Complexities of Real Oxide

Solid Solution Systems

Alexandra Navrotsky
University of California
at Davis
 The complexity and richness of natural minerals
and multicomponent ceramics (like UO2 spent nuclear
fuel) arises not only from the large number of phases
and crystal structures, but also from the variety of solid
solutions, complex elemental substitutions, order-
disorder relations, and exsolution phenomena one
encounters. Indeed, a pure mineral or ceramic of end-
member composition is the exception rather than the
rule. Elemental substitutions in minerals may be
classified in terms of the crystallographic sites on
which they occur and the formal charges of the
chemical elements (ions) which participate.
For a correct description, the thermodynamic
punishment must fit the structural crime. Yet the
formalism must be tractable, transparent, and useful.
Herein lies the challenge.
Charge Coupled Substitutions in Minerals
 Examples of charge-coupled
substitutions
• Mg2SiO4-Fe2SiO4, Mg2SiO4-Mg2GeO4
• NaAlSi3O8-CaAl2Si2O8
• ZrO2-YO1.5
• CoO-Li0.5Co0.5O
• LaGaO3-SrGaO2.5
( Any expression one writes for a free energy of mixing,
an activity, or an activity coefficient has buried in it some
assumptions about the mixing process on an atomic scale.
Therefore one must make sure those assumptions are
reasonable. There is no escaping this.
( Equations, whose form is constrained by theoretical
considerations and whose parameters are physically
reasonable, are more reliably extrapolated than arbitrary
polynomials fit to data in a small P, T, X range.
Models which simultaneously include constraints
imposed by phase equilibria, calorimetry, and crystal
chemistry are more reliable than those based on any one
source alone.
General Reaction

xA A + xBB =A(xA)B(xB)

ΔGºmix = ΔHºmix - TΔSºmix .

DH > 0, clustering and phase separation

DH < 0, ordering and compound formation

Partial molar quantities and activities

GºT(solid solution) = xA µºT(A) + xBµºT(B) + xA∆µº(A) + xB∆µº(B)

Integral free energy of mixing

ΔGºmix = xAΔµºT(A) + xBΔµºT(B)

The thermodynamic activity is defined as

Δµº(A) = RT ln a(A) and ∆µº(B) = RT ln a(B)

The changes in chemical potential on

mixing can be related to partial molar
enthalpies and entropies of mixing:

∆µºT(A) = ∆h¯ºT(A) - TΔs¯ºT(A) , ∆µºT(B) =

∆h¯ºT(B) - TΔs¯ºT(B)
FeAl2O4-FeCr2O4 :

One mole of ions mixed

a(Fei0.5Al O2) = xA, where A = Fe0.5Al O2. and a(Fei0.5Cr O2)

= xB, where B = Fe0.5CrO2

Two moles of ions mixed, entropy an extensive parameter

∆Smix = -2R[xA ln xA + xBln xB]

∆µ(FeCr2O4) = -2RT ln xA, ∆µ(FeAl2O4) = -2RT ln xB

a(FeCr2O4) = xA2 , a(FeAl2O4) = xB2

Multicomponent solid solutions: no unique choice of
components

Spinel (Fe2+,Ni)(Cr Fe3+)2O4 a ss between Fe3O4 and NiCr2O4

or FeCr2O4 and NiFe2O4.

Fe3O4 + NiCr2O4 = Nife2O4 + FeCr2O4 DG not zero

“reciprocal term” must be incorporated.

Clinoptilolite zeolites, occurring in the tuffs at Yucca

Mountain: (Na,K)6Al6Si30O72.20H2O
a(Nax6Al6Si30O72.20H2O) = [x(Nax6Al6Si30O72.20H2O)]6

a(NaAlSi5O12.3.67H2O) = x (NaAlSi5O12.3.67H2O)
Regular, Subregular and Generalized Mixing Models

Starting point : useful but inherently contradictory

assumption that, though the heats of mixing are not
zero, the configurational entropies of mixing are those
of random solid solution.

∆Gºmix, ex = ∆Hºmix-T∆Sºmix, ex

For a two-component system, the simplest formulation is:

∆Gexcess = ∆Hmix = xAxB = WH xAxB

Generalization
• For a binary system, the Guggenheim or Redlich-Kister based on a
GmEmixing
power-series expression for the excess molar Gibbs energy of
which reduces to zero when either x1 or x2 approach unity:

GmE  RT x1 ln f1  x2 ln f 2   RTx1 x2   r x1  x2 

r

where the coefficients r are called interaction parameters. Activity

coefficients can be obtained by the partial differentiation of over the mole
fraction x1 or x2:
ln f1  x22  0  1 3x1  x2    2 x1  x2 5 x1  x2   ...

ln f 2  x12  0  1 3x2  x1    2 x2  x1 5 x2  x1   ...

Generalization
• The subregular model is equivalent to the asymmetric Margules model in the
Thompson-Waldbaum notation

G E  RT x1 ln f1  x2 ln f 2   x1 x2 W12 x2  W21x1 

where the parameters are related to those used in the Redlich-Kister model as
W12  RT  0  1 ; W21  RT  0  1 

and, in general, depend on temperature and pressure. In the Thompson-

Waldbaum model, the activity coefficients of end-members are expressed as

RT ln f 2  2W12  W21 x12  2W21  W12 x13

RT ln f1  2W21  W12 x22  2W12  W21 x23

 Some more details on
configurational entropy,
grounded in statistical
mechanics
Order- Disorder Phenomena

If ordering slow, several series of solid solutions, each

having a differing degree of order, can exist.

Thermodynamics of mixing one set of species (e.g. Na,

K or Na, Ca in feldspars) may depend on the degree of
order of another (Al, Si).

Extent of ordering depends on temperature in a complex

fashion. Risky extrapolation.

Enthalpy and entropy of mixing depend strongly on T.

DS and DG of mixing can be asymmetric because the

configurational entropy term itself departs from
symmetrical behavior. A solvus may develop.
Observed degree of order is often kinetically
controlled. Low T, can not order. High T, can not
quench
Metastable disordered solid solutions may form.
Strong tendency to ordering is manifested in
significant negative heats of mixing and sometimes
leads to compound formation, (e.g. dolomite. DH, DS
and DG of mixing depend strongly on the degree of
order.
Destabilizing energetics of mixing in the disordered
state may be present at the same time as stabilizing
effect of ordering, leading to complex interplay
between ordering and exsolution (conditional
spinodal).
Change in symmetry: First or higher order phase
transitions lead to unconventional phase diagram
topologies. Lattice parameters can vary
nonlinearly with composition (depart from Vegard’s
rule)
 Structural Aspects of Solid
Solutions in Relation to their
Stability and Miscibility
• Fluorite-based structures
• Spinels
• Carbonates
 Order- Disorder Phenomena
Extent of ordering depends on T.
Observed degree of order is often kinetically controlled. Low
T, can not order. High T, can not quench. Metastable disordered
solid solutions may form.
Strong tendency to ordering is manifested in significant
negative heats of mixing and sometimes leads to compound
formation, (e.g. dolomite. DH, DS and DG of mixing depend
strongly on the degree of order. They can be asymmetric
because the configurational entropy term itself departs from
symmetrical behavior. A solvus may develop.
Order-disorder reactions often involve a change in the
symmetry of the structure. First-order or higher order phase
transitions leading to unconventional phase diagram
topologies. Lattice parameters can vary nonlinearly with
composition (depart from Vegard’s rule)
Fluorite Structure
 Fluorite Derivatives
• Parent cubic structure: CeO2, UO2,
PuO2, high T ZrO2 and HfO2
• Tetragonal and monoclinic distortions:
ZrO2 and HfO2
• Oxygen excess phases UO2+x, PuO2+x (?)
• Oxygen vacancy phases, M3+ and M2+
doping, e.g. YSZ, YxZr1-x O2-0.5x
• Pyrochlore
Crystal structure of defect-fluorite (Fm3m)

O
Zr+4
Gd+3
VÖ2
 Cubic stabilized MO2

 M4+ = Ln3+ + 0.5 oxygen vacancy

 High oxide ion conductivity which goes
through a maximum with increasing
doping
 Structural evidence for short range order
in cubic solid solutions
 Low T long range ordered phases
sluggish to form
Local ordering of vacancies in C-type rare
earth structure (bixbyite) Y2O3
Enthalpy of formation from m-ZrO2 and C-YO1.5 of c-
YxZr1-xO2-0.5x (YSZ)
 X-ray diffraction patterns of (a) Disordered
, Zr0.43Y0.57O1.96 c-YSZ phase
(b) Ordered Y4Zr3O12 δ-phase,
ΔH (ordered – disordered) is 0.4 ± 1.4 kJ/mol =
0short range order rules!!!
1500
(a)Disordered
(a) Disordered
1250
1250
Intensity
Intensity

1000
1000
750
750
500
500
250
250
0
0
10 20 30 40 50 60 70 80 90
10 20 30 40 50 60 70 80 90
2q
2q
1500
1500 (b) Ordered
1250
(b) Ordered
Intensity

1250
1000
Intensity

1000
750
750
500
500
250
0
250
0 10 20 30 40 50 60 70 80 90
10 20 30 40 50
2q 60 70 80 90
2q
Interaction Parameter for
Mixing in Fluorite Phase
 Generalizations

• Strong ionic size control on properties

• Negative heats of mixing related to siting
of bacanciues
• Prediction UO2-LnO1.5 should
have little stabilization unless U
is oxidized
Enthalpies of formation from oxides (UO2, UO3 and CaO or YO1.5) of samples with
as-synthesized oxygen contents. (b) Enthalpies of formation of modeled fully reduced
(all uranium tetravalent) UO2-CaO and UO2-YO1.5 solid solutions relative to UO2
and CaO or YO1.5. The correction for the effect of oxidation was made assuming that
oxidation of U4+ to U6+ in the solid solution matrix has the same enthalpy as
oxidation of UO2 to UO3.

a) b)
20 Ca 20
Y
0 0
D Hf , kJ/mol

-20 -20
0

-40 -40
Ca
Y
-60 -60

0 . 0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0
dopant concentration y in U1-yMyOz dopant concentration y in U1-yCayO2-y and U1-yYyO2-y/2
 Conclusions: Fluorite
 Short range order dominates the
thermodynamics
 Strongly negative heats of mixing are
compensated by much less than random
entropies of mixing
 The m-c transition has a much higher
enthalpy for HfO2 than ZrO2
 The ceria system is different because of
different short range order
 Ionic size determines the ordering and
enegetics
Spinel Structure
 SPINELS
• AB2O4, two octahedral and one
tetrahedral site per formula unit
• Normal A[B2}O4, inverse B[AB]O4,
random A1/3B2/3[A2/3B4/3]O4
• Cation distribution varies with T
• Effect on enthalpy and entropy of mixing
and thermodynamic properties
Octahedral Site Preference Energies

Experimental thermodynamic basis of site

preference energies and enthalpies of
formation of spinels. Crystal field effects
are but a small contribution
 “Thermochemistry of Iron Manganese Oxide Spinels”, S.
Guillemet-Fritsch, A. Navrotsky, P. Tailhades, H. Coradin, M.
Wang, J. Solid State Chemistry 178, 106-113 (2005)

20.0
(a)
DHf (from c-Fe 3O4 and
t-Mn3O4) (kJ/mol)

0.0

-20.0

-40.0

-60.0
0.0 0.2 0.4 0.6 0.8 1.0
x = Mn/(Mn+Fe)

Calorimetric studies of heats of formation of iron manganese

spinels confirm the ideas of oxidation-reduction energetics
presented in 1968 and quantify effects of tetragonal distortions.
Calcite and Dolomite Structure
Energetics in CaMg(CO3)2-CaFe(CO3)2
 CONCLUSIONS
• Must consider structural details to
formulate thermodynamics properly
• Many unanswered questions, lots of
work for you, the students and future
generation of investigators.
• Lots of fun !!