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CERAMICS
INTERNATIONAL
Ceramics International 40 (2014) 2869–2876
www.elsevier.com/locate/ceramint

Microwave synthesis and sintering of forsterite nanopowder produced

by high energy ball milling
H. Barzegar Bafrooein, T. Ebadzadeh, H. Majidian
Ceramic Division, Materials and Energy Research Center, P.O. Box 14155-4777, Karaj, Alborz, Iran

Received 30 September 2013; accepted 6 October 2013

Available online 18 October 2013

Abstract

This paper reports the development of a new process for the synthesis and sintering of forsterite nanopowder via microwave-assisted high
energy ball milling of a powder mixture containing silica gel and Mg(OH)2. X-ray diffraction (XRD), FTIR spectrometer, BET, scanning electron
microscopy (SEM) and Transmission electron microscopy (TEM) techniques were utilized to characterize the as-milled and annealed samples. X-
ray diffraction results showed that highly ordered forsterite can be obtained through the calcination of the as-milled powder over 900 1C. In
addition, SEM and TEM observations of the synthesized powders showed that the particle size of the powder lies in the nanometer range, also
being compared with the BET results (about 45 to 64.5 nm). Microwave sintering (MS) of the forsterite nanopowder produced with high energy
ball milling and subsequent microwave heating resulted in remarkable enhancement in densification in comparison with conventional sintering
(CS) at lower temperatures.
& 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Keywords: A. Sintering; Microwave heating; Synthesis; Forsterite; High energy ball milling

1. Introduction Forsterite (Mg2SiO4) is an important material of olivine family

of crystals in the magnesia–silica system with orthorhombic
Modern technologies constantly require materials with structure [2]. The extremely low electrical conductivity of
special properties to achieve breathtaking innovations. This, forsterite makes it an ideal material for tunable laser [3–5].
in turn, requires constant improving of scientific and techno- Moreover, it shows good refractoriness with high melting point
logical fabrication as well as working procedures. Nanocrystal- (1890 1C), low thermal expansion, good chemical stability and
line materials are single-phase or multi-phase materials, whose excellent insulation properties even at high temperatures [6–8].
crystal size is in the order of a few (typically 1–100) The manufacturers of the SOFC (solid oxide fuel cells) find
nanometers at least in one dimension. Because of the extre- forsterite interesting due to its linear thermal expansion
mely small size of the grains, a large fraction of the atoms in coefficient perfectly matching the other cell components and
these materials is located in the grain boundaries and thus the a very high stability in fuel cell environments [9]. In the recent
material exhibits enhanced combinations of physical, mechan- years, much attention has been paid to the development of
ical, and magnetic properties (compared to material with a microwave telecommunication technologies because of the
more conventional grain size, i.e., 41 μm). Therefore, nano- increased requirements for microwave applications. Among
crystalline materials show increased strength, high hardness, these materials, forsterite Mg2SiO4 has attracted a great deal of
extremely high diffusion rates, and consequently reduced attention due to its low dielectric constant and loss tangent
sintering times for powder compaction [1]. Forsterite is a [10,11]. Furthermore, forsterite bioceramic possesses good
crystalline magnesium silicate with chemical formula biocompatibility and mechanical properties and might be
Mg2SiO4, named after the German naturalist Johann Forster. suitable for hard tissue repair [12–14]. Various techniques
including the heating of mixed powders prepared by the
n
Corresponding author. Tel.: þ98 2636204130; fax: þ 98 2636280030. alkoxy method [15], the polymer matrix method [16],
E-mail address: hadi.merc@gmail.com (H. Barzegar Bafrooei). the citrate–nitrate route [17], the sol–gel method [18–20], the

0272-8842/$ - see front matter & 2013 Elsevier Ltd and Techna Group S.r.l. All rights reserved.
http://dx.doi.org/10.1016/j.ceramint.2013.10.025
2870 H. Barzegar Bafrooei et al. / Ceramics International 40 (2014) 2869–2876

combustion method [21] and high energy ball milling have

been used to synthesize forsterite [22–24]. It is been recently
found that microwave energy can be used to synthesize
ceramic powders where reactions of component oxides at
elevated temperatures are involved [25]. Microwave synthesis
of materials is fundamentally different from the conventional
synthesis in terms of its heating mechanism. In the microwave
furnace, the interaction of microwaves with the material
generates heat within the sample volume [26]. Moreover,
microwave energy heats the material on a molecular level
which leads to uniform heating, whereas conventional heating
systems would heat the sample up from the surface towards the
interior zones, giving rise to steep thermal gradients [27]. The
microwave assisted preparation of nanopowders is a new
method that includes the hydrothermal, hydrolysis and co-
precipitation methods [28–30]. In this paper, a novel approach
which is the combination of ball milling and microwave
heating for the synthesis and sintering of forsterite has been
developed.

2. Experimental

2.1. Materials

Silica gel and magnesium hydroxide (Mg(OH)2) were used

as the starting materials for the synthesis of forsterite. Figs. 1
and 2(a, b) show the XRD and morphology of the initial
powder agglomerates. The XRD pattern of raw materials was
Fig. 1. (a) XRD and (b) SEM Mg(OH)2 powder before high energy ball
characterized according to those of silica gel (amorphous milling.
pattern) and Mg(OH)2 (XRD JCPDS data reference code
007-0239). The Mg(OH)2 powder has an angular shape with
a mean agglomerate diameter of about 5 mm. Silica gel powder 2.3. Characterization
has a spherical shape with a mean agglomerate size of about 1–
2 mm. The agglomerate size of powders was determined using The structural properties of the samples were investigated
scanning electron microscope (SEM). Also several micro- by X-ray diffraction (Simens D-500 system) technique using
graphs were used for agglomerate size measurement and the a CuKα monochromatized radiation source and Ni filter in the
average value was reported. range 2θ=10–80. The morphology, microstructure and the
particle size of the high energy ball milled powders and
2.2. Experimental procedure sintered samples were examined by a Philips scanning
electron microscope (SEM) operating at 20 kV and Transmis-
The milling experiment was carried out with Planetary Mill. sion electron microscopy (TEM, TecnaiF20, Phillip, Hol-
A zirconia vial with diameter of 80 mm and 25 zirconia balls with land). The density of the sintered samples was measured
diameter of 15 mm were used as the milling medium. The required according to the Archimedes method. FTIR spectroscopy of
amount of powder mixture for 15:1 ball to powder mass ratio the test materials was carried out by a Fourier transform
(BPMR) was taken from the homogeneous mixture of powders infrared spectrometer (Bruker, V33 spectrophotometer) from
and placed in the bowl for ball milling. The raw materials were 400 to 4000 cm 1, using KBr pellets containing 1% weight
milled in air at room temperature for 0.25, 5, 10, 20, 30 and 40 h, sample in KBr. Also, the surface area (BET) was determined
respectively. The rotation speed of the disk was 270 rpm and that by nitrogen adsorption at 196 1C using an automated gas
of the vials was 675 rpm. The milled powders were calcined at adsorption analyzer (Micrometrics, Gemini 2375). The BET
500–1200 1C by microwave heating in the air. Powders pre- surface area was used to calculate the mean particle size [D]
pressed up to  49.5% of the theoretical density were sintered (Eq. (1)).
in two different ways: (i) conventional sintering (CS) via
continuous heating up to different temperature (1150–1350 1C) D ¼ 6=sρ ð1Þ
with a heating rate of 10 1C/min, (ii) microwave sintering (MS)
through heating up to the same temperature with conventional where ‘s’ is the BET surface area (m2/g) and ‘ρ’ is the density
sintering in a 1.1 kW, 2.45 GHz multimode microwave cavity of forsterite (kg/m3). The density of forsterite was considered
(Bosch, Germany). as 3.27  103 (kg/m3).
 H. Barzegar Bafrooei et al. / Ceramics International 40 (2014) 2869–2876 2871

patterns. Subsequent thermal treatment is necessary to synthe-

size the forsterite structure. Fig. 4 shows the diffraction
patterns of the powders milled for 40 h after several thermal
treatments at temperatures between 500 and 1200 1C. At the
lowest tested temperature (500 1C), a forsterite-structured
material was crystallized. As the calcination temperature
increased up to 900 1C, pure forsterite was obtained. However,
the calcination at high temperatures resulted in an increase in
peak intensity which is ascribed to the enhancement of
crystallite size. Hence, XRD provides some valuable evidence
that the pure forsterite phase can be obtained by high-energy
ball milling of powders calcined at 900 1C using microwave
processing. In this case, the calcination temperature decreases
to 100 1C as compared to conventional solid state reaction of a
high-energy ball milled powder [20]. Therefore, the calcination
temperature of forsterite was determined to be 900 1C.
Observations via scanning electron microscopy revealed that
the milling process strongly affects the particle morphology
and size. Fig. 5 shows the SEM micrographs of the powders
milled for different times. During the milling, the particles are
constantly impacted and fractured leading to a considerable
reduction of the particle size as a result of the energy provided
during the ball milling. Initially, they formed larger aggregates,
then broken up in further steps of the milling process.
Consequently, uniform grain size distribution is observed with
the increase of milling time. It can be seen that the milled
powders after 0.25 and 5 h contain larger particles and
Fig. 2. (a) XRD and (b) SEM silica gel powder before high energy ball
agglomerates but with the increase of milling time up to
milling. 20 h, the particles and agglomerates size will decrease.
However, with further increase of the milling time, the
microstructure becomes finer and more homogenous. Fig. 6
presents the SEM images of the powder high energy ball
milled for 40 h and heat treated at different temperatures. After
heat treatment at 500 1C, no particle coarsening occurred and
the shape and size remained almost the same as those of milled
powder. It can be seen that the particle sizes lightly increased
as a function of calcination temperature and this is in good
agreement with the particle size estimated using the BET
method. The TEM micrograph of the single-phase forsterite
nanopowder obtained from 40 h high energy ball milling with

Fig. 3. The XRD patterns of the mixture of initial precursor at various

ball-milling times.

3. Results and discussion

Fig. 3 shows the XRD patterns of the mixtures after various

milling times at room temperature. The XRD patterns of initial
powders after 0.25 h of high energy milling corresponded to
those of Mg(OH)2 phases. Increasing the milling time to 40 h
was observed to result in the broadening of XRD peaks as well
as a significant decrease in their intensity as a consequence of
refinement of crystallite size and the enhancement of the lattice Fig. 4. XRD patterns of the mixtures initial precursors milled for 40 h and
strain. Once crystalline phase was observed in the XRD calcined at different temperatures by microwave heating.
2872 H. Barzegar Bafrooei et al. / Ceramics International 40 (2014) 2869–2876

Fig. 5. SEM micrograph of the mixture of the initial precursors milled for different times, (a) 0.25 h, (b) 5 h, (c) 10 h, (d) 20 h, (e) 30 h and (f) 40 h.

subsequent calcination at 900 1C by microwave heating is precursors milled for 0.25 h, the observed bonds in the FT-IR
shown in Fig. 7. It is clear that the average particle diameter of spectrum corresponded to silica gel and magnesium hydroxide.
product was less than 100 nm. Based on the results obtained As the FTIR spectra shown in Fig. 8, the sharp and intense
by TEM investigations, it may be concluded that high energy peak at 3697 cm 1 was due to the OH group in magnesium
ball milling with subsequent calcination can be useful for hydroxide, the strong peak at around 440 cm 1 was assigned
synthesizing the forsterite nanopowder. The infrared spectra of to the Mg–O stretching vibration [31,32]. The intense bands
the ball milled and synthesized forsterite powders in the 4000– related to the siloxane stretching (Si–O–Si) of these groups at
400 cm 1 range are shown in Fig. 8. For the mixture of initial 470, 800, and 1090 cm 1 are ascribed to the bending modes,
 H. Barzegar Bafrooei et al. / Ceramics International 40 (2014) 2869–2876 2873

Fig. 6. SEM micrograph of the mixtures initial precursors milled for 40 h and calcined at (a) 500 1C, (b) 600 1C, (c) 700 1C, (d) 800 1C, (e) 900 1C, (f) 1000 1C,
(g) 1100 1C and (h) 1200 1C, by microwave heating.
2874 H. Barzegar Bafrooei et al. / Ceramics International 40 (2014) 2869–2876

Table 1
Surface area, particle size and crystallite size of spinel nanopowders at different
temperatures.

Sample Surface area (m2 g 1

) Particle size (nm)

Ball milled for 40 h 30.7 –

Calcined at 900 1C 40.1 45
Calcined at 1000 1C 38.8 47
Calcined at 1100 1C 34.3 53
Calcined at 1200 1C 27.5 64.5

Fig. 7. TEM of the mixture of initial precursors milled for 40 h and calcined at
900 1C by microwave heating.

Fig. 9. Relative density of forsterite ceramics prepared using conventional and

microwave sintering techniques.

temperatures. Increasing the surface area of the mixture of

initial precursors is due to the rapid decomposition accom-
panied by the appearance of considerable stresses, which leads
to decomposition of the particles. With increasing temperature
from 900 to 1200 1C, the surface area decreases as the particle
size increases due to the grain growth. By increasing the
temperature above 1000 1C, the surface diffusion can be
activated and caused sintering by formation of necks between
particles. Therefore, the surface area reduces as the particle
Fig. 8. FTIR spectra of ball milled mixture of initial precursors at (a) 0.25 h, size increases with a higher rate above 1000 1C. Nanocrystal-
(b) 40 h and the calcined powders at (c) 600 1C, (d) 800 1C and (e) 1000 1C. line forsterite powder was sintered at different temperatures
using conventional and microwave sintering techniques, and
symmetric vibration and asymmetric stretching of the Si–O–Si, the relative densities obtained are shown in Fig. 9. It can be
respectively [33]. With increasing milling time to 40 h, the seen that the relative density of the conventional sintered
intensity of bonds related to the mixture of initial precursors samples has improved by increasing the sintering temperature,
decreased and these bonds were observed to broaden. The merely reaching 93.7% of the theoretical value at 1300 1C for
infrared spectra of forsterite powder obtained after 40 h milling 120 min. The variation of the relative density of the
and subsequent annealing at different temperature is illustrated microwave-sintered samples is similar to that of the
in Fig. 8c–e. The spectra clearly display the peaks of Si–O conventional-sintered sample. However, its relative density
bands in the SiO4 tetrahedron that prove the formation of reaches up to 96.2% of the theoretical value at 1250 1C
forsterite as it is shown in the XRD pattern of this sample. The without soaking time. Fig. 10 shows SEM images of the
bands related to the characteristic peaks of forsterite appear at fracture surface of forsterite prepared using conventional and
1007, 986, 960, 873, and 838 cm 1 (SiO4 stretching), at 616, microwave sintering techniques. It can be seen that there is a
527, and 507 cm 1 (SiO4 bending), and at 475 cm 1 for marked difference between fracture surfaces of the forsterite
modes of octahedral MgO6. Band positions for the prepared samples. In Fig. 10(a), it can be seen that the foraterite
forsterite agreed with the results reported in previous studies ceramics produced by conventional processing are rather
[2,20]. The effect of calcination temperature on the surface porous; thus, the densification of the ceramic is insufficient.
area and particle size is shown in Table 1. The surface area For microwave processing, the densification in the sintered
increases at 900 1C (E 40.1 m2/g); while decreases at higher specimen is enhanced considerably, as shown in Fig. 10(b).
 H. Barzegar Bafrooei et al. / Ceramics International 40 (2014) 2869–2876 2875

possessed smaller grain size, better densification and more

uniform grain growth.

Reference

[1] C. Suryanarayana, Mechanical alloying and milling, Prog. Mater. Sci. 46

(2001) 1–184.
[2] C. Kosanovic, N. Stubicar, N. Tomasic, V. Bermanec, M. Stubicar,
Synthesis of a forsterite powder by combined ball milling and thermal
treatment, J. Alloys Compd. 389 (2005) 306–309.
[3] S.A. Boppart, G.J. Tearney, B.E. Bouma, J.F. Southern, M.E. Brezinski,
J.G. Fujimoto, Noninvasive assessment of the developing Xenopus
cardiovascular system using optical coherence tomography, Proc. Natl.
Acad. Sci. USA 94 (1997) 4256–4261.
[4] B.R. Washburn, S.A. Diddams, N.R. Newbury, J.W. Nicholson,
M.F. Yan, C.G. Jorgensen, Phaselocked erbium-fiber-laser-based fre-
quency comb in the near infrared, Opt. Lett. 29 (2004) 250–252.
[5] L. Lin, M. Yin, C. Shi, W. Zhang, Luminescence properties of a new red
long-lasting phosphor: Mg2SiO4:Dy3 þ , Mn2 þ , J. Alloys Compd. 455
(2008) 327–330.
[6] G.W. Brindley, R. Hayami, Kinetics and mechanism of formation of
forsterite (Mg2SiO4) by solid state reaction of MgO and SiO2, Philos.
Mag. Lett. 12 (1965) 505–514.
[7] A. Douy, Aqueous synthesis of forsterite (Mg2SiO4) and enstatite
(MgSiO3), J. Sol–Gel Sci. Technol. 24 (2002) 221–228.
[8] A.G.M. Othman, N.M. Khalil, Sintering of magnesia refractories through
the formation of periclase–forsterite-spinel phases, Ceram. Int. 31 (2005)
1117–1121.
[9] V. Petricevic, S.K. Gayen, R. Alfano, K. Yamagishi, Laser action in
chromium-doped forsterite, Appl. Phys. Lett. 52 (1988) 1040–1043.
[10] F. Tavangarian, R. Emadi, Effects of mechanical activation and chlorine
ion on nanoparticle forsterite formation, Mater. Lett. 65 (2011) 126–129.
[11] L. Cheng, P. Liu, X.M. Chen, W.C. Niu, G.G. Yao, C. Liu, X.G. Zhao,
Q. Liu, H.W. Zhang, Fabrication of nanopowders by high energy ball
milling and low temperature sintering of Mg2SiO4 microwave dielectrics,
J. Alloys Compd. 513 (2012) 373–377.
[12] F. Tavangarian, R. Emadi, Nanostructure effects on the bioactivity of
forsterite bioceramic, Mater. Lett. 65 (2011) 740–743.
[13] H. Ghomi, M. Jaberzadeh, M.H. Fathi, Novel fabrication of forsterite
scaffold with improved mechanical properties, J. Alloys Compd. 509
(2012) L63–L68.
[14] M.H. Fathi, M. Kharaziha, Two-step sintering of dense, nanostructural
forsterite, Mater. Lett. 63 (2009) 1455–1458.
[15] M.T. Tsai, Hydrolysis and condensation of forsterite precursor alkoxides:
modification of the molecular gel structure by acetic acid, J. Non-Cryst.
Fig. 10. SEM images of fracture surface of the forsterite at (a) 1200 1C for
Solids 298 (2002) 116–130.
120 min using conventional sintering, and at (b) 1250 1C without soaking time.
[16] M.H.E. Martin, C.K. Ober, C.R. Hubbard, W.D. Porter, O.B. Cavin, Poly
(methacrylate) precursors to forsterite, J. Am. Ceram. Soc. 75 (1992)
Also, compared with CS samples, MS samples show smaller 1831–1838.
grain size as shown in SEM images. [17] A. Saberi, Z. Negahdari, B. Alinejad, F. Golestani-Fard, Synthesis and
characterization of nanocrystalline forsterite through citrate–nitrate route,
Ceram. Int. 35 (2009) 1705–1708.
[18] A. Kazakos, S. Komarneri, R. Roy, Preparation and densification of
4. Conclusions forsterite (Mg2SiO4) by nanocomposite sol–gel processing, Mater. Lett. 9
(1990) 405–409.
In this paper, the microwave assisted high-energy ball [19] D.G. Park, J.C. Duchamp, T.M. Duncan, J.M. Burlitch, Preparation of
milling technique was used to prepare nanosized forsterite forsterite by pyrolysis of a xerogel: the effect of water, Chem. Mater. 6
(1994) 1990–1995.
(Mg2SiO4). The results showed that the single-phase forsterite [20] K.P. Sanosh, A. Balakrishnan, L. Francis, T.N. Kim, Sol–gel synthesis of
was formed at the relatively low temperature of about 900 1C forsterite nanopowders with narrow particle size distribution, J. Alloys
without unreacted SiO2 and MgO phases. Powders with Compd. 495 (2010) 113–115.
nanosized microstructures were formed. Moreover, BET [21] K. Mostafavi, M. Ghahari, S. Baghshahi, A.M. Arabi, Synthesis of
results determined that the particle sizes of synthesized Mg2SiO4:Eu3 þ by combustion method and investigating its lumines-
cence properties, J. Alloys Compd. 555 (2013) 62–67.
powders lie in the range of 45–64.5 nm, respectively. From [22] F. Tavangarian, R. Emadi, A. Shafyei, Influence of mechanical activation
the study of forsterite ceramics prepared by microwave and thermal treatment time on nanoparticle forsterite formation mechan-
sintering and conventional sintering, it is seen that MS samples ism, Powder Technol. 198 (2010) 412–416.
2876 H. Barzegar Bafrooei et al. / Ceramics International 40 (2014) 2869–2876

[23] F. Tavangarian, R. Emadi, Synthesis of nanocrystalline forsterite [29] H. Mohebbi, T. Ebadzadeh, F.A. Hesari, Synthesis of nano-crystalline
(Mg2SiO4) powder by combined mechanical activation and thermal NiO–YSZ by microwave-assisted combustion synthesis, Powder Technol.
treatment, Mater. Res. Bull. 45 (2010) 388–391. 188 (2009) 183–186.
[24] F. Tavangarian, R. Emadi, A. Shafyei, Influence of mechanical activation [30] N Shojaee, T Ebadzadeh, A Aghaei, Effect of concentration and heating
and thermal treatment time on nanoparticle forsterite formation mechan- conditions onmicrowave-assisted hydrothermal synthesis of ZnO nanor-
ism, Powder Technol. 198 (2010) 412–416. ods 61 (2010) 1418–1423Mater. Charact. 61 (2010) 1418–1423.
[25] D. Mingos, P. Michael, Microwave syntheses of inorganic materials, [31] W. Jiang, X. Hua, Q. Han, X. Yang, L. Lu, X. Wang, Preparation of
Adv. Mater. 5 (1993) 857–859. lamellar magnesium hydroxide nanoparticles via precipitation method,
[26] T. Ebadzadeh, M.H. Sarrafi, E. Salahi, Microwave-assisted synthesis and Powder Technol. 191 (2009) 227–230.
sintering of mullite, Ceram. Int. 35 (2009) 3175–3179. [32] D. An, X. Ding, Z. Wang, Y. Liu, Synthesis of ordered arrays of
[27] T. Ebadzadeh, Formation of mullite from precursor powders: sintering, micro- magnesium hydroxide nanoparticles via a simple method, Colloid Surf.
structure and mechanical properties, Mater. Sci. Eng. A355 (2003) 56–61. A: Physicochem. Eng. Asp. 356 (2010) 28–31.
[28] S. Barison, M. Fabrizio, S. Fasolin, F. Montagner, C. Mortalo, A microwave- [33] N. Pijarn, A. Jaroenworaluck, W. Sunsaneeyametha, R. Stevens, Synth-
assisted sol–gel Pechini method for the synthesis of BaCe0.65Zr0.20Y0.15O3-d esis and characterization of nanosized-silica gels formed under controlled
powders, Mater. Res. Bull. 45 (2010) 1171–1176. conditions, Powder Technol. 203 (2010) 462–468.