2013 Louisiana Transportation Conference

Session 28: Materials and Testing- Application of XRF, XRD

Topic
the application of non-destructive elemental and micro-structural analysis of construction Materials such as cement, fly ash, metals, glass, and paint pigments etc. utilizing X-Ray Fluorescence and X-ray Diffraction technology Moderator: Richie Charoenpap

Presenter: Stephen Williams

Materials Testing
Archimedes and the golden crown

http://www.math.nyu.edu/~crorres/Archimedes/Crown/CrownIntro.html

X-Ray Analysis
XRF: X-Ray Fluorescence

XRD: X-Ray Diffraction

Quantitative and qualitative analysis of elements (XRF) and compounds (XRD)
Wilhelm Conrad Rntgen
Discovered X-Rays 8 November 1895 Nobel Prize 1901
http://en.wikipedia.org/wiki/Wilhelm_R%C3%B6ntgen

X-Rays
A rainbow of colors

X-rays are part of the electromagnetic spectrum

X-Ray Lines
Characteristic radiation

Siegbahn Notation

The Nobel Prize in Physics 1915

William Henry Bragg William Lawrence Bragg

Bragg's Law was derived by physicist Sir William Lawrence Bragg in 1912

n = 2d sin
Wavelength is a function of d spacing and diffraction angle
http://en.wikipedia.org/wiki/Bragg%27s_law

Diffraction and Braggs Law

A A' A" B B' B"
n dsi

C C' C"

C x B x D

d
d

dsi n

= d sin + d sin = 2d sin (Braggs law)

Characteristic X-Ray Lines

Elements produce lines with discrete energies depending on the atomic number of the element Moseleys Law (1913)
Frequency K 1( AtomicNumber K 2)
K1 & K2 are constants
http://en.wikipedia.org/wiki/Moseley%27s_law

XRF
Quantitative Elemental Analysis

Alternative Technologies: Elemental Analysis

Solids
Liquids Total OC, TN, TS, TOX Arc-Spark OES Chemical Methods XRF ICP-MS ICP-AES GFAAS AAS
1 ppq 1 ppt 1 ppb 1 ppm 1,000 ppm 100%

TRACE

BULK

Periodic Table of the Elements: XRF

Examples of XRF Samples

Pressed Powders

Metals Fused Beads

Liquids

XRF techniques
Energy Dispersion
Uses a detector that can distinguish different energies

Wavelength Dispersion
Uses single crystals or multi-layer to diffract selected wavelength into the detection system

Theory of XRF, Peter Brouwer ISBN: 90-9016758-7 3rd Edition

Fundamental Parameters

Can calculate the relative XRF intensities for elemental components Given measured intensities, concentrations can be estimated using iterative calculations Detector performance still needs to be calibrated using real materials

XRF Calibration: S and Fe in Water

Calibration using raw intensity data

Calibration using matrix corrections

Optical Emission: Calibration

OBLF VeOS OES

17

Applications for XRF

Steel Making

Cement Manufacturing

Sample Preparation: Issues

Physical form of the material affects the analysis results Matrix correction only accounts for absorption and enhancement

Corr. countrate (kcps)

Pressed Powders
200

100

R2 = 0.9642 0 0 50 100

Conc SiO 2 (w t % )
Corr. countrate (kcps)

Fused Beads
200

100 R2 = 0.9996 0 0 50 100

Conc SiO 2 (w t % )

Universal vs. In Type Calibrations

Fused Bead Calibration
Pressed Powder Calibrations

Fused Bead Ref erence calibrat ion

Pressed powder, production control calibrations

Countrate (kcps)

200

100

0 0 50 100

SiO 2 (w t % )

Some Sample Preparation Equipment

Herzog Press Rocklabs shatterbox and grinding bowl

Herzog Milling Machine

PANalytical Fusion Machine

Buehler Polishing disk

Phosphorous Content in Asphalt

Terry Arnold Federal Highway Administration Turner Fairbank Highway Research Center McLean VA

PANalytical XRF systems

Epsilon 3 Energy dispersive spectrometer Axios Wavelength dispersive spectrometer

XRD
Qualitative phase identification

Quantitative phase analysis

X-Ray Diffraction of Crystaline materials

A A' A"

C C'

C"

C x B x D

B B' B"
n dsi

d
d

dsi n

= d sin + d sin = 2d sin (Braggs law)

Atoms, Crystals and Crystallites

http://en.wikipedia.org/wiki/Rutile

Particles may consist of many crystallites

http://en.wikipedia.org/wiki/Aragonite

Norelco XRD Serial #2 Circa1942

Qualitative Phase Analysis

The diffraction pattern is a fingerprint of the crystal structure

Large numbers of materials have been documented ICDD

Uses of X-ray Diffraction

Most popular use of X-Ray Powder Diffraction is Qualitative Phase Identification Quantitative applications have always existed.

XRD Samples

Basic Optics using the XCelerator Detector

Diffraction pattern of Quartz

Intensity (counts)

Angular Position
160000

90000

Relative intensities
40000

10000

0 20 30 40 50 60 70 80 2Theta ()

Pigment TiO2: Anatase and Rutile

Rutile Chemistry Color Hardness Density TiO2 Brilliant white 6.5 4.2 Anatase TiO2 Pale yellow white 5.5 3.9

Crystal type
I/Ic Common uses

Tetragonal, space group 136

3.54 Pigments, refractory ceramic, sunscreen, cosmetics, etc

Tetragonal, space group I41/amd

5.04 photcatalyst

Unit cell structure

XRD of TiO2

Bottom scan Titanium metal, middle scan Anatase, above 550 C converts to more stable Rutile form (top scan)

Easy to quantify RIR method works perfect, no standards, no calibration, no monitors, just measure height or area of most intense peak for each to calculate.

Phase Composition of Cement

Robert Herman Bogue: Calculation of compounds in Portland cement, 1929 Estimate the compounds from the elemental analysis
Alite: C3S, or tricalcium silicate Belite: C2S, or dicalcium silicate Aluminate phase: C3A, or tricalcium aluminate Ferrite phase: C4AF, or tetracalcium aluminoferrite

http://www.understanding-cement.com/bogue.html

Hugo Rietveld
The Rietveld method uses all XRD peaks and the complete profile for the analysis: Rietveld is the only practical method to directly quantify phases in clinker/cement

http://en.wikipedia.org/wiki/Hugo_Rietveld

Quantitative Rietveld Analysis of Clinker

Counts 1) 2) 3) 4) C3A C4AF C3S C2S

(4 main phases only)

2000

1500

1000

500

0 100 0 -100 20 30 2Theta 40 50

38

Free Lime in Cement

Free Lime Measurement
Counts 6000

CaO

10.0% CaO

4000

0.25% CaO

C2S C2S
2000

36.50

37 Position [2Theta]

37.50

38

Residual Stress
y
d

sin2y

Unstressed sample

y d

Stressed sample
http://en.wikipedia.org/wiki/Residual_stress

sin2y

Residual Stress determined by XRD

Monocapillary optic

Lab XRD system

X-ray Lens

Bearings, Car Wheels, structural elements

Sample Preparation in XRD

Preferred Orientation

Extreme problem for samples with crystalrelated shape or non-spherical particles

Preferred orientation

Random orientation

Mica Thin Layer Sample: Dusted vs. Pressed

dusted

pressed
hk0

Sample Preparation for Powdered Materials

Packed Powders

Low Background holders

Capillaries

Solid Samples

PANalytical XRD systems

Empyrean XRD

XPert Powder XRD

The End
Thank You

Powder Diffraction: Poly-Crystalline Sample

= 2 d sin()