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A Size-Dependent Phase Map and Phase Transformation Kinetics for

Nanometric Iron(III) Oxides (γ→ε→α Pathway)

Article  in  The Journal of Physical Chemistry C · May 2016

DOI: 10.1021/acs.jpcc.6b05287

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Size-Dependent Phase Map and Phase Transformation Kinetics for

Nanometric Iron(III) Oxides (γ → ε → α Pathway)
Seungyeol Lee and Huifang Xu*
NASA Astrobiology Institute, Department of Geoscience, University of Wisconsin−Madison, Madison, Wisconsin 53706, United
States
*
S Supporting Information

ABSTRACT: Nanometric iron(III) oxide has been of great interest

in a wide range of fields due to its magnetic properties, eminent
biochemical characteristics, and potential for technological applica-
tions. Among iron oxides, ε-Fe2O3 is considered as a remarkable
phase due to its giant coercive field at room temperature and
ferromagnetic resonance capability. Here we present the first size-
dependent phase map for ε-Fe2O3 via a γ → ε → α pathway together
with the activation energies for the phase transformations, based on
X-ray powder diffraction (XRD) and high-resolution transmission
electron microscopy (HRTEM). HRTEM images of ε-Fe 2O 3
nanocrystals show both inversion and pseudohexagonal twins,
which are fundamentally important for understanding the correlation
between its nanostructure and magnetic properties. Two activation
energies for γ-Fe2O3 → α-Fe2O3 phase transformations are 186.37 ± 9.89 and 174.58 ± 2.24 kJ mol−1, respectively. The results
provide useful information about the size, crystal structure, and transformation of the nanometric iron oxide polymorphs for
applications in areas of developing engineered materials.

1. INTRODUCTION Fe2O3 in varying contents depending on the reaction temper-

Nanometric iron oxides are important functional materials due to
their magnetic properties, eminent biochemical characteristics,
and technological applications.1−5 To date, five crystalline
polymorphs of Fe2O3 are known, (i) α-Fe2O3 (i.e., hematite),
(ii) β-Fe2O3, (iii) γ-Fe2O3 (i.e., maghemite), (iv) ε-Fe2O3, and
(v) ζ-Fe2O3, all of which have different morphologies, various
sizes, and magnetic properties.3−6 Among ferric oxide, the ε-
Fe2O3 is considered as a remarkable phase due to its giant
coercive field (Hc) at room temperature, coupled magneto-
electric properties, and ferromagnetic resonance capability that is
a distinctive property in other metal oxides.1,5,7 The ε-Fe2O3 was
also reported in ancient black-glazed Chinese Jian wares, which
formed by heating iron-bearing clays at ∼1300 °C.8 The natural
ε-Fe2O3 (luogufengite) is discovered on vesicles’ surfaces of
basaltic scoria.
The ε-Fe2O3 is a dark brown nanocrystal that has an
orthorhombic structure with the Pna21 space group. The
structure of ε-Fe2O3 consists of triple chains of iron octahedra
sharing edges with corner sharing iron tetrahedra that run parallel
to the a-direction, which is isomorphous with AlFeO3 and
GaFeO3.5,9 The ε-Fe2O3 is considered as an intermediate
polymorph between γ-Fe2O3 and α-Fe2O3. It is difficult to
synthesize large ε-Fe2O3 crystals as a pure phase, because ε-
Fe2O3 is considered thermodynamically unstable.3,5,10 The γ-
Fe2O3 → ε-Fe2O3 → α-Fe2O3 pathway is widely recognized as a
simple way to prepare ε-Fe2O3 nanoparticles.3−5,10 Synthetic
procedures lead to a mixture of ε-Fe2O3 with α-Fe2O3 and γ-
ature, supporting silica matrix, and presence of other metal ions
(e.g., Al3+, Ba2+, and Ca2+).1,3,7,8,11,12 Among the synthetic
methods, Kelm and Mader13 proposed a synthesis route via
thermal decomposition of an Fe(III)-dominated clay mineral of
nontronite [∼(Na0.3−2x,Cax)Fe2(Si,Al)4O10(OH)2·nH2O, an
iron(III) end member of smectite]. The method can produce
almost pure ε-Fe2O3 nanoparticles since SiO2 matrix increases
the stability of ε-Fe2O3 nanocrystals.13
In this article, we present the first quantitative phase map for
polymorphs of Fe2O3 via a γ → ε → α pathway, based on high-
resolution transmission electron microscopy (HRTEM) and X-
ray powder diffraction (XRD). This map is important because
the development of nanotechnologies requires control of the
size, structure, and growth conditions of individual components.
Furthermore, we report a detailed description of the crystal
structure and kinetic properties of the nanometric Fe2O3
polymorphs.
2. EXPERIMENTAL METHODS
2.1. Synthesis. Iron(III) oxide nanoparticles were prepared
through the thermal decomposition of clay mineral nontronite
(S. W. Bailey XRD Laboratory collection, University of
Wisconsin−Madison) from Quincy, WA. We followed a
procedure similar to the synthesis method of Kelm and
Received: May 25, 2016

© XXXX American Chemical Society A DOI: 10.1021/acs.jpcc.6b05287

J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C Article

Mader.13 The crushed nontronite was inserted at an alumina boat

in the furnace from 800 to 1100 °C. After heating, the samples
were quenched in cold water. Isolation of the ferric oxides was
performed from the amorphous SiO2 by dissolving in the 10 M
NaOH solution at 80 °C for 2 days. After washing with distilled
water five times, iron(III) oxide powder was obtained.
2.2. Measurements. XRD patterns were collected using a
Rigaku Rapid II XRD system (Mo Kα radiation) in the
Geoscience Department at the University of Wisconsin−
Madison. Diffraction data were recorded on a 2-D image plate
detector. The original two-dimensional diffraction rings were
then converted to produce conventional 2θ versus intensity
patterns using Rigaku’s 2DP software. Percentages of mineral
phases in the sample were calculated using the Rietveld method.
Input structure models of hematite and maghemite for Rietveld
analysis are from Blake et al.14 and Shmakov et al.15 A pseudo-
Voigt method was used for fitting the peak profiles.
High-resolution TEM images and selected-area electron
diffraction (SAED) analyses were carried out using a Philips
CM200-UT microscope operated at 200 kV in the Materials
Science Center at the University of Wisconsin−Madison.
Chemical analyses were obtained by using an X-ray energy-
dispersive spectroscopy (EDS) method (spot size 5 with a beam
diameter of ∼50 nm) with minerals of fayalite, anorthite,
forsterite, and titanite as standards for quantifying elements of Fe,
Al, Ti, and Ca.
2.3. Consecutive Reactions. The modeling was carried out
using the first-order consecutive reactions. An initial reactant A
reacts to make some intermediate B (k1), which then reacts to
make a final product C (k2). By setting up the change in
concentration of A, B, and C, these differential phases can be
integrated to get equations for three time-dependent concen-
trations:
A = A 0 exp(− k1t )

B = A 0[exp(− k1t ) − exp( − k 2t )]/(k 2 − k1)

C = A 0[k 2(1 − exp(k1t )) − k1(1 − exp( − k 2t ))]/(k 2 − k1)

When the concentration of substrate (A), intermediate (B),
and final product (C) are determined by time, we can calculate
the reaction rate constants (k1 and k2). More information on the
model is found in refs 16 and 17.
3. RESULTS AND DISCUSSION
3.1. Polymorphous Transformations of Nanometric
Iron Oxide. The Fe2O3 polymorphous transformations of γ-
Fe2O3 to α-Fe2O3 via ε-Fe2O3 are observed in a range from 850
to 1000 °C (Figure 1). The reaction rates of the γ → ε → α
transformation progressively increase as the reaction temper-
ature increases (Figure 1). Sharpness of the diffraction peaks
increases as annealing time increases, indicating the growth of the
crystals (Figure 1).
Bright-field TEM images and SAED analyses identity the ferric
oxide nanocrystals (γ, ε, and α) and 15 Å nontronite (Figure 2).
The natural nontronite shows continuous SAED rings, indicating
the turbostratic disorder in stacking (Figure 2a). Figure 2b shows
the roughly rod shapes of ε-Fe2O3 inside the silica matrix. The
SiO2 matrix serves as an antisintering agent, which extends the
life of the metastable ε-Fe2O3.13,18
The size of ferric oxide nanoparticles is significantly influenced
by the annealing temperatures and times (Figure 2c−f). The ε-
Fe2O3 is typically ∼50 nm and ranges from ∼10 to ∼200 nm.
B DOI: 10.1021/acs.jpcc.6b05287
Figure 1. Powder X-ray diffraction patterns of Fe2O3 polymorphs from
thermal decomposition of nontronite heated at different temperatures
(800−1100 °C) and annealing times. Mole fractions of the Fe2O3
polymorphs were calculated using the Rietveld method. Diffraction
peaks from the reference minerals of ε-Fe2O3, α-Fe2O3 (ref 14), and γ-
Fe2O3 (ref 15) are also illustrated at the bottom.
Overall, α-Fe2O3 crystals are larger than ε-Fe2O3 crystals,
whereas γ-Fe2O3 crystals are smaller than ε-Fe2O3 crystals
(Figure 2, parts e and f). The size variation is important because
the phase transformations of iron oxide nanoparticles take place
once they reach a certain critical size.3,19,20
The average chemical formulas for γ-Fe2O3
(Fe1.67Al0.18Mg0.12Ca0.03O3), ε-Fe2O3
(Fe1.82Al0.10Mg0.04Ca0.03Ti0.01O3), and α-Fe2O3
(Fe1.93Ti0.04Al0.03O3) are calculated from EDS spectra, respec-
tively (shown in Figure S1). It was suggested that the alkaline
earth ions (Ca and Mg) stabilize the metastable ε-Fe2O3,
increasing the size of nanoparticles.4,21 In addition, cation
substitution may affect the average particle size of iron oxide
nanoparticles.1,21−25
High-resolution TEM images show that ε-Fe2O3 commonly
displays (001̅), (011), (011̅), (01̅1), and (01̅1̅) faces (Figure 3a−
c). The shape of ε-Fe2O3 is generally elongated along the a-axis
with combinations of sphenoid, pinacoid, and pedion forms
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C Article

Figure 2. Bright-field TEM images and selected-area electron diffraction (SAED) patterns of iron oxide nanocrystals: (a) 15 Å nontronite; (b) iron oxide
nanocrystals in matrix of amorphous SiO2; (c−f) iron oxide crystals from the different heating temperatures and reaction times after leaching amorphous
silica using 10 M NaOH solution. Scale bar = (a−d) 200 nm, (e) 50 nm, and (f) 500 nm.

(Figure 3a−c). Figure 3b shows the inversion twinning of ε-
Fe2O3, further illustrated in Figure 4a. The pseudohexagonal
twin relationships are frequently observed in the ε-Fe2O3
nanocrystals.26 The ε-Fe2O3 has (1̅10) ∥ (010) and (100) ∥
(130) in a (110) twinning relationship (Figure 3d) due to
pseudohexagonal symmetry, which is illustrated in Figure 4b.
Figure 3e shows the ∼60° rotation orientation relationship
between crystals with [100]ε and [110]ε zone-axes sharing the
interface of (001). The pseudohexagonal twinning operation is
the same as in that the isostructural phases κ-Al2O3.27
The twinning in ε-Fe2O3 can make it difficult to understand
the correlation between the microstructure and magnetic
properties. The nonzero orbital momentum in the ε-Fe2O3
results from the uncompensated magnetic moment of tetrahedral
Fe3+ and octahedral Fe3+ positions.28 The inversion or rotational
twin operations are also able to change the Fe3+ magnetic
moments to influence the net magnetization of ε-Fe2O3, leading
to an unexpectedly significant orbit-coupling phenomenon.23
A HRTEM image shows the crystal interface of ε-Fe2O3 and α-
Fe2O3 along the c-axis (Figure 3f). Both iron oxides have the
hexagonal arrangement of oxygen atoms on their (001) surfaces.
It is proposed that the pseudohexagonal packing of the ε-Fe2O3
(001) surface could serve as the substrate/interface for α-Fe2O3,
which is illustrated in Figure 4c. The unusual small hematite
crystal (Figure 3f) may be as a result of quenching during the
synthetic procedure.29
Rietveld refinement analyses were performed to quantify
concentrations of iron oxide polymorphs (shown in Figure S2).
The lattice parameters of the ε-Fe2O3 were refined on the basis of
the determined space group Pna21. The Al3+ prefers to occupy
the tetrahedral Fe site in the ε-Fe2O3 because of its smaller ionic
C DOI: 10.1021/acs.jpcc.6b05287
radius.5,30 Calculated fractional coordinates and occupancies for
the structure are listed in Table S1. The unit cell parameters of ε-
Fe2O3 are lower than those of aluminum-bearing ε-Fe2O3 heated
at 1050 °C30 (Figure 5) because the low annealing temperature
may result in the ordering of Al in the tetrahedral sites. The unit
cell volume of the ε-Fe2O3 increases as the temperature increases
(Figure 5).
3.2. Size-Dependent Phase Map. A size-dependent phase
map of nanosized iron(III) oxide is illustrated based on
maximum sizes of γ-Fe2O3 and ε-Fe2O3 nanocrystals (Figure
6). The TEM images show that the particle size of nanometric
iron oxide is dependent on annealing temperature and time. The
γ-Fe2O3 to ε-Fe2O3 phase transition takes place once the γ-Fe2O3
nanoparticles reach a certain critical size between ∼9 nm at 1100
°C and ∼14 nm at 800 °C (Figure 6). Similarly, Tronc et al.11
obtain the ε-Fe2O3 nanoparticles from 10 nm of γ-Fe2O3 particles
in silica xerogel by using the thermal transformation. We sort the
maximum size of the ε-Fe2O3 into two types: single crystals and
twinned crystals (Figure 6). The critical size of the ε-Fe2O3 to α-
Fe2O3 phase conversion is approximately between ∼150 nm at
1100 °C and ∼80 nm at 800 °C (Figure 6). Twined crystals have
larger sizes than single crystals in general. Pure ε-Fe2O3 phase
generally converts to the α-Fe2O3 polymorph if the particle size
exceeds a value of ∼30 nm without silica matrix.5 However, the
large ε-Fe2O3 nanocrystals, with sizes up to 200 nm, can be stable
within silica matrix.12,13,18 It is also affected by alkaline earth
metals (Mg and Ca) and Al concentration in the reaction
system.1,5,21,31
Due to the slow decomposition rate of nontronite and
extremely long annealing time, we cannot accomplish the
experiment below 800 °C. Direct γ-Fe2O3 to α-Fe2O3 phase
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C Article

Figure 3. HRTEM images and fast Fourier transform (FFT) patterns of iron oxide nanoparticles: (a) the single ε-Fe2O3 nanocrystal along the [100]
zone-axis; (b) the inversion twinning relationship of ε-Fe2O3; (c) rod shape of ε-Fe2O3 elongated along the a-axis; (d) the composition plane boundaries
are (1̅10) ∥ (010) and (100) ∥ (130) of ε-Fe2O3 in a (110) twinning relationship; (e) the (001) twin boundaries between [100]ε and [110]ε with ∼60°
rotation relationship; (f) the (001) crystal interface of [110]α and [110]ε. Scale bar = (a, b, d−f) 10 nm and (c) 20 nm.

Figure 4. Structure models showing the twin relationships and crystal interfaces: (a) the inversion twin relationship in Figure 3b, (b) the (110) twinning
relationship in Figure 3d, and (c) the crystal interfaces between ε-Fe2O3 and α-Fe2O3 along the c-axis in Figure 3f.

transformation is reported at temperatures ranging from 370 to
600 °C in the absence of a silica matrix,20,32 in which the phase
transition temperature decreases as the particle size decreases,
due to a reduction in the activation energy of the system.32 The
triple point is set at ∼700 °C, because cation substitution for Fe
could result in the γ-Fe2O3 → α-Fe2O3 phase transformation to
∼700 °C.33 Navrotsky et al.34 reported that γ-Fe2O3 nanocrystals
become thermodynamically stable with respect to α-Fe2O3 at
sizes of about 16 nm under dry conditions, which is close to the
dashed line between γ-Fe2O3 and α-Fe2O3 phases in our phase
map (Figure 6). The phase boundary between maghemite and
D DOI: 10.1021/acs.jpcc.6b05287
hematite is also controlled by relative humidity.35 As observed in
soils, the size of maghemite decreases as the humidity increases.36
3.3. Kinetics of Nanometric Iron Oxide Polymorphs (γ
→ ε → α Pathway). In all the experiments, the Fe2O3
polymorphous transformations (γ → ε → α pathway) are
observed between 850 and 1000 °C (Figure 1). The mole
fractions of the Fe2O3 polymorphs are calculated from XRD
patterns by using Rietveld refinement method (shown in Table
S2).
Because all the three polymorphs exist in the reactions, a
consecutive reaction method is used to calculate the phase
transformation kinetics, in which initial γ-Fe2O3 reacts to make
J. Phys. Chem. C XXXX, XXX, XXX−XXX
The Journal of Physical Chemistry C
Figure 5. Comparisons of unit cell parameters of synthetic ε-Fe2O3 (blue symbols) and aluminum-substituted ε-Fe2O3 synthesized at 1050 °C (red
squares) (ref 30).
Figure 6. Size-dependent phase map of nanometric iron(III) oxide (γ →
ε → α pathway) based on the TEM observations: blue dots, the
maximum size of γ-Fe2O3 crystals; dark brown dots, the maximum size
of twinned ε-Fe2O3 crystals; brown circles, the maximum size of ε-Fe2O3
single crystals.
some intermediate ε-Fe2O3, which then reacts to make a final
product of α-Fe2O3. The kinetics of the transformation of γ → ε
→ α polymorphs occurring at 1000, 900, and 850 °C are
calculated using the first-order consecutive reaction model
(Figure 7). The first-order kinetic reaction is also used in
previous studies for the γ → ε transition.19,20 Both rate constants
(k1 and k2) increase as annealing temperature increases, and the γ
→ ε transformation is faster than the ε → α transition at all three
temperatures due their differences in crystals sizes (Figure 7).
The γ → ε and ε → α transition activation energies are 186.37
± 9.89 and 174.58 ± 2.24 kJ mol−1, respectively, based on the
Arrhenius equation: k = k0 exp(−Ea/RT) (Figure 8). We believe
this is the first reported activation energy for the ε-Fe2O3 to α-
Fe2O3 phase transformation. Two difference activation energies
for γ-Fe2O3 → α-Fe2O3 were reported to the 176 ± 31 and 152 ±
17 kJ mol−1, respectively.19,20 However, it is difficult to calculate
the restricted activation energy of the nanocrystals because the
activation energy may also be size-dependent.19,31
4. CONCLUSION
We have presented the first size-dependent phase map for
nanosized Fe2O3 polymorphs (γ, ε, and α) with their phase
transformation activation energies, based on HRTEM and
quantitative XRD. Combining the phase map with their kinetic
properties predicts the stability regime of the nanosized Fe2O3 as
the function of crystal size, temperature, and annealing times. As
it is a challenge to synthesize pure phase ε-Fe2O3 nanocrystal, the
E DOI: 10.1021/acs.jpcc.6b05287
Article
proposed size-dependent phase map will help to improve
controlled synthesis of ε-Fe2O3 nanocrystal, a promising material
for many future applications.4,5 In addition, the method will be
useful for determining size-dependent phase maps in other
systems.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.6b05287.
Further details on the TEM-EDS spectra, XRD pattern
(Mo Kα), atomic coordinates of synthetic ε-Fe2O3, and
the experimental results of the γ/ε and ε/α transitions
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*Phone: 1-608-265-5887. Fax: 1-608-262-0693. E-mail: hfxu@
geology.wisc.edu.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This study was supported by the NASA Astrobiology Institute
(N07-5489). The authors thank Mr. Franklin Hobbs for reading
the manuscript and two anonymous reviewers for providing
many helpful suggestions.
■
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G DOI: 10.1021/acs.jpcc.6b05287
J. Phys. Chem. C XXXX, XXX, XXX−XXX

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