Application of XRD in ceramics

cubic F http://www.cas.muohio.edu/~marcumsd/p293/lab3/lab3.htm

KCl or Br : basis coordinence 6

KBr

KCl a   2 

In coordination 6 : rCl- = 1.81 Å and rBr- = 1.96 Å

same planes diffract BUT cubic lattice parameter a   2 
Application to the study of ceramics

control of a firing-milling reaction processing

Al2O3 + MgO  MgAl2O4
Study of solid solutions
Vegard ‘s Law

NiS2-xSex
cubic
 * What is a defined structure ?
* Crystalline structure : mixed oxides
* spinel AB2O4
* fluorite A2B2O8
* pyrochlore A2B2O7
* perovskite ABO3

* Well-known crystallisation
* Oxidation state
* Coordination
3 defined compounds (fusion
congruent)
BaAl3O19 - ( 3 Al203 - 1 BaO )
BaAl2O4 - ( 1 Al203 - 1 BaO )
Ba3Al2O6 - ( 1 Al203 - 3 BaO )
1 crystalline structure : 1 diffraction pattern

La3+

Fe3+

octahedral coordination of Fe3+

Depending on :

* the A/B ratio

* the nature of the A and B cations

* oxidation state
* coordination

* the ionic radii of A and B cations

* Which structure ?
 a mixing of A and B cations will result in a specific defined structure
*Spinel MgAl2O4 A2+ coordination 4
B3+ coordination 6

Tetrahedral octahedral
*Fluorite Ce2Zr2O8 A4+ coordination 8
B4+ coordination 6

O2-

*Pyrochlore Sm2Sn2O7 A3+ coordination 8 A2+

B4+ coordination 6 B5+

*Perovskite LaCoO3 A3+ coordination 12 A2+

B2+ coordination 6 B4+
Calcination of the resin: control of the crystallynity by XRD

LaCo0.5Fe0.5O3
LaCoO3 : rhombohedral LaFeO3 : orthorhombic
 Series LaCoxFe1-xO3

LaCoO3 : Vcell=337.01 Å3 LaFeO3 : Vcell=244.43 Å3

z = number of units per cell = 6 z = number of units per cell = 4
 acub = = 3.83 Å  acub = = 3.93 Å

 two solid solutions: different properties!

XRD CeZrOx. Sol-gel (gris) and coprecipitation (black), calcination: 680°C
Δ, ceria fluorite (cubique) ♦, zirconia tetragonale; * zirconia monoclinique
 Synthesis of modified Ce2Zr2O8 fluorites

CexZr4-xO8 : Végard’s law

x  4 : 2 : acub
coordinence 6 rZr4+ = 0.72 Å rCe4+ = 0.87 Å

cubic solid solution

Average crystallinity particle size:

Debye-Scherrer

t : Mean size of the ordered domain – grain size

q : Bragg angle of h k l reflexion (in radian)
(sometimes denoted as Δ(2θ))
b : line broadening half maximum intensity (FWHM) (in radian)
K : Scherrer shape factor constant (~ 0.9)
λ : X ray waveleght
 (FHMW) 2q
In class problem PeakDegree Degree
1 1.9237 29.189
2 1.5183 33.78
3 1.9151 48.613
4 1.7958 57.245
In class problem (Calculations)

Peak I (a.u.) I/Io JC (FHMW) 2q

1 356.9 100 Peak º (Degree) º (Degree) Grain size (nm) %
2 84.9 23.8 1 1.9237 29.189 4.27 100
3 149.6 41.9 2 1.5183 33.780 5.47 23.8
4 93.8 26.3 3 1.9151 48.613 4.56 41.9
Max. 356.9 4 1.7958 57.245 5.04 26.27

Grain size (nm)

Main peak 4.27
Weighted 4.59
HW7
(data in .xls file)
 Case study: Cerium oxides
CeO2 shows two possible crystal structures:
• Cubic
please check:
https://materialsproject.org/materials/mp-20194/
• Tetragonal
please check:
https://materialsproject.org/materials/mp-1018664/

Ce2O3 shows two possible crystal structures:

• Trigonal
please check:
https://materialsproject.org/materials/mp-2721/
• Monoclinic
please check:
https://materialsproject.org/materials/mp-561149/
Remember:
Two representations of CeO2 unit cell
Anions in the corner and the faces – Cations in the sites
Cerium cations: 4
anion (O2-)
4 sites x (1) = 4
cation (Ce4+) Oxygen anions: 8
8 corner x (1/8) = 1
12 edges x (1/4) = 3
6 face x (1/2) = 3
1 sites x (1) = 1
4Ce4+8O2-  4 (CeO2)

Cations in the corner and the faces – Anions in the sites

Cerium cations: 4
anion (O2-)
8 corner x (1/8) = 1
cation (Ce4+) 6 face x (1/2) = 3
Oxygen anions: 8
8 sites x (1) = 8
4Ce4+- 8O2-  4 (CeO2)
 In class problem Anions in the corner…
Reduction (schematically) of Ce(4+) to Ce(3+) 2 CeO2 + H2  Ce2O3 + H2O

4 (CeO2) 4 (CeO2)
Cerium cations: 8 Cerium cations: 8
Oxygen anions: 16 Oxygen anions: 12
No into the unit cell
 In-class problem Cations in the corner…
Reduction (schematically) of Ce(4+) to Ce(3+)

4(CeO2.CeO2) 4(CeO2.”CeO”) 4(Ce2O3)

Reduction of Ce(4+) keeping cubic structure (~like fluorite - pyrochlore)

Cerium cations: 4 Cerium cations: 4

8 corner x (1/8) = 1 8 corner x (1/8) = 1
6 face x (1/2) = 3 6 face x (1/2) = 3

Oxygen anions: 8 Oxygen anions: 7

8 sites x (1) = 8 7 sites x (1) = 7
4Ce4+- 8O2-  4 (CeO2) 4Ce4+7O2-  4 (CeO(2-d))
 (Ce2Ce2O8) (Ce24+Ce23+O7)
 Out-class problem Cations in the corner…
Reduction of Ce(4+) to Ce(3+) in Ce(1-x)ZrxO2
Fluorite crystal structure (AX2) adopted by ZrO2 and CeO2.
The cubic CeO2 structure can be stabilized to room temperature by
doping with Zr4+ )
anion (O2-)
cation (Ce4+)

anion (O2-)
cation (Ce4+)
cation (Ce3+)
cation (Zr4+)

Charge transfer mechanism: a) with adsorption of oxygen vacancies, situation in which the
cerium ion assumes valence Ce+4, and b) with the emission of reaction species, when the
cerium ion possesses valence Ce+3