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25/06/2015

X-ray powder diffraction (XRD):


Basic principles & practical applications
Ruben Snellings
VITO (BE)
ruben.snellings@vito.be

For starters
Belgian national
MSc in Geology
2007-2011: PhD in Geology (KULeuven, BE),
Pozzolanic properties of natural zeolites
2011-2012: Post-doc (UGent, BE),
Recyclable Concrete
2012-2014: Post-doc/Marie Curie Fellow (EPFL, CH),
SCM reactivity + XRD responsible
2014-now: Researcher (VITO, BE),
Sustainable binders

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2014, VITO NV

The menu/contents
Why use X-ray powder diffraction to study cements?
Basics on Scattering, Diffraction and X-rays
Practical guidelines for XRD experiments
Data Analysis: The Rietveld Method
Examples of applications
Practical guidelines for XRD data analysis

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XRD and cement why?


Delivers information on:
Individual phases contained in (hydrated) cement:
Content (also during hydration)
Crystal structure,
Why would you need this?
To describe hydration kinetics and mechanisms
Parametric studies on effect of e.g. grinding, sulfation, temperature
Advantages vs. other techniques (SEM, TGA, calorimetry)?
Takes less time
Extracts wealth of information
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XRD & cement since when?


1993:
1st Rietveld QPA on cement
(Taylor & Aldridge)

1928:
1st XRD studies on cement
(Hansen, Brownmiller)
1900

1950

1895:
Discovery of X-rays
(Rntgen)
1912:
XRD on crystals
(von Laue)

2000

2000s:
Spread of XRD in cement science

1969:
Rietveld method
for neutron diffraction
(Rietveld)

2050

1977:
Rietveld method
for XRD
(Cox, Young, Thomas)

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1987:
Rietveld method
for quantitative analysis
(Hill & Howard)

XRD & cement - challenges


Multitude of phases
Peak overlap
Sensitivity of hydrates to decomposition
Many correlated parameters
Aim of this workshop:
Explain the basics of XRD
Identify common pitfalls
Demonstrate best practice

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Basic principles of XRD

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Scattering basics
Scattering geometry

q
kf

ki
2
Incident radiation:
Wavevector:
ki
|ki| = 2/
Energy: Ei
Polarisation:
pi

Wavevector transfer:
q = kf - ki
Energy transfer:
E = Ef - Ei
Polarisation change:
p25/06/2015
i pf
2014, VITO NV

Scattered radiation:
Wavevector:
kf
Energy: Ef
Polarisation:
pf
Scattering angle 2
8

Scattering basics
Elastic scattering

Q
k

k0
2
Incident radiation:
Wavevector:
k0
|k0| = 2/

Wavevector transfer:
Q = k - k0
Scattering angle 2
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2014, VITO NV

Scattered radiation:
Wavevector:
k
|k| = 2/

Diffraction on crystals
For an incident beam to be diffracted by a crystal, its
wavelength must be of the same order of magnitude as the
interatomic distances (a few angstrms)

Laue experiment (1912)


Incoming X-rays

crystal
Photographic
plate
Diffracted
beams

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Diffraction on crystals
Bragg condition
The diffraction by a 3D lattice of points is equivalent to a reflection
of the incident beam on a family of net planes

plane 1
plane 2

D
I

The beams IC and GD scattered by 2


adjacent planes must be in phase to get
constructive interference

FG + GH = n
with FG = GH = d.sin

n = 2d sin

Braggs law
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Diffraction on crystals
Single crystal vs powder diffraction
single
crystal

powder

2
Data compressed into one dimension

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Powder diffraction: laboratory configurations


X-ray source

detector

X-ray source

detector

2
sample

sample

Reflection geometry

Transmission geometry

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Laboratory Bragg-Brentano (reflection)

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Laboratory Transmission mode

Laboratory source
Synchrotron source (ESRF)
Multichannel detector for
fast data acquisition

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Data Analysis: the Rietveld method


Rietveld (1969): diffraction pattern analysis by a
curve fitting procedure
First proposed for neutron diffraction
Least-squares minimization between observed and
calculated profiles
Extended to XRD profiles in the 1970s

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Inside the powder diffraction pattern


3. Peak widths
influenced by size/strain of
crystallites the microstructure
1. Peak positions
determined by size and
symmetry of the unit cell
the lattice

Counts

2. Peak Intensities
determined by the
positions of the atoms in
the unit cell the motif

2 - degrees
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Inside the powder diffraction pattern


3. Peak widths
influenced by size/strain of
crystallites the texture
1. Peak positions
determined by size and
symmetry of the unit cell
the lattice

Counts

2. Peak Intensities
determined by the
positions of the atoms in
the unit cell the motif

2 - degrees
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Inside the powder diffraction pattern


Peak positions
Braggs law

d-spacing formulae
Cubic (a)

= 2dhkl sin
1
2 + 2 + 2
=
2

Triclinic (a, b, c, , , )
1
2
1
= 2 [2 2 2 2 + 2 2 2 2 + 2 2 2 2

+ 2 2 + 22
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Inside the powder diffraction pattern


3. Peak widths
influenced by size/strain of
crystallites the texture
1. Peak positions
determined by size and
symmetry of the unit cell
the lattice

Counts

2. Peak Intensities
determined by the
positions of the atoms in
the unit cell the motif

2 - degrees
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Inside the powder diffraction pattern


Peak intensities
For a crystalline phase j in a powder sample:

, = 2 , 2,

Structure factor

Scale factor
Lorentz-polarization
factor

Preferred orientation
factor
Absorption factor

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Inside the powder diffraction pattern


Peak intensities
Structure factors

= exp 2 + +

exp

Vector quantity (magnitude F and phase )


Summation over all atoms n in unit cell
X-ray form factor fn (2)
Site occupation on
Interference term: exp(2i{hx + ky + lz})
Debye-Waller factor Wn
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Inside the powder diffraction pattern


Peak intensities
X-ray form factors fn (2): the nature of the atoms
X-rays interact with atomic electron cloud
The higher Z, the higher fn
The higher , the lower fn

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Inside the powder diffraction pattern


Peak intensities

Interference term: the position of the atoms

exp(2i{hx + ky + lz})

Reflects atomic structure


Vector dot product between the position of the atom n (rn) in the unit
cell and the scattering vector (Qhkl):
= + +

= + +

Not a smooth function of 2


Reflections with similar d spacings may have large or small
interference terms

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Inside the powder diffraction pattern


Peak intensities: the structure model
Contains lattice parameters
(a, b, c, alpha, beta, gamma)
Symmetry group, space group
Asymmetric unit: atomic coordinates, occupancy, etc.

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Inside the powder diffraction pattern


Peak intensities
Debye-Waller factors (Wn) or atomic displacement (ADP) factors
Thermal vibrations
atomic position is not frozen
time and space average of atoms is larger
destructive interference
reduction of peak intensities
2

exp = exp
=
exp

2
42
2 2
= exp
2

Un is mean-square atomic displacement


Bn often preferred since values are around 1
The lighter the atom the larger the ADP

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Inside the powder diffraction pattern


3. Peak widths
influenced by size/strain of
crystallites the microstructure
1. Peak positions
determined by size and
symmetry of the unit cell
the lattice

Counts

2. Peak Intensities
determined by the
positions of the atoms in
the unit cell the motif

2 - degrees
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Inside the powder diffraction pattern


Peak widths and shapes
Depend on source, instrument and sample
1. Peak description by analytical functions

Gaussian, Lorentzian, or mixed (Pseudo-Voigt)- symmetric


functions

Extended versions (TCHZ,


Pearson VII,)

fwhm dependence on 2
Gauss: = 2 + +

+
Lorentz: =

1
2

Caglioti et al. (1958)

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Inside the powder diffraction pattern


Peak widths and shapes
Depend on source, instrument and sample
2. Peak description by separating contributions from source and
instrument to that of sample (fundamental parameters
approach)
Instrument Source Sample

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Peak shape

[Cheary et al. 2004]

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Inside the powder diffraction pattern


Peak widths and shapes
Depend on source, instrument and sample
2. Peak description by separating contributions from source and
instrument to that of sample (fundamental parameters approach)

Allows analysis of sample texture (crystallite size, strain)

Size contribution

= /

(Scherrer formula)

Volume weighted mean crystallite size

Strain contribution

= 40

0 =d/d or mean strain


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Practical guidelines for XRD experiments

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Particle size
For representative measurements:
High number of particles need to
diffract (particle statistics)
Particle sizes < 10-20 m required
Ideally 1-5 m
Extensive dry grinding may lead to
amorphization
Wet grinding preferable
Sample spinning improves statistics

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Sample loading
Preferred orientation to be avoided
Front-loaded

Back-loaded

Slice
(cement paste)
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Hydration stoppage
Harsh drying conditions effect ettringite AFm phases
To be avoided for QPA

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Ambient exposure
Hydrated cement samples are prone to carbonation
Ex. 2 h exposure of fresh slice to air
Both fresh and dried samples are sensitive to carbonation

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Sample preparation
Hydrating
sample

Raw sample

Compacted
(slice)

Ground

Compacted
(slice or just
mixed)

Hydrated sample
(stopped)

Compacted
(slice)

1.

+ teflon coated
sample holder
+ kapton film
Placed in the sample
holder with Kapton film

Directly placed in sample


holder. Polishing on 1200
sandpaper

Fresh mix
Good AFt/AFm peaks.
Problem with carbonation
if measurements take too
long

In-situ

Wet slice

Powder

Causes strong preferential


orientation. Decrease in
AFt/AFm intensities with
isopropanol.

Dry slice

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2.

Ground, spread on
samples holder, back
loading is recommended

Slice of paste

Hydration is observed
every 15 minutes. Good
AFt/AFm peaks.

Ground

Better random orientation


(with back loading).
Artefacts linked to drying.

Dry
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Sample preparation
Fresh or dried slices/powders?
Fresh
Limited disturbance of
hydrates
Slice surface will be prone to
dessication: drastic change in
H2O content, difficult to
quantify
Freshly cut sample are prone
to carbonation

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Dried
AFt/AFm reflections reduced
by vacuum drying
Also isopropanol treatment
has an effect on AFt/AFm
phases
Possible carbonation
Bound H2O has to be
measured by TGA

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Reporting XRD data


Data collection properties and settings
Equipment
Diffractometer geometry

X-ray source
Diffractometer optics*
*devices depend on equipment

Detector

Sample

Scan parameters

Manufacturer
Model
Measurement setup
Goniometer radius
X-ray radiation
Generator operation
Incident divergence slit
Incident anti-scatter slit
Incident Soller slits
Specific beam conditioning devices
Receiving anti-scatter slit
Receiving Soller slits
Type
Model
Scanning mode
Detector length
Dimensions
Spinning speed
Sample type
Sample pre-treatment
Sample loading
Angular range
Step size
Time per step
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Total measurement
2014,time
VITO NV

Examples
Panalytical, Bruker, Rigaku,
XPert3 Powder, D8 Advance,
Bragg-Brentano, transmission; -, -2
240 mm
CuK1,2 ( = 1.5408 ),
45 kV, 40 mA
0.5 (fixed, programmable)
0.5
0.04 rad
Johansson monochromator, Gbbel
Mirror,
0.5 (fixed, programmable)
0.04 rad
Point scintillation counter, linear position
sensitive (1D), 2D position sensitive
XCelerator, Lynxeye,...
Step, continuous,
2.122 2 (1D detector),
26 mm diameter, 25 x 15 mm,
8 rpm
Powder, slice
Grinding, hydration stoppage, etc.
Back loading, side-loading,
5-70 2
0.02 2
30 s
30 min

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Data analysis the Rietveld method

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Data Analysis: the Rietveld method


Rietveld (1969): diffraction pattern analysis by a
curve fitting procedure
First proposed for neutron diffraction
Least-squares minimization between observed and
calculated profiles
Extended to XRD profiles in the 1970s

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Applications of the Rietveld method in powder diffraction

Phase identification (crystalline and amorphous)


Crystal structure refinement
Crystal structure determination (not trivial)
Quantitative phase analysis
Microstructural analyses (crystallite size microstrain)
Texture analysis (orientation)

Kinetic studies

Thermal expansion

Polymorphism

Phase transitions
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In-situ chemistry

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The Rietveld method: basics

Observed
pattern

Iterative LS
minimization

Crystal structure(s)
Calculated
pattern

=1

Phase scale factors


Other sample
characteristics

Diffraction optics

Instrumental factors

, 2 2, , +
=1

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The Rietveld method: the intensity equation


=

=1

, 2 2, , +
=1

The intensity yi(calc) at 2 angle i is determined by:


background contribution
overlapping diffraction peaks depending on:
diffraction intensities of the individual peaks
peak shape and peak position with respect to i
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Agreement tests
How good is good enough?
Need to monitor progress of fit
Need to compare different model fits
Need to measure data quality
Solutions:
Visual inspection of fit
Numeric factors
R-factors
Goodness of fit
Durbin-Watson statistic
Monitoring of chemical parameters
bond lenghts and angles for structure refinements

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Overview of numeric agreement factors


=

=
=

1
2

where

(R-pattern)

1
2

(R-weighted pattern)

=2 1
2

=1

(Goodness-of-fit indicator)

1
2

(R-expected)
(Durbin-Watson statistic)

where =
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Examples

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XRD latest developments and applications


Latest developments:
1. Spread of Rietveld quantitative phase analysis (software
developments spread of expertise)
2. New, performant detector systems enable in situ studies, acquisition
of large, systematic sets of data
Applications/examples:
1. Quantitative phase analysis
a.
b.
c.

2.

Anhydrous cements
Hydrated cements
Blended cements/novel cements

Durability studies tracking of deterioration processes

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Examples and applications


1.

Rietveld refinement: steps towards convergence

2.

Quantitative phase analysis

3.

Durability studies

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Example 1: refinement strategy

Mix of TiO2 (rutile) and Ca3SiO5 (alite, major phase in cement) at RT

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Example 1: refinement strategy


Background (2 coefficients refined)

Rwp = 53.8%
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Example 1: refinement strategy


Rutile introduced

Rwp = 43.9%
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Example 1: refinement strategy


Alite introduced

Rwp = 37.0%
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Example 1: refinement strategy


Alite and rutile lattice parameters
refined

Rwp = 10.4%
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Example 1: refinement strategy


Alite and rutile peak width refined

Rwp = 8.74%
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Example 1: refinement strategy


Alite and rutile atomic displacement factors introduced

Rwp = 8.37%
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Example 1: refinement strategy


Alite preferred orientation correction introduced

Rwp = 7.64%
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Example a-c Quantitative phase analysis

Quantifying the phase composition of cements

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Example 2: quantitative phase analysis of Portland cement


=

=1

, 2 2, , +
=1

Phase scale factors Sj yield mass fractions mj



=

M
Z
V

= mass per formula unit


= number of formula units per unit cell
= unit cell volume

If amorphous or unidentified phases are present, absolute QPA


can be obtained using internal or external standard addition.

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QPA: accounting for amorphous/unknown phases


Approaches to determine the amorphous content:
1.

Internal standard approach:

Addition of a known amount of standard to the sample

2.

External standard approach:

The absolute phase contents are calculated by comparison to a separately


measured standard monitor sample (the standard must be measured using
identical measurement conditions as the sample)

3.

PONKCS method

Calibration needed of individual amorphous phases. Different amorphous phases


can be quantified separately.

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QPA: accounting for amorphous/unknown phases


Internal standard method: sample preparation and choice of
standard
Avoid amorphisation during mixing/grinding (use McCrone micronising mill)
Avoid reactions between the sample and the lubricant or the internal
standard during grinding
Choose the correct internal standard:

Choose the correct amount of internal standard

Should be complete crystalline (or of known crystallinity)


Should have the right Lin. Absorption Coefficient (LAC)
Should have the right hardness
Should preferably be highly symmetrical with adequate peak positions
The standard should not be present in the sample

To remember:
1.
2.

No knowledge of sample chemistry required


Additional sample preparation needed (mixing and grinding)
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QPA: accounting for amorphous/unknown phases


Internal standard method: calculation
The weight fraction of phase k is calculated as follows:

where

ws = known crystallinity of the internal standard;


fs = weight fraction of the standard in the sample.

Or departing from the Rietveld calculation output:

wk =

Calc.PhaseCont.k % of Std.Added

100(%)
Calc.PhasCont .Std
% of Sample
= 1

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QPA: accounting for amorphous/unknown phases


External standard method: calculation
The weight fraction of phase k is calculated using:

Where ws is the crystallinity of the standard


m and ms are the mass attenuation coefficients of the bulk sample and the
standard, resp.
ms is calculated from the XRF oxide composition and TG bound water

Again, the amorphous weight fraction is:


= 1

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4. Amorphous content determination


MAC calculation
Chemical composition
needs to be known:
Calculation:
=

To note:
H2O has a low MAC,
cement pastes will have
much lower MACs than
anhydrous cement.

White cement

Slag

White Cement

anhydrous

anhydrous
w/c 0.4
mass
mass fraction
fraction mass fraction

Oxide

MAC
[cm2/g]

CaO

124.04

0.7221

0.3388

0.5158

SiO2

36.03

0.2136

0.3067

0.1526

Al2O3

31.69

0.0143

0.1881

0.0102

Fe2O3

214.9

0.0035

0.0040

0.0025

MgO

28.6

0.0086

0.1148

0.0061

Na2O

24.97

0.0044

0.0000

K2O

122.3

0.0011

0.0038

0.0008

SO3

44.46

0.019

0.0192

0.0136

TiO2

124.6

0.009

0.0157

0.0064

P2O5

39.66

0.004

0.0001

0.0029

H2O

10.07

0.2857

SUM

0.9952

0.9956

0.9966

MAC

101.46

66.86

75.26

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Example 2a: quantitative phase analysis of Portland cement


Portland cement is a complex mix of phases, whole patten fitting
methods (e.g. Rietveld) can deal with peak overlap in the XRD scans

Differences in strength development and durability can be


correlated with the phase composition
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Example 2a: quantitative phase analysis of Portland cement


Rietveld QPA in production process and quality control in cement
plants:

Rapson and Storer (2006)

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Example 2b: Hydration kinetics of blended cement


In-situ XRD of a hydrating zeolite blended cement

Snellings et al. (2010)

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Example 2b: Hydration kinetics of cement


In-situ synchrotron XRD of a hydrating cement paste

Snellings et al. (2010)

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Example 2c: PONKCS quantification of amorphous phases


Partial Or No Known Crystal Structure (PONKCS) method
Calibration of a phase of unknown structure:
Mix of the amorphous phase and a standard (weight fractions
known)
2
=

Peak phase
calibration factor

2 =

In unknown mixes the refined amorphous phase scale factor can


then be recalculated into a weight fraction

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Example 2c: PONKCS quantification of amorphous phases


Partial Or No Known Crystal Structure (PONKCS) method (Scarlett & Madsen, 2006)
Application to cements (Snellings et al., 2014)
E.g. Anhydrous blended cement

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% Measured

Slag

39.8

Slag

0.3

% Weighed

Slag

39.5

Absolute
deviation

Slag

0.3

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Example 2c: PONCKS quantification of amorphous phases


Partial Or No Known Crystal Structure (PONCKS) method (Scarlett & Madsen, 2006)
Application to cements model mixes (Snellings et al., 2014)
E.g. hydrated blended cement distinction MK/C-S-H

Binary mix Average

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Sample

Wt%
MK

White
Cement 70
MK 30

27.5

Weighe
d
Wt%
Wt%
MK
MK

Absolute
deviation

0.5

Wt% MK

27.8

0.3

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Example 2c: PONKCS quantification of amorphous phases


Partial Or No Known Crystal Structure (PONKCS) method (Scarlett & Madsen, 2006)
Application to cements model mixes (Snellings et al., 2014)

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Example 3 Durability testing

Quick ponding tests as a proxy for chloride and sulfate resistance


Delivers:
Calibration of transport/thermodynamic models for concrete service life
predictions
Most of the material from H. Kamyab, P. Henocq, M. Antoni (EPFL)

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Method : Quick Ponding tests on paste


Paste sample

exposed surface

wax

15, 20, 38 h
1,2 weeks
NaCl 0.5 M
Na2SO4 0.05 M

Removal of 200 m layers


by polishing

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15 min measurement time


to avoid surface carbonation

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Method: Quick ponding Cl/sulfate


Identify Friedels salt/gypsum at different depths
Time-depth profiles of chloride/sulfate binding in the matrix
Needed for modelling: mass balance of deterioration reactions
CC-blended cement
0.5 M NaCl 400 m depth

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time

depth

CC-blended cement
0.5 M NaCl - 15 h

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Method: Quick ponding Cl/sulfate


Identify Friedels salt/gypsum at different depths
Time-depth profiles of chloride/sulfate binding in the matrix
Needed for modelling: mass balance of deterioration reactions
Counts

6000

Limestone blended cement


1-3_29d_poli_1
28 d immersion in 0.05 M Na2SO4

CaCO3

Slice 1 (200 m depth)


4000

AFt
2000

AFt

10

15

AFt

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2014,
VITO
NV
Position [2Theta] (Copper (Cu))

30

35

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Method: Quick ponding Cl/sulfate


Identify Friedels salt/gypsum at different depths
Time-depth profiles of chloride/sulfate binding in the matrix
Needed for modelling: mass balance of deterioration reactions
Counts

2000

Limestone blended cement


1-3_29d_poli_2
28 d immersion in 0.05 M Na2SO4

CaCO3

Slice 2 (300 m depth)

AFt
1000

AFt

AFt
Gyp
Gyp
0
10

15

20
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VITO NV (Copper (Cu))
Position

25

30

3576

Method: Quick ponding Cl/sulfate


Identify Friedels salt/gypsum at different depths
Time-depth profiles of chloride/sulfate binding in the matrix
Needed for modelling: mass balance of deterioration reactions
Counts

2000

Limestone blended cement


28 d immersion in 0.05 M Na2SO4

1-3_29d_poli_3

Slice 3 (460 m depth)

CH
CH

1000

Gyp

AFt

CaCO3

G
AFt

AFt

CH
0
10

15

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Position [2Theta] (Copper (Cu))

25

30

35

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Method: Quick ponding Cl/sulfate


Identify Friedels salt/gypsum at different depths
Time-depth profiles of chloride/sulfate binding in the matrix
Needed for modelling: mass balance of deterioration reactions
Limestone blended cement
28 d immersion in 0.05 M Na2SO4
1-3_29d_poli_4

Counts

3000

CH

Slice 4 (600 m depth)

CH
2000

1000

CaCO3

AFt
AFt

CH

AFt

0
10

15

20
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Position
[2Theta]

25

30

35

78

Method: Quick ponding Cl/sulfate


Example of sulfate ingress modelling (Stadium) by P. Henocq
DOH=17 10-11 m2/s ( close to DOH determined by migration test)
XRD can be used to verify/calibrate modelled
dissolution/precipitation mechanisms
Presence of Ca(OH)2 induces the peak of gypsum

Gypsum

Portlandite

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Practical guidelines for data analysis

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Qualitative phase analysis


Identification of crystalline phase based on characteristic peak
fingerprint patterns
Database of trustworthy PDF patterns includes
Major clinker phases and polymorphs (Ca silicates, aluminates,
ferrites)
Minor clinker phases (alkali sulfates, oxides)
Sulfate addition phases
Common SCM phases (except natural pozzolans)
Hydrate/carbonate phases
Search/match table for rapid manual identification
Often many phases are suggested by the software, difficult to find
plausible matches for minor phases
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Qualitative phase analysis


Identification of all phases in a cement is not trivial: additional
information is very useful:
Microscopic observations
Bulk sample chemistry
Knowledge of the origin of the materials
Phase enrichment using selective dissolution is particularly
useful to identify minor phases
Iterative procedure between pattern fitting and
identification helps to spot minor phases

ID

QPA

All peaks
covered?

Yes

Final QPA

No
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Qualitative phase analysis: phase enrichment


Selective dissolution: OPC
OPC is a complex mixture of phases, several phases show strongly
overlapping reflection patterns
Selective dissolutions concentrate minor phases: important aid in
identification
CEMI 52.5R

Aluminate, ferrite,
sulphates
Ca-silicates

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Quantitative phase analysis - refinement tips


Always good to:
start with good literature structure models
minimize the number of refined variables
final refinement should include all varied parameters

In QPA:

Refine only scale factors and lattice parameters


Constrain parameter variation within a sensible interval
Check fit and contribution of individual phases visually
Check for parameters hitting limits of preimposed interval

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Parameters to be refined for QPA


Reflection peak properties
Position
Intensity

Profile shape, width

Crystal structure parameters


Lattice symmetry
Unit cell parameters
Atom type
Atomic fractional coordinates
Site occupancies
Atomic displacement parameters
Crystallite size
Lattice strain

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Refined in Rietveld QPA


Not applicable, fixed
Yes
No
No
No
No
Yes, usually part of analytical peak
shape function
No

85

Parameters to be refined for QPA


Data analysis properties and settings
Analysis software
Qualitative analysis
Quantitative analysis
Phase information
Refinement strategy

Pattern references
Crystal structure references
Refined global parameters, and
sequence of refinement
Refined phase specific parameters,
and sequence of refinement

Parameter constraints
Fixed parameters
Figures

Measured diffraction patterns,


calculated patterns, difference plot

Numerical criteria of fitting


Result presentation

Agreement indices
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Back-calculation
approach
2014,
VITO NV

Examples
Diffrac.Suite Eva, HighScore,
Topas (Academic), HighScore (Plus),
GSAS, FullProf,
PDF number, COD number,
ICSD number, publication reference
Specimen displacement,
background type and number of
coefficientsa
Scale factors, lattice parameters,
peak shape type and parameters,
site occupanciesa, preferred
orientation correctiona,
Limits on lattice parameter shift,
peak shape parameters,
Atomic positions, atomic
displacement parameters,
At least one figure enabling a visual
assessment of the data collection
and analysis quality
Rwpb, Rpc,
86
g/100 g anhydrous, g/100 g paste,

Data analysis: recalculation formulae


Rietveld QPA results need to be rescaled to take into
account the incorporation of bound water
Calculation of the Degree of Hydration (DOH):
Correction must be made for the dilution effect
Free
Water

Bound H2O
Hydrates

Anhydrous
cement

, = , / 1 ,

Measured by XRD
on dried sample

time

,
= 1
= 0
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88

Data analysis: recalculation

(1+w/c)

not in [%]

/(1+w/c)

/(1+H2Obound)
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Data analysis: recalculation formulae


fresh specimen (disc):
per 100g paste

m=mXRD

per 100g anhydrous

m=mXRD(1+w/c)

dried specimen (powder):


per 100g paste

m=mXRD*(1+H2Obound)/(1+w/c)

per 100g anhydrous

m=mXRD*(1+H2Obound)

Wt.% C3S

H2Obound on ignited basis

*Data from Arnaud


Muller, hydration
of white cement +
10% SF

Age (days)

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Conclusions & Perspectives

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XRD a tool for routine analysis


XRD has become a quantitative characterisation tool in cementitious materials
+ Assets
+ Phase assemblage characterisation: quantification of individual phases
+ Straightforward sample preparation
+ Short measurement times
+ Accessible in most material science labs
+ Automated analysis possible (e.g. cement production)

Limitations
Accuracy: 2-3 wt.% for major phases, 1-2 wt.% for minor phases (can be
better)
Expert knowledge needed for non-routine analyses

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But theres more


XRD should be used together with other techniques to verify and
complete the characterisation of the microstructure
See poster for examples of electron microscopy
Book on microstructural charactisation of cementitious materials:

Edited by K. Scrivener, R. Snellings, B. Lothenbach


Chapters on Sample preparation, Calorimetry, Chemical
shrinkage, XRD, TGA, Solid NMR, H NMR, Electron
microscopy, MIP, Gas sorption,

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