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Preparation of tin oxide

Article in Journal of the Australian Ceramic Society · January 2007

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 56 H. Taib and C.C. Sorrell

PREPARATION OF TIN OXIDE

H. TAIBa,b*and C.C. SORRELLa
a
School of Materials Science and Engineering,
University of New South Wales, Sydney, NSW 2052, Australia
b
Faculty of Mechanical and Manufacturing Engineering, Universiti Tun Hussein Onn Malaysia,
86400 Parit Raja, Batu Pahat, Johor, Malaysia
*email: [email protected]

ABSTRACT
Submicron tin oxide (SnO2) was obtained from the thermal decomposition of tin oxalate (SnC2O4)
precipitated at room temperature from mixed solutions of tin (II) chloride and oxalic acid. The
o
concentrations were in the range 0.04 M to 0.20 M and decomposition was done at 800 C for 1
hour.
The work was intended to focus on the effects of initial solution concentration on the particle size
of the calcined SnO2. This was done by:
i) Increasing the oxalic acid concentration at fixed tin (II) chloride concentration
ii) Increasing the tin (II) chloride concentration at fixed oxalic acid concentration
The particle and agglomerate sizes of the calcined SnO2 also were assessed in terms of the
morphology of the precipitated SnC2O4, which was calcined to SnO2.
The SnC2O4 morphology showed a mixture of individual elongated prisms and elongated
prismatic intergrowths. However, the occurrence of the intergrowths did not correlate with the
precipitation conditions.
After calcining, pure tetragonal SnO2 of consistent , spherical, individual, particle size of ~75 nm
was observed, regardless of precipitation conditions. The consistent particle size probably is due
to the low solution concentration range used.
Crushing and grinding the calcined SnO2 powders resulted in agglomerated platelets, with a mean
diameter in the range ~0.5 micron. It is likely that surface water adsorption on the fine particles
facilitated the establishment of plasticity, which allowed the deformation between mortar and
pestle during grinding. There was no apparent relationship between the starting solution
concentration, addition method, and SnO2 particle and agglomerate size.

KEYWORDS: Tin oxide, precipitation, X-ray diffraction, morphology, particle size,

agglomeration

INTRODUCTION described. The objective of the work focused on

Tin oxide (SnO2) is a wide band gap n-type investigating the feasibility of rapid precipitation of
semiconductor with applications including solar SnO2 powders, where the effects of the
cells, gas sensors, transistors, electrodes, liquid concentrations of the starting material on the
crystal displays, and catalysts [1-6]. precipitated tin oxalate (SnC2O4) and SnO2 particle
The properties of SnO2 that influence its potential sizes, morphologies, and agglomeration were
applications depend on the different phases of its studied.
fabrication history, viz., synthesis routes and
methods. In addition to the chemistry of the
material, the morphological properties of powders EXPERIMENTAL PROCEDURE
influence their physical and chemical properties.
Sample Preparation
There are several methods for the synthesis of SnO2,
including microemulsion, hydrothermal synthesis, The starting materials were tin (II) chloride
gel combustion, and hydrolytic processes, including dihydrate (98 wt%, BDH, VWR International Ltd.,
sol gel [6-9]. Precipitation is one of most widely Germany) and oxalic acid dihydrate (99.5 wt%
used techniques to produce SnO2 powders [10-12]. Ajax FineChem, Australia).
In the present work, a method for obtaining Tin (II) chloride dihydrate and oxalic acid dihydrate
submicron SnO2 powders by precipitation is were individually dissolved in distilled water using
 J. Aust. Ceram. Soc. 43 [1] (2007) 56-61 57

250 mL volumetric flasks. Aqueous solutions of Powder Characterisation

250 mL of oxalic acid of variable concentrations X-Ray Diffraction
then were added dropwise to 250 mL of aqueous
Mineralogical analyses of all samples were done
solution of tin (II) chloride of fixed concentration
using an X-ray diffractometer (XRD, Siemens
using a peristaltic pump. During the addition, the o
aqueous mixture was agitated using a magnetic D5000, Germany). Samples were analysed over 5 -
o o
stirrer (8 mm Ø x 70 mm L) at a controlled speed of 60 2θ at a scanning speed of 1 /min 2θ and step
840 rpm. The addition time interval was consistent o
size 0.02 2θ.
at 15 min.
Field Emission Scanning Electron Microscopy
Nine samples of SnC2O4 powders were prepared
The particle sizes and morphologies of SnC2O4 and
using concentrations of both tin (II) chloride and
SnO2 were assessed using a field emission scanning
oxalic acid in the range 0.04 M to 0.20 M, as shown
electron microscope (FESEM, Hitachi S900, Japan)
in Table 1.
at an accelerating voltage of 4 kV.
Table 1: Sample groups and designations Laser Diffraction Particle Size Analysis
Concentration (M) The mean diameters of SnO2 were analysed by
Group Sample
SnCl2 H2C2O4 laser diffraction dynamic light scattering (90Plus
SN11 0.04 0.04 Particle Size Analyzer, Brookhaven Instrument
SN12 0.04 0.08 Corp., USA). The suspensions were sonified for 3
1 SN13 0.04 0.12 min and allowed to stabilise for 1 min before each
SN14 0.04 0.16 analysis. The samples prepared then were analysed
o
SN15 0.04 0.20 for 3 min at 25 C.
SN21 0.04 0.20
SN22 0.08 0.20
2 SN23 0.12 0.20 RESULTS AND DISCUSSION
SN24 0.16 0.20 Phase Development
SN25 0.20 0.20
The precipitated product consisted principally of
The samples were classified into two main groups: SnC2O4, with small amounts of tin oxychloride
i) Group 1: Fixed tin (II) chloride concentration (Sn4[OH]6Cl2) and an unidentified phase, as shown
(0.04 M) with additions of five concentrations o o
in Figure 1. The peak between 10 and 15 2θ
of oxalic acid (0.04-0.20 M, at 0.04 M derives from the Perspex sample holder.
increments) − five samples. The existence of tin oxychloride phase may be due
ii) Group 2: Five concentrations of tin (II) to the hydrolysis of tin (II) chloride [15], which can
chloride (0.04-0.20 M, at 0.04 M increments) occur during the dissolution of tin (II) chloride
with additions of fixed oxalic acid dihydrate in distilled water to form the aqueous
concentration (0.04 M) − five samples solution of tin (II) chloride. It is probable that the
white colloid that was observed in all cases.
Each precipitate was filtered and washed using a
The unreacted tin (II) chloride or oxalic acid was
No. 42 Whatman filter paper in a Buchner filter
removed during the washing. Since all
funnel with the assistance of a vacuum pump to
compositions except SN11 and SN25 (which were
accelerate the filtration process.
stoichiometric) contained excess oxalic acid, this
The precipitate was washed by rinsing in a filter
phase probably was the only one washed away.
funnel with flowing distilled water. This process
was repeated several times in order to remove the After calcination, the precipitated white SnC2O4
excess retained chloride ions. Complete removal of powder was decomposed to a grey-white powder,
the chloride ions was confirmed with the silver which was identified as SnO2 of high purity, as
nitrate test applied to the supernatant [13]. In order shown in Figure 2.
to reduce agglomeration by interparticle bridging
[14], the precipitate was washed twice with ethanol SnC2O4 and SnO2 Particles Characteristics
(99.8 wt%, Ajax FineChem, Australia). With one exception (sample SN11), the SnC2O4
The washed precipitate was dried in a drying oven
o particle morphologies consisted of mixtures of
at 120 C for 24 hours, after which it was hand- individual and intergrowths of elongated prisms, as
ground lightly with an agate mortar and pestle, the shown in Figure 3. Sample SN11 consisted of
precipitate was placed in an alumina crucible and imperfectly euhedral and equiaxed particles. It is
o
calcined in a muffle furnace by heating at 120 C/h likely that this morphology resulted from the use of
o
and soaking at 800 C for 1 h. The calcined powder the two lowest levels of concentration, which
then was hand-ground vigorously for 15 min with would have decreased the ionic collision frequency
an agate mortar and pestle. and increased the diffusion distance, thereby
minimising grain growth relative to the other
samples.
58 H. Taib and C.C. Sorrell

▲
SN11
▲
▲ ■▲ ▲▲
Intensity (a.u)

Perspex ○ ▲ ■ ▲▲ ▲
▲ ○ ▲ ▲■
■ ▲ ▲

SN25

5 10 15 20 25 30 35 40 45 50 55 60
Degrees Two Theta
Figure 1: X-ray diffraction patterns of samples for Group 1 (top) and Group 2 (bottom):
▲ − tin oxalate (SnC2O4), ■ − tin oxychloride (Sn4[OH] 6Cl2), ○ − unknown

♦
♦
SN11
♦
Perspex
Intensity (a.u)

♦ ♦
♦ ♦

SN25

5 10 15 20 25 30 35 40 45 50 55 60
Degrees Two Theta

Figure 2: X-ray diffraction patterns for samples SN11 (Group 1) and SN21 (Group 2): ♦ − tin oxide (SnO2)
Calcination of SnC2O4 to SnO2 yielded spherical the basis of the use of this material as a humidity
particles of a very consistent diameter of ~75 nm, sensor [17]. It is clear that the development of this
regardless of the concentration of the solution or plasticity resulted from adsorption of water vapour
addition method. The calcined cake consisted of a on the fine particle surfaces and this plasticity
foamed body, which resulted from the gas release resulted in the agglomeration of the particles.
during decomposition. In the case of the oxidation Owing to the compression-shear forces applied
of VOC2O4 to V2O3, it has been proposed that the during grinding, the resultant laminar flow caused
reaction gases form a shell around the oxide the agglomerates to adopt a platy morphology, as
particles during calcination, which can limit shown in Figure 4.
agglomeration [16]. In order to break up this mass, Although the grinding procedure was consistent for
the cake was ground vigorously using an agate all samples (done over a period of 3 weeks), it
mortar and pestle. It was noted that this procedure would be a simplication to assume that the nature
resulted in the development of tackiness and and degree of agglomeration were identical,
consequent adherence to the mortar. The particularly with variations in the relative humidity.
physisorption (or chemisorption) of water on the Consequently, the agglomerate size was assessed
surface of SnO2 is a well known phenomenon and by laser diffraction dynamic light scattering.
 J. Aust. Ceram. Soc. 43 [1] (2007) 56-61 59

(a) (b)
30 µm

(c) (d)

Figure 3: FESEM micrographs of lightly ground SnC2O4:

Group 1: (a) SN11, (b) SN12 and Group 2: (c) SN21, (d) SN25

a b
600 nm

c d

Figure 4: FESEM micrographs of vigorously ground SnO2:

Group 1: (a) SN11, (b) SN12 and Group 2: (c) SN21, (d) SN25
60 H. Taib and C.C. Sorrell

As shown in Table 2, the mean agglomerate size The calcined precipitated powder consisted of
was in the range 383-657 nm (0.38-0.66 µm), individual spherical particles of ~75 nm diameter.
although there was no correspondence between the There was no relationship between either the
concentration of the solution or the addition method. solution concentration or the addition method and
The conclusions that can be made from these data the particle size of the calcined SnO2.
are: Hand-grinding in the presence of water vapour
i) The agglomerate size is relatively small, being resulted in the formation of platy agglomerates of
submicron. ~0.5 µm diameter owing to the induction of
plasticity deriving from physisorption (or
ii) The agglomerate size is fairly consistent, chemisorption) of water on the surfaces of the
indicating a corresponding grinding particles. Again, there was no relation between the
consistency. agglomerate size and the experimental conditions.
iii) The standard deviations are small, confirming
the consistency of the agglomerate size.
ACKNOWLEDGEMENT
Table 2: Mean diameters of SnO2 agglomerates The authors would like to thank the Universiti Tun
Hussein Onn Malaysia (UTHM) and the Ministry
Mean Agglomerate Diameter (nm)
of Higher Education, Malaysia, for financial
Group 1 Group 2 support for this work.
53 59
SN11 ± 48 SN21 ± 30
2 8
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