Neutron diffraction techniques

Chromium metal may be analyzed by various instrumental techniques including flame and furnace AA spectrophotometry (at 357.9 nm) ICP emission spectrometry (at 267.72 or 206.15 nm), x-ray fluorescence and x-ray diffraction techniques, neutron activation analysis, and colorimetry. 

Electron scattering /diffraction techniques Neutron diffraction / scattering Optical microscopy... 

Since the recognition in 1936 of the wave nature of neutrons and the subsequent demonstration of the diffraction of neutrons by a crystalline material, the development of neutron diffraction as a useful analytical tool has been inevitable. The initial growth period of this field was slow due to the unavailability of neutron sources (nuclear reactors) and the low neutron flux available at existing reactors. Within the last decade, however, increases in the number and type of neutron sources, increased flux, and improved detection schemes have placed this technique firmly in the mainstream of materials analysis. 

As with other diffraction techniques (X-ray and electron), neutron diffraction is a nondestructive technique that can be used to determine the positions of atoms in crystalline materials. Other uses are phase identification and quantitation, residual stress measurements, and average particle-size estimations for crystalline materials. Since neutrons possess a magnetic moment, neutron diffraction is sensitive to the ordering of magnetically active atoms. It differs from many site-specific analyses, such as nuclear magnetic resonance, vibrational, and X-ray absorption spectroscopies, in that neutron diffraction provides detailed structural information averaged over thousands of A. It will be seen that the major differences between neutron diffraction and other diffiaction techniques, namely the extraordinarily... 

Intimate information about the nature of the H bond has come from vibrational spectro.scopy (infrared and Raman), proton nmr spectroscopy, and diffraction techniques (X-ray and neutron). In vibrational spectroscopy the presence of a hydrogen bond A-H B is manifest by the following effects ... 

B. N. Brockhouse (McMaster University) and C. G. Schull (Massachusetts Institute of Technology) pioneering contributions to neutron scattering techniques for studies of condensed matter (namely neutron spectroscopy and neutron diffraction techniques, respectively). 

Investigations based on equation (a) are indirect. Direct structural studies using diffraction techniques (X-ray or neutron), or electron microscopy, while they cannot detect the low concentrations of defects present in NiO or CoO are indispensible to the study of grossly non-stoichiometric oxides like FeO, TiOj, WOj etc., and particularly electron microscopes with a point-to-point resolution of about 0.2 nm are widely used. The first direct observation of a point defect (actually a complex of two interstitial metal atoms, and two oxygen atoms in Nb,2029) was made" using electron microscopy. 

Blasie and his colleagues have determined the separate profile structures of the lipid bilayer and of the Ca transport ATPase molecule within the sarcoplasmic reticulum membrane to 11 A resolution by a combination of X-ray and neutron diffraction techniques [128,140,187-199]. 

As a conclusion of this section, it can be said that the method used has to be carefully chosen according to the sample studied and/or the expected results. Conventional XRD may be sufficient to localise a single cation species in a dehydrated zeolite whereas for bicationic zeolites more elaborate techniques like anomalous XRD or MAS and MQMAS NMR may be necessary. If the focus of the study is more on the influence of adsorbed molecules on the distribution of the cations, neutron scattering may be needed to complete the work. Finally, highly dealuminated zeolites may be difficult to study with diffraction techniques, in this case NMR techniques may be the best available option. 

The techniques available to achieve molecular structure determinations are limited. They include structural analysis with diffraction techniques—such as electron, neutron, and x-ray diffraction—and various absorption and emission techniques of electromagnetic radiation—such as microwave spectroscopy and nuclear magnetic resonance (NMR). For molecules with unpaired spins a companion technique of electron spin resonance spectroscopy (ESR) is highly informative. 

X-ray, neutron, and electron diffraction techniques are used to determine crystal structures and can thus be used for molecular structure determinations. Because of its high resolution and applicability to small and often weakly diffracting samples, x-ray crystallography and powder diffraction are by far the methods of choice for most structure determinations on crystalline compounds,... 

The location of a compound within a lipid bilayer can be studied using X-ray diffraction [167], neutron diffraction [164], fluorescence quenching techniques [163], differential scanning microcalorimetry [164], or NMR techniques [168,169],... 

The accurate spatial location of these atoms generally needs a sophisticated approach, for example, the study of a complete deuterated set of isotopic derivatives in microwave spectroscopy or the use of neutron diffraction techniques. We shall see below that a set of CNDO/2 calculations combined with suitable experiments (microwave spectroscopy and/or electron diffraction) may help to solve the geometrical and conformational analysis of compounds containing many hydrogen atoms. 

Physical properties and detection of liquid Zintl compounds have been discussed and problems of gradual development of stoichiometries in non-clustering liquid ionic alloys, and their agreement with those persisting in the solid, have been considered. Neutron diffraction techniques and the results of their applications (Ga, Tl, alkali alloys) have been described. 

FIGURE 5. Comparison of 1SN- H bond distances obtained by solid state NMR techniques with distances obtained by single-crystal neutron-diffraction techniques. Reprinted with permission from Reference 108. Copyright (1987) American Chemical Society... 

Although we felt the distances in the Pt-oxo unit were unequivocal based on the disorder-free X-ray structures, we endeavored to use an additional structural method to assess this unprecedented structure, neutron diffraction. As an independent structural technique, neutron diffraction can determine not only the absolute structure of molecules but also the location of hydrogens. The latter are almost never located in even the best X-ray crystallographic structure determinations of polytungstates. 

A compilation of metal to donor atom distances in complexes, as determined by X-ray and neutron diffraction techniques up to early 1988, provides a comprehensive summary of such data... 

The structures of iron oxides have been determined principally by single crystal X-ray diffraction or neutron diffraction with supplementary information coming from infrared spectroscopy, electron diffraction and high resolution electron microscopy. A few years after the first successful application of X-ray diffraction to crystal structure determination, this technique was used to establish the major features of the structures of magnetite (Bragg, 1915 Nishikawa, 1915) and hematite (Bragg Bragg, 1918). 

Like X-ray diffraction patterns, neutron and electron diffraction patterns provide averaged information about the structure of a compound. Details of these techniques are given in works by Hirsch et al. (1965) and West (1988). Neutron diffraction involves interaction of neutrons with the nuclei of the atoms. As the neutrons are scattered relatively evenly by all the atoms in the compound, they serve to indicate the positions of the protons in an oxide hydroxide. This technique has been applied to elucidation of the structure and/or magnetic properties of goethite (Szytula et al., 1968 Forsyth et al., 1968), akaganeite (Szytula et al., 1970), lepidocrocite (Oles et al., 1970 Christensen Norlund-Christensen, 1978), hematite (Samuelson Shirane, 1970 Fernet et al., 1984) and wiistite (Roth, 1960 Cheetham et al., 1971 Battle Cheetham, 1979). A neutron diffractogram of a 6-line ferrihydrite was recently produced by Jansen et al. (2002) and has helped to refine its structure (see chap. 2). 

Cadmium in acidified aqueous solution may be analyzed at trace levels by various instrumental techniques such as flame and furnace atomic absorption, and ICP emission spectrophotometry. Cadmium in solid matrices is extracted into aqueous phase by digestion with nitric acid prior to analysis. A much lower detection level may be obtained by ICP-mass spectrometry. Other instrumental techniques to analyze this metal include neutron activation analysis and anodic stripping voltammetry. Cadmium also may be measured in aqueous matrices by colorimetry. Cadmium ions react with dithizone to form a pink-red color that can be extracted with chloroform. The absorbance of the solution is measured by a spectrophotometer and the concentration is determined from a standard calibration curve (APHA, AWWA and WEF. 1999. Standard Methods for the Examination of Water and Wastewater, 20th ed. Washington, DC American Public Health Association). The metal in the solid phase may be determined nondestructively by x-ray fluorescence or diffraction techniques. 

The section Analysis starts with elemental composition of the compound. Thus the composition of any compound can be determined from its elemental analysis, particularly the metal content. For practically all metal salts, atomic absorption and emission spectrophotometric methods are favored in this text for measuring metal content. Also, some other instrumental techniques such as x-ray fluorescence, x-ray diffraction, and neutron activation analyses are suggested. Many refractory substances and also a number of salts can be characterized nondestructively by x-ray methods. Anions can be measured in aqueous solutions by ion chromatography, ion-selective electrodes, titration, and colorimetric reactions. Water of crystallization can be measured by simple gravimetry or thermogravimetric analysis. 

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