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Abstract
Silver iodide particles were synthesized in the process of ultrasonic spray pyrolysis using aqueous solutions of thermodynamically stable silver
iodide clusters as precursor. The AgI particles were collected in solvents of different polarities such as water, 2-propanol and toluene. In order to
study influence of solvent and aging time on the morphological and structural properties of the AgI particles ultra-filtration was employed to isolate
solid material from solution. The scanning electron microscopy showed that morphology of the AgI particles is different for different solvents. The
AgI particles with hexagonal/triangular shape were obtained in water and toluene, while in 2-propanol hollow spheres were formed. The X-ray
diffraction analysis, besides wurtzite hexagonal and zinc blende cubic phases, revealed appearance of tetragonal high-pressure AgI modification
for sample collected in toluene and for sample aged in 2-propanol. The aging in toluene induced transformation of all three modifications into
single phase with one preferred orientation.
© 2007 Elsevier B.V. All rights reserved.
0254-0584/$ – see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2007.06.035
I. Lj.Validžić et al. / Materials Chemistry and Physics 107 (2008) 28–32 29
frequency of 1.7 MHz for aerosol generation, and horizontal electric furnace
with the quartz tube and a vessel for particle collection. The effective heating
length of reactor tube was 1.25 m with the maximum temperature of 300 ◦ C in
the middle of the furnace. The flow rate of air was 30 l h−1 . The flow rate of
aerosol droplets was assumed to be equal to the flow rate of gas carrier, and
residence time of aerosol droplets in the furnace was found to be 1 min.
The obtained AgI powders were collected in different solvents such as water,
2-propanol and toluene. In the first series of experiments AgI particles were
separated from solvents containing excess of KI immediately after synthesis,
while in the second set of experiments aging time of AgI particles was 2 weeks.
The separation process was performed using ultra-filtration through a Milli-
pore membrane of 0.01 m pore size, and solid AgI was characterized using
optical and structural techniques. All samples were prepared under the same
experimental condition.
Absorption spectra of the precursor solution, as well as solutions obtained
after the process of USP were measured using a Perkin-Elmer Lambda 35
UV–vis spectrophotometer. Diffuse reflectance measurements of solid AgI were
performed on the same instrument using the Labsphere RSA-PE-20 accessory.
The scanning electron microscopy (SEM) measurements were performed
using JEOL JSM-6460LV instrument. The solid AgI samples on a Millipore
membrane were coated with thin layer of gold deposited by sputtering process.
The thickness of the gold film was up to 40–50 nm.
The X-ray diffraction (XRD) measurements were carried out on a Philips
PW-1050 automatic diffractometer, using Cu K␣ radiation. Measurements were
performed in the 2θ range from 10◦ to 120◦ with scanning step width of 0.02◦
and time of 10 s per step.
Fig. 4. SEM images of AgI particles collected in toluene: (A) immediately after the process of USP and (B) after 2 weeks of aging. (C) Particle size distribution
(PSD) of AgI particles collected in toluene: (a) immediately after the process of USP and (b) after 2 weeks of aging.
of AgI in 2-propanol induced appearance of new tetragonal respectively). Because of that we are not certain which one
phase (peaks at 14.6◦ , 29.3◦ and 34.5◦ can be only attributed to of three crystal phases survived aging in toluene. However,
tetragonal phase). Tetragonal modification of AgI is known as a tetragonal AgI phase is our favourite because experimentally
high-pressure modification which can exist at room temperature determined position of the XRD peak (24.1◦ ) is just in between
only if pressure is between 2.8 and 3.8 kbar [30]. Appearance of positions of very close to each other (1 1 3) and (2 2 2) tetragonal
unusual structures as a function of aging time has been observed crystal planes (23.986◦ and 24.185◦ , respectively). Also, noticed
with some other halides [15]. For example, yellow orthorhom- tendency that decrease of solvent polarity promotes appearance
bic form of HgI2 that spontaneously converts to the tetragonal of tetragonal AgI phase supports above mentioned statement.
modification at temperature above 204 K was isolated during the We believe that this is the first example of AgI particles with
aging process at room temperature. single crystal phase synthesized under standard experimental
The XRD patterns of the AgI particles collected in toluene conditions. A similar situation has been observed for a different
immediately after the process of USP and after aging of 2 weeks material (BaTiO3 ), where the cubic phase is registered at room
are shown in Fig. 5(E and F). All three AgI phases (hexagonal, temperature for samples prepared under special conditions [31].
cubic and tetragonal) coexist in sample obtained immediately The stabilization at room temperature of the cubic phase in this
after the process of USP. The XRD pattern of the AgI sample material was attributed to small crystallite size.
aged 2 weeks in toluene clearly showed presence of only one In conclusion, we showed that it is possible to synthesize AgI
diffraction peak at 24.1◦ . It is obvious that during the aging pro- particles in wide size range by using thermodynamically sta-
cess in toluene hexagonal, cubic and tetragonal crystal phases ble silver iodide clusters as precursor and the USP as method.
transformed into single phase with one preferred orientation. These particles, collected and aged in different solvents, exhibit
According to the JCPDS data positions of (0 0 2) hexagonal, extraordinary reach behaviour in the structural and morpholog-
(1 1 1) cubic, as well as (1 1 3) and (2 2 2) tetragonal crystal ical sense. Proper choice of solvent and aging can lead to the
planes are very close (23.706◦ , 23.726◦ , 23.986◦ and 24.185◦ , formation of AgI particles with desired morphology or even
32 I. Lj.Validžić et al. / Materials Chemistry and Physics 107 (2008) 28–32
References