Laboratory scale-up of two-stage laser chemistry separation of13C from CF2HCl

The laboratory scale-up of a two-stage laser enrichment process for carbon isotopes, involving infrared multiphoton dissociation of freon-22, is described. Unmodified commercial equipment and materials were used. An initial study of the effect of fluence, laser frequency, freon-22 pressure and pressure of argon, nitrogen and trifluoromethyl chloride was made in short irradiation cells (constant fluence) in order to define optimum process parameters. The process was then scaled to higher throughput in longer cells (1–5 m) in which compensation for beam-energy depletion by absorption was made by reduction in the beam area by focussing. From the scale-up experiments, measurements of yield and enrichment of the tetrafluoroethylene product gave demonstrated production rates. These, coupled with measurements of the absorption, allowed extrapolation to production rates assuming total utilization of the available output energy.Using a 100 W TEA CO₂ laser (10 J, 10 Hz) we have demonstrated production rates of 0.20 g h^–1 carbon-12 at 99.99% carbon-12, 11 mg h^–1 carbon-13 at 72% carbon-13 and 2 kg per annum carbon-13 at 50%. Energy absorption measurements imply a capability to produce 3 kg per annum carbon-13 at over 95% carbon-13 in a two-stage process.The apparatus was used to produce gram quantities of carbon-13 depleted freon-22 (99.99% carbon-12). A comparison of the infrared multiphoton dissociation of this material with that of natural freon-22 (1.11% carbon-13) showed that under the conditions required to give selective dissociation of¹³CF₂HCl that¹²CF₂HCl was excited as a result of a dominantly radiative interaction and that collisional transfer from¹³CF₂HCl molecules played a minor role.Issued as NRCC 23639Summer Student 1983, Acadia University, N.S., Canada     

Hopf bifurcations in time-delay systems with band-limited feedback

We investigate the steady-state solution and its bifurcations in time-delay systems with band-limited feedback. This is a first step in a rigorous study concerning the effects of AC-coupled components in nonlinear devices with time-delayed feedback. We show that the steady state is globally stable for small feedback gain and that local stability is lost, generically, through a Hopf bifurcation for larger feedback gain. We provide simple criteria that determine whether the Hopf bifurcation is supercritical or subcritical based on the knowledge of the first three terms in the Taylor-expansion of the nonlinearity. Furthermore, the presence of double-Hopf bifurcations of the steady state is shown, which indicates possible quasiperiodic and chaotic dynamics in these systems. As a result of this investigation, we find that AC-coupling introduces fundamental differences to systems of Ikeda-type [K. Ikeda, K. Matsumoto, High-dimensional chaotic behavior in systems with time-delayed feedback, Physica D 29 (1987) 223–235] already at the level of steady-state bifurcations, e.g. bifurcations exist in which limit cycles are created with periods other than the fundamental “period-2” mode found in Ikeda-type systems.     

A numerical model for the 3-D non-linear vibrations of an N-string

We present a non-linear numerical model describing the 3-D vibrations of a planar network of N sections of string which are connected together at one common mobile extremity. We call such a network N-string. For small-amplitude vibrations perpendicular to the N-string equilibrium plane, the numerical results coincide with the already known analytical solutions of the linear model. This non-linear model makes it possible to describe small- or large-amplitude 3-D vibrations of any kind of N-string subjected to an initial plucking. The equations of motion are also presented in a dimensionless form and a vast dimensionless physical parameter space is identified. The numerical model can be extended to more complex networks of strings.     

Design of photonic band gap structures through a dual-beam multiple exposure technique

We present a dual-beam multiple exposure technique that can generate complex 2-D and 3-D band gap template structures in a photosensitive material. The system parameters related to the planar interference pattern produced by two laser beams and reorientation effect of the sample relative to these planes is presented. Structures such as the 2-D, square and hexagonal arrays of dielectric “rods” and “holes” and the 3-D, cubic, Yablonovite and other profiles are given. We perform band gap calculations on these structures when the dielectric contrast has been increased using a backfill process and discuss techniques for increasing the band gap by sculpting the dielectric profile.     

Spray-drying as a tool to disperse conductive carbon inside Na<Subscript>2</Subscript>FePO<Subscript>4</Subscript>F particles by addition of carbon black or carbon nanotubes to the precursor solution

In this work, Na₂FePO₄F-carbon composite powders were prepared by spray-drying a solution of inorganic precursors with 10 and 20 wt% added carbon black (CB) or carbon nanotubes (CNTs). In order to compare the effect of CB and CNT when added to the precursor solutions, the structural, electrochemical, and morphological properties of the synthesized Na₂FePO₄F-xCB and Na₂FePO₄F-xCNT samples were systematically investigated. In both cases, X-ray diffraction shows that calcination at 600 °C in argon leads to the formation of Na₂FePO₄F as the major inorganic phase. ⁵⁷Fe Mössbauer spectroscopy was used as complementary technique to probe the oxidation states, local environment, and identify the composition of the iron-containing phases. The electrochemical performance is markedly better in the case of Na₂FePO₄F-CNT (20 wt%), with specific capacities of about 100 mAh/g (Na₂FePO₄F-CNT) at C/4 rate vs. 50 mAh/g for Na₂FePO₄F-CB (20 wt%). SEM characterization of Na₂FePO₄F-CB particles revealed different particle morphologies for the Na₂FePO₄F-CNT and Na₂FePO₄F-CB powders. The carbon-poor surface observed for Na₂FePO₄F-CB could be due to a slow diffusion of carbon in the droplets during drying. On the contrary, Na₂FePO₄F-CNT shows a better CNT dispersion inside and at the surface of the NFPF particles that improves the electrochemical performance.