MTN 307 Materials Characterization

X-ray Diffraction Geometry

Dr. K.S. Suresh
kssiitr@gmail.com

Diffractometer
 Source
 Optics
 Detector

Incident Beam Part

Diffracted Beam Part

Sample
Source

Incident Beam
Optics

Diffracted Beam
Optics
Detector

X-ray generation
X-ray tube

X-rays
Be window
W cathode

Rotating anode

Electrons

Metal anode

Small angle anode

Small focal spot

Large angle anode

Large focal spot

 Slits To limit the size of beam (Divergence slits) To alter beam profile (Soller slit angular divergence )  Narrow slits Lower intensity + Narrow peak .

Mirror focusing and remove Kα2 Mono-chromator Si remove Kα2 Graphite .

Beam Profile Mirror Parallel beam Source Soller slit Detector Mirror Sample Para-focusing Detector Sample Source .

Point focus Detector Sample Source .

Parallel beam Para-focusing X-rays are aligned X-rays are diverging Lower intensity for bulk samples Higher intensity Higher intensity for small samples Lower intensity Instrumental broadening independent of orientation of diffraction vector with specimen normal Instrumental broadening dependent of orientation of diffraction vector with specimen normal Suitable for GI-XRD Suitable for Bragg-Brentano Texture. stress Powder diffraction .

Detectors  Single photon detector (Point or 0D)  scintillation detector NaI  proportional counter. Xenon gas  charge coupled devices (CCD)  Area detectors (2D)  wire  CCD  3D detector X-ray photon Photoelectron or Electron-hole pair Photomultiplier tube or amplifier Electrical signal . Xenon gas  semiconductor  Position sensitive detector (Linear or 1D)  gas filled wire detectors.

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NaCl crystals in a tube facing X-ray beam .

e charge of electron. m linear absorption coefficient . m mass of the electron. e-2M temperature factor. r radius of diffractometer circle • m0 permeability of free space. l wavelength. v volume of unit cell • F structure factor • p multiplicity factor •  Bragg angle.Integrated intensity for a flat specimen diffractometer • Integrated intensity per unit length of diffraction line ? = ?0 ??3 32?? ?0 ? 4 4? ?2 1 ?2 ?2 ? 1+???2 2? ???2 ????? ? −2? ? • I0 intensity of incident beam • A cross sectional area of incident beam.

Diffraction geometry Sample Incident Beam Film .

Lorentz-Polarization factor .

5 0.038 5 0.45 49.09 0.046 0.559.15 3 45 45 22.533.30 39.045 0.037 16 100.037 18 0.11 0.0925 0.037 20 0.5 0.556.30 4 66 2+k22/ 2+l22/ hLattice 22+k22+l22 Parameter.549.088 Not Constant so it is FCC Not NotSimple BCC Cubic .584.050 0.70 6 0.5 0.069.15 0.75 8 0.88 84.0 0.0 0.5 0.09 0.10 41.050 0.99 24 0.050 0.40 11 0.038 0.9 0.050 0.0 0.9 0.54056Å Simple BCC Cubic S1 (mm) ()() sin2 sinh22+k2+l2 (mm) 38 19.039.70 59. a (Å) h2sin +l22h2+ksin 66 78 78 83 33.88 9 0.037 0.048 0.038 12 8 0.10 0.037 63 0.45 84 0.049 0.99 27 110. wavelength=1.5 0.038 0.036 14 0.40 83 97 97 113 21 0.58 12 0.58 16 0.73 20 0.097 113 118 118 139 56.11 38 19.041.0 0.Indexing the XRD patterns FCC.055 0.036 10 0.022.73 19 0.11 42 0.081 139 168 168 69.

15 4 0.99 27 0.5 0.036 4.30 8 0.5 0.9 0.037 4.70 19 0.037 4.037 4.5 0.0 0. butt different lattice constant .023 168 84.58 16 0.023 118 59.5 0.45 12 0.046 113 56.978 97 49.40 11 0.037 4.978 78 39. a (Å) 38 19.5 0. wavelength=1.038 3.039 83 41.11 3 0.0 0.Precise lattice parameter calculation FCC.88 24 0.54056Å S1 (mm) () sin2 h2+k2+l2 sin2/ h2+k2+l2 Lattice Parameter.0 0.023 45 22.036 4.037 4.023 139 69.038 3.023 So it is FCC.73 20 0.0 0.978 66 33.038 3.

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Diffraction Methods Method Wavelength Angle Specimen Laue Variable Fixed Single Crystal Rotating Crystal Fixed Variable (in Single part) Crystal Powder Fixed Variable Powder .

Laue Method Transmission Zone axis Reflection Zone axis crystal crystal Film Incident beam • • • Incident beam Film Uses Single crystal Uses White Radiation Used for determining crystal orientation and quality .

Rotating Crystal Method  Determination of unknown crystal structures .

Powder Method Sample Incident Beam Film • Useful for determining lattice parameters with high precision and for identification of phases .

08 1.55 1.54 1.15 30 89.99 60 53.09 5 I1: Intensity of the strongest peak .Intensity (a.70 2.u.70 1.25 30 84.94 1.82 100 45.40 1.42 3.63 30 65.) Analysis of Single Phase 2(˚) d (Å) (I/I1)*100 27.25 10 31.71 5 56.42 20 76.11 1.

519 1.151 1.63 Å • Search JCPDS manual to find the d group belonging to the strongest line: between 2.443 5. d2.619 1.891 NaCl 5-628 2.82x 1.26x 1. d2: 1.411 (BePd)2C 18-225 .82x 1.578 2.994 1. only NaCl has d3: 1.82.84-2.194 2.499 3.Procedure • Note first three strongest peaks at d1.892 (NH4)2WO2Cl4 22-65 2.632 3.63 Å • It is NaCl……………Hurrah Specimen and Intensities Substance File Number 2.82 Å • Out of these.996 1.999 2.632 1.261 1.152 0.261 1.622 4.263 1.99 and d3: 1.411 0.824 1.54x 1.941 0.668 (ErSe)2Q 19-443 2.80 Å • There are 17 substances with approximately similar d2 but only 4 have d1: 2.998 1.891 1.204 1. and d3 • In the present case: d1: 2.829 1.

08 13 20 1.13 28 Observed Normalized 3.287 171.22 phase is Cu2O • If more phases.088 1.Presence of Multiple phases d (Å) I/I 0.83 0.278 1.50 100 20 • It turns out that 1st and 3rd strongest lies to Cu2.743 separated out I/I1 28 1.80 * 52 72 1.04 * 17 1.01 5 7 2. and d3.47 2.28 * 28 2.8293 9 0.0436 0.29 39 1 d (Å) 2.g.135belong 37Pattern for Cu 9 and then all other peaks for Cu can be1.233 4 1.808 46 9 1. d1.9038 3 4 0.8083 8 5 0.510 27 1.81 * * 8 10 .020 9 several alternatives 2.0674 0.01 Lines 5 • Several permutations combinations possible 2.09 * 100 3. more pain to solve  1. the first three strongest lines show(Å) 2.98 5 7 4 1 • More Complex Remaining Pattern of Cu2O 3.09 1.98 5 2 0.91 0.47 I/I1 72 d d (Å) I/I1 • e.465 100 • Then take any of the two lines together and match 1.29 * 20 • Look for first three lines and it turns out that the 36 4 1.50100 20 1.9795 1.22 4 intensities 1.13 18 • Now separate the remaining lines and normalize the1. d2.

Diffraction from a variety of materials (From “Elements of X-ray Diffraction”. B. Cullity. Addison Wesley) .D.

Lattice Strain do No Strain 2 Uniform Strain   d  strain 2 Non-uniform Strain Broadeing b   2  2 d tan  d 2 .

Residual Stress .

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Built in 1972 in Lanskrona. while travelling from La Harve. Sweden . France to Boston. USA.Hull Failure of MSC Carla container vessel Failed on 24 November 1997.

. after plastic deformation that is caused by applied mechanical loads. thermal loads or phase changes. Mechanical and thermal processes applied to a component during service may also alter its residual stress state.Residual Stress • The stress resident inside a component or structure after all applied forces have been removed • Residual stresses are generated.

Types of residual stress .

From theory of elasticity For Isotropic material .

For isotropic elastic solids .

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When s33 = 0. .