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ISSN 10876596, Glass Physics and Chemistry, 2013, Vol. 39, No. 2, pp. 182–192. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © D.A. Zamyatin, Yu.V. Shchapova, S.L. Votyakov, N.N. Eremin, V.S. Urusov, 2013, published in Fizika i Khimiya Stekla.

Structure and Thermodynamic Properties of Zircon–Coffinite Solid

Solutions according to the Semiempirical Atomistic Simulation Data
D. A. Zamyatina, Yu. V. Shchapovaa, S. L. Votyakova, N. N. Ereminb, and V. S. Urusovb
a
Institute of Geology and Geochemistry, Ural Branch, Russian Academy of Sciences,
Pochtovyi per. 7, Ekaterinburg, 620075 Russia
email: dzamyatin85@gmail.com
b
Department of Geology, Moscow State University, Moscow, 119991 Russia
Received August 18, 2011

Abstract—Structure and thermodynamic properties of zircon, coffinite, and zircon–coffinite solid solutions
were subject to semiempirical atomistic simulation on the assumption of compositional disordering of mixed
crystals: (Zr1 – x, Ux)SiO4, where x = 0.02, 0.05, 0.08, 0.11, 0.14, 0.28, 0.50, 0.72, and 0.86. The solid solu
tions significantly depart from the Vegard and Retgers laws. The (Zr1 – x, Ux)SiO4 mixed crystal structure is
characterized by anisotropic expansion (largely in the a and b directions) under growth in x related to anisot
ropy of structural relaxation degree of the cation–oxygen interatomic spacing in the (Zr, U)O8 polyhedron.
Increase in x parameters is accompanied by increase in average size of cation–oxygen polyhedrons and
silica–oxygen tetrahedrons and by growth of interatomic spacing dispersion; maximum dispersion values are
observed at x = 0.5–0.6. The distortions in local structures of ZrO8 and UO8 dodecahedrons and silica–oxy
gen tetrahedrons in the solid solution were analyzed on the basis of calculated functions of interatomic dis
tance distribution. The obtained results demonstrate the possibility to assess numerically the structural (geo
metrical) disordering degree of the compositionally disordered solid solution depending on its composition.
The calculated thermodynamic characteristics of solid solutions forecast the following solubility range limits:
2 mol % USiO4 in zircon and 5 mol % ZrSiO4 in coffinite under ~1750 K.

Keywords: zircon, coffinite, solid solution, semiempirical atomistic simulation, GULP, parameters of poten
tials, local structure, thermodynamic parameters, mixing properties, and solubility range
DOI: 10.1134/S108765961302017X

INTRODUCTION there are data on solid solutions with the coffinite

Synthetic matrixes based on zircon (zirconium
orthosilicate, ZrSiO4) are regarded as a promising
material of waste forms to recover radioactive ele
ments [1, 2]. Natural zircon is a very important min
eralgeochronometer and concentrator of isomorphic
trace elements, including radioactive uranium. Zircon
can form solid solutions with coffinite (uranium
orthosilicate, USiO4) isostructural to it in a limited
range of compositions (for instance, [3]). The prop
erties of the mixed system such as zircon–coffinite
(Zr1 – x, Ux)SiO4 (x is USiO4 mole fraction) are poorly
studied in spite of the fact that they are very important
for forecasting of stability, superficial reactivity, and
chemical properties of synthetic wasteforms and nat
ural materials under different temperatures and pres
sures. The few experimental data [2, 4, 5] are indica
tive of poor mixability of zircon and coffinite and non
ideality of solid solutions, but the solubility range has
not been determined yet. The USiO4 solubility range
in zircon is estimated at x = 0.02–0.04 [4] and at x <
0.10 under 1173 K [5]. The natural zircon samples
commonly contain <5000 ppm U [6]; meanwhile,
mole fraction of up to x = 0.11 [3, 7]. Similar uranium
contents (x ~ 0.10) were noted for zircon inclusions in
the Chernobyl technogenic lavas as complex con
glomerates formed from hightemperature melts in
the course of the accident at the Chernobyl Electric
Power Station in 1986 [8, 9]. Highuranium natural
zircons are suggested to be thermodynamically unsta
ble [3, 10, 11]; in this case, the occurrence of exsollu
tion structures typical of unstable solutions is related
to the low cation diffusion factors of zircon [12]. In
some works (for instance, [13]), the researchers sug
gest that the mutual solubility range and stability of
natural solid solutions such as zircon–coffinite can be
improved relative to synthetic samples owing to the
occurrence of additional elements, for instance, Y, P,
and OHgroups.
Thermodynamic properties of solid solutions
depend on local tension and structure deformation
appearing under cation substitution [14–16]. The zir
con–coffinite system is expected to be characterized
by relatively high structural tensions due to the great
difference in ionic radiuses of Zr4+ and U4+ cations
(0.84 and 1.00 Å, respectively [17]). It should be noted

182
 STRUCTURE AND THERMODYNAMIC PROPERTIES
that, in the case with the natural uraniumbearing zir
cons, the pattern of local tensions and structural
deformations can be additionally complicated by dis
ordering effects (metamictization) due to selfirradia
tion of the samples under αdisintegration of uranium
isotopes [18]. The experimental studies of deforma
tion structure of the zircon–coffinite solid solutions
have a short story. The (Zr1 – x, Ux)SiO4 technogenic
microcrystals (x = 0.006–0.116) from the Chernobyl
lavas were studied by Raman microspectroscopy [19].
Having analyzed the frequency shift of SiO4 tetrahe
dron oscillations, the authors noted the growth of
average Si–O distance in the solid solution with
increase in the USiO4 content under insignificant dis
tortion of a tetrahedron form. The line broadening of
SiO4 tetrahedron lattice modes with increase in the
USiO4 content was interpreted as the result of growing
deformations and tensions in the solution structure.
Based on the different broadening of modes with dif
ferent symmetry, it can be suggested that the most sig
nificant local structure distortions are characteristic
for the plane direction (ab) and the least significant
distortions are typical of the direction c in crystals.
This suggestion is in good agreement with the data on
anisotropy of zircon structural disordering under radi
ation damage [20].
The application of computer simulation methods
to study structure and thermodynamic properties of
the zirconbased actinidebearing solid solutions is
limited by the recent work [13]; the point impurity
defects of U4+ → Zr4+ were studied previously [21–
24]. The authors of [13] estimated the thermodynamic
properties by the calculation of total energy of compo
sitions and configurations of solid solutions using the
DFT/LDA method (VASP program), application of
obtained data to calculate the optimum set of param
eters of cation interaction in solutions, determination
of excess mixing enthalpy of two solid solutions using
the MonteCarlo algorithm, and by the following
thermodynamic integration and calculation of free
energy and mixing entropy values. As a result, the
authors obtained the coffinite solubility limit in zircon
attaining 0.01 mol % at 1000 K indicating almost no
solubility at all and forecasted the formation of exsol
lution structures due to thermodynamic instability of
the (Zr1 – x, Ux)SiO4 solid solution relative to minerals
and constituent simple oxides. The local structure of
solid solutions was not studied previously.
Hence, the data on thermodynamic properties of
the zircon–coffinite solid solutions are very ambigu
ous, their structure is poorly studied, and investigation
in this direction remains a topical materials science
task. The detailed information on mixing properties
and structure of compounds with a covalent chemical
bonding can be acquired using semiempirical struc
tural simulation by the method of atom pair potentials
[25]. As was shown previously for the binary and ter
nary oxide and silicate solid solutions (for instance
GLASS PHYSICS AND CHEMISTRY Vol. 39 No. 2
183
[26]), such calculation data are in good compliance
with the experimental results.
This investigation objective is to simulate structures
and thermodynamic properties of the zircon–coffinite
solid solutions by the semiempirical method of inter
atomic potentials.
CALCULATION METHODS
The equilibrium structure of zircon and coffinite
and their solid solutions was estimated using the
GULP program [25]. This program represents a crys
tal as a complex of point ions participating in longdis
tance electrostatic (Coulomb) and shortdistance
interactions and following minimization of total
energy of interatomic interactions in a crystal (crystal
structural energy) under variations in coordinates of
all atoms. To calculate the structural energy, the Cou
lomb potentials of ion attraction–repulsion
2
e ZiZ j
=
Vijel (rij ) (Zi, Zj are charges of ions i and j, rij is
rij
ion spacing, and e is electron charge) are summed up
for the whole crystal using the Ewald method [27].
The shortdistance interactions are commonly
described by the Buckingham potential acting within
the sphere with a radius Rmax = 6–12 Å. The three
body angular deformation potential is used to simulate
the directional effects of the Si–O tetrahedron bonds;
the Morse potential is introduced to take into account
the effects of partial covalence bond character.
Numerical parameters in the functions constructed to
obtain the potentials (Table 1) were estimated by the
iterative approximation of calculated and experimen
tal values of zircon and coffinite structural and physi
cal characteristics [28–31] (Table 2). The calculations
were performed at the approximation of similar
numerical parameters of the silica–oxygen sublattice
potentials (Buckingham potential for Si–O, O–O and
threebody potential for O–Si–O) for all composi
tions of solid solutions. The startup values of effective
cation and ion charges were taken from our nonempir
ical, quantumchemical calculations of zircon and its
isomorphic uranium impurity [32] (+2.70, +3.07,
+2.30, and –1.27 el. ch. un. for Zr, U, Si, and O,
respectively). After the optimization procedure, the
indicated values attained +2.80, +2.80, +2.20, and
–1.25 e0, respectively.
Absolutely compositionally disordered solutions
were simulated due to absence of any experimental
data on disordering effects in cation distributions. The
BINAR program was used to create the disordered
uranium cation distribution in zircon positions [33].
The calculations were carried out using the zircon
extended cell (supercell) (Zr, U)64Si64O256 with a size
of 2 × 2 × 4. The BINAR program algorithm is based
on the analysis of disordering degree of numerous ran
dom configurations obtained by random location of
2013
184 ZAMYATIN et al.

Table 1. Parameters of interatomic potentials

Buckingham potential Atom 1 Atom 2 A, eV ρ, Å C, eV Å6 rmin, Å rmax, Å

Si O 301 0.318 0 0 8
Zr O 1139.9 0.315 0 0 8
V B (r ) = A exp(− r ) − Cr −6
ρ U O 1638.3 0.319 0 0 8
O O 4048.394 0.27047 0 0 8
Morse potential Atom 1 Atom 2 D, eV a, Å –2 r0, Å rmin, Å rmax, Å

⎛
( −a(r −r0)
) ⎞
2 Zr Si 1.45 1.85 2.5 0 8
V M (r ) = D ⎜ 1 − e − 1⎟
⎝ ⎠ U Si 0.83 1.85 2.3 0 8
kB,
Threebody potential Atom 1 Atom 2 Atom 3 θ0, deg rmin, Å rmax, Å
eV rad–2
Si O O 1.09724 109.47 0 1.9
0 (Si–O)
Vth(θ) = 1 kB (θ − θ 0 )
2
2 3.5
(O–O)

uranium and zircon atoms in the crystal sublattice
using the random number generator and by rejection
of configurations not meeting the disordering crite
rion. This criterion represents a sum of squared devia
tions of a number of heterogeneous atomic pairs in the
second coordination sphere for random configuration
from the statistical theoretical histogram (Pearson’s
fitting criterion χ2). As a result, we obtain the solid
solution configuration corresponding to the disor
dered location of cations by positions to the fullest
extent.
Structure and properties were estimated for zircon
and coffinite minerals and for (Zr1 – x, Ux)SiO4 solid
solutions, where x = 0.02, 0.05, 0.08, 0.11, 0.14, 0.28,
0.50, 0.72, and 0.86.
RESULTS AND DISCUSSION
Zircon and coffinite local structure and properties.
It is known that the solid solution final members—zir
con and coffinite—are isostructural and are charac
terized by the tetragonal crystallizations system, the
space group I41/amd; all cations occupy the positions
with symmetry 4 2m; oxygen occupies the position
with symmetry m [34] (designations after [35]). The
isolated SiO4 tetrahedrons (somewhat extended along
the axis c) have joint ribs along the axis c and joint tops
along the directions a, b with the MeO8 (Me = Zr, U)
dodecahedrons. The dodecahedrons have four elon
gated Me–Oe bonds providing the relation to SiO4 tet
rahedrons by joint ribs in the direction c and four com
pressed Me–Oc bonds providing the relation to SiO4
tetrahedrons by joint tops in the directions a, b. All
oxygen atoms are crystallographically equivalent and
have a trinary coordination (Me, Me, Si).
The application of interaction potentials and
numerical parameters in Table 1 provided the possibil
ity to attain a satisfactory consistency of experimental
and calculated structural and other physical charac
teristics of zircon and coffinite (Table 2). In particular,
the calculated constant values of the zircon lattice a
and c deviated from the experimental data [28] by δa =
0.1 and δc = 0.5%; this fact is indicative of some
improvement in consistency between the semiempiri
cal atomistic simulation data and experimental results
relative to δa = –0.2% and δc = 1.0% [21], δa =
⎯0.7 and δc = 1.5% [22], and δa = –2.5 and δc = 5.4%
[23]. The calculated values of the cation–oxygen
ranges deviate insignificantly from the experimental
data [28, 29]: by 2.6% at most for Zr–Oc, Zr–Si, and
Si–O and by 4.5% for Zr–Oe in zircon; by 1.7% at
most in coffinite. The estimated macroscopic proper
ties are in satisfactory compliance with the experimen
tal data (Table 2); most elastic moduli are character
ized by similarity of calculated values to the experi
mental data [30, 31] that are variable for zircon
samples of different origin and describe better the zir
con elastic properties than the following calculation
results: (C11 = 560, C12 = 28.7, C13 = 151.8, C33 =
669.9, and C44 = 102.7 GPa) [22] and (C11 = 450.2,
C12 = 62.8, C13 = 177.8, C33 = 509.4, C44 = 112.9, and
C66 = 10.7 GPa) [23]. As a whole, the applied model
should be regarded as adequate enough to forecast the
zircon and coffinite structure and properties and can
be used in the simulation of solid solutions.
The zircon–coffinite solid solution structure. Con
centration dependences of deviations Δf = fcalc – fadd of
calculated fcalc parameters (fcalc is lattice constant a, b,
c; ρ is density) from the additive dependence on solid
solution composition fadd = f1 (1–x) + f2 x (x is mole

GLASS PHYSICS AND CHEMISTRY Vol. 39 No. 2 2013

 STRUCTURE AND THERMODYNAMIC PROPERTIES 185

Table 2. Calculated and experimental characteristics of zircon and coffinite

Zircon Coffinite
Structural data
Experiment Experiment
Parameters Calculation Deviation**, % Calculation Deviation, %
[28] [29]
a, Å 6.613 6.607 0.1 7.076 6.995 1.2
c, Å 6.01 5.982 0.5 6.332 6.263 1.1
Volume V, Å 3 262.89 261.12 0.7 317.03 306.45 3.5
Density, g/cm3 4.63 4.6–4.7 – 6.92 5.1–7.2 –
Me*–Si spacing, Å 3.006 2.991 0.5 3.17 3.132 1.2
Me–Oc spacing, Å 2.133 2.13 0.1 2.357 2.319 1.6
Me–Oe spacing, Å 2.371 2.269 4.5 2.491 2.513 –0.9
Si–O spacing, Å 1.581 1.622 –2.5 1.609 1.582 1.7
O–Oi spacing, Å 2.476 2.43 1.9 2.502 2.518 –0.6
2.674 2.494 7.2 2.915 2.948 –1.1
2.633 2.752 –4.3 2.688 2.616 2.8
2.841 2.842 0.0 3.05 3.308 –7.8
3.105 3.071 1.1 3.43 3.391 1.2
Physical properties
Experiment Experiment
Parameters Calculation Calculation
[30] [31]
Entropy at 300 K, 96.19 – – 118.0
J/mole · K
Heat capacity Cv, 107.7 – – 114.2
J/mole · K
C11, GPa 313.5 423.7 258.5 241.7
C12, GPa 44.1 70.3 179.1 15.2
C13, GPa 95.4 149.5 154.2 66.9
C33, GPa 377.1 490 380.5 285.4
C44, GPa 76.6 113.6 73.3 62.4
C66, GPa 46.2 48.5 111.3 18.3
Dielectric constant 10.51 8.3–9.0 – 7.1
Note: ( *) Me = Zr, U; (**) Relative difference of experimental and calculated parameters.

fraction of USiO4; f1 and f2 are zircon and coffinite
parameter values) are given in Fig. 1. As is seen in
Fig. 1a, the constants a(b) are characterized by posi
tive deviations from the additive function (Vegard
law), while the constant c is characterized by negative
deviations. This result is indicative of anisotropy of
structural deformations in the mixed crystal: increase
in elementary cell size appears to be greater in the
directions a(b) and less significant in the direction c
than might be expected with account for growth of
average cation size in dodecahedron positions under
the U → Zr substitution. The calculations yielded the
negative deviation of mole volume ΔV of the zircon–
coffinite system and positive deviation of density Δρ
(Fig. 1b) from the additive dependence on composi
tion (Retgers law). The traditional theory of solid solu
tions relates such behavior with the interactions
between cations substituting each other and possible
formation of superstructures [36]. It is quite possible
that the interactions between U and Zr in adjacent
dodecahedrons are really characteristic for the (Zr1 – x,
Ux)SiO4 solid solution. This suggestion is based on our
data on electronic structure of uranium impurity in
zircon [32] that demonstrated significant differences
in electronic structure of oxygen atoms O(Zr, U, Si)
common for the ZrO8 and UO8 dodecahedrons rela
tive to oxygen atoms O(Zr, Zr, Si) in zircon. Mean
while, it should be noted that we were not focused on
simulation of the ordering effects and the obtained

GLASS PHYSICS AND CHEMISTRY Vol. 39 No. 2 2013

186 ZAMYATIN et al.

Δa regularity for ΔV and Δρ should be regarded as a result

0.015 (a)
Δb
of specific geometrical features of the zircon structure
causing its anisotropic deformation under the Zr → U
Δa, Δb, Δc, Å

0.010 Δc substitution.
The solid solution formation is accompanied by the
0.005 considerable distortions in local structures of the ZrO8
and UO8 dodecahedrons relative to pure components,
such as zircon and coffinite, due to variation of both
average spacing values (size of polyhedrons) and their
–0.005 scatter. The variations in average values of cation–
oxygen spacing are adequately approximated by the
0.12 linear dependences on solution composition (Fig. 2),
(b) which graphically occur between straight lines corre
0.10 sponding to a virtual crystal (additive variations in
interatomic spacing, Fig. 2) and straight lines corre
0.08 sponding to constancy of individual cation–oxygen
spacing (bond alternation model, Fig. 2). Increase in
Δd, g/cm3

0.06 the parameter x is accompanied by increase in average

cation–oxygen spacing; in this case, the increase in
0.04 Zr–Oc and U–Oc spacing is more significant than in
0.02 Zr–Oe and U–Oe. When passing from zircon to coffi
nite, average spacing of four short Me–Oc bonds
0 increases by 10%, while that of four long Me–Oe
0 0.2 0.4 0.6 0.8 1.0 bonds increases by 5%.
x, mol
The average relaxation degree of cation positions
Fig. 1. Concentration dependences of deviations of (a) (cation–oxygen bond length) relative to their hypo
calculated lattice and (b) density constants from additive thetic relaxation in a virtual crystal can be numeri
dependence on solid solution composition. The curve of
variations in these values depending on the composition is cally described by the position site compliance
indicated with a dashed line. parameter [37]:

2.5
1
2
2.4

ZrSiO4
Rzo

2.3 3
USiO4

2.2

2.1
0 0.2 0.4 0.6 0.8 1.0
x, mol

Fig. 2. Concentration dependences of the (1) U–Oe, (2) Zr–Oe, (3) U–Oc, and (4) Zr–Oc average interatomic distances in the
(Zr1 – x, Ux)SiO4 solid solutions. Linear approximation of calculated values is indicated with a solid line; additive variations in
interatomic distances in the virtual crystal model are indicated with a dashed line; a dash–dot line indicates individual distances
of impurity cation–oxygen in a host crystal in the bond alternation model.

GLASS PHYSICS AND CHEMISTRY Vol. 39 No. 2 2013

 STRUCTURE AND THERMODYNAMIC PROPERTIES 187

(a) (b) (c)

(Si–O)z
(Zr–Oc)z (Zr–Oe)z (U–Oc)c (U–Oe)c

x = 0.02

x = 0.02 x = 0.02
x = 0.05
x = 0.05
x = 0.05

x = 0.08
x = 0.08 x = 0.08

x = 0.11 x = 0.11 x = 0.11

x = 0.14 x = 0.14
x = 0.14

2.0 2.1 2.2 2.3 2.4 2.5 2.1 2.2 2.3 2.4 2.5 2.6 1.50 1.54 1.58 1.62 1.66
Zr–O, Å U–O, Å Si–O, Å

Fig. 3. Distribution functions of the (a) Zr–O, (b) U–O, and (c) Si–O interatomic distances in the supercell composed of
384 atoms for the (Zr1 – x, Ux)SiO4 solid solutions, x = 0.02–0.14. The dashed lines correspond to calculated distances for (Zr–
Oc)z, (Zr–Oe)z, (Si–O)z in zircon and (U–Oc)c, (U–Oe)c in coffinite.

Rsol.solut. − R way for zircon and uranium atoms in the directions

cs = , a(b). Meanwhile, the cs value of Zr–Oe is much lower
Radd − R
where Rsol.solut. is average value of cation–oxygen spac
ing in a solution with given composition, Radd is addi
tive value of cation–oxygen spacing in a virtual solu
tion with given composition, and R is spacing in a pure
crystal [26]; the closer cs to 1, the closer a solid compo
sition to a virtual crystal. cs = 0.48 for Zr–Oc and 0.39
for Zr–Oe that is indicative of less variability (site
compliance) of average Zr–Oe spacing in the mixed
crystal relative to Zr–Oc. This result can be explained
by anisotropy in the conjugated SiO4 and ZrO8 poly
hedrons in the zircon structure (joint tops due to
Me⎯Oc bonds in the directions a(b) and joint ribs due
to the Me–Oe bonds in the direction c) leading to the
facilitated structure deformability in the directions
a(b) relative to the direction c. These data explain the
reason of anisotropy of the mixed crystal elementary
cell deformation. The analogous conclusion on
anisotropy of local deformations of the zircon–coffi
nite solid solutions was made [19] on the basis of
experimentally identified differences in expansion of
Roman spectra corresponding to oscillation modes of
different symmetry. The obtained result is also consis
tent with the known data on anisotropic (largely, in the
directions a, b) decrease in the zircon lattice constant
values under annealing of radiation damage in its
structure [20, 38]. The cs values attain 0.44 and 0.57 for
U–Oc and U–Oe interatomic spacing, respectively.
The cs value of U–Oc is similar to that of Zr–Oc; i.e.,
the cation–oxygen bond lengths relax in an analogous
than that of U–Oe; i.e., the average interatomic spac
ing of Zr–Oe appears to be a more conservative value
than that of U–Oe.
The calculated average values of oxygen–silica
spacing also increase monotonously in the solid solu
tion from 1.58 to 1.61 Å under the transition from zir
con to coffinite. Oxygen–silica tetrahedrons grow by
3 × 10–4 Å/mol % U with increase in the uranium con
tent in zircon. These variations are consistent with the
red shift of valence vibration frequencies ν1 (974 cm–1)
and ν3 (1008 cm–1) of SiO4 tetrahedrons
under increase in the uranium concentration in zircon
identified by the Roman spectroscopy [19].
Taking into account the shift values of these lines
(⎯0.67 cm–1/mol % U and –0.75 cm–1/mol % U,
respectively [19]) on the assumption of key effect of
the bond length on vibration frequency, the size
parameter of vibration frequency shift of the oxygen–
silica tetrahedrons in the solid solution can be esti
mated at ~2.4 × 103 cm–1/ Å.
The spacing distribution functions representing the
dependences of a number of cation–oxygen inter
atomic distances on values of these distances (in the
supercell composed of 384 atoms) are demonstrated in
Fig. 3 for solid solutions with x = 0.02–0.14. The solu
tions with such composition are of special interest
because they are used in practice. It is seen that the
positions of main maximums of Zr–Oc, Zr–Oe, and
Si–O distances are similar to the calculated values for
defectless crystalline zircon (Figs. 3a, 3c); increase in

GLASS PHYSICS AND CHEMISTRY Vol. 39 No. 2 2013

188 ZAMYATIN et al.
0.06
0.05
Sx, Å 0.04
0.03
0.02
0.01
0 0
0 0.2
Fig. 4. Concentration dependences of mean square deviation of the (1) Zr–Oc, (2) Zr–Oe, (3) Si–O, (4) U–Oc, and (5) U–Oe
(points) atomic distances from their average values in their supercell composed of 384 atoms for the (Zr1 – x, Ux)SiO4 solid solu
tions and concentration dependence of Zr(Eg) lattice vibration band width in the Roman spectra [19] (dashed line) obtained by
the approximation of experimental data.
x is accompanied by growth of indicated distances,
splitting of distribution peaks, and increase in their
width. Appearance and growth of additional peaks in
the Zr–O spacing distribution functions with increase
in x parameter reflect the distortions in structure of the
second coordination sphere of impurity uranium.
According to the data obtained in the course of the
analysis of local deformations, the Zr–Oe spacing of
~2.32 Å in length (somewhat lower that the calculated
value of major peak) appears in the ZrO8 dodecahe
drons related to UO8 through the SiO4 tetrahedrons in
the axis direction c. Somewhat compressed distances
of Zr–Oc (~2.07–2.09 Å) and somewhat elongated
distances of Zr–Oe (~2.40 Å) appear in the ZrO8
dodecahedrons related to UO8 by joint ribs. The adja
cent SiO4 tetrahedrons are also deformed thus provid
ing the appearance of new peaks (1.55 and 1.62 Å) in
the Si–O spacing distribution function. Analogous
variations are observed in the distribution of U–Oc
and U–Oe distances (Fig. 3b); in this case, the
increase in average uranium–oxygen distances in the
solid solution and their similarity to the calculated val
ues of defectless coffinite (Fig. 3b) is provided by both
the shift of spacing distribution major peak (for U–Oc)
and the appearance of new distribution components
(for U–Oe). It should be noted that the last effect is
less noticeable for the Zr–O distribution due to statis
tically less significant distortions in the ZrO8 dodeca
hedrons at the background of undistorted matrix at x =
0.02–0.14. The second coordination sphere deforma
30
Zr(Eg) vibration band width, cm–1
25
20
15
1
2 10
3
4 5
5
0.4 0.6 0.8 1.0
x, mol
tion by point impurity atoms in zircon was analyzed in
detail previously [24].
The obtained data were used to calculate the mean
square deviation of interatomic distances from their
average values in the supercell:
∑ n (x − x )
i i
2
Sx = i
,
∑n −1 i
i
where xi is interatomic distance, ni is a number of such
distances in the supercell, and x = ∑ ni x i ∑ ni is
i i
average interatomic distance. The dependence of Sx
on solid solution composition is shown in Fig. 4. The
Sx values characterize in a numerical way the structural
(or geometric) disordering degree of the mixed crystal
that is, in our case, absolutely compositionally disor
dered judging by the supercell generation method. The
Sx values bring great physical sense, because they con
trol the heterogeneous broadening of spectral param
eters [39] and affect the system thermodynamic func
tions [14, 40]. Increase in the parameter x is accompa
nied by dispersion development for all types of
interatomic distances attaining the maximum values
in the range of x = 0.5–0.6. The most significant dis
persion of interatomic distances is characteristic for
the Zr–Oe bonds, where the average value in the
supercell appears the most conservative, as was indi
cated previously. The contributions of other inter
atomic distances, including Si–O, to the disordering
GLASS PHYSICS AND CHEMISTRY Vol. 39 No. 2 2013
 STRUCTURE AND THERMODYNAMIC PROPERTIES
are much lower and similar. Hence, the zirconium–
oxygen sublattice provides the major contribution to
the structural disordering of the solid solution. The
calculated Sx concentration dependences are com
pared in Fig. 4 with the concentration dependence of
Raman spectra Zr(Eg) lattice vibration band width
[19] obtained by the authors by the approximation of
experimental values for the samples with x = 0.006–
0.116 on the whole composition range using the func
tion Γ(x) = Wx(1 – x) + Γ0 (Γ(x), Γ0 = 2.8 cm–1 (band
width in solid solution and zircon at room tempera
ture; W = 107.9 is adjustable parameter). The estab
lished fact that the solid solution is the most disor
dered in the mean concentration range is consistent
with the data on the band sharp broadening with
increase in the uranium concentration. The predomi
nant scatter in Zr–O interatomic spacing relative to
Si–O is consistent with the experimental data in [19]
on more significant expansion of lattice modes involv
ing the vibrations of both cation and silica–oxygen
sublattices relative to the expansion of localized vibra
tion modes of the SiO4 tetrahedrons. It should be
noted that the calculations forecast an asymmetrical
form of the broadening–composition dependences
with the maximum shifted relatively to the center
towards the coffinite predominance field. There is no
experimental data on solid solutions similar to coffi
nite in the scientific literature. The performed calcula
tions demonstrate the possibility to estimate numeri
cally the structural disordering degree of the solid
solutions under the semiempirical atomistic simula
tion.
Thermodynamic properties of the (Zr1 – x, Ux)SiO4
system. Taking into account the additive character of
the thermodynamic function (TF), the solid solution
mixing functions (differences of solid solution TF and
mechanical mixture TF components) take the follow
ing form:
ΔGmix = ΔHmix – TΔSmix = ΔUmix + PΔV – TΔSmix , (1)
where ΔHmix, ΔUmix, and ΔSmix are enthalpy, energy,
and entropy, respectively;
ΔGmix = G(x) – x1G1 – x2G2, (2)
ΔHmix = H(x) – x1H1 – x2H2 , (3)
ΔUmix = U(x) – x1U1 – x2U2, (4)
where x1 and x2 are mole fractions of the solution com
ponents; H1, H2, U1, and U2 are enthalpy and energy of
forming pure components in the solution; H(x) and
U(x) are energy and enthalpy of the solid solution for
mation. Taking into account the fact that, under ordi
nary pressures, the work vs. pressure value PΔV can be
neglected under variations in volume, the mixing
enthalpy can be calculated by the approximation for
mula:
ΔHmix ≈ ΔUmix = U(x) – U1x1 – U2x2. (5)
GLASS PHYSICS AND CHEMISTRY Vol. 39 No. 2
189
The solid solution mixing entropy can be calcu
lated by the following formula:
ΔSmix = Sconf + ΔSvib, (6)
where ΔSvib = Svib(x) – S1x1 – S2x2 is vibration entropy
of mixing; Sconf = R(x1lnx1 + x2lnx2) is configurational
entropy of singleposition binary solid solution. Then,
it is accepted that the ΔSvib value depends only on
composition and is slightly dependent on tempera
ture; this suggestion is based on the calculation data on
temperature dependences of vibration entropy in zir
con, coffinite, and their solid solutions.
The equations (1), (5), and (6) make it possible to
estimate the thermodynamic functions of ΔHmix and
ΔGmix mixing in the whole composition and tempera
ture range using the values of structural energy U(x)
and vibration energy Svib(x) calculated for solid solu
tions and U1, U2 , S1, S2 for pure components (zircon
and coffinite) using the GULP program. Moreover,
the interaction between the solution components can
be estimated on the basis of calculated mixing
enthalpy:
Q = ΔHmix /x1x2. (7)
The higher the interaction value, the lower the
mutual solubility of the components. If the interaction
parameter does not depend on the solid solution com
position, the solution is considered to be regular, and
critical disintegration temperature of such solution
can be estimated at T = Q/4 (Q, cal/mole); in the gen
eral case, Q can be a certain composition function.
The Q value depends considerably on local deforma
tions of the solid solution structure.
The TF concentration dependences are demon
strated in Fig. 5. The system structural energy grows
with increase in the coffinite content in the solution
(Fig. 5a). The solid solution formation enthalpy in the
intermediate composition range is characterized by
relatively high values (Fig. 5b) and is, thus, indicative
of low mutual solubility of zircon and coffinite. The
interaction parameter can be approximated by the lin
ear dependence on composition (Fig. 5c). Hence, the
(Zr1 – x, Ux)SiO4 solutions are described by the subreg
ular model. The concentration dependences ΔGmix
under different temperature (Fig. 5e) calculated with
account for the entropy contribution (Fig. 5d) provide
the possibility to determine the critical solubility con
ditions in view of zero value of the second and third
free energy derivatives. For the compositions with x >
0.1, the curve ΔGmix bends corresponding to the sec
ond derivative zero are recorded only at T > 2000 K.
ΔGmix is positive at T < 1500 K in the whole composi
tion range and is, thus, indicative of no solubility. Fig
ure 5f demonstrates the solvus curve. The solubility
limit is 2 mol % USiO4 for zircon and 5 mol % ZrSiO4
for coffinite at ~1750 K. Hence, the calculation results
obtained for the compositionally disordered zircon–
coffinite solid solutions forecast much lower solubility
2013
190 ZAMYATIN et al.

(а) 7 (d) 1
2
–8900 6
5
U, kJ/mol

S, kJ/(mol K)
–9000
4

–9100 3
2
–9200
1
4
14 (b) 1 (e)

12 3
ΔHmix, kJ/mol

10 2

ΔGmix, kJ/mol
2 3
8 4
1 5
6 6
4 0
2
–1
0
2400
(c) (f)
2300
70
2200
2100
Q, kJ/mol

60
2000
T, K

50 1900
1800
40 1700
1600
30 1500
0 0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0
x x
Fig. 5. Concentration dependences of thermodynamic characteristics of the (Zr1 – x, Ux)SiO4 solid solutions with a view to a for
mula unit: (a) lattice structural energy, U; (b) mixing enthalpy, ΔHmix; (c) interaction parameter, Q; (d) (1) mixing entropy, ΔSmix;
(2) vibration entropy, ΔSvib; (solid line) configuration entropy, ΔSconf; (e) Gibbs mixing energy ΔG at T = (1) 1550, (2) 1750,
(3) 1800, (4) 1850, (5) 1900, and (6) 1950 K obtained by the approximation of calculated values by the fourth order polynominal;
(f) solvus of the zircon–coffinite system; the indicated errors of points correspond to the accuracy of graphical determination.

limits in the system relative to the experimental data
reporting the USiO4 solubility limit in zircon as x =
0.02–0.04 [4] and x < 0.10 at 1173 K [5]. Analogous
results were obtained in the calculation work of [13],
where the coffinite solubility limit in zircon was esti
mated at 0.01 mol % at 1000 K. It can be concluded
that pure waterfree synthetic and natural zircon–
coffinite solid solutions are thermodynamically non
equilibrium. The existence of natural zircons with up
to 5000 Ma–1 U [6] and over [3, 7] can be caused by the
occurrence of additional trace elements, for instance,
Y, P, and OHgroups, and by the miscibility range
expansion due to composition complication, and also
by the effects of mineral disordering and amorphiza
tion under αdisintegration of uranium and its child
elements.
CONCLUSIONS
We offered and substantiated the coordinated
parameters of interatomic potentials describing the
interaction between Zr, U, Si, and O atoms to estimate

GLASS PHYSICS AND CHEMISTRY Vol. 39 No. 2 2013

 STRUCTURE AND THERMODYNAMIC PROPERTIES
the zircon–coffinite solid solution structure and prop
erties.
We simulated the structure of pure components and
(Zr1 – x, Ux)SiO4 solid solutions, where x = 0.02, 0.05,
0.08, 0.11, 0.14, 0.28, 0.50, 0.72, and 0.86, on the
assumption of their compositional disordering.
Local structure and thermodynamic characteristics
were analyzed. The compositionally disordered zir
con–coffinite solid solutions demonstrate significant
deviations from the Vegard and Retgers laws. We
identified the anisotropic structural expansion
(largely, in the directions a, b) of the mixed crystal
such as (Zr1 – x, Ux)SiO4 due to increase in the x
parameter. Average cation–oxygen distances grow due
to increase in x; in this case, the increase in Zr–Oc and
U–Oc distances is more significant than that in Zr–Oe
and U–Oe; there is also some growth of the SiO4 tetra
hedrons. The dispersion of all interatomic distances
grows due to increase in x in the lowcoffinite range;
the dispersion is maximum for the U–Oc and U–Oe
bonds at x = 0.08–0.14; at x = 0–0.14 the scatter in
cation–oxygen interatomic spacing increases in the
range of Si → Zr → U. The cation–oxygen sublattice
provides the greatest contribution to the structural dis
ordering.
The distortions in local structures of the ZrO8 and
UO8 dodecahedrons and silica–oxygen tetrahedrons
in the solid solution were analyzed on the basis of cal
culated functions of the interatomic spacing length
distribution. The obtained results demonstrate the
possibility to estimate numerically the structural (geo
metric) disordering degree of the compositionally dis
ordered solid solution depending on its composition.
The calculation data on thermodynamic characteris
tics of solid solutions forecast the solubility limit of
2 mol % USiO4 for zircon and 5 mol % ZrSiO4 for
coffinite at ~1750 K.
ACKNOWLEDGMENTS
The work was supported by the Federal Target Pro
gram “Scientific and ScientificPedagogical Person
nel of Innovative Russia” for 2009–2013 (state con
tract no. 02.740.11.0727), Programs of the Presidium
of the Russian Academy of Sciences, nos. 20 and 23,
the Ural Branch of the Russian Academy of Sciences,
“Composition, Structure, and Physics of Radiation–
Thermal Effects in the Range of Oxide, Silicate, and
Phosphate Minerals as a Basis for Geochronometric
Constructions and Creation of Materials for Utiliza
tion of Highly Active LongLiving Radionuclides,”
and the Russian Foundation for Basic Research
(project nos. 090500513, 110500035, and 0905
00403).
GLASS PHYSICS AND CHEMISTRY Vol. 39 No. 2
191
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Vol. 39 No. 2 2013