the inner terminal in a ‘‘head‐to‐tail’’ elution mode. Polysaccharide LCP‐1 (10.7 mg) was successfully obtained in high purity in one step from 50.0 mg of a crude polysaccharide extracted from the lychee fruit (Litchi chinensis) within 100 min. LCP‐1 possess a number‐average molecular weight and weight‐average molecular weight of 1.05 × 10⁵ and 1.59 × 10⁵ kDa, respectively. The monosaccharide composition consists of the molar ratio of glucose, galactose, and arabinose of 1.3:3.5:1.     

Solution conformations of structured peptides: continuum electrostatics versus distance-dependent dielectric functions

To compare different implicit solvent potentials, the folding thermodynamics of the helical peptide RN24 and the β-hairpin peptide BH8 are studied by molecular dynamics simulation with adaptive umbrella sampling. As the potential energy functions, the analytical continuum solvent (ACS) potential and three simplified variants, termed EPSR₁, EPSR₄, and EPSR₁₀, are used. The ACS potential is a combination of the standard CHARMM force field for the internal energy (bonds, angles, dihedrals) and the van der Waals energy with the analytical continuum electrostatic (ACE) potential and a non-polar solvation potential. The EPSR potentials differ from the ACS potential by the use of Coulomb's law with a distance-dependent dielectric function to calculate the electrostatic energy. With the ACS potential, quantitative agreement with experiment is obtained for the helix propensity (RN24: 62% calculated vs 50–60% experiment) and the β-hairpin propensity (BH8: 33% calculated vs 19–37% experiment) of the peptides. During the simulations with the EPSR potentials, no significant formation of secondary structure is observed. It is shown that the preference for coil conformations over conformations with secondary structure by the EPSR potentials is due to an overestimation of the energy of salt bridge formation, independent of the magnitude of the Coulomb energy relative to the other energy terms. Possible improvements of the distance-dependent dielectric functions which may permit their application to the simulation of peptide folding, are discussed. Received: 11 July 1998 / Accepted: 22 September 1998 / Published online: 17 December 1998     

Evolution of Helical Mesostructures

An intriguing evolution from a simple internal helix to a hierarchical helical (HH) mesostructure with both internal and external helices or a complicated screwlike and concentric circular (CC) mesostructure is successfully observed. The complicated helical structures are determined by TEM studies and 3D electron tomography. We demonstrate a topological helix–coil transition between the internal and external helices to reveal the origin of the HH mesostructure and the relationship between the straight helical and HH rods. Moreover, the boundary condition of the helix–coil transition is clarified to explain in detail the formation of complex helical structures, such as the screwlike mesostructure. It is proposed that the final structural characteristics are determined exactly by the balance between the decrease in the surface free energy and the maintenance of the hexagonal packing in one individual rod, which explains the formation of unusual CC, HH, and screwlike morphologies in one pot. Our success has opened new opportunities in the characterization of complex porous architectures, thus paving a way to remarkable advances in the fields of synthesis, understanding, and application of novel porous materials.     

Electric field inside a "Rossky cavity" in uniformly polarized water

Electric field produced inside a solute by a uniformly polarized liquid is strongly affected by dipolar polarization of the liquid at the interface. We show, by numerical simulations, that the electric "cavity" field inside a hydrated non-polar solute does not follow the predictions of standard Maxwell's electrostatics of dielectrics. Instead, the field inside the solute tends, with increasing solute size, to the limit predicted by the Lorentz virtual cavity. The standard paradigm fails because of its reliance on the surface charge density at the dielectric interface determined by the boundary conditions of the Maxwell dielectric. The interface of a polar liquid instead carries a preferential in-plane orientation of the surface dipoles thus producing virtually no surface charge. The resulting boundary conditions for electrostatic problems differ from the traditional recipes, affecting the microscopic and macroscopic fields based on them. We show that relatively small differences in cavity fields propagate into significant differences in the dielectric constant of an ideal mixture. The slope of the dielectric increment of the mixture versus the solute concentration depends strongly on which polarization scenario at the interface is realized. A much steeper slope found in the case of Lorentz interfacial polarization also implies a higher free energy penalty for polarizing such mixtures.     

新型多尖端旋转电极甲烷偶联等离子体反应器

研制了一种新型的带有一个多尖端旋转电极对一个同心圆筒型固定电极的甲烷放电制备碳二烃的等离子体反应器.以氢气共存条件下甲烷偶联研究对此反应器作出了评价.在此反应器中，反应物流垂直穿过两电极之间的环行等离子体反应区.在大约40 V供电电压、20 kHz脉冲放电等离子体条件下，在长时间连续反应后没有产生大量积炭.在同样的条件下，此多尖端旋转电极工艺比固定的尖端 平板电极工艺具有较高的甲烷转化率、碳二烃单程收率以及较高的能量效率.     

The shape of the Lorentz cavity and the internal field in anisotropic fluids

The predictions of the ellipsoidal Lorentz cavity model for different cavity axial ratios are compared with the predictions of a microscopic molecular crystal model for different molecular axial ratios. The models agree when the cavity depolarisation factor equals the crystal Lorentz factor. Numerical calculations show that the axial ratio of the cavity equivalent to the molecule is roughly equal to the molecular axial ratio up to ≈ 5. but increases rapidly thereafter. For molecular axial ratios of 9 and above there is no equivalent cavity. Implications of the results for the internal field in liquid crystals are considered.     

Presence of in-plane anisotropy and oscillatory magnetoresistive behavior in epitaxial SrRuO3 thin films with orthogonal equivalent axes

In-plane magnetic hysteresis measurements performed on thin films of SrRuO₃ (SRO) deposited on (001)-oriented SrTiO₃ substrates showed orthogonal equivalent axes. This finding, nevertheless, was not conclusive argument to discard the presence of in-plane anisotropy in these samples. Certainly, measurements of the in-plane magnetoresistance (MR) featured anisotropic behavior with a well-defined angular dependence. The observed 180° periodicity of the function MR(θ) corresponded to that expected for the standard anisotropic magnetoresistance phenomenon (AMR). On the other hand, the longitudinal MR (zero Lorentz force) and transverse MR (nonzero Lorentz force), recorded at low temperatures and magnetic fields, displayed positive MR with a relatively broad maximum for the first field ramp up to 4 T. For the subsequent field sweep down, MR was negative for all field orientations. The described behavior was symmetric upon reversal of the applied magnetic field leading to a strong hysteretic behavior of MR.     

A new atomization cell for trace metal determinations by tungsten coil atomic spectrometry

A new metallic atomization cell is used for trace metal determinations by tungsten coil atomic absorption spectrometry and tungsten coil atomic emission spectrometry. Different protecting gas mixtures are evaluated to improve atomic emission signals. Ar, N₂, CO₂ and He are used as solvents, and H₂ and C₂H₂ as solutes. A H₂/Ar mixture provided the best results. Parameters such as protecting gas flow rate and atomization current are also optimized. The optimal conditions are used to determine the figures of merit for both methods and the results are compared with values found in the literature. The new cell provides a better control of the radiation reaching the detector and a small, more isothermal environment around the atomizer. A more concentrated atomic cloud and a smaller background signal result in lower limits of detection using both methods. Cu (324.7 nm), Cd (228.8 nm) and Sn (286.3 nm) determined by tungsten coil atomic absorption spectrometry presented limits of detection as low as 0.6, 0.1, and 2.2 μg L⁻¹, respectively. For Cr (425.4 nm), Eu (459.4 nm) and Sr (460.7 nm) determined by tungsten coil atomic emission spectrometry, limits of detection of 4.5, 2.5, and 0.1 μg L⁻¹ were calculated. The method is used to determine Cu, Cd, Cr and Sr in a water standard reference material. Results for Cu, Cd and Cr presented no significant difference from reported values in a 95% confidence level. For Sr, a 113% recovery was obtained.     

Characteristics and electrode erosion rates of a D.C. plasma torch operating with TiCl4 plasma gas

A stable TiCl₄ plasma was produced using a simplified d.c. torch. The arc was struck between two concentric ring electrodes, d mm apart, and rotated using a magnetic coil. The electrode material was a new TaC composite. The arc was operated at 100 A for up to I h using plasma gas containing 0–30% TiCl₄. The voltage was 24–60 V, depending on the TiCl₄ concentration. The electrode erosion rate was of the order of 20g/C. It is shown that the erosion rate is a function of the aerodynamic drag of the are column.     

A Computational Examination of the Sources of Statistical Variance in Particle Parameters During Thermal Plasma Spraying

Computational modeling is used to systematically examine many of the sources of statistical variance in particle parameters during thermal plasma spraying. Using the computer program LAVA, a steady-state plasma jet typical of a commercial torch at normal operating conditions, is first developed. Then, assuming a single particle composition(ZrO₂) and injection location, real world complexity (e.g., turbulent dispersion, particle size and density, injection velocity, and direction) is introduced ``one phenomenon at a time to distinguish and characterize its effect and enable comparisons of separate effects. Calculations are also performed wherein all phenomena are considered simultaneously to enable further comparisons. Both nonswirling and swirling plasma flow fields are considered. Investigating each phenomenon separately provides valuable insight into particle behavior. For the typical plasma jet and injection conditions considered, particle dispersion in the injection direction is mostsignificantly affected by (in order of decreasing importance): particle size distribution, injection velocity distribution, turbulence, and injection direction distribution or particle density distribution. Only the distribution of injection directions and turbulence affect dispersion normal to the injection direction and are of similar magnitude in this study. With regards to particle velocity and temperature, particle size is clearly the dominant effect.