Positron diffusion measurements

Traditionally, experimental values of Zeff have been derived from measurements of the lifetime spectra of positrons that are diffusing, and eventually annihilating, in a gas. The lifetime of each positron is measured separately, and these individual pieces of data are accumulated to form the lifetime spectrum. (The positron-trap technique, to be described in subsection 6.2.2, uses a different approach.) An alternative but equivalent procedure, which is adopted in electron diffusion studies and also in the theoretical treatment of positron diffusion, is to consider the injection of a swarm of positrons into the gas at a given time and then to investigate the time dependence of the speed distribution, as the positrons thermalize and annihilate, by solving the appropriate diffusion equation. The experimentally measured Zeg, termed Z ), is the average over the speed distribution of the positrons, y(v,t), where y(v,t) dv is the number density of positrons with speeds in the interval v to v + dv at time t after the swarm is injected into the gas. The time-dependent speed-averaged Zef[ is therefore... 

The contribution of positron diffusion length (L+ = 10 nm [22]) was removed from the escape depth values. The diffusion constant in a material is a function of diffusion length and annihilation rate D = L2X. Here, the rates for positrons and positronium are similar (X 2 ns 1). Thus the measured combined effective diffusion length of positrons L+ and positronium escape Lesc is l eff = L2+ + L2esc [30],... 

Positron lifetime measurements can be used to investigate the type and the density of lattice defects in crystals [293]. In solid materials positrons have a typical lifetime of 300 to 500 ps until they are annihilated by an electron. When positrons diffuse through a crystal they may be trapped in crystal imperfections. The electron density in these locations is different from the density in a defect-free crystal. Therefore, the positron lifetime depends on the type and the density of the crystal defects. When a positron annihilates with an electron two y quanta of 511 keV are emitted. The y quanta can easily be detected by a scintillator and a PMT. 

E. J. M. Hensen, A. M. de Jong, and R. A. van Santen have written Chapter 7, which introduces the tracer exchange positron emission profiling (TEX-PEP) as an attractive technique for in-situ investigations, for example, in a stainless steel reactor, of the adsorption and diffusive properties of hydrocarbons in zeolites under chemical steady-state conditions. Self-diffusion coefficients of hydrocarbons, labeled by proton-emitting C at finite loadings and even in the presence of another imlabeled alkane, may be extracted. The method is illustrated by adsorption and diffusion measurements of linear (n-hexane) and branched (2-methylpentane) alkanes in Fl-ZSM-5 and silicalite-1. 

The sizes and concentration of the free-volume cells in a polyimide film can be measured by PALS. The positrons injected into polymeric material combine with electrons to form positroniums. The lifetime (nanoseconds) of the trapped positronium in the film is related to the free-volume radius (few angstroms) and the free-volume fraction in the polyimide can be calculated.136 This technique allows a calculation of the dielectric constant in good agreement with the experimental value.137 An interesting correlation was found between the lifetime of the positronium and the diffusion coefficient of gas in polyimide.138,139 High permeabilities are associated with high intensities and long lifetime for positron annihilation. 

PALS is based on the injection of positrons into investigated sample and measurement of their lifetimes before annihilation with the electrons in the sample. After entering the sample, positron thermalizes in very short time, approx. 10"12 s, and in process of diffusion it can either directly annihilate with an electron in the sample or form positronium (para-positronium, p-Ps or orto-positronium, o-Ps, with vacuum lifetimes of 125 ps and 142 ns, respectively) if available space permits. In the porous materials, such as zeolites or their gel precursors, ort/zo-positronium can be localized in the pore and have interactions with the electrons on the pore surface leading to annihilation in two gamma rays in pick-off process, with the lifetime which depends on the pore size. In the simple quantum mechanical model of spherical holes, developed by Tao and Eldrup [18,19], these pick-off lifetimes, up to approx. 10 ns, can be connected with the hole size by the relation ... 

Sr was more stable in vivo but Ag was more lipophilic. These results suggest that generator-produced isotopes such as Rb-82 (T% = 75 sec) sequestered inside cryptands may be useful freely diffusible tracers for measuring blood flow by positron emission tomography. It would be more convenient to make this measurement with generator-produced isotopes than with water from cyclotron-produced oxygen-15 (Th = 122 sec). 

Here ct, ce and cp are the concentrations of the positive ions, electrons and the positron probability density at a point r measured from the center of the blob at time t. Dp is the diffusion coefficient of the positron, Di = De = Damb 0 is the ambipolar diffusion coefficient of the blob, a2 o2 ss a2 is the dispersion of the intrablob species, and a2 is the dispersion of the positron space distribution by the end of its thermalization. Decay rate Te-1 = 1/t + kescs is the sum of the electron solvation rate and possible capture by solute molecules t 2 = 1 /t2 + l/r + kpscs accounts for the free e+ annihilation, solvation and reaction with S. Similarly, t 1 = l/rjmr + hscs, where T r is the rate of the ion-molecule reaction. 

Since the positron traps in vacancy like open volume and positronium in pores, it will be possible to selectively detect impurities next to vacancies [71]. For metal indiffusion experiments one can design test structures of silicon, metal, low-/ layer samples. Two detector coincident measurements would be performed as a function of temperature and time to observe the chemical signature of the metal in the low-/ layer. The effectiveness of diffusion barriers can be tested by depositing the barrier prior to the low-/ layer. 

In crystals, impurities can take simple configurations. But depending on their concentration, diffusion coefficient, or chemical properties and also on the presence of different kind of impurities or of lattice defects, more complex situations can be found. Apart from indirect information like electrical measurements or X-ray diffraction, methods such as optical spectroscopy under uniaxial stress, electron spin resonance, channelling, positron annihilation or Extended X-ray Absorption Fine Structure (EXAFS) can provide more detailed results on the location and atomic structure of impurities and defects in crystals. Here, we describe the simplest atomic structures more complicated structures are discussed in other chapters. To explain the locations of the impurities and defects whose optical properties are discussed in this book, an account of the most common crystal structures mentioned is given in Appendix B. 

Various forms of spectroscopy have been applied to in situ studies of catalysis, and it is appropriate to cite a few examples. FT-IR is frequently employed for in situ investigations. The experimental configurations used can be either transmission studies of free-standing catalyst wafers [2] or diffuse reflectance measurements on samples in catalytic reaction chambers 13]. In situ Raman spectroscopy has also been applied [4]. X-rays have been used to study catalysts in situ, either by powder diffraction methods [5,6] or XAFS [7]. In situ imaging techniques are beginning to be applied to the measurement of spatial distributions and residence times in catalytic reactors. A recent example of this method employed positron-emission tomography [8]. 

The effect of copolymer composition on free volume and gas permeability of PECT copolymers as well as PET and PCT homopolymers was studied by Hill et al. (97). The free volume was studied by positron annihilation lifetime spectroscopy (PALS) in order to determine the relative size and concentration of free volume cavities in the copolymers. The logarithm of the permeability to oxygen and carbon dioxide increased linearly with the %mol content of 1,4-CHDM units in the copolymer, which was in agreement with the free volume cavity size and relative concentration observed by PALS measurements. Light et al. (98) studied the effect of sub-T relaxations on the gas transport properties of PET, PCT and PECT polyesters. They observed that modification of PET with 1,4-CHDM increased the magnitude of the p-relaxation, as well as the diffusion and solubility coefficients for oxygen and CO. ... 

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