Rietveld analysis

The analysis of siUcon carbide involves identification, chemical analysis, and physical testing. For identification, x-ray diffraction, optical microscopy, and electron microscopy are used (136). Refinement of x-ray data by Rietveld analysis allows more precise deterrnination of polytype levels (137). 

Rietveld analysis indicates that S4N4 undergoes a transition to a new... 

Michel, V., Ildefonse, P. and Morin, G. 1995 Chemical and structural changes in Cervus elephus tooth enamels during fossilization (Lazaret Cave) a combined IR and XRD Rietveld analysis. Applied Geochemistry 10 145-159. 

The Rietveld analysis is mainly used for refining the structures of crystalline phases and to perform quantitative analysis of multiphase samples. The quantitative analysis is possible since the Rietveld method can easily deal with diffraction patterns with strongly overlapped peaks, while preferred orientation can be quantitatively treated. 

In this section, we will describe the principal features of the main methods and the information that the Rietveld analysis generally delivers, especially related to the investigations on poor crystallites and multiphase compounds. This introduction is not exhaustive there are hundreds of articles that explore practically all of the aspects of this kind of analysis and now, 40 years after the first article [43], new improvements and results are still being published. 

The Rietveld Fit of the Global Diffraction Pattern. The philosophy of the Rietveld method is to obtain the information relative to the crystalline phases by fitting the whole diffraction powder pattern with constraints imposed by crystallographic symmetry and cell composition. Differently from the non-structural least squared fitting methods, the Rietveld analysis uses the structural information and constraints to evaluate the diffraction pattern of the different phases constituting the diffraction experimental data. 

Even if the main intent of the Rietveld analysis is the structure refinement in material science, sometimes the information relative to the structure is not the heart of the matter. 

The study of the peak shape gives important information relative to the microstructure of the sample even when it is included in the Rietveld code. Actually, in order to perform the Warren-Averbach analysis or other mi-crostructural studies, it is not necessary to use the Rietveld analysis, but it is often sufficient to operate with less complex, non-structural peak fitting procedures. 

There is, in any case, an important advantage in using the Rietveld analysis, which is the possibility of quanti-f5ing the phase to which we are ascribing the microstructure properties. 

The analytical power of XRF and XRD has lately been combined in an integrated XRF/XRD system, in which XRD powder measurements are examined for phase identification and Rietveld analysis on the basis of element concentrations. Process analysis, a former stronghold of XRF, can now be performed by highspeed XRD, which is supported by XRF element-analytical data. 

Tetrasulfur tetranitride (9a) adopts a cage structure with equal S-N bond lengths (1.62 A) and two weak transannular S- -S interactions of ca. 2.60 A at room temperature. Tetraselenium tetranitride and the hybrid l,5-Se2S2N4 also have similar structures (9b, 10).54 Rietveld analysis indicates that S4N4 undergoes a transition to a new orthorhombic phase at 397 K.55... 

II.A.1.1. X-Ray Diffraction. The X-ray patterns of silicalite-1 and TS-1 demonstrate a change from the monoclinic structure of the former to orthorhombic when Ti4+ is introduced into the silicalite framework (5). The Rietveld analysis of Millini et al. (75) demonstrates a linear dependence of the lattice parameters and unit cell volume on the extent of Ti substitution in silicalite-1 and constitutes confirmatory evidence for the location of Ti in framework positions. Millini and Perego (77) concluded that the upper limit for incorporation of Ti in the TS-1 framework is about 2.5%. 

The structure of a green rust LDH-type material with the formula [Fe 4Fe 2(OH)i2]S04-ca. 8H2O has been determined by Rietveld analysis [157]. The material exists as a one-layer polytype with the interlayers containing two planes of sulfate and water molecules giving a basal spacing of 1.1011 nm. The sulfate ions are oriented with their C3 axes perpendicular to the layers and alternate anions point up and down (as shown earlier in Fig. 14) and form a superlattice with parameter a = UoV5 = 0.5524 nm (Fig. 39). 

Akaganeite (named after the Akagane mine in Japan) is isostructural with hollan-dite. Compounds with this structure have a tetragonal or monoclinic unit cell. Bernal et al. (1959) and Keller (1970) both concluded that the unit cell of akaganeite was tetragonal with a = 1.000 nm and c = 0.3023 nm. The structural refinement of a natural sample using XRD and Rietveld analysis indicated, however, that the unit cell is monoclinic with a = 1.060 nm, b = 0.3039 nm, c = 1.0513 nm and p = 90.24° (Post Buchwald, 1991). There are eight formula units per unit cell. 

Izumi, F. (1993) Rietveld analysis program RIE-TAN and PREMOS and special applications. In Young, R.A. (ed.) The Rietveld Method, Oxford, Oxford University Press, 236-253 Jackson, B.P. Miller, W.P. (2000) Effectiveness of phosphate and hydroxide for desorption of arsenic and selenium species from iron oxides. Soil Sci. Soc. Am. J. 64 1616-1622 Jain, A. Raven, K.P. Loeppert, R.EI. (1999) Ar-senite and arsenate adsorption on ferrihy-drite Surface charge reductions and net OEI-release stoichiometry. Environ. Sci. Techn. 

The structural determination of Ba CugO for 6.8 < x < 7.0, was completed in several laboratories by Rietveld analysis of powder neutron d iffraction data (10-15). The neutron diffraction experiments confirmed the space group Pmmm and the main structural features found by x-rays by Siegriest et al. (7), but revealed that some of the oxygen assignments made in the x-ray studies were not entirely correct. The refined structural parameters obtained in four of these... 

A method known as Rietveld analysis has been developed for solving crystal structures from powder diffraction data. The Rietveld method involves an interpretation of not only the line position but also of the line intensities, and because there is so much overlap of the reflections in the powder patterns, the method developed by Rietveld involves analysing the overall line profiles. Rietveld formulated a method of assigning each peak a gaussian shape and then allowing the gaussians to overlap so that an overall... 

FIGURE 2.11 Rietveld analysis of perovskite with partial substitution of Ti with Ca. (Courtesy of the Royal Society of Chemistry.)... 

Metal sulfide powder samples were weighed and placed in a glass desiccator containing an open vial of metallic mercury. The desiccator was placed in a laboratory oven at 70 or 90°C for up to 24 days. The concentration of Hg(0) in the desiccator was calculated to be -1500 ppm 70°C and -2500 ppm 90°C. During the exposure period, the desiccator was periodically removed, cooled, and the metal sulfide samples weighed. The period of time that the samples were out of the oven was taken into account when reporting the Hg(0) exposure duration. XRD and quantitative data analysis, Rietveld analysis, was used to identify and quantify the post-reaction crystalline-phase constituents. 

Fig. 9. Unit ceil parameters of TS-1 by Rietveld analysis. A, B, and C axis dimensions D volume. (From Millini et al., 1992.)...

To further clarify matters, the modified synthesis method was repeated and the products analyzed by XRD with Rietveld analysis. In no case could framework Tiiv in excess of x = 0.025 be found. Instead, Ti02 phase was present, and its amount was shown to quantitatively account for the remaining titanium (Millini et al., 1992). 

Neutron diffraction studies have the advantage of being able to determine guest and host (both O and H/D) positions. With the difficulty of preparing single crystals of gas hydrates, most diffraction studies are performed on powder samples. Powder x-ray and neutron diffraction can be used with Rietveld analysis of the data for detailed structure determination (Rawn et al., 2003 Hester et al., 2006a). 

The program just described, for Rietveld analyses using generalized coordinates, has been used in the structural analysis of isotactic polypropylene recently undertaken both with x-ray and with neutron powder diffraction data. We believe this analysis (Immirzi, in preparation) to be the first Rietveld analysis of a polymer done from x-ray data. Rietveld analyses of polymers from neutron data have been done but, at least in the polyethylene case reported by Willis and co-workers (15), there was no use of generalized coordinates. 

XRD and grazing-incidence synchrotron radiation diffraction (GISRD) plots of a hybrid sample at different depths from the surface showed the abundance of a-Al203, AT and mullite to vary with depth (Fig. 5.13). As the depth increased, the abundance of both mullite and AT decreased, but that of aAl203 increased. The composition depth profiles as determined from the Rietveld analysis are shown in Fig. 5.13(a). From the results it can be seen... 

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