Analysis methods in neutron and X-ray reflectometry

Reflectivity analysis has focused on two key areas; overcoming the phase problem and achieving reliable scattering length density profiles using modelling methods. Significant recent advances are the application of Bayes' theorem, the use of a genetic algorithm and the exploitation of magnetic reference layers and anomalous reflection.     

Simultaneous determination of three components by X-ray spectrometry after neutron activation

A method is described for the simultaneous determination of cadmium, antimony and praseodymium by 14-MeV neutron activation analysis based on characteristic X-ray spectrometry. The results of analysis show a relative error not higher than ±5%, when diluted with H₃BO₃ /90%/ and utilizing the internal standard method to minimize the interelement effects.     

Non-destructive determination of niobium in steel by neutron activation followed by X-ray spectrometry

Neutron activation followed by X-ray spectrometry and magnetic deflection of interfering β particles is applied to the non-destructive determination of niobium in steels. AMS 5643 (17-4PH) and B.C.S. No. 320–330 steel samples containing Nb in the range of 0.02–0.3% were analyzed. By using Nb₂O₅ in cellulose as standard, an overall error of ±20% was obtained.     

Structure of H(D)TaO3 determined by powder X-ray and neutron diffraction

Pure crystalline samples of HTaO₃ and DTaO₃ have been prepared. The crystal structure has been solved using powder X-ray and neutron diffraction (at 2 K and room temperature) and has been shown to consist of Ta(O,OH)₆ octahedra sharing vertices with the oxygen atoms displaced toward the vacant perovskite A sites. The compound is isomorphous with HNbO₃, D_xWO₃, and D_xReO₃ and contains hydrogen atoms as hydroxide groups.     

Simultaneous determination of four components by X-ray spectrometry after 14 MeV neutron activation

14 MeV neutron activation followed by X-ray spectrometry was applied to the simultaneous nondestructive determination of cadmium, antimony and bromine, utilizing praseodymium as an internal standard. The results of analysis show a relative error not higher than ±5%, when the samples were diluted with H₃BO₃ -5% to minimize the interelement effects.     

Time-resolved in situ studies of oxygen intercalation into SrCoO2.5, performed by neutron diffraction and X-ray absorption spectroscopy

Electrochemical oxidation of the antiferromagnetically ordered SrCoO(2.5), with brownmillerite-type structure, to the cubic ferromagnet SrCoO(3), with perovskite structure, has been investigated in situ by neutron diffraction as well as by X-ray absorption fine structure (XAFS) spectroscopy in specially designed electrochemical cells. The neutron diffraction experiments were performed twice, using two different wavelengths (lambda = 1.2921(2) and 4.74 A) in order to better discriminate structural and magnetic changes as functions of the charge transfer. From the neutron diffraction experiments, two intermediate phases, SrCoO(2.75) and SrCoO(2.82)(+/-)(0.07), were characterized. No superstructure reflections were observed for the corresponding SrCoO(2.75) phase. Instead we observed here, for the first time, 3D oxygen ordering during an oxygen intercalation reaction, as established for SrCoO(2.82)(+/-)(0.07), which can be described as a tetragonal unit cell, related to the perovskite cell by a approximately 2(a radical2) and c approximately 2a. The structure of this intermediate phase confirms the strongly topotactic character of the oxygen intercalation reaction. We were also able to prove, from in situ XAFS spectroscopy at the Co absorption edge, that the evolution of the Co valence state from formally +3 for SrCoO(2.5) to +4 for the final reaction product (SrCoO(3.0)) does not proceed continuously but gives evidence for the formation of O(-) species for stoichiometries corresponding to SrCoO(2.82)(+/-)(0.07). The use of neutrons (vs X-rays) in the diffraction experiments and the choice of the transmission (vs fluorescence) mode in the XAFS experiment guarantee that the obtained data well represent bulk and not just surface properties.     

Structure determination of triplet diphenylcarbenes by in situ X-ray crystallographic analysis

Crystalline-state photoreactions of the following diphenyldiazomethanes were investigated by in situ X-ray crystallography, spectroscopy, and theoretical calculations: bis(2,4,6-trichlorophenyl)diazomethane (1-N2), bis(2,4,6-tribromophenyl)diazomethane (2-N2), bis(2,6-dibromo-4-methylphenyl)diazomethane (3-N2), bis(2,6-dibromo-4-tert-butylphenyl)diazomethane (4-N2), (2,4,6-tribromophenyl)-(2,6-dimethyl-4-tert-butylphenyl)diazomethane (5-N2), bis(4-bromophenyl)diazomethane(6-N2), and diazofluorene (7-N2). Crystal structures of photoinduced triplet diphenylcarbenes (DPCs) of 1, 2, and 4 were determined. We found remarkable differences between their structural information obtained in the crystalline state and that previously obtained spectroscopically in a glass matrix. Although the triplet DPCs of 1, 2, and 4 have significantly different stabilities in solution, only subtle differences in their structural parameters, except for their C(:)-Ar bond lengths, are observed. It is noteworthy that the average bond length of C(:)-Ar for 4 (1.374 A) is considerably shorter than those for (3)1 and (3)2 (1.430 and 1.428 A, respectively), provided that the two C(:)-Ar bonds being compared were chemically equivalent. The most likely explanations for the small and large differences in bond lengths in 1, 2, and 4 may be derived from the packing effect. The packing patterns of 1 and 2 are identical, but that of 4 is totally different from those of 1 and 2. Moreover, these results are interpreted as indicating that triplet DPCs undergo relaxation upon softening of the environments. Theoretical calculations indicate that the potential energy surface of triplet DPCs in terms of the carbene angle is extremely flat and changes in the angles have little effect on the energies. Triplet DPCs with a sterically congested carbene center are trapped in a structure dictated by the precursor structure in a rigid matrix, even if this is not the thermodynamically most stable geometry, but undergo geometrical relaxation upon softening the matrix to relieve steric compression. ESR studies indicate that the interplanar angles are more flexible than the bond angles.     

Halogen determination in Arctic aerosols by neutron activation analysis with Compton suppression methods

The study of halogens particularly bromine and chlorine in Arctic aerosolshas received a great deal of attention in the past decade in ozone depletionduring polar sunrise studies. Iodine has also been studied as part of geochemicalcycling. We have shown that all three of the above elements can be determinedsimultaneously with very low detection limits using epithermal NAA in conjunctionwith Compton suppression methods. Besides lowering the background considerably,Compton suppression can eliminate or minimize the overlapping peak of the620 keV photopeak arising form the 1642 keV double escape peak of ³⁸Cl interfering with the 616.9 keV photopeak of ⁷⁹Br(n,) ⁸⁰ Br reaction. Iodine is ideally determined by epithermal NAAbecause of its very good resonance integral cross-section. Although chlorineis usually determined using thermal neutrons via the ³⁷Cl(n,) ³⁸Cl reactions, epithermal NAA is still feasible for the Arcticaerosol, since it has a major sea-salt component.     

Structure and interactions of block copolymer micelles of Brij 700 studied by combining small-angle X-ray and neutron scattering

Spherical micelles of the diblock copolymer/surfactant Brij 700 (C(18)EO(100)) in water (D(2)O) solution have been investigated by small-angle X-ray scattering (SAXS) and small-angle neutron scattering (SANS). SAXS and SANS experiments are combined to obtain complementary information from the two different contrast conditions of the two techniques. Solutions in a concentration range from 0.25 to 10 wt % and at temperatures from 10 to 80 degrees C have been investigated. The data have been analyzed on absolute scale using a model based on Monte Carlo simulations, where the micelles have a spherical homogeneous core with a graded interface surrounded by a corona of self-avoiding, semiflexible interacting chains. SANS and SAXS data were fitted simultaneously, which allows one to obtain extensive quantitative information on the structure and profile of the core and corona, the chain interactions, and the concentration effects. The model describes the scattering data very well, when part of the EO chains are taken as a "background"contribution belonging to the solvent. The effect of this becomes non-negligible at polymer concentrations as low as 2 wt %, where overlap of the micellar coronas sets in. The results from the analysis on the micellar structure, interchain interactions, and structure factor effects are all consistent with a decrease in solvent quality of water for the PEO block as the theta temperature of PEO is approached.     

Oxygen determination by fast neutron activation

A method for the determination of oxygen based on the reaction¹⁶O(n, p)¹⁶N is suggested. The samples are irradiated in stainless steel capsules with fast neutrons. The total neutron flux passing through the sample is proportional to the flux passing through the wall of the capsule. Therefore, the activity induced in the capsule according to the reaction⁵⁶Fe(n, p)⁵⁶Mn can be used to monitor the neutron flux through the sample. Thus, the necessity of maintaining the sample in an exact position during the irradiation is eliminated.     

X-ray fundamental parameter methods for the determination of some elements in hydrocarbons by WDXRF

Summary X-ray fundamental parameter methods have been applied to the determination of some elements such as Fe, Ca, Zn, Ba and S in solutions of hydrocarbons analysed by means of a wavelength dispersive spectrometer. A comparison is carried out for methods with standards as well as without standards. The influence of different kinds of standards on the results has been investigated. The use of aqueous salt solutions has led to more accurate values than the use of solid standards. The same random errors have been obtained for both kinds of standards. Results obtained without standards are slightly less accurate than those obtained with aqueous standards.     

Comparison of sample crystallinity determination methods by X-ray diffraction for challenging cellulose I materials

Cellulose crystallinity assessment is important for optimizing the yield of cellulose products, such as bioethanol. X-ray diffraction is often used for this purpose for its perceived robustness and availability. In this work, the five most common analysis methods (the Segal peak height method and those based on peak fitting and/or amorphous standards) are critically reviewed and compared to two-dimensional Rietveld refinement. A larger (\(n=16\)) and more varied collection of samples than previous studies have presented is used. In particular, samples (\(n=6\)) with low crystallinity and small crystallite sizes are included. A good linear correlation (\(r^{2} \ge 0.90\)) between the five most common methods suggests that they agree on large-scale crystallinity differences between samples. For small crystallinity differences, however, correlation was not seen for samples that were from distinct sample sets. The least-squares fitting using an amorphous standard shows the smallest crystallite size dependence and this method combined with perpendicular transmission geometry also yielded values closest to independently obtained cellulose crystallinity values. On the other hand, these values are too low according to the Rietveld refinement. All analysis methods have weaknesses that should be considered when assessing differences in sample crystallinity.     

Structure and dynamics of halogenoethanol-water mixtures studied by large-angle X-ray scattering, small-angle neutron scattering, and NMR relaxation

To clarify the structure of solvent clusters formed in halogenoethanol-water mixtures at the molecular level, large-angle X-ray scattering (LAXS) measurements have been made at 298 K on 2,2,2-trifluoroethanol (TFE), 2,2,2-trichloroethanol (TCE), and their aqueous mixtures in the TFE and TCE mole fraction ranges of 0.002 < or = x(TFE) < or = 0.9 and 0.5 < or = x(TCE) < or = 0.9, respectively. The radial distribution functions (RDFs) for TFE-water mixtures have shown that the structural transition from inherent TFE structure to the tetrahedral-like structure of water takes place at x(TFE) approximately 0.2. In the TCE-water mixtures inherent TCE structure remains in the range of 0.5 < or = x(TCE) < or = 1. Small-angle neutron scattering (SANS) experiments have been performed on CF(3)CH(2)OD- (TFE-d(1)-) D(2)O and CF(3)CD(2)OH- (TFE-d(2)-) H(2)O mixtures in the TFE mole fraction range of 0.05 < or = x(TFE) < or = 0.8. The SANS results in terms of the Ornstein-Zernike correlation length have revealed that TFE and water molecules are most heterogeneously mixed with each other in the TFE-water mixture at x(TFE) approximately 0.15, i.e., both TFE clusters and water clusters are most enhanced in the mixture. To evaluate the dynamics of TFE and ethanol (EtOH) molecules in TFE-water and ethanol-water mixtures, respectively, (1)H NMR relaxation rates for the methylene group within alcohol molecules have been measured by using an inversion-recovery method. The alcohol concentration dependence of the relaxation rates for the TFE-water and ethanol-water mixtures has shown a break point at x(TFE) approximately 0.15 and x(EtOH) approximately 0.2, respectively, where the structural transition from alcohol clusters to the tetrahedral-like structure of water takes place. On the basis of the present results, the most likely structure models of solvent clusters predominantly formed in TFE-water and TCE-water mixtures are proposed. In addition, effects of halogenation of the hydrophobic groups on clustering of alcohol molecules are discussed from the present results, together with the previous ones for ethanol-water and 1,1,1,3,3,3-hexafluoro-2-propanol- (HFIP-) water mixtures.