Surfaces neutron diffraction analysis

A porous particle contains many interior voids known as open or closed pores. A pore is characterized as open when it is connected to the exterior surface of the particle, whereas a pore is closed (or blind) when it is inaccessible from the surface. So, a fluid flowing around a particle can see an open pore, but not a closed one. There are several densities used in the literature and therefore one has to know which density is being referred to (Table 3.15). True density may be defined as the mass of a powder or particle divided by its volume excluding all pores and voids. True density is also referred to as absolute density or crystalline density in the case of pure compounds. However, this density is very difficult to be determined and can be calculated only through X-ray or neutron diffraction analysis of single-crystal samples. Particle density is defined as the mass of a particle divided by its hydrodynamic volume. The hydrodynamic volume includes the volume of all the open and closed pores. Practically, the hydrodynamic volume is identified with the volume included by the outer surface of the particle. The particle density is also called apparent or envelope density. The term skeletal density is also used. The skeletal density of a porous particle is higher than the particle one, since it is the mass of the particle divided by the volume of solid material making up the particle. In this volume, the closed pores volume is included. The interrelationship between these two types of density is as follows (ASTM, 1994 BSI, 1991) ... 

A neutron diffraction analysis of oxymyoglobin (Phillips, 1984) located 120 water molecules at the protein surface. Peters and Peters (1986) analyzed these and earlier X-ray results (Hanson and Schoen-born, 1981 Takano, 1977a,b) and described networks formed of protein polar groups and water molecules. The network structures found for myoglobin appear to be like those for other globular proteins. 

Another major difference between the use of X rays and neutrons used as solid state probes is the difference in their penetration depths. This is illustrated by the thickness of materials required to reduce the intensity of a beam by 50%. For an aluminum absorber and wavelengths of about 1.5 A (a common laboratory X-ray wavelength), the figures are 0.02 mm for X rays and 55 mm for neutrons. An obvious consequence of the difference in absorbance is the depth of analysis of bulk materials. X-ray diffraction analysis of materials thicker than 20—50 pm will yield results that are severely surface weighted unless special conditions are employed, whereas internal characteristics of physically large pieces are routinely probed with neutrons. The greater penetration of neutrons also allows one to use thick ancillary devices, such as furnaces or pressure cells, without seriously affecting the quality of diffraction data. Thick-walled devices will absorb most of the X-ray flux, while neutron fluxes hardly will be affected. For this reason, neutron diffraction is better suited than X-ray diffraction for in-situ studies. 

Some of the techniques included apply more broadly than just to surfaces, interfaces, or thin films for example X-Ray Diffraction and Infrared Spectroscopy, which have been used for half a century in bulk solid and liquid analysis, respectively. They are included here because they have by now been developed to also apply to surfaces. A few techniques that are applied almost entirely to bulk materials (e.g.. Neutron Diffraction) are included because they give complementary information to other methods or because they are referred to significantly in the 10 materials volumes in the Series. Some techniques were left out because they were considered to be too restricted to specific applications or materials. 

Analyses of insertion electrodes include structural analysis by XRD, neutron diffraction, HRTEM with electron diffraction, chemical analysis by EDAX, XPS and dissolution followed by ICP, morphological analysis by electron microscopy, surface area measurements by gas adsorption, and electrochemical analysis by voltammetry chronopotentiometry (primary techniques) and fine electrochemical tools such as EIS, PITT, GITT, and... 

Another feature that has not been systematically covered concerns additional means of determining properties of adsorbates. Examples here are the classical spectroscopies, with their surface variants (secs. 1.7.10-12), reflection methods, including elllpsometry, reflectometry and evanescent wave studies, NMR. X-ray analysis, neutron diffraction and dielectric spectroscopy. The theory of the last mentioned phenomenon for bulk phases has been discussed in sec. I.4.5f if applied to adsorbates, the technique can give information on the various degrees of freedom that polar molecules may have, say, for water adsorbed on oxides. For thicker water layers containing ions, measurement of the surface conductivity may yield additional information see also sec. I.6.6d. The reason for not systematizing these techniques is that we do not consider them typically "surface methods, but rather surface variants of bulk methods. 

A multifaceted characterization effort to stndy these materials as a function of thermal treatment has been undertaken. The techniques include BET surface area measurements. X-ray diffraction, chemisorption, scanning and high-resolution transmission electron microscopy, analytical electron microscopy, neutron activation analysis, atomic absorption spectroscopy, FTIR and isotopic tracer studies. The details of catalyst preparation have been previously... 

Surface-oriented tribological analysis bonding state Thin film structure, internal pressure defects, etc. (including neutron diffraction) Surface-oriented tribological analysis, bonding state, lubricant film thickness (+ ion gun)... 

By the 1980s most of the aluminosilicate zeolites currently used industrially were known, and the emphasis shifted to the study of these materials using a range of powerful new techniques that came of age at this time. These included, in particular, solid state NMR, X-ray and neutron powder diffraction analysis, high resolution electron microscopy and computational methods. All were ideal for the study of structural details of solids that were rarely available, and never used in industrial applications, other than as microcrystalline powders. All these techniques are applicable to the bulk of the solid - this in turn makes up the (internal) surface, which is accessible to adsorbed molecules. Since the techniques are able to operate under any conditions of gas pressure, they may be used to extract structural details in situ under the operating conditions of ion exchange, adsorption and catalysis. In particular, zeolitic systems have proved ideal for the study, understanding and subsequent improvement of solid acid catalysts. 

Auger Electron Spectroscopy Molecular Electronics Photoelectron Spectroscopy Surface Chemistry Vacuum technology X-Ray Analysis X-Ray, Synchrotron Radiation and Neutron Diffraction... 

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