University of Technology Department of Materials Engineering

X-Ray Characterization of Materials

Dr. Saad B. H. Farid Formerly: Chief Researchers Currently: Assistant Professor

Generation of Monochromatic X-ray

Schematic Electronic transitions in an atom Emission processes indicated by arrows

The schematic of a typical x-ray emission spectrum, for clarity indicating only the presence of continuous background and three characteristic wavelengths: K1, K2, and K, which have high intensities.

The spectra of the unfiltered beams from a copper target (Z=29) filtered by nickel (Z=28)

Left - the schematic of the x-ray emission spectrum shown as the solid line overlapped with the schematic of the () function of the properly selected -filter material (dotted line). Right - the resultant distribution of intensity after filtering as a function of the wavelength. 3

Modern filtration technique utilizing divergent Monochromators (Crystal monochromators include pyrolitic graphite, Si, Ge, and LiCl). Usually graphite Monochromator is employed.

A point Lattice, each point may represent atom(s) or molecule

A unit cell, the bold a, b and c represents vectors of the unit cell.

Crystal Systems and Bravais Lattices

Crystal Diffraction Laue 1912

1914 Nobel prize Max von Laue (1879-1960)

In 1912, the German physicist von Laue reasoned that, if crystals were composed of regularly spaced atoms, and if x-rays were electromagnetic waves of wavelength about equal to the inter-atomic distance in crystals, then it should be possible to diffract x-rays by means of crystals. Under his direction, experiments to test this hypothesis were carried out: a crystal of copper sulfate was set up in the path of a narrow beam of x-rays and a photographic plate was arranged to record the presence of diffracted beams, if any. The very first experiment was successful and showed without doubt that x-rays were diffracted by the crystal out of the primary beam to form a pattern of spots on the photographic plate. These experiments proved, at one and the same time, the wave nature of x-rays and the periodicity of the arrangement of atoms within a crystal.

Lattice spacing typically

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Typical Laue X-ray diffraction pattern Laue X-ray diffraction YAlO3 c-axis normal to picture

Symmetry of the pattern

Symmetry of the crystal

Each spot corresponds to a different crystal plane Some Applications: alignment of single crystal info on unit cell info on imperfections, defects in crystal
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He also attacked the problem of crystal structure with the new tool of x-ray diffraction and, in the following year, solved the structures of NaCl, KC1, KBr, and KI, all of which have the NaCl structure; these were the first complete crystal-structure determinations ever made.

The account of these experiments was read with great interest by two English physicists, W. H. Bragg and his son W. L. Bragg. The latter, although only a young student at the time it was still the year 1912 successfully analyzed the Laue experiment and was able to express the necessary conditions for diffraction in a somewhat simpler mathematical form than that used by von Laue.

Systematic absences: It is the absence of certain (h k l) diffracted x-ray due to cancelations of out of phase equivalent reflections

Symmetry There are 32 unique combination of symmetry elements called point groups Glide planes: is the combination of a mirror reflection plane with a corresponding translations (1/2 or 1/4 units) parallel to the plane, results in a total of five possible crystallographic glide (shift) planes occurs. Screw axes: Screw axes perform a rotation simultaneously with a translation along the rotation axis. In other words, the rotation occurs around the axis, while the translation occurs parallel to the axis. Crystallographic screw axes include, only two-, three-, four- and six-fold rotations

When glide planes and screw axes is added to them, we have 230 unique space symmetry called space groups
All are listed in International tables for crystallography
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Reciprocal lattice
The concept of a reciprocal lattice was first introduced by Ewald and it quickly became an important tool in the illustrating and understanding of both the diffraction geometry and relevant mathematical relationships. Let a, b and c be the elementary translations in a three-dimensional lattice (called here a direct lattice) A second lattice, reciprocal to the direct lattice, is defined by three elementary translations a*, b* and c*, which simultaneously satisfy the following two conditions:

What is V, V*

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Where is the reciprocal lattice ?! Diffraction methods Reciprocal Lattice and Ewald's Sphere Where and when the Bragg's condition is met Which is the possible Braggs reflections (Related to the symmetry and beyond the 11 scope of this lecture)

Oscillating, Weissenberg, precession and de Jongh Bouman photographs

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For single crystals Structure factor Single Crystal X-ray Crystallography is a complete solution of Crystal Structure. Also called The Phase Problem of X-ray Crystallography (FC calculations) This is beyond the Scope of this presentation
1. Structure amplitude: Shared by multiple atoms in the unit cell 2. Population factor: In general, gi =1/n, where n is the multiplicity of the symmetry element 3. Temperature factor: also known as "atomic displacement parameters; atoms are in a continuous oscillating motion about their equilibrium positions 4. Atomic scattering factor: the ability to scatter radiation varies depending on the type of an atom 5. Phase angle: "phase problem" in diffraction analysis; due to lost phase angles in measurable intensities

Intensity of powder diffraction peaks 1. Integrated intensity: The area under the peak fitted to Gaussian or Lorentz Distribution 2. Scale factor: to compensate diffraction geometry and Sample shape 3. Multiplicity factor: equivalent Braggs angle for reflections such as h00, -h00 4. Lorentz-polarization factor : intensity that reaches the detectors 1/sin2 5. Absorption factor: dependent on both the geometry and properties of the sample and the focusing method 6. Preferred orientation: departure from random distribution of the orientations of crystallites 15 7. Extinction factor: back-reflection within the same crystallite and multiple crystallites

Crystallite size, not crystal or particle size !!!

The chief problem in determining particle size from line breadths is to determine B from the measured breadth B of the diffraction line. Of the many methods proposed, Warren's is the simplest. The unknown is mixed with a standard which has a particle size greater than 1000A, and which produces a diffraction line near that line from the unknown which is to be used in the determination. B2=B2Measured-B2Standard then B=0.9/tcos

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The simulated powder diffraction pattern of copper (space group Fm3m, a =3.615 A, Cu K1, K2 radiation, Cu atom in 4(a) position with x = 0, y = 0, z = 0).

Two powder diffraction patterns of LaB6 collected using different 's

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Diffraction pattern of a powder specimen of hydroxyapatite

A powder diffraction file (PDF) of hydroxyapatite. (Reproduced with permission from the International Centre for Diffraction Data, ICDD.)

Qualitative XRD Analysis Basic principles. The powder pattern of a substance is characteristic of that substance and forms a sort of fingerprint by which the substance may be identified.

The experimental diffraction pattern of a silicon and Al2O3 mixture. Numbers with three digits mark the Miller indices of corresponding crystallographic planes

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A typical card from the ASTM file is reproduced in Fig. 14-1. At the upper left appear the d values for the three strongest lines (2.28, 1.50, 1.35A) and, in addition, the largest d value (2.60A) for this structure. The lower right-hand portion of the card, gives d values listed versus the relative intensities I/I1, expressed as percentages of the strongest line in the pattern. Analysis 1- Manual analysis and match details are given of the method used for 2- Computerized match followed by manual obtaining the pattern (radiation, camera analysis. The computer program is supplied diameter, method of measuring intensity, etc.), with database of standard x-ray patterns of and a reference to the original experimental inorganic and/or organic compounds. work. The rest of the left hand portion of the Search criteria should be applied like expected card contains room for various crystallographic, number of elements and element types. optical, and chemical data which are fully In all analysis, nothing can be accomplished 19 described on introductory cards of the set. from scratch !!!

Quantitative XRD Analysis

Quantitative analysis by diffraction is based on the fact that the intensity of the diffraction pattern of a particular phase in a mixture of phases depends on the concentration of that phase in the mixture. The relation between intensity and concentration is not generally linear, since the diffracted intensity depends markedly on the absorption coefficient of the mixture and this itself varies with the concentration. Methods

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5. Rietveld refinement: of multiple phase samples may be used for relatively accurate quantitative analysis. It requires knowledge of the atomic structure for each phase present in the mixture. It refines the difference between observed and calculated Ihkl 6. Full pattern decomposition: does not require the atomic structure to be known and it produces intensities of individual Bragg peaks. Thus, multiple reflections from each phase can be used to compute intensity ratios required in methods described in items 1 through 4 above, which increases the accuracy of the analysis. The use of multiple Bragg peaks in evaluating an average intensity ratio, to some extent diminishes the detrimental influence of preferred orientation as long as it remains small to moderate. This method, however, requires lattice parameters and therefore, is applicable to indexed patterns only. The phase composition is actually determined using any of the first four methods listed above by using intensities of several strong or all Bragg peaks instead of a single reflection.
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X-ray fluorescence
The most intense lines of this spectrum are the K and K lines if the element were bombarded with x-rays of high enough energy (fluorescence). They are always called "characteristic lines" to emphasize the fact that their wavelengths are fixed and characteristic of the emitting element. The primary radiation (Fig. 15-1) causes the sample to emit secondary fluorescent radiation, which is then analyzed in a spectrometer. This method, commonly known as fluorescent analysis, give information about the chemical elements present in the sample, irrespective of their state of chemical combination or the phases in which they exist. The wavelength of each spectral line is calculable from the corresponding Bragg angle and the interplanar spacing of the analyzing crystal used.

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The useful range of fluorescent wavelengths extends from about 0.5 to about 2.5A. The lower limit is imposed by the maximum voltage which can be applied to the x-ray tube, which is 50 kv in commercial instruments. The two main problems in fluorescent analysis, namely the achievement of adequate intensity and adequate resolution.

There is a common Mistake; it is the calculation of relative contents by simply dividing intensities !

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Qualitative analysis In qualitative work sufficient accuracy can be obtained by automatic scanning of the spectrum, with the counter output fed to a chart recorder. Interpretation of the recorded spectrum will be facilitated if the analyst has on hand (a) a table of corresponding values of and 2 for the particular analyzing crystal used, and (b) a single table of the principal K and L lines of all the elements arranged in numerical order of wavelength. Since it is important to know whether an observed line is due to an element in the sample or to an element in the x-ray tube target, a preliminary investigation should be made of the spectrum emitted by the target alone. For this purpose a substance like carbon or plexiglass is placed in the sample holder and irradiated in the usual way; such a substance merely scatters part of the primary radiation into the spectrometer, and does not contribute any observable fluorescent radiation of its own. The spectrum so obtained will disclose the L lines of tungsten, if a tungsten-target tube is used, as well as the characteristic lines of whatever impurities happen to be present in the target. Quantitative analysis In determining the amount of element A in a sample, the single-line method is normally used: the intensity Iu of a particular characteristic line of A from the unknown is compared with the intensity Is of the same line from a standard, normally pure A. The way in which the ratio Iu / Is varies with the concentration of A in the sample depends markedly on the other elements present and cannot in general be predicted by calculation. It is therefore necessary to establish the variation by means of measurements made on samples of known composition. Figure 15-8 illustrates typical curves of this kind for three binary mixtures containing 24 iron.

Matrix Effect in X-ray Fluorescence Analysis: These curves show that the intensity of a fluorescent line from element A is not in general proportional to the concentration of A. This nonlinear behavior is due mainly to two effects: (1) Matrix absorption: As the composition of the alloy changes, so does its absorption coefficient As a result there are changes both in the absorption of the primary radiation traveling into the sample and in the absorption of the fluorescent radiation traveling out. (2) Multiple excitation: If the primary radiation causes element B in the specimen to emit its characteristic radiation, of wavelength fB, and if fB is less than KA, then fluorescent K radiation from A will be excited not only by the incident beam but also by fluorescent 25 radiation from B.

Specimen preparation Metals and alloys may be converted to powder by filing or, if they are sufficiently brittle, by grinding in a small agate mortar. In either case, the powder should be filed or ground as fine as possible, preferably to pass a 325-mesh screen, in order to produce smooth, continuous diffraction lines. The screened powder is usually annealed in evacuated glass or quartz capsules in order to relieve the strains due to filing or grinding. In addition, care should be taken to avoid the "preferred orientation" of the powder particles (crystals) as it is a usual practice in sampling of e.g. silicon powder. Fluorescence Wavelength Dispersive Systems WDS A wavelength dispersive spectrometer may be a single channel instrument in which a single crystal and a single detector are used for the measurement of a series of wavelengths sequentially; or a multichannel spectrometer in which many crystal/detector sets are used to measure elements simultaneously. The angular dispersion d/d of a crystal of spacing 2d is given by: It will be seen from Eq. (3-8) that the angular dispersion will be high when the 2d-spacing is small. This is unfortunate as far as the range of the spectrometer is concerned, because a small value of 2d means in turn a small range of wavelengths coverable. Thus, as with the resolution and peak intensities, the obtaining of high dispersion can only be obtained at the expense of cutting down the wavelength range covered by a particular crystal. Energy Dispersive Systems EDS The energy dispersive spectrometer consists of the excitation source and the spectrometer/detection system. The spectrometer/detector is typically a Si(Li) detector which is a proportional detector of high intrinsic resolution. A multichannel analyzer is used to collect, integrate and display the resolved pulses. While similar properties are sought from the energy dispersive system as with the wavelength dispersive system, the means of selecting these optimum conditions are very different. Since the resolution of the energy dispersive system is equated directly to the resolution of the detector, this feature is of paramount importance. I.e. this technique gives better resolution.
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Measurements of film thickness, stress measurements, microcrack detection, topography, structure of thin films, texture analysis, etc. They are not mere characterization of materials but tests for produced parts

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