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+
9 x=0 1 2 4
" direct spinel

(B ) ( A B ) O
Td Oh
3+ 2+ 3+
9 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:

9 MgAl2O4s.dat -> Sample obtained by conventional high

temperature solid state reaction

9 MgAl2O4b.dat -> Sample obtained by sol-gel reaction

at low temperature

neutron powder diffractometer: 3T2 (LLB, Saclay)

. λ = 1.227 Å
. Resolution parameters: U = 0.276, V=0.340, W=0.147
3T2 high resolution neutron powder diffractometer
(LLB, Saclay)

Number of effective counters = f(2θ)

Data file format = f(diffractometer setup, measurement)

. Multicounters diffractometers:
LLB: 3T2, G42 ILL: D2B, D1A

Countings list contains NPTS couples of data (Ni, Yi):

i: number of point
Ni: number of counters with effective counting at 2Theta_i
Yi: mean counting at 2theta_i angle
sigYi = SQRT(Yi/ni)
" INSTR=1 or INSTR=6 (in FP)
. Single counter diffractometer (step by step measurement) and
fixed PSD diffractometer:
same number of effective counters for every 2theta_i

" INSTR=0 or INSTR=5 (in FP)

 Part #1:

Start the analysis using the first file (well crystallized

powder) in order to obtain the resolution function of the
instrument. Start directly with WinPLOTR trying to
determine "ab initio" the unit cell, background, etc.
¾ How to display the neutron pattern with WinPLOTR ?

1. Double click on the WinPLOTR icon on the desktop

¾ How to display the neutron pattern with WinPLOTR ?

2. Launch WinPLOTR through a command line:

. Open a DOS console (Start / Execute / cmd)

. Go to the working directory:

c:\> cd d:\data\FP_exercices\mgal2O4

. Run WinPLOTR:

d:\data\fp_exercices\mgal2O4> winplotr 3 mgal2O4s.dat

Program to be launched
format File name
 Unit cell parameters determination: pattern indexation

. Symmetry ?
. Unit cell parameters ?

d *2 = h2a *2 + k2b*2 + l 2c*2 + 2klb*c* + 2hla *c* + 2hka *b*

List of Bragg lines angular positions

. Accuracy and exactitude of 2θ positions

!! . Single phase ?
. Zero shift of the goniometer
 Automatic indexation programs

. DICVOL91 (Boultif & Louër, 1991)

cell parameters variation in finite domains
+ reduction of ranges by successive dichotomy
method
(exhaustive method)

. TREOR90 (Werner et al, 1972)

permutation of hkl Miller indices of first lines
of the diffraction pattern
(semi-exhaustive method: tries and errors)

. ITO15 (Visser, 1969)

particular relationship in reciprocal space
 How to determine 2θ position with WinPLOTR ?

1. Profile refinement (pseudo-Voigt function)

9.Zoom on a particular angular range (one or several Bragg lines)
9 Option « Calculation / Profile fitting » (or « Fit » button)
9 Select (with the mouse) starting parameters for the least square refinsment
procedure
. Background (right and left values)
. Intensity and 2θ position
. Full width at haft maximum
How to determine 2θ position with WinPLOTR ?

1. Profile refinement
Next angular range:

. calculation / reload data file

. Select new 2θ angular range
How to determine 2θ position with WinPLOTR ?
1. Profile refinement
 How to determine 2θ position with WinPLOTR ?
1. Profile refinement

Output file: filename_PF.REF

Refined angular positions: to be copied in DICVOL, TREOR input file

 How to determine 2θ position with WinPLOTR ?
2. Automatic peak search
Zoom on a particular angular range
. ~20 Bragg lines are necessary for indexation
. Low angles Bragg lines are very important (low Miller indices)
 How to determine 2θ position with WinPLOTR ?
2. Automatic peak search: Point selection / Automatic peak search
 How to determine 2θ position with WinPLOTR ? :
2. Save positions : Point selection / Save as DICVOL, TREOR, ITO
 Input DICVOL file: MgAl2O4s.DIC

! DATA FILE: MgAl2O4s.dat

! INSTRM: 1
DICVOL input parameters:
14 2 1 0 0 0 0 0 ! N,ITYPE,JC,JT,JH,JO,JM,JTR
20.0 20.0 20.0 0.0 1500.0 90.0 125.0 ! AMAX,BMAX,CMAX,VOLMIN,VOLMAX,BEMIN,BEMAX
1.22700 0.000 0.000 0.000 ! WAVE,POIMOL,DENS,DELDEN
0.000 0.000 1 ! EPS,FOM, ISUP
15.11003 57.15203 21.57045
24.78773 109.18742 18.60364
29.16271 201.49445 23.49654
30.48857 331.67642 24.17402
35.35245 511.11243 21.91205
38.65351 52.79015 19.60816
43.66076 57.97029 18.93721
46.46254 330.61948 21.01819
50.86000 981.52209 23.04868
53.36502 40.48660 20.11416
59.69897 83.06899 20.06502
60.46622 221.72400 20.27625
63.45730 213.71033 22.85244
65.65189 103.91086 22.77873

2θ positions intensity background

WinPLOTR: Run DICVOL
 WinPLOTR: Run DICVOL / create PCR file

Resolution parameters
9 profile function (G for N, PV for X-rays)
9 U, V, W (Caglioti)
 Input file for FullProf: MgAl2O4s_1.PCR
COMM Dicvol solution: 1 (Automatic generated PCR file)
!Job Npr Nph Nba Nex Nsc Nor Dum Iwg Ilo Ias Res Ste Nre Cry Uni Cor Opt Aut
1 0 1 14 2 0 1 1 0 0 1 0 0 0 0 0 0 0 0
!
!Ipr Ppl Ioc Mat Pcr Ls1 Ls2 Ls3 Syo Prf Ins Rpa Sym Hkl Fou Sho Ana
0 0 1 0 1 0 4 0 0 3 1 0 0 -2 0 0 0
! lambda1 Lambda2 Ratio Bkpos Wdt Cthm muR AsyLim Rpolarz
1.227000 1.227000 1.0000 40.0000 3.0000 0.0000 0.0000 50.0000 0.0000
!
!NCY Eps R_at R_an R_pr R_gl Thmin Step Thmax PSD Sent0
10 0.30 1.00 1.00 1.00 1.00
!
! 2Theta/TOF Background
15.110 21.570
24.788 18.604
29.163 23.497
30.489 24.174
35.352 21.912
38.654 19.608
43.661 18.937
46.463 21.018
50.860 23.049
53.365 20.114
59.699 20.065
60.466 20.276
63.457 22.852
65.652 22.779
!
! Excluded regions (LowT HighT)
0.00 10.06
70.71 180.00
!
0 !Number of refined parameters
 Input file for FullProf: MgAl2O4s_1.PCR

JobTyp: select teh type of job: calculation, refinement, incident radiation

0 refinement of X-rays data
1 refinement of neutron data (cwl, N+M)
2 calculation of X-rays pattern
3 calculation of neutron patterni (cwl, N+M)
-1 refinement of neutron data (tof, N+M)
-3 calculation of neutron pattern (tof, N+M)
 Input file for FullProf: MgAl2O4s_1.PCR

!
! Zero Code Sycos Code Sysin Code Lambda Code
0.00
!
phase 1:
!
!Nat Dis Mom Pr1 Pr2 Pr3 Jbt Irf Isy Str Furth ATZ Nvk Npr More
0 0 0 0.0 0.0 1.0 2 0 0 0 0 0.00 0 0 0
P M 3 M <--Space group symbol
! Scale Shape1 Bov Str1 Str2 Str3 Strain-Model
1.0000 0.00 0.0000 0.0000 0.0000 0.0000 0
0.00000 0.00 0.00 0.00 0.00 0.00
! U V W X Y GauSiz LorSiz Size-Model
0.3060 -0.4680 0.2360 0.00000 0.00000 0.00000 0.00000 0
0.00 0.00 0.00 0.00 0.00 0.00 0.00
! a b c alpha beta gamma
8.082300 8.082300 8.082300 90.000000 90.000000 90.000000
0.00 0.00 0.00 0.00 0.00 0.00
! Pref1 Pref2 Asy1 Asy2 Asy3 Asy4
0.00000 0.00000 0.00000 0.00000 0.00000 0.00000
0.00 0.00 0.00 0.00 0.00 0.00
 Input file for FullProf: MgAl2O4s_1.PCR

Jbt: structure factor model and refinement method for the phase

0 cristallographic Rietveld
1 magnetic (mx, my, mz) Rietveld
-1 magnetic (polar coord.) Rietveld
2 constant scale factor « profile matching »
-2 idem 2 with |F| « profile matching »
3 constant relative intensities « profile matching »
-3 constant |F| « profile matching »
4 cristallographic + rigid body Rietveld
5 magnetic (conic) Rietveld
10 cristallogr. + magnetic (mx, my, mz) Rietveld
-10 cristallogr. + magnetic (pol. coord.) Rietveld
15 commensurate modulated crist. + magn Rietveld
-15 commensurate modulated crist. + magn. (pol. coord.) Rietveld
 Input file for FullProf: MgAl2O4s_1.PCR

Irf: génération des réflexions, utilisation d’un fichier de réflexions

0 automatic generation of reflections list from space group symbol

1 h,k,l,mult list is read from CODFILn.hkl file
-1 satellites reflections are generated from space group space symbol
2 h,k,l,mult, Int. Is read from CODFILn.hkl file
3 h,k,l,mult, Freal, Fimag list is read from CODFILn.hkl file
4/-4 integrated intensities list is given as observations (single crystal case)
 Input file for FullProf: MgAl2O4s_1.PCR
Parameters to modify: RUN #1

.Space group symbol: Pm-3m Æ Fd-3m

. Extend the angular range to the whole pattern
. Background points:
WinPLOTR: . Points selection / Select background points
. Save background points

Editor: . « Copy/Paste » the list of background points from « back.xy »

to .PCR file

Parameters to refine: Run #n:

. Cell parameters, zero shift

. Profil paramters
. Profile function (NPROF=7)
. Angular resolution: U, V, W, X, Y
. WDT (remove « steps » in background)
. Low angles asymetry
. Background points
 Background points ?
WinPLOTR / Points selection / Background points

➵
Select background points through mouse clicks !
Profile matching refinement of MgAl2O4s.dat
 Part #2:

Refine the structure allowing the distribution of Md and

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

B3+ in Td site
λ=
B3+ total
 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 ÎMgAl2O4

. Inverse: Al on A site and Mg,Al on B site ÎAl (MgAl) O4
. Mixte: Mg,Al on A site and Mg,Al on B ÎMg1-xAlx Al2-xMgx O4
Introduction of a structural model: Rietveld refinement

Parameters to refine:

RUN #1:

. Scale factor

RUN #n:

. Scale factor
. Structural parameters: cationic distribution, oxygen positions
. Thermal displacement parameters (cation, anion)

Last runs:

+ Profile parameters:
. Angular resolution, low angles asymetrie
. Cell parameters: cell parameters, zero shift
. + background points
Introduction of a structural model: Rietveld refinement

Extract from the PCR file:

F D 3 M <--Space group symbol

!Atom Typ X Y Z Biso Occ In Fin N_t Spc /Codes
O O 0.26100 0.26100 0.26100 0.64384 4.00000 0 0 0 0
41.00 41.00 41.00 51.00 0.00
MG_T MG 0.12500 0.12500 0.12500 0.33537 0.70094 0 0 0 0
0.00 0.00 0.00 31.00 21.00
AL_T AL 0.12500 0.12500 0.12500 0.33537 0.29906 0 0 0 0
0.00 0.00 0.00 31.00 -21.00
AL_O AL 0.50000 0.50000 0.50000 0.33537 1.70094 0 0 0 0
0.00 0.00 0.00 31.00 21.00
MG_O MG 0.50000 0.50000 0.50000 0.33537 0.29906 0 0 0 0
0.00 0.00 0.00 31.00 -21.00

B3+ in Td site 0.29906

λ= 3+
= ≈ 0.15
B total 0.29906 + 1.70094
 Part #3:

This sample contains a small parasitic phase of MgO

space group: Fm –3 m (a = 4.22 Å)

Mg (4a)
O (4b)

=> atomic positions: WinPLOTR/ tools / space group infos

Determine the percentage of this impurity

 Quantitative analysis: weight fraction determination

S j .Z j . f j2 .M j .V j t j S j . ATZ j .V j
Wj = =
N N
ATZ j = Z j . fj2 .M j t j
∑ ( S .Z .f
i
i i i
2
.M i .Vi ti ) ∑ ( S . ATZ .V )
i
i i i

Sj scale factor of phase j

Zj number of formula units per cell

fj is used to transform site multiplicities used in PCR file to their real values.
For a stoichiometric phase f=1 if these multiplicities are calculated by dividing the
Wickoff multiplicity m of the site by the general multiplicity M. Otherwise,
f=Occ.M/m, where Occ is the occupation number in PCR file.
In a general case, the user can put the ATZ value to 0.0 in PCR file: the right
value of ATZ will be calculated automatically.

Mj is the molecular weight

Vj is the volume of the unit cell

 .PCR file: introduction d’une seconde phase (MgO)

Parameters to refine:

RUN #1:

. Scale factor for both phases

Run #n:

+ Phase 2:
. Cell parameters
. Overal thermal factor

+ Phase 1:
. Structural parameters

+ profile parameters: same values for both phases (minor phase #2)
Final refinement (2 phases): W2 < 1.0 %
 Part #4:

Obtain the best refinement of profile parameters using

NPROF=7 (Voigt function). Use the refined parameters to
construct an Instrumental Resolution Function (IRF)
 Part #4:

Extract from the PCR file (Rietveld mode or pattern matching):

!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 655560.25 0 7 0
…

! U V W X Y GauSiz LorSiz Size-Model

0.175394 -0.192435 0.091543 0.000000 0.062491 0.000000 0.000000 0
121.000 111.000 101.000 0.000 171.000 0.000 0.000
! a b c alpha beta gamma
8.083027 8.083027 8.083027 90.000000 90.000000 90.000000
31.00000 31.00000 31.00000 0.00000 0.00000 0.00000

H G2 = U tan 2 θ + V tan θ + W

H L = X tan θ + Y cos θ
 Mgal2o4s.IRF file

IRESO=1: U,V,W,X,Y,Z value with

HG2 = Ui tan2 θ + Vi tan θ + Wi H L = X i tan θ + Yi cosθ + Zi

Content of the IRF file:

! IRF from MgAl2O4_sharp 3T2

! U V W X Y Z
0.179491 -0.197008 0.095126 0.000000 0.056029 0.000000
 Part #5:

Refine the second diffraction pattern obtained with a

sample prepared at low temperature (not well
crystallized). Determine the cation distribution (λ value)
and the microstructural parameters: domain crystallite
size, microstrains.
Display the mgal2o4b.dat file
 Refine the mgal2o4b.dat file

9 start from the PCR file of the mgal2o4s.dat file refinement

(pattern matching mode) and change:

* background points
* use mgal2o4s.irf resolution file (IRESO=1)
Fixed resolution parameters χ2=25
 Fixed resolution parameters χ2=25

Profile shape problem: Lorentzian type broadened lines

Isotropic size effect: refined Y parameter (lorentz part)

χ2≈1.
Isotropic size effect: refined Y parameter (lorentz part)

χ2≈1.
Microstructural output file : mgal2o4b.mic

Apparent_size = 72 Å
Isotropic strain effect: refined X parameter (lorentz part)

χ2≈1.3
Isotropic strain effect: refined X parameter (lorentz part)

χ2≈1.3
Microstructural output file : mgal2o4b.mic

Average maximum strain = 88 10-4

 Cationic distribution in MgAl2O4_b sample

9 Include the atomic positions in the .PCR file

9 Refine Td and Oh sites occupancies

F D 3 M <--Space group symbol

!Atom Typ X Y Z Biso Occ In Fin N_t Spc
/Codes
O O 0.26100 0.26100 0.26100 0.82605 4.00000 0 0 0 0
0.00 0.00 0.00 161.00 0.00
MG1 MG 0.12500 0.12500 0.12500 1.13882 0.41698 0 0 0 0
0.00 0.00 0.00 171.00 181.00
AL1 AL 0.12500 0.12500 0.12500 1.13882 0.58302 0 0 0 0
0.00 0.00 0.00 171.00 -181.00
AL2 AL 0.50000 0.50000 0.50000 1.13882 1.41698 0 0 0 0
0.00 0.00 0.00 171.00 181.00
MG2 MG 0.50000 0.50000 0.50000 1.13882 0.58302 0 0 0 0
0.00 0.00 0.00 171.00 -181.00

B3+ in Td site 0.58302

λ= 3+
= ≈ 0.29
B total 2.