Applications of

Applications of
the
the
Rietveld
Rietveld
method
method
Thierry Roisnel
Laboratoire de Chimie du Solide et Inorganique Molculaire
UMR6511 CNRS Universit de Rennes 1 (France)
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. Structure refinement
1.1 Unit cell determination
indexation of diffraction pattern:
. Determination of cell parameters
. Crystal symmetry
. (hkl) Miller indices for every Bragg line
*2 2 *2 2 *2 2 *2 * * * * * *
2 . 2 . 2 . = = + + + + +
hkl hkl
Q d h a k b l c klb c lhc a hka b
Simple problem:
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: Lau 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
. X-rays (conventionnal):
. Instrumental resolution
weak cell distortions
. Laboratory device
. Form factor:
. decrease with sin/:
Low diffracted intensity at high angles
. Increase with Z
diffracted intensities dominated by heavy atoms
1.4 Crystal structure refinement: X-rays versus
neutron data
. 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 sin/:
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 cm
3
)
FullProf exercices
(http://www-llb.cea.fr/fullweb/fp2k/fp2k_exercices.htm)
Exercice #1: Analysis of the spinel MgAl
2
O
4
(ref. V. Montouillot, PhD Thesis, Univ. Orlans 1998)
Spinel structure : cubic unit cell (space group: F d 3 m)
AB
2
X
4
: A
2+
(Mg, Ca, Fe
II
, Zn) tetrahedral (Td) &
B
3+
(Al, Fe
III
, Mn
III
, ) octaedral (Oh) sites
X: O
2-
AB
2
X
4
spinel structrure
Different ways to fill the Td (n
Td
=8) and Oh sites (n
Oh
=4):
( ) ( )
Td Oh
2 3 2 3
1 x x x 2 x 4
A B A B O
+ + + +

x=0
x=1
( ) ( )
Td Oh
2 3
1 2 4
A B O
+ +
( ) ( )
Td Oh
3 2 3
1 1 1 4
B A B O
+ + +
direct spinel
inverse spinel
Exercice #1: Analysis of the spinel MgAl
2
O
4
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 MgAl
2
O
4
Two neutron powder diffraction data files:
MgAl2O4s.dat -> Sample obtained by conventional high
temperature solid state reaction
neutron powder diffractometer: 3T2 (LLB, Saclay)
. = 1.227
. Resolution parameters: U = 0.276, V=0.340, W=0.147
MgAl
2
O
4
exercice
Refine the structure allowing the distribution of Mn and
Al between the two available cationic sites. Calculate the
value of the spinel structure:
3
3
B inTdsite
B 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
-1 at origin: setting 2 !
. .
: .
:
:
: ' (0.0 1.0)
=

i
i i
g
i
g
i
m
occ P
m
coef
m multiplicityof site i
m multiplicityof general site
P pourcentaged occupationdusitei

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 AB
2
O
4
:
. Directe: Mg on A site and Al on B site MgAl
2
O
4
. Inverse: Al on A site and Mg,Al on B site Al (MgAl) O
4
. Mixte: Mg,Al on A site and Mg,Al on B Mg
1-x
Al
x
Al
2-x
Mg
x
O
4
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 )
2.Micro-structure refinement
( ) ( ) ( ) x f x g x =
Observed profile
Intrinsic profile
Instrumental profile
Diffracted intensity for a phase is proportional to the quantity of irradiated
matter (absorption effects are not taken into account).
3.Quantitative phase analysis and
Rietveld method
For a multiple phase pattern:
1
( )
=
= +
h, h,
h
ci i i
N
y b I T T S

With:
S

Scale factor for phase

3.Quantitative phase analysis
. .
m
S
M Z V

. . . m S M Z V

with
m

Mass of the phase in the sample

Molecular weight
Number of molecules per unit cell
Volume of the unit cell
3.Quantitative phase analysis
1 1
( )
.( )
= =
= =

N N
i i i
i i
m S ZMV
W
m S ZMV

determination of weight fraction w

of every phase
present in the sample
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
2
2
1 1
( ) . .
.( ) . .
= =
= =
i
N N
i i i
i
i i i
i
t A S ZMV f V S
S
TZ
t
W
S ZMV f V ATZ

with
Scale factor in FullProf (refinable variable)
FullProf parameter
Brindley factor (particle absorption contrast
factor).
t is tabulated as a function of (
i
-).R
FullProf parameter
S

2
=
i i i i i
Z M ATZ f t
i
t
3.Quantitative phase analysis in FullProf
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 Mof the space group.
Otherwise, f=occ.M/m, where occ. is the occupation number in the
PCR file
i
f
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)
refine the structural parameters as usually
2. Crystal structure is well known:
2.1 create hkl file containing hkl list with corresponding F
2
(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)
Winplotr (Si3N4)
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: {F
hkl
} 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:
A S C
m m m =
Sample weight
Amorphous phase weight
Crystalline part
weight
Amorphous phase weight fraction:
1
C A
S S
m m
m m
=
3.Quantitative phase analysis:
determination of an amorphous phase
content ?
. . . . m k S M Z V

=
1 1
. . . .
N N
C i i i i i
i i
m m k S M Z V
= =
= =

For each crystalline phase:
For N crystalline phase sample:
Introduction of an internal standard in the powder:
(m
st
is known)
. . . .
st st st st st
m k S M Z V =
. . .
st
st st st st
m
k
S M Z V
=
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.: -Si
3
N
4
and _Si
3
N
4
mixture
Neutron data: Si
3
N
4
: 93% wgt
Si
3
N
4
: 7% wgt
3.Rietveld Q.P.A.: -Si
3
N
4
and _Si
3
N
4
mixture
X-rays data: Si
3
N
4
: 91.6% wgt
Si
3
N
4
: 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