Applications of the Rietveld

method

Thierry Roisnel

Laboratoire de Chimie du Solide et Inorganique Moléculaire

UMR6511 CNRS– Université de Rennes 1 (France)
 1. Structure refinement

Crystal structures
Magnetic structures (neutron data)

1.1 Isomorphic or partially known structure

structure refinement + difference Fourier maps examination

1.2 Unknown structure

1.1. Unit cell determination

1.2 Space group determination
1.3 Crystal structure determination:
1.4 Structure refinement (Rietveld method)
 1.1 Unit cell determination

indexation of diffraction pattern:

. Determination of cell parameters

. Crystal symmetry
. (hkl) Miller indices for every Bragg line

Simple problem:
*2
Qhkl = dhkl = h2 a *2 + k 2b*2 + l 2c *2 + 2klb* .c * + 2lhc * .a * + 2hka * .b*

Needs only a list of angular positions of Bragg lines:

. Accuracy and precision of Bragg positions !

!! . Single phase ?
. Diffractometer zero-shift ?
 1.2 Space group determination

. Whole profile refinement of the diffraction pattern (FullProf):

. No structural model
. Cell parameters previously determined (1.1)
. Space group: Lauë group

. Detailed examination of systematic absences:

. Extinctions due to Bravais lattice
. Extinctions to symmetry elements
 1.3 Crystal structure determination

. Extraction of integrated intensities + Use of traditionnal

methods used in single crystal crystallography:
. Direct methods (EXPO, SHELXS …)
. Patterson map

. Direct space methods:

. Genetic algorithm, Monte Carlo, Simulating annealing
1.4 Crystal structure refinement: X-rays versus
neutron data

. X-rays (conventionnal):

☺ . Instrumental resolution
" weak cell distortions
. Laboratory device

. Form factor:
. decrease with sinθ/λ:
" Low diffracted intensity at high angles

. Increase with Z
" diffracted intensities dominated by “heavy” atoms
. Neutrons : interaction neutron with atom nuclei

☺ . Scattering power is independent of atomic number:

" localization of “light” atoms (H/D, Li…):
" important contrast: cationic distribution (ex: Fe/Mn)

. Low absorption:
" experiments versus external parameter (temperature,
pressure)

. Scattering powder is independent of sinθ/λ:

" accurate thermal displacement parameters

. Gaussian profile function

. Neutron diffraction

. Instrumental resolution

. Need a particular installation (nuclear reactor, spallation source)

. Large volume of powdered sample (2-3 cm3)

 FullProf exercices

(http://www-llb.cea.fr/fullweb/fp2k/fp2k_exercices.htm)

Exercice #1: Analysis of the spinel MgAl2O4

(ref. V. Montouillot, PhD Thesis, Univ. Orléans 1998)

Spinel structure : cubic unit cell (space group: F d –3 m)

AB2X4: A2+ (Mg, Ca, FeII, Zn…) tetrahedral (Td) &

B3+ (Al, FeIII, MnIII, …) octaedral (Oh) sites
X: O2-
 AB2X4 spinel structrure

Different ways to fill the Td (nTd=8) and Oh sites (nOh=4):

(A ) (A )
Td Oh
2+ 3+ 2+ 3+
1− x Bx x B2−x O4

( A ) (B ) O
Td Oh
2+ 3+
x=0 1 2 4
" direct spinel

(B ) ( A B ) O
Td Oh
3+ 2+ 3+
x=1
1 1 1 4
" inverse spinel
Exercice #1: Analysis of the spinel MgAl2O4
Space Group: F d -3 m

Setting 1:
Tetrahedral A-positions (Mg,Al) 8a (1/4,1/4,1/4)
Octahedral B-positions (Mg,Al) 16d (5/8,5/8,5/8)
Oxygen positions (O) 32e (x,x,x) x=0.386

Setting 2:
Tetrahedral A-positions (Mg,Al) 8a (1/8,1/8,1/8)
Octahedral B-positions (Mg,Al) 16d (1/2,1/2,1/2)
Oxygen positions (O) 32e (x,x,x) x=0.261
Exercice #1: Analysis of the spinel MgAl2O4

Two neutron powder diffraction data files:

MgAl2O4s.dat -> Sample obtained by conventional high

temperature solid state reaction

neutron powder diffractometer: 3T2 (LLB, Saclay)

. λ = 1.227 Å
. Resolution parameters: U = 0.276, V=0.340, W=0.147
 MgAl2O4 exercice

Refine the structure allowing the distribution of Mn and

Al between the two available cationic sites. Calculate the
λ value of the spinel structure:

B3+ in Td site
λ=
B3+ total

Winplotr (mgal2o4s)
 Introduction of a structural model: Rietveld refinement

JBT=0 cristal. Structure factor

IRF=0 automatic generation of reflections from the space group symbol

!Phase 1: MgAl2O4-sharp
!Nat Dis Ang Pr1 Pr2 Pr3 Jbt Irf Isy Str Furth ATZ Nvk Npr More
5 0 0 0.0 0.0 1.0 0 0 0 0 0 0.00 0 7 0
F d –3 m <-- space group symbol
!Atom Typ X Y Z Biso Occ In Fin N_t Spc /Codes
MgA MG 0.12500 0.12500 0.12500 0.30000 0.50000 0 0 0 0
0.00 0.00 0.00 0.00 61.00
AlA AL 0.12500 0.12500 0.12500 0.30000 0.50000 0 0 0 0
0.00 0.00 0.00 0.00 -61.00
AlB AL 0.50000 0.50000 0.50000 0.30000 1.50000 0 0 0 0
0.00 0.00 0.00 0.00 61.00
MgB MG 0.50000 0.50000 0.50000 0.30000 0.50000 0 0 0 0
0.00 0.00 0.00 0.00 -61.00
O O 0.26100 0.26100 0.26100 0.60000 4.00000 0 0 0 0
0.00 0.00 0.00 0.00 0.00

mi
-1 at origin: setting 2 ! occi = α .
mg
.Pi

α: coef .
mi : multiplicity of site i
mg : multiplicity of general site
Pi : pourcentage d ' occupation du site i (0.0 − 1.0)
 Introduction of a structural model: Rietveld refinement
!Phase 1: MgAl2O4-sharp
!Nat Dis Ang Pr1 Pr2 Pr3 Jbt Irf Isy Str Furth ATZ Nvk Npr More
5 0 0 0.0 0.0 1.0 0 0 0 0 0 0.00 0 7 0
F d –3 m <-- space group symbol
!Atom Typ X Y Z Biso Occ In Fin N_t Spc /Codes
Mg_T MG 0.12500 0.12500 0.12500 0.30000 0.50000 0 0 0 0
0.00 0.00 0.00 0.00 61.00
Al_T AL 0.12500 0.12500 0.12500 0.30000 0.50000 0 0 0 0
0.00 0.00 0.00 0.00 -61.00
Al_O AL 0.50000 0.50000 0.50000 0.30000 1.50000 0 0 0 0
0.00 0.00 0.00 0.00 61.00
Mg_O MG 0.50000 0.50000 0.50000 0.30000 0.50000 0 0 0 0
0.00 0.00 0.00 0.00 -61.00
O O 0.26100 0.26100 0.26100 0.60000 4.00000 0 0 0 0
0.00 0.00 0.00 0.00 0.00

spinel AB2O4:

. Directe: Mg on A site and Al on B site MgAl2O4

. Inverse: Al on A site and Mg,Al on B site Al (MgAl) O4
. Mixte: Mg,Al on A site and Mg,Al on B Mg1-xAlx Al2-xMgx O4
 2.Micro-structure refinement

Ω(x )= f (x )⊗ g(x )
Observed profile
Intrinsic profile
Instrumental profile

Micro-structural features:

* apparent size of coherent domains in the direction perpendicular

to the diffraction planes

* apparent strains in the direction perpendicular to the diffraction

planes:

Origin of micro-strains: . Defaults: dislocations, vacancies

. local fluctuations of composition (solid solutions )
 3.Quantitative phase analysis and
Rietveld method
Diffracted intensity for a phase φ is proportional to the quantity of irradiated
matter (absorption effects are not taken into account).

For a multiple phase pattern:

Nφ

yci = bi + ∑ Sφ ∑ I h,φ Ωφ (Ti − Th,φ )

φ =1 h

With: Sφ Scale factor for phase φ

 3.Quantitative phase analysis

mφ
Sφ mφ Sφ .M φ .Zφ .Vφ
M φ .Zφ .Vφ

with
mφ Mass of the phase φ in the sample

Mφ Molecular weight

Zφ Number of molecules per unit cell

Vφ Volume of the unit cell

 3.Quantitative phase analysis

determination of weight fraction wφ of every phase φ

present in the sample

mφ Sφ ( ZMV )φ
Wφ = Nφ
= Nφ

∑ m ∑ S .(ZMV )
i =1
i
i =1
i i
 3.Quantitative phase analysis in FullProf

Take care of:

. Sample preparation: homogeneity, number of particles

with random orientation (beware of preferential orientation)

. Correct calculation of structure factors for every phase

 3.Quantitative phase analysis in FullProf

Sφ ( ZMV )φ . fφ2 tφ Sφ ATZφ .Vφ

Wφ = Nφ
= Nφ

∑ i
S
i =1
.( ZMV ) .
i if 2
ti ∑ S ATZ .V
i =1
i i i

with
Sφ Scale factor in FullProf (refinable variable)

ATZ i = Z i M i f i 2 ti FullProf parameter

Brindley factor (particle absorption contrast

ti factor).
t is tabulated as a function of (µi-µ).R
FullProf parameter
 3.Quantitative phase analysis in FullProf

fi Used to transform the site multiplicities in PCR FullProf input file, to

their real values. For a stoichimetric phase, f = 1 if these
multiplicities are calculated by dividing the Wyckoff multiplicity m
of the site by the general multiplicity M of the space group.
Otherwise, f=occ.M/m, where occ. is the occupation number in the
PCR file

☺ In order to GET PROPER VALUES OF WEIGHT FRACTIONS LET

THE PROGRAM RE-CALCULATE ATZ by putting them to ZERO.
The correct ATZ value to be rewritten in the PCR input file.
( ✮First atom in the PCR file has to be fully occupied ✮)
 3.Quantitative phase analysis in FullProf

1. Crystal structure has to be refined:

JBT=0 (IRF=0) Winplotr (Si3N4)

refine the structural parameters as usually

2. Crystal structure is well known:

2.1 create hkl file containing hkl list with corresponding F2

(JLKH=5)

2.2 refine the pattern without entering atomic positions

JBT=-3, IRF=2 (Profile Matching mode with constant
relative intensities for the current phase, but
refinable scale factor)
 3.Rietveld Q.P.A.

☺ easy to operate (automatic analysis in FullProf)

no internal standard
non destructive method
up to 16 phases in FullProf
polymorphism
neutron case: large amounts of powder analysis (real samples)
industrial applications (cements, clays …)

structure model dependent: {Fhkl} have to be known

beware of preferential orientation
 3.Quantitative phase analysis:
determination of an amorphous phase
content ?

If an amorphous phase is present in the sample:

mA = mS − mC
Amorphous phase weight Crystalline part
weight

Sample weight

Amorphous phase weight fraction:

mA mC
=1 −
mS mS
 3.Quantitative phase analysis:
determination of an amorphous phase
content ?

For each crystalline phase: mφ = k . Sφ .M φ .Zφ .Vφ

N N
For N crystalline phase sample: mC = ∑ mi = k . ∑ Si .M i .Z i .Vi
i =1 i =1

Introduction of an internal standard in the powder:

(mst is known)

mst = k . S st .M st .Z st .Vst mst

k=
S st .M st .Z st .Vst
 3.Quantitative phase analysis:
determination of an amorphous phase
content ?

Remarks:

same strategy can be applied for unknown

structure phase

difficult to manage for bulk sample

if the structure of the amorphous phase is known,

a QPA can be realized through broadening line
treatment for the amorphous phase (small coherent
diffraction domains)
 3.Rietveld Q.P.A.: α-Si3N4 and β_Si3N4 mixture

Neutron data: αSi3N4: 93% wgt

βSi3N4: 7% wgt
 3.Rietveld Q.P.A.: α-Si3N4 and β_Si3N4 mixture

X-rays data: αSi3N4: 91.6% wgt

βSi3N4: 8.4% wgt
Some references on Q.P.A.by Rietveld method

R.J. Hill & C.J. Howard, J. Appl. Cryst. 20, 467-476 (1987)
Quantitative phase analysis from neutron powder diffraction data using the
Rietveld method

G.W. Brindley, Phil. Mag. 36, 347-369 (1945)

The effect of grain or particle size on X-ray reflections from mixed
powders and alloys considered in relation to the quantitative determination of
crystalline substances by X-ray methods

D.L. Bish & S.A. Howard, J. Appl. Cryst. 21, 86-91 (1988)
Quantitative phase analysis using the Rietveld method

J.C. Taylor, Powder Diffraction 6, 2-9 (1991)

Computer programs for standardless quantitative analysis of minerals
using the full powder diffraction profile

R.J. Hill, Powder Diffraction 6, 74-77 (1991)

Expanded use of Rietveld method in studies of phase abundance in
multiphase mixtures