1 Synthesis of Titanium dioxide by ultrasound assisted sol-gel technique:

Effect of Calcination and Sonication Time.

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D. V. Pinjari a, Krishnamurthy Prasad b, B. Pawar b, A. B. Pandit a and S. T.

Mhaske b*

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Chemical Engineering Division, Institute of Chemical Technology, Matunga,

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Mumbai - 400 019. INDIA.

b

Department of Polymer and Surface Engineering,

Institute of Chemical Technology, Matunga, Mumbai - 400 019. INDIA.

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*Author to whom correspondence should be addressed

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Email: stmhaske@gmail.com Tel: +91-22-33611111; Fax: +91-22-4145614

23Abstract:
24

Nanostructured Titanium dioxide was synthesized using both conventional and

25ultrasound assisted sol-gel technique. All the specimens were subjected to a calcinations
26temperature of 750C. Calcination time was varied from 30 min to 3 hours to study the
27effect of calcination time on the properties of the synthesized TiO 2. The TiO2 specimens
28were characterized using X- Ray Diffraction (XRD) and Scanning Electron Microscopy
29(SEM). The sonication time was also varied. The influence of the calcination and
30sonication time on the phase transformation process from anatase to rutile and its
31consequent effect on the crystallite size and % crystallinity of the synthesized TiO 2 was
32studied and interpreted. It was found that 100% phase transformation was observed after
333 hours of calcinations for the ultrasound assisted sol-gel synthesized TiO 2. The study on
34the phase transformation via variation of sonication time yielded some interesting results.
35It was seen as the time period of sonic impulse was increased an initial increase followed
36by a decrease in rutile content was observed. In general the ultrasound assisted process
37helped create TiO2 material with a higher % rutile than the conventional sol-gel process.
38
39Keywords: Sol-Gel, Acoustic Cavitation (Ultrasound), Titanium dioxide (TiO 2),
40Calcination Time, Sonication Time.

411. Introduction
42

The physical methods of nanoparticle synthesis have a few

43inherent disadvantages which limits their usage. They cannot prepare

44nanoparticles having controlled size distribution and also the sizes that
45may be synthesized are often at the 100 nm and above level which is
46not good enough for the newer demands of the nanoparticle industry.
47

On the other hand precipitating clusters of inorganic compounds from a solution

48of chemical compounds has been an attractive proposition for researchers, primarily
49because of the simplicity with which experiments can be conducted in a laboratory. This
50is especially true if the goal is to just have a nanocrystalline powder, instead of a
51dispersible nanoparticulate powder [1]. Solution processing can be classified into three
52major categories. In addition there are various sub-categories like hydrothermal synthesis
53and polyol techniques but the three most widely used techniques are:
54

1. Sol-Gel Processing.

55

2. Precipitation Method.

56

3. Water-Oil Micro-emulsions (Reverse Micelle) method.

57

The sol-gel process is a versatile solution process for making ceramic and glass

58materials. The sol-gel process, as the name implies, involves the evolution of inorganic
59networks through the formation of a colloidal suspension (sol) and gelation of the sol to
60form a network in a continuous liquid phase (gel). A sol is a dispersion of the solid
61particles, with diameter of 1-1000 nm [2], in a liquid where only the Brownian motions
62suspend the particles.

63

A gel is a state where both liquid and solid are dispersed in each other, which

64presents a solid network containing liquid components. The precursors for synthesizing
65these colloids consist of a metal or metalloid element surrounded by various reactive
66ligands. Metal alkoxides are most popular because they react readily with water. The
67most widely used metal alkoxides are the alkoxysilanes, such as tetramethoxysilane
68(TMOS) and tetraethoxysilane (TEOS). However, other alkoxides such as aluminates,
69titanates, and borates are also commonly used in the sol-gel process, often mixed with
70TEOS.
71

Applying the sol-gel process, it is possible to fabricate ceramic or glass materials

72in a wide variety of forms: ultra-fine or spherical shaped powders, thin film coatings,
73ceramic fibers, microporous to nanoporous inorganic membranes, monolithic ceramics
74and glasses, or extremely porous aerogel materials.
75

The sol-gel process is widely used for manufacturing nanoparticles of various

76metal oxide materials like TiO2 [3-5], ZnO [6, 7], SiO2 [8, 9], WO3 [10], etc. The solgel
77route is very attractive because it is relatively easy to perform and allows us to tailor the
78morphology of particles by relative rate of hydrolysis and condensation reactions [1]. The
79sol-gel synthesis of metal oxides involves the following steps:
80
81

1. Sol formation: In this step, the metal alkoxide is dispersed in an acidic solution to
form a clear sol.

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2. Gel formation: In this step, the sol is reacted with water forming a gel which is

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nothing but the metal hydroxide complex formed by reaction of the precursor with

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water.

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3. Dehydration: Generally a large excess of water is taken in the Gelation step to

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ensure maximum conversion of the sol to gel. The excess water is removed in the

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dehydration stage which may involve the use of high temperature operations like

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azeotropic distillation.

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4. Calcination: The fourth and final step of the sol-gel process is the Calcination

90

step. This is nothing but a high temperature assisted bond breakage and

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reconfiguration process. Calcination is generally done at temperatures exceeding

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300C and can also be carried out temperatures as high as 1200C. Calcination

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deals with breaking of M-OH (where M represents metallic element like Si, Ti,

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Al, etc.) bonds to form a metal oxide material MO x where x is the oxidation

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number and generally x has the lowest permissible value.

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Three main reactions occur during the sol-gel process: hydrolysis, alcohol

98condensation, and water condensation. However, the characteristics and properties of a

99particular sol-gel inorganic network are related to a number of factors that affect the rate
100of hydrolysis and condensation reactions, such as, pH, temperature and time of reaction,
101reagent concentrations, catalyst nature and concentration, H2O/Si molar ratio (R), aging
102temperature and time, and drying. Of the factors listed above, pH, nature and
103concentration of catalyst, H2O/Si molar ratio (R), and temperature have been identified as
104most important [11].
105

The sol-gel technique requires annealing treatment of the amorphous precipitates,

106to induce crystallization. The annealing process consists of two stages viz; Dehydration
107and Calcination. Dehydration is carried out in an air-circulating oven at a suitable

108temperature while the calcination is done in a muffle furnace. The calcinations procedure
109is used for conversion of the Titanyl hydroxide complex into Titanium dioxide. The
110temperature to which the material is subjected to and the time frame of exposure to the
111high temperatures used in the calcinations process is a huge influence on the crystalline
112properties of the synthesized nanomaterial. The Calcination step perhaps has the most
113influence on the properties of the synthesized material. The two factors that can control
114the Calcination process are:
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1. Calcination Temperature.

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2. Calcination Time.

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Selection of proper Calcination temperature is of extreme importance in the sol-

118gel process. Metal oxide materials occur in various crystalline polymorphs and generally
119these polymorphs are interconvertible polymorphs. Reversible and irreversible phase
120transformations are a common feature in metal oxide chemistry. Some crystalline phases
121have better packing and higher crystallinity in comparision to others but occur at only
122higher temperature. A typical example being Titanium dioxide (TiO 2) of which the more
123crystalline rutile phase may be created at temperatures of 600C and above. Titanium
124dioxide occurs in mainly two crystalline polymorphs viz; anatase and rutile. The major
125distinction between the two phases is in their differing behaviour under ultraviolet
126irradiation. Anatase is photocatalytic in nature i.e. it produce free-radicals on account of
127excitation by the UV radiation whereas rutile is a UV absorber [12]. Thus, for obtaining
128phase purity ad selectivity in synthesis, selection of optimum calcination temperature is
129essential.

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The effect of calcination temperature on the properties of TiO2 synthesized by

131ultrasound assisted (US) and conventional sol-gel (NUS) synthesis was put forward in
132our previous work [13]. As Calcination temperature was increased in both the US and
133NUS synthesized TiO2 there was an increase in the % rutile content. The effect of
134increased surface area and consequent increased rate of heat transfer to the bulk made it
135possible to obtain 100% phase transformation in the US synthesized TiO 2 at 750C a full
136100C lesser than the temperature required for 100% phase transformation in the NUS
137synthesized TiO2.
138

The effect of Calcination time on a particular material seems to be of particular

139importance as the time period to which a material is subjected to high temperatures will
140play a role in deciding what kind of crystalline microstructure will be developed in the
141material. A fleeting Calcination procedure will not afford enough time for the lattice
142structure to get developed completely thus creating a material with an inferior crystalline
143structure. A sufficiently slow Calcination process will perhaps allow the lattices to get
144oriented properly thus creating a more ordered microstructure thereby creating a more
145crystalline material.
146

Acoustic cavitation technique is extremely useful for synthesizing nanomaterials.

147Basically the extreme transient conditions generated in the vicinity and within the
148collapsing cavitational bubbles have been used for the size reduction of the material to
149the nano scale. In acoustic cavitation, it generates a transient localized hot zone with
150extremely high temperature gradient and pressure. The sonochemical precursors used are
151destructed due to sudden changes in temperature and pressure and are finally resulting in

152the formation of nanoparticles. The acoustic cavitation technique has a potential to

153produce nanoparticles in large volume.
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In this paper, the effect of calcination and sonication time on the properties of sol-

155gel (US and NUS) synthesized TiO2 was studied and the trends in the properties of the
156synthesized TiO2 were interpreted.
157
1582. Materials and Methods
1592.1 Materials
160Titanium Tetraisopropoxide (TTIP) precursor was obtained from Spectrochem Pvt. Ltd.,
161India. 2 propanol (99.9% pure) was purchased from s. d. Fine Chemicals Ltd, Mumbai,
162India. Glacial acetic acid solution was ordered from Merck Ltd, Mumbai, India.
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1642.2 Preparation of TiO2 by conventional (Non-Ultrasound assisted (NUS) Sol-Gel
165Method.
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5 mL of Titanium Tetraisopropoxide (TTIP) precursor was added dropwise to 30

167mL of 2-propanol. The resulting clear solution was added dropwise under stirring to 5 mL
168of glacial acetic acid solution. The sol thus obtained was left at ambient temperature for
16924 hours. For getting nearly 100% conversion (i.e. for ensuring complete hydrolysis of
170TTIP precursor), the solution needed to be kept as such for approximately 1 day.
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The sol obtained after 24 hours was then converted into a gel by adding it to 30

172mL of distilled water under stirring. The obtained gel was then dehydrated in an air
173circulating oven at 110 oC for 3 hours. The dehydrated material was then calcined in a
174muffle furnace (Expo Hi Tech Mumbai, India, Power input = 2 KW and Length x Breadth

175x Height = 30 cm x 10 cm x 10 cm) at 750 oC for varying time periods from 30 min to 3
176hours. The white powder obtained after calcinations was cooled, ground and weighed to
177check for yield of the process.
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1792.3 Preparation of TiO2 by Ultrasound assisted (US) Sol-Gel Method
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The mixture of TTIP precursor, 2-propanol and glacial acetic acid solution was

181subjected to sonication using an Ultrasonic Horn (ACE 22 KHz) at 40% amplitude

182actually delivering 29.2 watts of power for 10 minutes with a 5 second pulse and 5
183second relaxation cycle. Thus, the sol obtained after keeping it for 24 hours was again
184ultrasonically irradiated by keeping same parameters (output power and pulse &
185relaxation cycle). The remaining procedure including the volume of the reactants was
186kept the same (as reported in section 2.2). The purpose behind the dual sonication has
187been reported earlier [13] After calcination the TiO2 powder (white in color) obtained was
188cooled, ground, checked for yield and characterized using the same techniques as that
189used for the NUS sol-gel synthesized specimens.
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The calcinations times that the specimens were subjected to were 0.5, 1, 2 and 3

191hours respectively. Accordingly, the NUS sol-gel synthesized TiO 2 specimens were
192labeled as TNUS 0.5, TNUS 1, TNUS 2, TNUS 2 and TNUS 3 while the US sol-gel
193synthesized TiO2 specimens were labeled as TUS 0.5, TUS 1, TUS 2 and TUS 3. Keeping
194in mind, heating rate for NUS and US sol gel specimens were kept same.
195

After the time period of calcination was optimized for both the NUS and US

196specimens, a new set of US specimens were synthesized by varying the sonication time at
197time t =0 h and t = 24 h. Initially, the US specimens were synthesized by using a

198sonication time of 10 minutes and t = 0 h and t = 24 h. two new sets of specimens were
199synthesized using sonication time of 5 minutes and 15 minutes at t = 0 h and t = 24 h and
200were labeled as TUS(5) and TUS(15) respectively.
201
2023. Characterization
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The TiO2 specimens were first characterized by studying their X-Ray Diffraction

204patterns on a Rigaku Mini-Flex X-Ray Diffractometer. Crystallite sizes were determined

205using the Debye-Scherrer equation. Scanning Electron Microscopy of the specimens was
206carried out on a JEOL JSM 680LA 15 kV SEM to estimate the surface characteristics of
207the specimen. Together the XRD and SEM methods provide exact knowledge regarding
208the crystallite size and crystalline characteristics of the synthesized TiO2.
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2104. Results and Discussions
211

Initially, the subject of the study was to optimize the Calcination time required for

212attaining 100% phase transformation from anatase to rutile in the synthesized titanium
213dioxide.
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Table 1 shows the average yields obtained for the synthesis and it is observed that

215the US synthesis has got a much higher % yield than the corresponding NUS process and
216this is attributed to the ability of acoustic cavitation to improve the reaction kinetics by
217improved mass transfer (on account of the micro-mixing caused by the acoustic shock
218wave release on collapse of the cavitation bubble) and increase in reaction rates due to
219radical formation due to the adverse conditions created by bubble collapse.
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2234.1 X-ray Diffractometer (XRD) Study for Calcination Time optimization
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The XRD patterns of the TiO2 specimens prepared by non ultrasound (NUS) sol-

225gel method are shown in Figure 1. The anatase form of TiO 2 shows a peak at 2 = 25o
226while the presence of rutile form is indicated by a peak at 2 = 28 o. % Rutile was
227calculated by the following non-linear equation [14, 15]:
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% R = 100/[(A/R)*0.884 + 1] (1)

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Where % R = Rutile content in percent, A = Peak Intensity of the peak at 2 =

23025, R = Peak Intensity of the peak at 2 = 28

231

The crystallite sizes of the specimens were calculated by using the Debye-

232Scherrer equation. The equation takes the form:

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Dhkl = K/ (Bhkl x cos hkl).. (2)

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Where B is the width of the peak at half maximum intensity of a specific phase

235(hkl) in radians, K is a constant that varies with the method of taking the breadth (0.89 <
236K < 1). Here, in this work, for calculation purpose K = 0.9, is the wavelength of
237incident X-rays, = 1.54 for Cu Ka, is the center angle of the peak, D is the crystallite
238length or primary crystallite size.
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2404.1.1 Phase transformation in TiO2 synthesized by Conventional (NUS) sol gel method
241

The X-Ray diffraction patterns of the specimens synthesized by the convention

242i.e. Non-Ultrasound assisted sol-gel technique is shown in Figure 1. From the XRD
243patterns it is clear that with an increase in calcination time there is an increase in the

244rutile content. This is proved by a continuous increase in the intensity of the peak at 2
245= 28.
246

The specimen calcined for 30 min i.e 0.5 hours (TNUS 0.5) shows the least rutile

247content while the specimen calcined for 3 hours (TNUS 3) shows the maximum rutile
248content amongst the NUS synthesized specimens (Figure 3). This is attributed to the fact
249that when sufficiently large amount of time was provided for the calcination process the
250heat supplied could permeate into the recesses of the specimen and an exposure to the
251high temperature (750C) brought about the phase transformation in the TiO2 specimens
252from the meta-stable anatase phase to the more stable rutile phase.
253

The % crystallinity of the specimens was determined by the method described

254previously [13] as expected, with an increase in rutile content, there is an increase in %

255crystallinity (Figure 4). The rutile polymorph of TiO 2 shows better packing density,
256specific gravity and lower unit cell volume which results in it having higher %
257crystallinity than anatase which on its part has lower packing density, specific gravity and
258higher unit cell volume.
259

The trends in crystallite size and predominant crystalline phase are reported in

260Table 2. Supporting the trend in % crystallinity, there is an increase in average crystallite

261size as the calcination time is increased thereby serving as an indicator for increasing %
262rutile content. Thus, TNUS 0.5 which has been calcined for the least amount of time
263shows a lower crystallite size (24nm) than TNUS 3 which has been calcined for a longer
264duration (35nm).
265

2664.1.2 Phase transformation in TiO2 synthesized by Ultrasound assisted (US) sol gel
267method
268

The X-Ray diffraction patterns of the specimens synthesized by the ultrasound

269assisted ie US sol-gel technique is shown in Figure 2. The major facet of the effect of
270calcination time on the % rutile of the US synthesized specimens was the 100%
271conversion from anatase to rutile observed in the specimen TUS 3.
272

Acoustic cavitation causes an increase in the effective surface area, thereby

273increasing the rate of heat transfer to the bulk of the specimen. This rate is faster than that
274for the NUS synthesized specimens, thus, 100% phase transformation occurs at a much
275lower temperature for the US synthesized specimens than for the NUS synthesized
276specimens.
277

As calcination time is increased from 0.5 h to 3 h as seen in the NUS specimens

278there is an increase in the % rutile but what stands out is the fact that the increase in the
279% rutile amongst the US specimens is much more pronounced than that observed
280amongst the NUS specimens (Figure 3). This is attributed to the effect on the system of
281the dual sonication process:
282

The pre-hydrolysis sonication was done to ensure an efcient micromixing of the

283various reactants in the reaction system. This was done, therefore, to ensure that the
284reactants were contacted properly in the highly adverse conditions exerted onto the
285system during the 10 min of pre-hydrolysis sonication.
286

The post-hydrolysis sonication was intended to encourage formation of

287nanoparticles (as nuclei) with smaller average particle sizes. This also ensured that during
288calcination the heat was transferred more efciently into the bulk of the material thereby

289ensuring that all of the particles in the bulk were subjected to the highest possible
290temperature in the lowest possible time.
291

The combined effects of the dual sonication help in acceleration of phase

292transformation from anatase to rutile, thereby, the US synthesized specimens show faster
293progression in phase transformation from TUS 0.5 to TUS 3.
294

The crystallite size study in the case of the US synthesized specimens yielded

295results similar to the NUS specimens in-so-far as the trends in values were concerned.
296Thus, the two synthesis techniques were in-principle having a similar effect on the
297synthesized material. The only difference was that the effect of phase transformation
298observed in the US synthesized specimens was much more pronounced than that in the
299case of the NUS synthesized specimens.
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3014.2 Scanning Electron Microscopy study
302

The SEM micrographs of the specimens are shown in Figure 5. As seen in our

303previous work, the TiO2 synthesized using the US method and calcinated at 750C was
304shown to be having a block-type structure [16]. This is now observed in the micrograph
305of specimen TUS 3 (Figure 5A). No such block-type structure is observed in the
306corresponding NUS specimen TNUS 3 (Figure 5B). The reason for this can be explained
307as follows, the specimen synthesized by the US method and calcinated for 3 hours at
308750C ie TUS 3 was shown to be a 100% rutile polymorph form of TiO 2 and thus is more
309crystalline than the anatase+rutile nature possessing TNUS 3. Therefore, the surface
310micrograph of TUS 3 showed a more close packed and ordered appearance than that of
311TNUS 3.

312

From the study it was found that for the US synthesized specimens a calcination

313time of 3 h was enough to produce 100% phase transformation from anatase to rutile in
314the synthesized titanium dioxide. Therefore, using that calcination time, two new titanium
315dioxide specimens were synthesized using the ultrasound assisted sol-gel method but
316using a sonication time of 5 minutes and 15 minutes respectively. These specimens were
317studied using the XRD and SEM methods also and their properties (morphology and
318phase presence) were compared with the TNUS 3 and TUS 3 specimens.
319
3204.3 XRD study of the specimens synthesized with varying sonication times
321

The X-ray diffractograms of the specimens synthesized using differing sonication

322times are shown in Figure 6. What is obvious from the figure is that the titanium dioxide
323synthesized by the US method shows the presence of 100% rutile (due to absence of any
324peak at 2 = 25) when calcinated at 750C irrespective of the amount of sonication time
325used during the synthesis. From the diffractograms we can get the data related to the %
326Rutile, % crystallinity and crystallite sizes of the specimens and which is shown in Figure
3277, Figure 8 and Table 3 respectively.
328

From Figure 7 it is seen that there is no difference in the % Rutile values (100%)

329obtained for the three US synthesized specimens while the NUS specimen (TNUS 3)
330shows a much lower % Rutile value and therefore we can conclude that the US process
331indeed, hugely accelerates the phase transformation in titanium dioxide from anatase to
332rutile.
333

The trend in % crystallinty (Figure 8) also reflects the trend in the rutile content.

334The Rutile polymorph of TiO2 shows better packing and more stable crystalline structure

335than the meta-stable anatase polymorph and therefore the US specimens which show
336rutile as the pre-dominant phase, therefore, show higher % crystallinity than the single
337NUS specimen. However, it is seen that the specimen TUS 3 is showing the highest %
338crystallinity amongst all. To explain this we have to study the trends in crystallite size and
339also the yield of the reaction.
340

The values of crystallite size (Table 3) show that the specimen TUS 3 is having

341the highest crystallite size. This further seems to indicate that TUS 3 is that specimen
342which is having the most rutile character out of the rest. However, there is not much of a
343significant difference in that aspect amongst the US specimens but they do show a
344marked increase in rutile content and crystallinity from the lone NUS specimen.
345
3464.4 % yield study of the specimen obtained using various sonication times
347

The % yields obtained for the various specimens are seen in Table 4. It is seen

348again that the US specimens show a good improvement in the % yields as compared to
349the NUS specimen which is attributed to the reasons extensively discussed in the
350beginning of Section 4. It is seen that initially as the sonication time is increased we see
351an increase in the yield from TUS(5) to TUS 3 and thereafter we see a decrease in %
352yield from TUS 3 to TUS(15). This is attributed to the fact that as the sonication time is
353increased, the extent of bubble collapse occurring in the system increases and an
354increased exposure to such cavitating conditions results in improvement in mass transfer
355and reaction rates and thus a consequent increase in yields. However, as the sonication
356time the reaction system is subjected to increases beyond a certain margin, the high
357instantaneous temperatures generated in the reaction system will result in partial

358vapourisation of the volatile 2-propanol used as the reaction medium. This results in a
359shift of the reaction equilibrium to the left by Le-Chateliers principle and therefore we
360see a reduction the yields. In addition, the high velocity acoustic streaming at higher
361sonication times will result also in asymmetric bubble collapse in the fluid, thus totally
362disrupting the formation of a close-packed crystal structure. Therefore, the TiO 2
363synthesized at higher sonic time input shows lower % crystallinity which is seen in the
364values obtained in Figure 8. in the case of TUS 3 (ie a 10 minute sonication time ) the
365likely scenario is that there would be an ideal balance between high temperature and
366high energy collapse which would not cause local volatilization of 2-propanol but rather
367the generated heat energy would be utilized solely for accelerating the phase
368transformation process.
369
3704.5 SEM study of the specimens synthesized at various sonication times
371

The SEM micrographs of the specimens synthesized at various sonication times

372are shown in Figure 9. It is seen that with increase in sonication times we see a slow
373development of a block type structure in the synthesized TiO2. The development of an
374ordered surface morphology is hence, a characteristic of the US process. The structure
375however, seems to vanish at the specimen TUS(15) which seems to suggest that the
376higher sonication times are having a detrimental effect on the synthesized product. At
377lower sonication times, the heat generated due to bubble collapse hastens the phase
378transformation from a meta-stable anatase to more stable and crystalline rutile form
379which thereby shows an increasingly ordered surface morphology but at higher
380sonication times the integrity of the block type structure is lost. It may be due to the fact

381that the more sustained impact of the acoustic shock waves at higher sonication times, on
382the surface of the TiO2 ruptures the formed block type structure.
383
3845. Conclusion
385

The effect of calcination and sonication time on the phase transformation of sol-

386gel synthesized (conventional and ultrasound-assisted) TiO2 was studied. It was found
387that with increasing calcination time (at constant temperature of 750C), there was an
388increase in the rutile content of the specimens, signifying that at lower calcination times
389the entire bulk of the specimen could not be exposed to the high temperature thereby the
390meta-stable anatase phase was intact. The introduction of ultrasound and hence, acoustic
391cavitation as a reaction aid helped produce specimens with a lesser degree of
392agglomeration and thus helped the high temperature reach the inner recesses of the
393specimen quicker, hastening the phase transformation and achieve 100% conversion from
394the anatase phase (favoured by the conventional sol-gel process) to the rutile phase. After
395the optimization of calcination time was set at 3 h, the sonication time was also vaied to
396study the effect of sustained ultrasound contact on the reaction system. It was seen that as
397the sonication time was increased from 0 (NUS) to 10 min, there is an increase in the
398rutile content, crystallinity and % yields. Increase beyond that time resulted in a
399detrimental effect on the system due to the cavity collapse energy being utilized for
400purposes other than accelerating phase transformation. Thus, a calcination time of 3 h and
401a sonication time of 10 min were determined as being the optimum parameters for
402obtaining 100% rutile TiO2.
403

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446List of table and figures

447Table
448Table 1: Crystallite size (nm) and dominant crystalline phase of the TiO 2 specimens
449synthesized at different calcination times.
450Table 2: Average % yields obtained for the NUS and US sol-gel processes
451Table 3: Crystallite sizes of the specimens synthesized using varied sonication times
452Table 4: % Yields of the specimens obtained using varied sonication times
453
454Figures
455Figure 1: X-ray diffraction patterns of conventional sol-gel synthesized nano-TiO 2 at
456various calcination times.
457Figure 2: X-ray diffraction patterns of ultrasound assisted sol-gel synthesized nano-TiO 2
458at various calcination times.
459Figure 3: Variation of % Rutile of the TiO 2 specimens (NUS and US) with calcination
460time.
461Figure 4: Variation of % crystallinity of the TiO 2 specimens (NUS and US) with
462calcination time.
463Figure 5: SEM Micrographs of Synthesized TiO 2: (A) TNUS 3 at 10000X, (B) TUS 3 at
46410000X.
465 Figure 6: X-Ray diffractograms of the specimens synthesized at various sonication times.
466Figure 7: % Rutile of the specimens synthesized at various sonication times.
467Figure 8: % Crystallinity of the specimens synthesized using various sonication times.

468Figure 9: SEM micrographs of the specimens synthesized using various sonication times.
469A: TNUS 3, B: TUS(5), C: TUS 3, D: TUS(15).