Pulsed-field gradient nuclear magnetic resonance study of transport properties of fluid catalytic cracking catalysts

Pulsed-field gradient nuclear magnetic resonance (PFG NMR) has been applied to study molecular diffusion in industrial fluid catalytic cracking (FCC) catalysts and in USY zeolite for a broad range of molecular displacements and temperatures. The results of this study have been used to elucidate the relevance of molecular transport on various displacements for the rate of molecular exchange between catalyst particles and their surroundings. It turned out that this rate, which may determine the overall rate and selectivity of FCC process, is primarily related to the diffusion mode associated with displacements larger than the size of zeolite crystals located in the particles but smaller than the size of the particles. This conclusion has been confirmed by comparative studies of the catalytic performance of different FCC catalysts.     

Light-induced charge separation in anatase TiO2 particles

Ultraviolet light-induced electron-hole pair excitations in anatase TiO(2) powders were studied by a combination of electron paramagnetic resonance and infrared spectroscopy measurements. During continuous UV irradiation in the mW.cm(-2) range, photogenerated electrons are either trapped at localized sites, giving paramagnetic Ti(3+) centers, or remain in the conduction band as EPR silent species which may be observed by their IR absorption. Using low temperatures (90 K) to reduce the rate of the electron-hole recombination processes, trapped electrons and conduction band electrons exhibit lifetimes of hours. The EPR-detected holes produced by photoexcitation are O(-) species, produced from lattice O(2-) ions. It is found that under high vacuum conditions, the major fraction of photoexcited electrons remains in the conduction band. At 298 K, all stable hole and electron states are lost from TiO(2). Defect sites produced by oxygen removal during annealing of anatase TiO(2) are found to produce a Ti(3+) EPR spectrum identical to that of trapped electrons, which originate from photoexcitation of oxidized TiO(2). Efficient electron scavenging by adsorbed O(2) at 140 K is found to produce two long-lived O(2)(-) surface species associated with different cation surface sites. Reduced TiO(2), produced by annealing in vacuum, has been shown to be less efficient in hole trapping than oxidized TiO(2).     

Structure of mercaptobiphenyl monolayers on mercury

The molecular-scale structure and phase behavior of single-component Langmuir films of 4'-methyl-4-mercaptobiphenyl (MMB) and 4'-perfluoromethyl-4-mercaptobiphenyl (FMMB) on mercury were studied using surface tensiometry, grazing incidence X-ray diffraction, and X-ray reflectivity. At low coverages, a condensed but in-plane disordered single layer of surface-parallel molecules is found for both compounds. At high coverages, both compounds exhibit in-plane-ordered phases of standing-up molecules. For MMB, the biphenyl core dominates the structure, yielding a centered-rectangular unit cell with an area A(x) of 21.8 A(2)/molecule, with molecules tilted by approximately 14 degrees from the surface normal in the nearest-neighbor direction, and a coherence length xi of >1000 A for the crystalline domains. For FMMB, the perfluoromethyl group dominates the structure, yielding a hexagonal unit cell with untilted molecules, an area A(x) of 24.2 A(2)/molecule, and a much smaller xi of approximately 110 A. The structure is discussed in comparison with self-assembled monolayers of MMB on crystalline Au(111) and similar-length alkanethiolate SAMs on Au(111) and on mercury. The differences in the structure are discussed and traced to the differences in the substrate's surface structure, and in the molecular cross section and rigidity.     

Energy spectrum of particles accelerated in relativistic collisionless shocks

We analytically study diffusive particle acceleration in relativistic, collisionless shocks. We find a simple relation between the spectral index s and the anisotropy of the momentum distribution along the shock front. Based on this relation, we obtain s=(3beta(u)-2beta(u)beta(2)(d)+beta(3)(d))/(beta(u)-beta(d)) for isotropic diffusion, where beta(u) (beta(d)) is the upstream (downstream) fluid velocity normalized to the speed of light. This result is in agreement with previous numerical determinations of s for all (beta(u),beta(d)), and yields s=38/9 in the ultrarelativistic limit. The spectrum-anisotropy connection is useful for testing numerical studies and constraining anisotropic diffusion results. It suggests that the spectrum is highly sensitive to the form of the diffusion function for particles traveling along the shock front.     

Ring resonator in a Sagnac interferometer as a birefringence magnifier

A novel birefringence magnification technique that uses a ring resonator in a Sagnac interferometer is proposed and demonstrated. An enhancement factor of 38 was obtained experimentally. The scheme can be used to increase measurement sensitivity to small birefringence and polarization mode dispersion and to decrease the threshold for nonlinear switching and laser mode locking by a Sagnac interferometer.     

Astrophysical neutrinos: flavor ratios depend on energy

Electromagnetic (and adiabatic) energy losses of pi's and mu's modify the flavor ratio (measured at Earth) of neutrinos produced by pi decay in astrophysical sources, Phi v: phi v mu: phi v tau, from 1:1:1 at low energy to 1:1.8:1.8 at high energy. The transition occurs over 1-2 decades of v energy, and is correlated with a modification of the neutrino spectrum. For gamma-ray bursts, e.g., the transition is expected at approximately 100 TeV and may be detected by km-scale v telescopes. Measurements of the transition energy and energy width will provide unique probes of the physics of the sources. Pi and mu energy losses also affect the ratio of ve flux to total v flux, which may be measured at the resonance (6.3 PeV): It is modified from 1/6(1/15) at low energy to 1/9 (practically 0) at high energy for neutrinos produced in p p (p gamma) interactions.     

Cross sections and transverse single-spin asymmetries in forward neutral-pion production from proton collisions at sqrt[s]=200 GeV

Measurements of the production of forward high-energy pi(0) mesons from transversely polarized proton collisions at sqrt[s]=200 GeV are reported. The cross section is generally consistent with next-to-leading order perturbative QCD calculations. The analyzing power is small at x(F) below about 0.3, and becomes positive and large at higher x(F), similar to the trend in data at sqrt[s]< or =20 GeV. The analyzing power is in qualitative agreement with perturbative QCD model expectations. This is the first significant spin result seen for particles produced with p(T)>1 GeV/c at a polarized proton collider.