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Materials Letters 85 (2012) 138–141

Contents lists available at SciVerse ScienceDirect

Materials Letters
journal homepage: www.elsevier.com/locate/matlet

Structural and optical characterization of hemimorphite with flower-like

morphology synthesized by a novel low-temperature method
Ivana Lj. Validžić a,n, Miodrag Mitrić a, Bojan M. Jokić b, Mirjana I. Čomor a
a
Vinča Institute of Nuclear Sciences, University of Belgrade, P.O. Box 522, 11001 Belgrade, Serbia
b
Faculty of Technology and Metallurgy, University of Belgrade, Karnegijeva 4, 11000 Belgrade, Serbia

a r t i c l e i n f o a b s t r a c t

Article history: We report on novel, low temperature synthesis of well crystallized hemimorphite zinc silicate
Received 17 April 2012 Zn4Si2O7(OH)2(H2O) (ZSO) with flower-like morphology, via one-pot method that includes the
Accepted 28 June 2012 assistance of a non-ionic block copolymer. The morphology of the synthesized ZSO powder was
Available online 6 July 2012
observed by SEM and FESEM. The structure of the ZSO sample was refined down to the R-factor of 8.6%.
Keywords: The refinement revealed the ZSO powder that belongs to the orthorhombic system with space group
Crystal structure Imm2, and ZnO nanoparticles as a minor phase in the synthesized powder. The photoluminescence (PL)
Optical materials and properties and diffuse reflectance spectroscopy (DRS) measurements demonstrated optical properties of the minor
Luminescence ZnO phase.
Electron microscopy
& 2012 Elsevier B.V. All rights reserved.
X-ray technique

1. Introduction Typically, 50 ml of 0.1 M ZnCl2 solution was mixed with 100 ml

Zinc silicate (ZSO), a representative member of the family of
silicate compounds, has attractive features and thus is suitable for
various applications in coating [1], in protecting steel from corrosion
[2], in cathode ray tubes [3], as a host for up conversion of
luminescent materials [4], as catalyst [5], etc. Hemimorphite
(ZSO), one of the three crystalline phases formed by zinc silicates,
belongs to the orthorhombic system with space group Imm2 [6,7]. A
unique synthetic route that can provide high quality materials
regarding their morphology and crystallinity, with enhanced prop-
erties (photoluminescent and catalytic) for improved performance
in some fields, has not yet been developed and remains a challenge.
In this paper, we have described a novel low temperature
synthetic method for the production of well crystallized ZSO pow-
ders, with minor ZnO content. The properties of the ZSO powder were
studied in detail using scanning electron microscopy (SEM), field
emission scanning electron microscopy (FESEM) with energy disper-
sive spectroscopy (EDS), X-ray powder diffraction (XRPD), photolu-
minescence (PL) and UV–vis diffuse reflectance spectroscopy (DRS).
2. Experimental procedure
All chemicals (Na2WO4  2H2O (Riedel-de Haën 99%), ZnCl2
(Merck 99%), non-ionic surfactant Pluronic F68 (polyoxyethy-
lene–polyoxypropylene block copolymer, Mn  8400 (Aldrich))
and NaOH (Fluka 98%)) were of the highest purity available.
n
Corresponding author. Tel.: þ381 11 8066428; fax: þ381 11 3408607.
E-mail address: validzic@vinca.rs (I.Lj. Validžić).
of copolymer solution (10 g/l). The pH was adjusted to 12 with
0.1 M NaOH solution [8]. As a source of Si small glass balls were
added into the flask. Then, under vigorous stirring, 50 ml of 0.1 M
Na2WO4  2H2O was added dropwise. After that, the mixture was
refluxed at 95 1C for 120 h. During the reflux, precipitation of ZSO
took place. The precipitated ZSO powder was separated from the
solvent containing copolymer immediately after synthesis by ultra-
centrifugation. The precipitate was centrifugally washed with
ethanol and distilled water and then annealed at 95 1C for 18 h.
It should be emphasized here that Na2WO4 allowed at relatively
high pH and heating time the release of Si from small glass balls
without participating in the reaction and the precipitation of ZSO
(see text below). In the absence of Na2WO4, however, even if the
small glass balls are present, ZSO cannot be obtained. To confirm
that the heating time is not responsible for the crystallinity of the
synthesized sample or the remained ZnO phase in it, the heating
was prolonged (120 h).
The scanning electron microscopy (SEM) images were
obtained using a JEOL JSM-6460LV instrument. The field emission
scanning electron microscopy (FESEM) ones by a TESCAN Mira3
XMU at 20 kV.
The chemical composition of the sample was analyzed using
an Isis 3.2 energy dispersive spectrometer (EDS), with a SiLi X-ray
detector connected to an SEM JEOL JSM-5800 and a computer
multi-channel analyzer.
Diffuse reflectance spectra (DRS) of the ZSO pellet were obtained
using a Thermo Scientific Evolution 600 UV–vis spectrophotometer.
Photoluminescence (PL) spectra of the ZSO pellet were
recorded on a Fluorolog-3 Model FL3-221 spectrofluorometer
system (Horiba Jobin-Yvon), using a 450-W xenon lamp as the

0167-577X/$ - see front matter & 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2012.06.111
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I.Lj. Validžić et al. / Materials Letters 85 (2012) 138–141 139

excitation source and a R928 photomultiplier tube as the
detector.
The X-ray powder diffraction (XRPD) pattern was obtained on
an automated Philips PW-1050 X-ray diffractometer using CuKa
radiation (operated at 40 kV and 30 mA). Diffraction data for
structural analysis were collected in the 2Y range of 10–1101,
count time for 12 s/step and step size of 0.021. Structure analysis
was done by the use of the KOALARIE computing program [9]
based on the Rietveld full profile refinement method [10]. The
sample for XRPD measurement was prepared following the
standard protocol [11].
3. Results and discussion
The morphology and microstructure of the ZSO powder were
studied by SEM and FESEM. Low magnification images (Fig.1A
and B) reveal the ZSO structure composed of nanorod and
nanoleaf bundles with bush-like forms between them, and all
assembled in floral arrangements. Similar morphologies for ZSO
have already been observed [12,13]. High magnification SEM and
FESEM images (not given here) show local population of small
nanoparticles of undefined shapes. This is in accordance with the
structural analysis, which revealed the presence of ZnO as the
minor phase with nanocrystallites in the ZSO synthesized powder
(see text below).
Fig. 2 shows the SEM microstructure and EDS analysis of the
ZSO powder. The results confirmed, detecting only Zn, O and Si,
the purity of our samples. The absence of tungsten proves that
Na2WO4 present at relatively high pH and heating time allows the
release of Si from small glass balls and that it does not take part in
the precipitation of the ZSO powder.
Optical properties of the ZSO powder were studied using a
combination of PL and DRS techniques. Fig. 3A shows the emis-
sion spectra of ZSO sample with the minor phase being ZnO, at
different excitation energies (3.54 eV (a), 3.87 eV (b) and 4.13 eV
(c)). The PL spectra show significant peak broadening and strong
emission between 2.24 and 3.8 eV with maxima around  3 eV.
Broad emission bands were then fitted to the Gaussian peaks for a
better understanding of the contribution from various kinds of
defects or phases. The PL spectrum excited at 3.54 eV (a) was
fitted to three Gaussian peaks centered at 3.14, 2.92 and 2.67 eV.
The broad luminescence band excited at 3.87 eV (b) was fitted to
four Gaussian bands peaked at 3.25, 3.15, 2.84 and 2.78 eV. The
last PL spectrum excited at 4.13 eV (c) was fitted to four Gaussian
bands peaked at 3.66, 3.25, 2.91 and 2.67 eV. Sun et al. [12] found
that the PL spectra of ZSO consist of a strong emission peak
located at 2.84 eV and several weak ones at 3.25, 2.97 and

Fig. 1. SEM (A), bars: first row 5 mm the other two rows 1 mm; and FESEM (B), bars: up left 20 mm, up right and down left 5 mm, down right 2 mm; micrographs of the ZSO
structure.

Fig. 2. SEM microstructure and EDS analysis of the ZSO powder.

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140 I.Lj. Validžić et al. / Materials Letters 85 (2012) 138–141

Fig. 3. PL spectra of the ZSO pellet excited at 3.54 eV (a), 3.87 eV (b) and 4.13 eV (c) with their deconvoluted Gaussian peaks (A), and plot for the determination of Eg of the
ZSO pellet (B).

Fig. 4. Final Rietveld plot of ZSO powder (with corresponding planes) containing ZnO as the minor phase and the standard pattern of ZSO (JCPDS 01-075-1583, black) and
ZnO (JCPDS 01-075-0576, red). (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

2.65 eV. Similar PL bands, centered at 2.84, 2.97, 2.66 and 2.62 eV,
were observed by Yang et al. [13]. It is clear that our findings are
in satisfactory agreement with the so far observed PL bands. On
the other hand, only Chouillet et al. [14] observed and proved the
minor ZnO phase in the synthesized zinc silicate. They also found
that the optical absorption could be assigned completely to the
minor ZnO phase. This corresponds well with our results (Fig. 3B).
Reflectance data were converted to Fkm (R) values (similar to
absorption) using the Kubelka–Munk equation. The presented
Tauc’s plot (Fig. 3B) used to estimate the band gap shows an
energy gap of 3.2 eV, which is characteristic of the ZnO semi-
conductor (minor phase confirmed by XRPD measurements,
discussion follows). Many authors [15–17] observed PL bands
for micro and nano ZnO particles at the same position as those
found for ZSO (from 3.66 to 2.67 eV, see Ref. [15]). Due to the fact
that DRS spectra correspond to the ZnO minor phase, we believe
that PL bands can also be assigned to this phase. It should be
emphasized here that even if ZnO is not observed in the XRPD
pattern (for instance as a well-dispersed ZnO amorphous phase or
nanoparticles with extremely small crystalline domains), the
photoluminescence can reveal its presence, as already shown in
our previous paper (see Ref. [8]). Also, according to the literature,
ZSO has a large band gap of 5.5 eV [12,18].
A typical XRPD pattern of the ZSO powder refluxed and
annealed at 95 1C for 120 h is shown in Fig. 4. All main peaks
revealing good crystallinity of the sample were indexed to the
orthorhombic system with space group Imm2. This is in good
agreement with the standard pattern of ZSO ((JCPDS, Card no.
01-075-1583 black) with corresponding planes, given in Fig. 4. Also,
there are relatively broad diffraction peaks of ZnO (JCPDS, Card no.
01-075-0576 red). The structure of ZSO was refined down to the
R-factor of 8.6%. The unit cell parameters are: (a) a¼8.37388 Å,
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I.Lj. Validžić et al. / Materials Letters 85 (2012) 138–141 141

b¼10.72164 Å and c¼ 5.11878 Å. The structural refinement also References

revealed the presence of the ZnO phase, at the level of 9.6 mass%, in
the synthesized ZSO powder and confirmed the nanosizes of the [1] Pereyra AM, Canosa G, Giudice A. Ind Eng Chem Res 2010;49:2740–6.
ZnO particulates. [2] Thomas A. Surf Coat Aust 2009;46:10–8.
[3] Blasse G, Grabai BC. Luminescente materials. Berlin: Springer-Verlag; 1994.
[4] Gerner P, Fuhrer C, Reinhard C, Gudel HUJ. Alloys Compd 2004;380:39–44.
[5] Breuer K, et al., editors. Angew Chem Int, 38; 1999. p. 1401–5.
4. Conclusions [6] Ito T, West JZ. Kristallogr 1932;83:1–8.
[7] Bahclay G, Cox EZ. Kristallogr 1960;113:23–9.
In summary, ZSO powders with flower-like particle morphology [8] Validžić ILj, Savić TD, Krsmanović RM, Jovanović DJ, Novaković MM, Popović
MC, et al. Mater Sci Eng B 2012;177:645–51.
were synthesized by a novel low temperature method with the [9] Cheary RW, Coelho AAJ. Appl Crystallogr 1992;25:109–21.
assistance of block copolymer. XRPD analysis of the synthesized [10] Rietveld HJ. Appl Crystallogr 1969;2:65–71.
powder showed a well-crystallized major ZSO phase and, despite [11] Pecharsky VK, Zavalij PY. Fundamentals of powder diffraction and structural
characterization of materials. Springer; 2005 [chapter 3 (11) pp. 292–293].
prolonged heating time the presence of ZnO as the minor phase in
[12] Sun Y, Zou R, Tian Q, Wu J, Chen Z, Hu. J. CrystEngComm 2011;13:2273–80.
the powder. Intense photoluminescence bands observed can be [13] Yang J, Sun Y, Chen Z, Zhao X. Mater Lett 2011;65:3030–3.
completely assigned to this minor ZnO phase. [14] Chouillet C, Villain F, Kermarec M, Lauron-Pernot H, Louis CJ. Phys Chem B
2003;107:3565–75.
[15] Kumari L, Li WZ, Vannoy CH, Leblanc RM, Wang DZ. Mater Res Bull
2010;45:190–6.
Acknowledgments
[16] Song R, Liu Y, He L. Solid State Sci 2008;10:1563–7.
[17] Ma P, Wu Y, Fu Z, Wang W. Adv Powder Technol 2012;23:170–4.
This study was financially supported by the Ministry of Educa- [18] Sun XW, Kwok HS. Appl Phys A: Mater Sci Process 1999;69:S39–43.
tion and Science of the Republic of Serbia (Projects 172056, III 45020
and III 45015).