Ceramics International 44 (2018) 19338–19344

Contents lists available at ScienceDirect

Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Silica-free hydrothermal synthesis of ε-Fe2O3 nanoparticles and their T

oriented attachment to nanoflakes with unique magnetism evolution
⁎
Ji Ma, Kezheng Chen
Lab of Functional and Biomedical Nanomaterials, College of Materials Science and Engineering, Qingdao University of Science and Technology, Qingdao 266042, China

A R T I C LE I N FO A B S T R A C T

Keywords: It is a general consensus that ε-polymorph of Fe2O3 is not easy to synthesize in the form of bare nano-sized
Transition metal oxides objects owing to its significant thermal instability. Thus, a supporting medium (e.g., silica matrix in most cases)
Powders: Chemical preparation is always necessary for its successful high-temperature synthesis at the sacrifice of its yield. In this study, op-
Magnetic properties timized amounts of protons and nitrate ions were employed in a hydrothermal synthetic route to facilitate the
growth of pure ε-Fe2O3 nanoparticles. The absence of silica matrix ensured a high yield of ε-Fe2O3 product, and
moderate reaction temperature of mere 200 °C was conducive to its scalable energy-efficient production. These ε-
Fe2O3 nanoparticles exhibited large room-temperature coercivity of ca. 16.3 kOe, which was found to be de-
generated to 36 Oe as prolonging the reaction time due to the phase and structure evolution. The preformed ε-
Fe2O3 nanoparticles and post-formed α-Fe2O3 phase would co-align with each other to form nanoflakes for long-
time reaction, being of a character of oriented attachment. The concomitant distorted lattice spacing and dis-
ordered atomic configuration not only contributed to the degeneration of ferromagnetism of ε-Fe2O3 phase, but
also induced unique spin glass behavior.

1. Introduction nanocomposite powders of ε-Fe2O3 nanoparticles confined into a silica

matrix, which is employed as a size restrictor for ε-Fe2O3 phase [12]. In
Facile and cost-effective methods for repeatable iron-oxides nano- these scenarios, yields of greater than 70% ε-Fe2O3 are difficult to ob-
particles are of crucial importance to their current and foreseen appli- tain [13]. On the other hand, for an analysis of physicochemical
cations, including catalytic [1], magnetic [2], electronic [3], and bio- properties of ε-Fe2O3 and its subsequent promising applications, α-
medical types [4]. Among four well-known polymorph crystal Fe2O3 and/or γ-Fe2O3 impurities may well drastically affect the overall
structures of Fe2O3, ε-Fe2O3 is the most elusive and one of the less physical behavior of the system, probably leading to some incorrect
studied polymorphs [5]. It has often been taken that ε-Fe2O3 is of an conclusions [5]. Collectively, if synthesized as a pure phase and with a
orthorhombic noncentrosymmetric structure with Fe atoms occupying high yield, ε-Fe2O3 will definitely enter a class of the most important
four distinct nonequivalent crystallographic sites, including one tetra- functional magnetic materials. In this context, its practical exploitation
hedral site and three different octahedral sites [6]. Thus, its crystal will probably overcome the current material limits of certain techno-
structure can be described as the intermediate between hematite (α- logical applications demanding high magnetic hardness. And then, it
Fe2O3) and maghemite (γ-Fe2O3). will give rise to new technological areas benefiting from its remarkable
Despite of its promising properties including giant coercivity (HC), coupled magnetoelectric properties and ferromagnetic resonance cap-
magneto-resistance and millimeter-wave ferromagnetic (FM) resonance ability, both unusual for simple iron oxides [14].
absorption [7], ε-Fe2O3 has not been fully exploited owing to the dif- But like so many answers, it just leads to more questions. The crux
ficulties encountered in its synthesis, initially obtaining the material as of present dilemma is that the formation of ε-Fe2O3 requires the mu-
a pure phase, and lately in tailoring it in a suitable shape useful to be tually exclusive conditions of high temperature and small size [15–17].
integrated in devices. Up to now, numerous synthetic routes, such as In this sense, the utilization of supporting medium (viz. silica matrix in
flame spray pyrolysis [8], plasma synthesis [9], chemical vapor de- most cases) seems to be quite essential with regard to the synthesis of ε-
position [10] and laser-assisted pyrolysis of a gas mixture [11], have Fe2O3 phase in the form of nanoparticles [13,15], nanorods [18,19] and
been developed to produce ε-Fe2O3. The majority of synthetic methods nanowires [20,21]. In this work, we report our recent effort in silica-
of ε-Fe2O3 investigated till now have been designed to yield free hydrothermal synthesis of ε-Fe2O3 nanoparticles. Proverbially,

⁎
Corresponding author.
E-mail address: [email protected] (K. Chen).

https://doi.org/10.1016/j.ceramint.2018.07.162
Received 16 April 2018; Received in revised form 28 June 2018; Accepted 18 July 2018
Available online 19 July 2018
0272-8842/ © 2018 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
J. Ma, K. Chen Ceramics International 44 (2018) 19338–19344

hydrothermal route has found its place in several branches of modern magnetic field down to the investigated temperatures. Then, closed
science and technology in view of its high solvation power, high com- hysteresis loops were measured by applying magnetic fields from 0 to
pressibility and mass transport of solvents [22]. Besides, its mild syn- + 50 kOe, then to −50 kOe, and in turn to + 50 kOe to the end. The
thetic conditions, simple manipulation, and good crystallization of the first 0 → + 50 kOe curve is called the initial magnetization curve.
products confer outstanding merits to this facile route. However, re- The thermo-magnetization [M(T)] curves were measured in zero
garding to the synthesis of metastable phases (e.g., ε-Fe2O3 crystals, field-cooled (ZFC) and field-cooled (FC) procedures. Firstly, the sample
metal alkoxides, amorphous phases) at relatively high temperatures in was cooled from 300 K down to 5 K in a zero magnetic field. Then the
the range, hydrothermal route should be examined very carefully be- magnetization of the sample was measured as heating it from 5 to 300 K
cause it always compromises thermodynamic non-equilibrium states in a given magnetic field. After that, the sample was cooled down again
and commonly yields products with high thermodynamic stability. In to 5 K with the applied field held constant, and the magnetization was
this scenario, the addition of protons and nitrate ions are found to be measured once more during the heating-up process from 5 to 300 K in
critical during hydrothermal procedure to yield pure ε-Fe2O3 phase the same magnetic field.
with no aid of supporting matrix. The merits of this synthetic route lie Collectively, even though the experimental uncertainty in the ab-
in three aspects: (i) no addition of silica matrix ensures a high yield of ε- solute magnetization is ca. 1%, the relative magnetization uncertainty
Fe2O3 phase; (ii) moderate reaction temperature of mere 200 °C not between field points for the same sample is smaller than the data point
only finds a way out of the dilemma between high temperature and size in the figure, and the statistical uncertainties (not shown in this
small size, but also is conducive to its scalable energy-efficient pro- study) are smaller than the point size. Moreover, any effect on magnetic
duction; (iii) by prolonging reaction time, the as-synthesized ε-Fe2O3 properties caused by the shape anisotropy of the sample will not be
nanoparticles can self-assemble into nanoflakes with a character of resolved in our experiments because the measurements were performed
oriented attachment, offering a realistic possibility to tailor ε-Fe2O3 in a on powders with randomly oriented particulates.
suitable shape useful to be integrated in devices.

2. Experimental 3. Results and discussion

2.1. Synthesis of ε-Fe2O3 products Protons (provided by (NH4)H2PO4 and (NH4)2HPO4 reagents) and
nitrate ions (provided by Fe(NO3)3·9H2O reagent) are employed in our
The analytically pure reagents Fe(NO3)3·9H2O, (NH4)H2PO4 and hydrothermal route to prolong the reaction process that approaches
(NH4)2HPO4 in experiments were purchased from Sinopharm Chemical final thermodynamic equilibrium states, so that metastable ε-Fe2O3
Reagent Co., Ltd. (China) and used as received without further pur- phase may be readily obtained by intentionally interrupting this reac-
ification. Typically, 3.2 mL of aqueous Fe(NO3)3·9H2O solution tion. Along this line, the reaction is artificially interrupted after 3 h, and
(0.5 mol/L) was mixed with 1.44 mL of isometric (NH4)H2PO4 and the morphology of the product is shown in the inset of Fig. 1a. Clearly,
(NH4)2HPO4 aqueous solution with equimolar concentration of this 3 h-product is composed of numerous nanoparticles of similar sizes,
0.1 mol/L. After ultrasonic agitation for 3 min, distilled water was and no large structures can be observed spreading over the SEM sub-
added to a final volume of 50 mL. Further vigorously stirring for 5 min, strate. Its phase composition can be determined by the XRD pattern as
the mixture was transferred into Teflon-lined stainless-steel autoclaves shown in Fig. 1a, wherein all diffraction peaks can be indexed to the
with a capacity of 100 mL for hydrothermal treatment at 200 °C for 3 h orthorhombic structure of ε-Fe2O3 (Pna21, JCPDS No. 52–1449).
to yield ε-Fe2O3 nanoparticles and 18 h to yield iron-oxide nanoflakes.
After the autoclave had cooled down to room temperature naturally,
the precipitates were centrifuged, washed with distilled water and ab-
solute ethanol, and finally dried in the air at 60 °C for 4 h. Experiments
utilizing the same procedures were repeated five times with consistent
results.

2.2. Characterization

The XRD patterns were recorded on a powder X-ray diffractometer

(Rigaku D/max-rA; Japan) equipped with a rotating anode and a Cu
-Kα1 radiation source (λ = 1.5406 Å) at a step width of 0.02°. Scanning
electron microscope (SEM) images were collected on a field emission
scanning electron microscope (JEOL JSM-6700F, Japan). Transmission
electron microscope (TEM) images were performed on the JEOL 2010
TEM (Japan) with an operating voltage of 200 kV. The high-resolution
transmission electron microscope (HRTEM) experiments were con-
ducted using a Field Emission Gun (FEG) JEOL 2010F microscope
(Japan) with a point resolution of 0.19 nm. The magnetic force mi-
croscope (MFM) image was taken by using a Digital Instruments mul-
timode microscope operated in tapping/lift™ mode and using com-
mercial magnetic etched silicon probe (MESP)-type MFM tips.

2.3. Magnetic measurements

Magnetic measurements were carried out using a commercial su-

perconducting quantum interference device magnetometer (SQUID
MPMS-XL5, U.S.A).
Magnetic hysteresis loops were measured according to the following Fig. 1. (a) XRD pattern, SEM image (inset) and (b) HRTEM image of ε-Fe2O3
procedure. At first, the sample was cooled from 310 K in a zero nanoparticles.

19339
J. Ma, K. Chen Ceramics International 44 (2018) 19338–19344

15 As is known, XRD can provide information on particle size in terms

(a)
of a volume average from the broadening of reflections by means of the
10
so-called Scherrer equation. Accordingly, the estimated volume-
weighted average value is about 15.3 nm. Similarly, the number-
5
weighted average size of 19.8 nm can be deduced from the TEM (not
M (emu/g)

shown) and typical HRTEM images in Fig. 1b, in which the 2.14 Å
0
fringe spacing corresponds to the (212) inter-planar spacing of ε-Fe2O3.
5K Irrespective of analyzing the relationship between volume distribution
-5
100 K function and number distribution function, the immediately apparent
200 K mismatch of these two average size values can be explained by the fact
-10
300 K
that (i) micro-strains often increase the peak broadening for nano-
particles, leading to smaller particle size according to Scherrer equa-
-15
-60000 -40000 -20000 0 20000 40000 60000 tion; (ii) the variations of the particle shape make the analysis based on
H (Oe) the assumption of spherical geometry less reliable and are probably the
12
origin of the disagreement between the average diameters as de-
(b) termined by XRD and TEM.
One of the most salient magnetic features of ε-Fe2O3 phase is its very
high coercivity (ca. 20 kOe), which can even be used as a sole criterion
to judge whether ε-Fe2O3 phase exists or not in the product. Fig. 2a
shows a set of magnetic hysteresis loops of the as-synthesized ε-Fe2O3
M (emu/g)

5K nanoparticles at 5, 100, 200 and 300 K in a full magnetic-field scan

0
100 K
from −50 to + 50 kOe. The coercivity can thus be calculated by using
200 K
the switching fields of the two branches of hysteresis loops, Hc1 for the
300 K
descending branch and Hc2 for the ascending branch, according to the
formula of HC= (Hc2−Hc1)/2. Linear fits of the magnetization data
at ± 300— ± 440 Oe, ± 300— ± 440 Oe, ± 15.1— ± 15.3
-12 kOe, ± 16.2— ± 16.4 kOe of the up (+) and down (−) branches of
-20000 0 20000
H (Oe) the loops at 5, 100, 200 and 300 K, respectively, have been used to
determine Hc2 and Hc1 values, respectively (Fig. 2b). The calculated
Fig. 2. Magnetic hysteresis loops of ε-Fe2O3 nanoparticles measured at different coercivity values are 370, 404, 15,120 and 16,299 Oe at 5, 100, 200
temperatures plotting from (a) − 50 to + 50 kOe, and (b) −20 to + 20 kOe. and 300 K, respectively, which are in good consistency with reported
values in previous literatures [23–25]. Suchlike huge room-temperature
coercive fields of ε-Fe2O3 nanoparticles are of various interpretations
but with no clear consensus about their origins. Possibly, it is related to

Fig. 3. SEM images of control samples after reacting between (a) Fe(NO3)3·9H2O and (NH4)2HPO4, (b) Fe(NO3)3·9H2O and (NH4)H2PO4, (c) FeCl3·6H2O and (NH4)
H2PO4/ (NH4)2HPO4 for 3 h. Their XRD patterns are shown in panel d, e, and f, respectively.

19340
J. Ma, K. Chen Ceramics International 44 (2018) 19338–19344

Fig. 4. (a) XRD pattern, (b) SEM image, (c) TEM image, (d) 3-D topographical MFM image (500 nm × 500 nm × 50 nm), and (e) HRTEM image of iron-oxide flakes.
Typical distorted regions in panel e are separately shown in panel f and g.

(i) symmetric Fe3+ cations with a half-filled d-shell; (ii) defects indu- microspheres consisting of aggregated nanoparticles are prevalent in
cing two possible orientations within a crystallite and thus enhancing (NH4)2HPO4 case due to its much lower H+ concentration. Apart from
the magnetocrystalline anisotropy of ε-Fe2O3 nanoparticles; (iii) single- these substantially morphological difference and size deviation, both
domain character of ε-Fe2O3 nanoparticles, which evokes high mag- the highest H+ concentration in (NH4)H2PO4 case and the lowest H+
netic anisotropy (K ~ 2 ×105 J/m3) and low values of saturation concentration in (NH4)2HPO4 case are not propitious to the formation
magnetization (MS ~ 15 A m2/kg), and hence yielding giant coercivity of ε-Fe2O3 phase. Fig. 3d and e illustrate that α-Fe2O3 is the preferential
according to the formula of HC ∝ K/MS. In any case, this surprisingly and final phase in the resultant 3 h-products, even though the crystal-
large room-temperature coercivity is generally believed to be affected linity is rather poor at high H+ concentration in (NH4)H2PO4 case.
by magnetocrystalline anisotropy as well as particle size and size dis- Thereby, the equimolar hybrid of two etching agents (NH4)H2PO4 and
tribution. (NH4)2HPO4 is fairly crucial in the successful synthesis of ε-Fe2O3 phase
In the preceding analysis, the goal of synthesizing pure ε-Fe2O3 and is thought to be one of the innovation points in our synthetic route.
phase via hydrothermal route at mere 200 °C with no aid of supporting The other innovation point is the utilization of nitrate ions coming from
matrix can be readily achieved by simply adding protons and nitrate Fe(NO3)3·9H2O reagent. If replaced by FeCl3·6H2O with other condi-
ions in reaction. In this case, optimizing the amount of (NH4)H2PO4, tions held constant, the resultant product is of tubular morphology
(NH4)2HPO4 and Fe(NO3)3·9H2O reagents is of utmost importance in mixed with concaved spindles (Fig. 3c). Similar to the other two cases,
determining the success of this synthetic route. In our aforementioned its phase composition is also assigned to hexagonal structured α-Fe2O3
hydrothermal procedure, the molar ratio of (NH4)H2PO4 and (R—3c, JCPDS No. 33–0664). The major role of nitrate ions during the
(NH4)2HPO4 reagents is set to be 1:1 with the same concentration of reaction is their thermal decomposition to gases (including oxygen and
0.1 mol/L. If no (NH4)H2PO4 reagent is added and the volume of nitrogen dioxide), which in turn degenerate the crystallinity of newly-
(NH4)2HPO4 aqueous solution (0.1 mol/L) is doubled with other con- formed iron oxide and prolong the reaction process approaching ther-
ditions held constant, the as-obtained particle is of spherical mor- modynamic equilibrium states.
phology with an average diameter of ca. 200 nm, as shown in Fig. 3a. As stated above, the hydrothermal reaction is intentionally inter-
By contrast, if the volume of (NH4)H2PO4 aqueous solution (0.1 mol/L) rupted at 3 h because such an abortive reaction is conducive to the
is doubled without the addition of (NH4)2HPO4 reagent, smaller-sized formation of metastable ε-Fe2O3 phase. Otherwise, more energetically
(ca. 15 nm) particles are finally obtained (Fig. 3b). According to our stable phases and morphologies will occur in an undisturbed reaction
previous reports [26,27], proton-etching effect is prevalent in these process. Fig. 4a shows an XRD pattern of the as-obtained product after
reactions and dominates the final morphologies and sizes of the pro- 18 h-reaction. As expected, apart from the previously observed ε-Fe2O3
ducts. In this context, scattered finite-sized particles are formed in phase (Pna21, JCPDS No. 52–1449), some reflection peaks can be un-
(NH4)H2PO4 case owing to severe proton-etching effect, whereas ambiguously indexed to hexagonal structure of α-Fe2O3 (R—3c, JCPDS

19341
J. Ma, K. Chen Ceramics International 44 (2018) 19338–19344

6
(a) 5 (b)
4
4 5K
2 100 K
M (emu/g)
200 K

M (emu/g)
3
0 300 K

5K 2
-2
100 K
-4 200 K 1
300 K
-6 0
-40000 -20000 0 20000 40000 0 10000 20000 30000 40000 50000
H (Oe) H (Oe)

3 0.5
(c) (d) 5K 100 K
2

200 K
1

M (emu/g)
M (emu/g)

300 K
0 0.0

-1 5K
100 K
-2 200 K
300 K
-3 -0.5
-40000 -20000 0 20000 40000 -5000 0 5000
H (Oe) H (Oe)
Fig. 5. (a) Magnetic hysteresis loops and (b) initial magnetization curves of iron-oxide flakes measured at different temperatures. FM-component loops deduced from
panel a are plotted from (c) − 50 to + 50 kOe, and (d) − 5 to + 5 kOe.

0.004
(a) 10 Oe 5000 (a) 10 Oe

0.003
4000
FC
1/M (g/emu)
M (emu/g)

0.002 3000

2000
0.001

1000
0.000
ZFC
0
0 50 100 150 200 250 300 0 50 100 150 200 250 300
T (K) T (K)
150
0.06
(b) 100 Oe
(b) 100 Oe
0.05

FC 100
0.04
1/M (g/emu)
M (emu/g)

0.03

50
0.02

0.01
ZFC
0
0.00 0 50 100 150 200 250 300
0 50 100 150 200 250 300
T (K)
T (K)
Fig. 7. The reciprocal of M vs. T curves at (a) 0.01 and (b) 0.1 kOe, with their
Fig. 6. ZFC and FC M(T) curves of iron-oxide flakes measured at (a) 0.01, and
high-temperature zone (marked as rounded rectangles) being plotted as insets.
(b) 0.1 kOe.

19342
J. Ma, K. Chen Ceramics International 44 (2018) 19338–19344

Curie-Weiss temperature of −174.4 and −126.2 K for Fig. 7a and b,

respectively. Such large negative Curie-Weiss temperatures indicate the
antiferromagnetic coupling between ε-Fe2O3 and α-Fe2O3 components
in nanoflakes is very strong [34].
The as-observed strong antiferromagnetic coupling together with
distorted atomic configuration may result in long-range magnetic dis-
orders, and hence yielding spin glass (SG) state, in which the interac-
tions between the magnetic moments are in conflict with each other.
This point is firstly evidenced by the large discrepancies between the
ZFC and FC magnetization in Fig. 6a and b [35]. Secondly, temperature-
dependent real part values of ac susceptibility (χ′) curves are plotted in
Fig. 8, wherein the peak height decreases and the position of peak
temperature (Tmax) shifts to higher temperatures with increasing fre-
quency. This phenomenon is consistent with a cooperative freezing of
Fig. 8. χ′(T) curves of iron-oxide flakes measured at three ac frequencies in an magnetic moments in spin glasses [36]. The presence of SG state is the
ac driving field of 2 Oe. root cause to the substantial deviation of magnetic behaviors between ε-
Fe2O3 nanoparticles (3 h-product) and ε-Fe2O3-contained nanoflakes
No. 33–0664). Moreover, the morphology of the product changes from (18 h-product).
granular shape to flake-like shape as prolonging the reaction time from
3 h to 18 h (Fig. 4b). The flake surface is rough in texture which, upon 4. Conclusions
closer scrutiny, reveals an assembly of nanoparticles (Fig. 4c). The
average diameter of these iron-oxide flakes is measured around 250 nm In summary, ε-Fe2O3 nanoparticles and ε-Fe2O3/α-Fe2O3 nanoflakes
and their thickness of 18.2 nm can be determined in a three-dimen- were sequentially synthesized in a hydrothermal route at mere 200 °C
sional (3-D) topographical MFM image (Fig. 4d). More strikingly, the with no aid of supporting matrix. Protons (coming from (NH4)H2PO4
typical HRTEM image in Fig. 4e shows a unique quasi single-crystalline and (NH4)2HPO4 reagents) and nitrate ions (coming from Fe
character of these nanoflakes, on which the finite-sized primary ε-Fe2O3 (NO3)3·9H2O reagent) were employed in this study to intentionally
and α-Fe2O3 nanoparticles co-align during their coalescence, which is prolong thermodynamic metastable states during the reaction.
often referred to as oriented attachment [28,29]. Because of the con- Optimization of their dosage was critical to the success of this synthetic
spicuous deviation of lattice constants between orthorhombic ε-Fe2O3 route. After reacting for a long time, the thermodynamic equilibrium
and hexagonal α-Fe2O3 phases, some of their crystallographic planes states were finally established, and the preformed ε-Fe2O3 nanoparticles
being of similar interplanar spacing contribute to their oriented as- and post-formed α-Fe2O3 phase attached with each other in a nearly
sembly. Inevitably, this will result in distortions between these two same crystallographic direction accompanied by distorted lattice spa-
phases, as shown in Fig. 4f and g, wherein one can hardly distinguish cing. Such phase and structure evolution not only degenerated coer-
these phases due to widespread ambiguous semi-coherent interfaces civity of ε-Fe2O3 phase, but also induced long-range magnetic disorders
and/or locally disordered atomic arrangements. This salient structure to yield spin glass state in iron-oxide nanoflakes.
feature may well exert great impact on magnetic properties of these
flakes, as will be discussed in the following sections. Acknowledgements
The magnetic hysteresis loops of these iron-oxide nanoflakes mea-
sured at 5, 100, 200 and 300 K are plotted in Fig. 5a. The hysteresis This work was supported by the National Natural Science
loops show smooth change of magnetization with applied magnetic Foundation of China [NSFC No. 51472133].
fields, suggesting that ε-Fe2O3 and α-Fe2O3 components are in intimate
contact and exchange coupled [30,31]. Further, in order to quantita- References
tively distinguish the ferromagnetic contribution of ε-Fe2O3 phase in
our product, the susceptibility χ is firstly determined from the extra- [1] V. Polshettiwar, R. Luque, A. Fihri, H. Zhu, M. Bouhrara, J.M. Basset, Magnetically
polation to zero of ∂M/∂H as a function of T/H by using initial mag- recoverable nanocatalysts, Chem. Rev. 111 (2011) 3036–3075.
[2] J. Nogués, J. Sort, V. Langlais, V. Skumryev, S. Suriñach, J.S. Muñoz, M.D. Baró,
netization curves in Fig. 5b [32]. Then, the ferromagnetic component of Exchange bias in nanostructures, Phys. Rep. 422 (2005) 65–117.
the magnetic hysteresis loops (Fig. 5c and d) can be readily obtained by [3] B. Wang, J.S. Chen, H.B. Wu, Z. Wang, X.W. Lou, Quasiemulsion-templated for-
subtracting χH from the total magnetization in Fig. 5a. The coercive mation of α-Fe2O3 hollow spheres with enhanced lithium storage properties, J. Am.
Chem. Soc. 133 (2011) 17146–17148.
fields of ε-Fe2O3 phase within iron-oxide nanoflakes are thus calculated [4] Y. Wang, P. Brown, Y. Xia, Swarming towards the target, Nat. Mater. 10 (2011)
to be 3694, 53, 40, 36 Oe at 5, 100, 200 and 300 K, respectively, which 482–483.
exhibit totally different variation tendency as compared to the pre- [5] J. Tuček, R. Zbořil, A. Namai, S. Ohkoshi, , ε-Fe2O3: an advanced nanomaterial
exhibiting giant coercive field, millimeter-wave ferromagnetic resonance, and
formed ε-Fe2O3 nanoparticles (viz. 3 h-product). It should be noted that magnetoelectric coupling, Chem. Mater. 22 (2010) 6483–6505.
there also exists an exchange bias (EB) field of −140 Oe at 5 K (de- [6] M. Gich, C. Frontera, A. Roig, E. Taboada, E. Molins, H.R. Rechenberg,
termined by the formula of HEB= (Hc2+Hc1)/2), further evidencing the J.D. Ardisson, W.A.A. Macedo, C. Ritter, V. Hardy, J. Sort, V. Skumryev, J. Nogués,
High- and low-temperature crystal and magnetic structures of ε-Fe2O3 and their
presence of antiferromagnetic coupling between ferromagnetic ε-Fe2O3 correlation to its magnetic properties, Chem. Mater. 18 (2006) 3889–3897.
and antiferromagnetic α-Fe2O3 phases at that low temperature. [7] L. MacHala, J. Tuček, R. Zbořil, Polymorphous transformations of nanometric iron
Apart from magnetic hysteresis loops, suchlike antiferromagnetic (III) oxide: a review, Chem. Mater. 23 (2011) 3255–3272.
[8] S. Lee, H. Xu, Size-dependent phase map and phase transformation kinetics for
coupling derived from different magnetic phases can also be traced in
nanometric iron(III) oxides (γ→ε→α pathway), J. Phys. Chem. C 120 (2016)
ZFC and FC M(T) curves, as shown in Fig. 6a and b. Obviously, these 13316–13322.
ZFC and FC curves do not overlap over the whole range of temperatures [9] A. Sivkov, E. Naiden, A. Ivashutenko, I. Shanenkov, Plasma dynamic synthesis and
up to 200 K. This indicates that ε-Fe2O3 and α-Fe2O3 components are obtaining ultrafine powders of iron oxides with high content of ε-Fe2O3, J. Magn.
Magn. Mater. 405 (2016) 158–168.
not free at low temperatures, but are instead strongly coupled by [10] D. Barreca, G. Carraro, D. Peeters, A. Gasparotto, C. Maccato, W.M.M. Kessels,
magnetic interactions [33]. Moreover, the linear fit for the temperature V. Longo, F. Rossi, E. Bontempi, C. Sada, A. Devi, Surface decoration of ε-Fe2O3
dependence of the inverse magnetization shows that the product ex- nanorods by CuO via a two-step CVD/sputtering approach, Chem. Vap. Depos. 20
(2014) 313–319.
hibits Curie-Weiss behavior above 200 K and gives an extrapolated [11] S. Martelli, A. Mancini, R. Giorgi, R. Alexandrescu, S. Cojocaru, A. Crunteanu,

19343
J. Ma, K. Chen Ceramics International 44 (2018) 19338–19344

I. Voicu, M. Balu, I. Morjan, Production of iron-oxide nanoparticles by laser-induced ferrite, Sci. Rep. 6 (2016) 27212.
pyrolysis of gaseous precursors, Appl. Surf. Sci. 154 (2000) 353–359. [25] S. Sakurai, J. Jin, K. Hashimoto, S. Ohkoshi, Reorientation phenomenon in a
[12] Y. Wang, J. Ma, S. Zuo-Jiang, K. Chen, Tailorable magnetic properties of ε-Fe2O3/ magnetic phase of ε-Fe2O3 nanocrystal, J. Phys. Soc. Jpn 74 (2005) 1946–1949.
SiO2 hybrid via alkaline etching, Ceram. Int. 43 (2017) 16482–16487. [26] C. Liu, J. Ma, H. Chen, Periodical structural conversion and its mechanism in he-
[13] M. Popovici, M. Gich, D. Nižňanský, A. Roig, C. Savii, L. Casas, E. Molins, K. Zaveta, matite: from nanospindles, to nanotubes, to nanotires, RSC Adv. 2 (2012)
C. Enache, J. Sort, S. de Brion, G. Chouteau, J. Nogués, Optimized synthesis of the 1009–1013.
elusive ε-Fe2O3 phase via sol-gel chemistry, Chem. Mater. 16 (2004) 5542–5548. [27] J. Ma, X. Zhang, K. Chen, G. Li, X. Han, Morphology-controlled synthesis of he-
[14] R. Zboril, M. Mashlan, D. Petridis, Iron(III) oxides from thermal processes- synth- matite hierarchical structures and their lithium storage performances, J. Mater.
esis, structural and magnetic properties, mössbauer spectroscopy characterization, Chem. A 1 (2013) 5545–5553.
and applications, Chem. Mater. 14 (2002) 969–982. [28] D. Li, M.H. Nielsen, J.R.I. Lee, C. Frandsen, J.F. Banfield, J.J. de Yoreo, Direction-
[15] M. Gich, A. Roig, E. Taboada, E. Molins, C. Bonafos, E. Snoeck, Stabilization of specific interactions control crystal growth by oriented attachment, Science 336
metastable phases in spatially restricted fields: the case of the Fe2O3 polymorphs, (2012) 1014–1018.
Faraday Discuss. 136 (2007) 345–354. [29] H. Xu, W. Wang, W. Zhu, L. Zhou, M. Ruan, Hierarchical-oriented attachment: from
[16] S. Sakurai, A. Namai, K. Hashimoto, S. Ohkoshi, First observation of phase trans- one-dimensional Cu(OH)2 nanowires to two-dimensional CuO nanoleaves, Cryst.
formation of all four Fe2O3 phases (γ → ε → β → α-phase), J. Am. Chem. Soc. 131 Growth Des. 7 (2007) 2720–2724.
(2009) 18299–18303. [30] H. Zeng, J. Li, J.P. Liu, Z.L. Wang, S. Sun, Exchange-coupled nanocomposite mag-
[17] M. Tadic, I. Milosevic, S. Kralj, M. Mitric, D. Makovec, M.L. Saboungi, L. Motte, nets by nanoparticle self-assembly, Nature 420 (2002) 395–398.
Synthesis of metastable hard-magnetic ε-Fe2O3 nanoparticles from silica-coated [31] L. Lu, Z. Ai, J. Li, Z. Zheng, Q. Li, L. Zhang, Synthesis and characterization of Fe-
akaganeite nanorods, Nanoscale 9 (2017) 10579–10584. Fe2O3 core-shell nanowires and nanonecklaces, Cryst. Growth Des. 7 (2007)
[18] J. Jin, S. Ohkoshi, K. Hashimoto, Giant coercive field of nanometer-sized iron oxide, 459–464.
Adv. Mater. 16 (2004) 48–51. [32] N.J.O. Silva, V.S. Amaral, L.D. Carlos, Relevance of magnetic moment distribution
[19] S. Sakurai, J. Shimoyama, K. Hashimoto, S. Ohkoshi, Large coercive field in mag- and scaling law methods to study the magnetic behavior of antiferromagnetic na-
netic-field oriented ε-Fe2O3 nanorods, Chem. Phys. Lett. 458 (2008) 333–336. noparticles: application to ferritin, Phys. Rev. B 71 (2005) 184408.
[20] S. Sakurai, K. Tomita, K. Hashimoto, H. Yashiro, S. Ohkoshi, Preparation of the [33] I.S. Lyubutin, C.R. Lin, Y.V. Korzhetskiy, T.V. Dmitrieva, R.K. Chiang, Mössbauer
nanowire form of ε-Fe2O3 single crystal and a study of the formation process, J. spectroscopy and magnetic properties of hematite/magnetite nanocomposites, J.
Phys. Chem. C 112 (2008) 20212–20216. Appl. Phys. 106 (2009) 034311.
[21] S. Ohkoshi, S. Sakurai, J. Jin, K. Hashimoto, The addition effects of alkaline earth [34] C. Lan, J. Gong, S. Liu, S. Yang, Synthesis and magnetic properties of single-crys-
ions in the chemical synthesis of ε-Fe2O3 nanocrystals that exhibit a huge coercive talline Na2- x Mn8O16 nanorods, Nanoscale Res. Lett. 6 (2011) 133.
field, J. Appl. Phys. 97 (2005) 10K312. [35] Y. Tian, W. Wang, Y. Chai, J. Cong, S. Shen, L. Yan, S. Wang, X. Han, Y. Sun,
[22] A. Rabenau, The role of hydrothermal synthesis in preparative chemistry, Angew. Quantum tunneling of magnetization in a metal-organic framework, Phys. Rev. Lett.
Chem. Int. Ed. Engl. 24 (1985) 1026–1040. 112 (2014) 017202.
[23] E. Taboada, M. Gich, A. Roig, Nanospheres of silica with an ε-Fe2O3 single crystal [36] U.C. Chung, J.L. Mesa, J.L. Pizarro, I. de Meatza, M. Bengoechea, J.R. Fernández,
nucleus, ACS Nano 3 (2009) 3377–3382. M.I. Arriortua, T. Rojo, Li1.43[FeII4.43FeIII
0.57(HPO3)6]·1.5H2O: a phosphite oxoanion-
[24] S. Ohkoshi, A. Namai, T. Yamaoka, M. Yoshikiyo, K. Imoto, T. Nasu, S. Anan, based compound with lithium exchange capability and spin-glass magnetic beha-
Y. Umeta, K. Nakagawa, H. Tokoro, Mesoscopic bar magnet based on ε-Fe2O3 hard vior, Chem. Mater. 23 (2011) 4317–4330.

19344