Advanced Powder Technology 27 (2016) 2168–2174

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Advanced Powder Technology

journal homepage: www.elsevier.com/locate/apt

Original Research Paper

Surface treatment of TiO2 nanoparticles to improve dispersion

in non-polar solvents
Mohammad Mehdi Jalili a, Kaveh Davoudi a, Erfan Zafarmand Sedigh a, Saeed Farrokhpay b,⇑
a
Department of Polymer Engineering, Science & Research Branch, Islamic Azad University, Tehran, Iran
b
School of Chemical Engineering, University of Queensland, St. Lucia, Brisbane, QLD 4072, Australia

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

Article history: Anatase TiO2 nanoparticles were treated with oleic or stearic acid, and the dispersion behaviour of the
Received 29 February 2016 treated and non-treated nanoparticles in non-polar solvents was studied. The dispersion stability of
Received in revised form 29 June 2016 the TiO2 nanoparticles was also visually examined. It was found that stearic acid covers the nanoparticles
Accepted 28 July 2016
surface more than oleic acid. Moreover, the influence of the UV irradiation on the chemical structure as
Available online 23 August 2016
well as the dispersion behaviour of the oleic acid and stearic acid treated nanoparticles was investigated.
The results showed that the stearic acid treated nanoparticles provide a better dispersion performance
Keywords:
after UV irradiation.
TiO2 nanoparticles
Oleic acid
Ó 2016 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder
Stearic acid Technology Japan. All rights reserved.
Dispersion

1. Introduction
Nanomaterials play an important role in producing high perfor-
mance composites. Due to their various properties such as optical,
antibacterial and UV resistance, the resultant nanocomposites can
be used in widespread applications such as coatings, plastics, solar
cells, and electrochemical devices [1–3].
Titanium dioxide (TiO2) has high potential to absorb a broad
range of ultraviolet rays [4]. TiO2 nanoparticles indeed act as inor-
ganic UV-absorber and exhibit more stability compared to the com-
mon organic UV absorbers or light stabilisers [5]. On the other hand,
it has been shown that TiO2 particles, particularly the anatase crys-
tal form, can degrade the surrounding organic matrix in which they
are dispersed [6]. However, surface modification of these particles
can be used to adjust their photocatalytic properties [7,8]. It is
worth mentioning that there are two types of photochemical reac-
tion proceeding on TiO2 surface when exposed to the UV light: the
photo-induced redox reactions of the adsorbed substances, and the
photo-induced hydrophilic conversion of the TiO2. Although the
former type has been known for many years, the latter is relatively
a new concept which has been only noticed during recent decades
[9,10]. When the surface of TiO2 is exposed to the UV light, it
becomes completely non-water-repellant (highly hydrophilic).
Therefore, the surface retains its properties for a couple of days
under the ambient condition without being exposed to the UV light
[10]. Moreover, it has been revealed that the degradation of poly-
mers can be accelerated when nano-sized TiO2 is employed [11].
Although some investigations have been carried out to examine
deterioration of organic compounds in the presence of TiO2
nanoparticles [12–14], there is still a lack of knowledge in this area.
Furthermore, nanoparticles have large surface area and high
surface energy comparing to traditional micro-sized powders and
as a result they have a high tendency to agglomerate. Thus, prepar-
ing such particles, which are usually inorganic, with high dis-
persibility in polymeric matrices is still challenging. For this
purpose, surface modification of nanoparticles has been noticed
as a key solution in many studies [15–19]. Organic acids have been
widely used for surface treatment of TiO2 nanoparticles. The sur-
face OH sites of TiO2 can react with the carboxylic functional
groups of modifier and cause an improved dispersion within an
organic media [20–24].
In this study, TiO2 nanoparticle were treated with oleic or stea-
ric acid, and the optimum process in which the maximum reac-
tions between these acids and the nanoparticles take place was
determined. The effect of surface treatment of TiO2 on its disper-
sion in non-polar solvent will be discussed.
2. Materials and experimental methods
2.1. Materials

⇑ Corresponding author. Titanium dioxide nanoparticle (anatase form) was obtained

E-mail address: s.farrokhpay@uq.edu.au (S. Farrokhpay). from Nanoshell (India) with average particle size of 20–30 nm.

http://dx.doi.org/10.1016/j.apt.2016.07.030
0921-8831/Ó 2016 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.
 M.M. Jalili et al. / Advanced Powder Technology 27 (2016) 2168–2174 2169

Oleic acid (OA) (86%), stearic acid (SA) (95%), n-Hexane (98%), etha-
nol (97%), carbon tetra chloride (99.9%), and anhydride toluene TiO2
(98%) were obtained from Merck Chemicals and were used as (a)
(b)
received.
(c)
(d)
2.2. Surface modification of TiO2 nanoparticles

Transmittance
(e)
Various levels of oleic acid were added to 100 mL n-hexane and Stearic acid
then stirred for 10 min at 60 °C. Then 1 g of TiO2 nanoparticles was
added to the mixture and stirred for 4 h at 60 °C. The amount of
oleic acid were 0.25 g, 0.50 g, 0.75 g, 1.00 g and 1.50 g for 1 g
nanoparticle. The mixtures were finally filtered, obtaining treated
TiO2 nanoparticles as wet powder. The wet powder was rinsed sev-
eral times with n-hexane and was dried in a vacuum oven for 24 h
at 65 °C. The treated TiO2 nanoparticles were kept in a desiccator
before further tests. A similar method was used to treat TiO2 4000 3500 3000 2500 2000
nanoparticles surface with stearic acid. Wavenumber (cm -1)

2.3. Dispersion stability test

TiO2
Dispersion stability of the treated and non-treated TiO2 (a)
nanoparticles was evaluated in toluene. For this purpose, disper-
(b)
sions of 1 wt% nanoparticles in 100 mL toluene were prepared
and shaken for 1 min. Then their sedimentation behaviour was (c)
examined during 24 h. Transmittance
(d)

2.4. Spectroscopy analysis (e)

A FTIR spectrometer (Nexus 870, USA) with OMNIC software Oleic acid
was used to analyze the samples in the transmittance mode.
A Transmission electron microscope (TEM) (Philips EM208,
Netherlands) was used to examine the morphology of TiO2
nanoparticles. All samples were dispersed in n-hexane by using
ultrasonic for 30 min.
The UV stability of the samples was evaluated using an air-
conditioned chamber exposing to an UV lamp (Philips TUV 15 W/ 4000 3500 3000 2500 2000
G15 T8, USA) (after 500 h). Wavenumber (cm-1)
Dispersions of 1 wt% TiO2 nanoparticles, both treated and non-
Fig. 1. FTIR transmittance spectra of TiO2 nanoparticles treated with various levels
treated ones, in 100 mL of non-polar solvents (toluene and CCl4) of (top) oleic acid, and (bottom) stearic acid. The amount of steric or oleic acid is
were prepared and shaken for 1 min and immediately transmit- 0.25 g (a), 0.50 g (b), 0.75 g (c), 1.00 g (d) and 1.50 g (e) for 1 g TiO2 nanoparticles.
tance spectra of the dispersions were obtained in the range of The spectra of untreated TiO2 and steric or oleic acid are also given for comparison.
200–800 nm by using a UV–visible spectrophotometer (Varian
2800–3000 cm 1 (as a proxy of adsorbed oleic or stearic acid)
Carry 100, USA).
was calculated by using the peak area tool of OMNIC software.
1H NMR spectra were obtained using FT-NMR 300 MHz Bruker
The values of the peak area then plotted as a function of the initial
(Germany). Chloroform-d (99.98%, Merck) was used as a deuter-
added oleic or stearic acid to the nanoparticles, as shown in Fig. 2.
ated solvent.
The plateau of adsorption for oleic or stearic acid is observed at
1.00 and 0.75 g/g, respectively. Therefore, these values were
3. Results and discussion selected as optimum levels for the rest of this study.

3.1. FTIR studies
3.1.1. Determining optimum amount of oleic or stearic acid
The TiO2 nanoparticles were treated with different amount of
oleic or stearic acid, and the FTIR spectra of the treated samples
are shown in Fig. 1. The asymmetric and symmetric CH2 stretching
bands (2800–3000 cm 1 [25]) are clearly observed in the spectra of
the treated samples while they are absent in the spectra of the bare
TiO2. This indicates the adsorption of oleic or stearic acid onto the
nanoparticle surface. Interestingly, the intensity of the CH2 peaks
(2800–3000 cm 1) increases when the amount of oleic or stearic
acid is increased. However, this growth seems to reach to its pla-
teau after a few additions.
In order to estimate the amount of the absorbed oleic or stearic
acid onto the TiO2 nanoparticles surfaces, the area under the CH2
peaks of the FTIR spectra of the treated nanoparticles in range of
3.1.2. Interaction of oleic or stearic acid with nanoparticles
The samples treated at the optimum dosage of oleic or stearic
acid (as explained above) were further analyzed. Fig. 3 presents
the FTIR spectra of the bare TiO2 nanoparticles, oleic and stearic
acid, and TiO2 nanoparticles treated with oleic or stearic acid.
The broad peak at about 1000 cm 1 in Fig. 3a is assigned to the
Ti-O groups of the nanoparticles. The peak at about 1500 cm 1 is
also assigned to the physically surface adsorbed water on the
TiO2 particles [8]. In Fig. 3b and c, peaks at 1460 and 936 cm 1
are assigned to the ‘‘in plane” and ‘‘out plane” OH groups [26].
Peaks at 2800–3000 cm 1 are assigned to the asymmetric and
symmetric CH2 stretching bands [25]. The COOH peaks of the oleic
or stearic acid (at 1700 cm 1 in Fig. 3b and c) disappear in the trea-
ted samples, and instead new peaks at 1525–1550 cm 1 are
formed (Fig. 3d and e). These peaks are assigned to the COOA. This
suggests that oleic or stearic acid is chemically attached as
2170 M.M. Jalili et al. / Advanced Powder Technology 27 (2016) 2168–2174
CH2 peak area (2800-3000 cm-1) (mm2)

120

100

80

60

40

20

0
0.00 0.25 0.50 0.75 1.00 1.25 1.50
Oleic or stearic acid amount (g/g nanoparcles)

Fig. 2. The adsorbed amount of oleic (dot line) or stearic acid (solid line) on the
nanoparticles (1 g), as a function of initial amount of added oleic or stearic acid. The
area of the FTIR peaks at 2800–3000 cm 1 was calculated using OMNIC software,
and were used as a proxy of the adsorbed oleic or stearic acid.

Fig. 4. Sedimentation analysis of TiO2 nanoparticles in anhydride toluene (a)

untreated, and treated nanoparticles with (b) oleic or (c) stearic acid.

mum amount of acids as discussed) were dispersed in toluene

Fig. 3. FTIR transmittance spectra of untreated TiO2 nanoparticles (a), oleic acid (b),
stearic acid (c), and TiO2 nanoparticles treated with oleic or stearic acid (d and e,
respectively).
and the behaviour of the dispersions was examined during 24 h.
Results in Fig. 4 show that the sedimentation behaviour of the
non-treated TiO2 nanoparticles is mainly dominated by floccula-
tion. Therefore, the separation of the suspension occurs quickly
resulting in the formation of two different phases (sediments in
the bottom and a clear supernatant on the top of the containers).
The interface between the sediment and the supernatant can be
clearly observed as time increases. However, there is distinct sed-
imentation behaviour for the treated TiO2 nanoparticles as shown
in Fig. 4b and c. The dispersions of treated TiO2 nanoparticles
remain stable during 1 h after which a translucent supernatant
forms. As shown in Fig. 4b and c, more columns of cloudy super-
natant can be formed at longer times for the stearic acid treated
TiO2 nanoparticles, comparing to those treated with oleic acid. Fur-
thermore, unlike the non-treated TiO2 nanoparticles, a sharp inter-
face between the supernatant and the sediments is not clearly
detectable for the acid treated nanoparticles. This indicates that
the acid modification can improve the stability of the TiO2
nanoparticles in non-polar organic solvents. Moreover, the results
of sedimentation tests demonstrate that more stable dispersions
can be achieved by treating the TiO2 nanoparticles with stearic
acid.

bidentate chelate (RACOOA) as previously observed by Basualto
et al. [27] in adsorption of oleic acid onto Fe3O4 nanoparticles.
3.2. Dispersion stability studies
To examine the dispersion stability of the TiO2 nanoparticles,
the treated and non-treated nanoparticles (treated with the opti-
3.3. TiO2 nanoparticles morphology
Fig. 5 shows the TEM images of the treated and non-treated
TiO2 nanoparticles dispersed in n-hexane. TEM is a popular analy-
sis method in a range of scientific fields, including surface science,
providing information on the particle morphology and surface
topography [28]. Fig. 5 clearly shows that the treated TiO2
 M.M. Jalili et al. / Advanced Powder Technology 27 (2016) 2168–2174 2171

Fig. 5. TEM micrographs of TiO2 nanoparticles dispersed in n-hexane for (a) non-treated sample, and treated with (b) oleic or (c) stearic acid.

Fig. 6. 1H NMR spectra of oleic acid, (a) before, and (b) after UV irradiation, as well as TiO2 nanoparticles treated with oleic, (c) before and (d) after UV irradiation (see Table 1
for the peak assignments).

nanoparticles, irrespective of the type of modifier, have less and reported that non-treated SiO2 nanoparticles tend to aggregate
smaller aggregates than the non-treated TiO2 particles. Farrokhpay due to the intermolecular hydrogen bonding [30]. Fig. 5 also
et al. [29] have previously used similar TEM analysis to investigate illustrates that the stearic acid treated TiO2 nanoparticles are rela-
the dispersion of rutile TiO2 in aqueous media. It has been also tively better dispersed than those particles treated with oleic acid
2172 M.M. Jalili et al. / Advanced Powder Technology 27 (2016) 2168–2174

Fig. 8. Schematic diagram of (a) dimer of unsaturated fatty acids, and (b) hydrogen
bonding between COOH groups in dimerization of carboxylates.

COOH group (‘‘A”). Peak at 11.90 is assigned to the COOH. Finally,

Fig. 7. 1H NMR spectra of stearic acid (a) before, and (b) after UV irradiation, as well
as TiO2 nanoparticles treated with stearic acid (c) before and (d) after UV irradiation
(see Table 1 for the peak assignments).
suggesting that stearic acid modifier performs better to saturate
the surface of TiO2 nanoparticles than oleic acid. This indeed re-
confirm what was previously discussed in FTIR and dispersion sta-
bility tests.
3.4. NMR analysis
Figs. 6a and 7a show that H NMR spectrum of the pure oleic or
stearic acid contain different signals corresponded to the hydrogen
atoms. The signal at 0.90 ppm is assigned to the hydrogen of
methyl groups (ACH3 marked as ‘‘D”). The signal at 1.25 ppm is
assigned to the hydrogens in ACH2A chains (marked as ‘‘C”). The
signals at 1.50 ppm and 1.97 ppm are assigned to the hydrogens
of two different ACH2A groups (‘‘B” and ‘‘M”). Peaks at 2.72 ppm
are assigned to the hydrogens in the CH2 attached to the end head
the signal at 5.50 ppm is assigned to the hydrogen of unsaturated
groups in oleic acid (ACH@CHA) marked as ‘‘N”. This, peak is
absent in the stearic acid spectra as stearic acid is a saturated
molecule. A summary of the NMR peaks analysis is given in Table 1.
Fig. 6b shows that after 500 h UV exposure, the intensity of the
hydrogen atom signal in the oleic acid spectra assigned to the
hydrogen of carbon double bond decreases (i.e. ‘‘N” signal). It is
noticed that the changes in the ‘‘C”, ‘‘D”, ‘‘B”, and ‘‘A” peaks are
minimal while the ‘‘M” peaks is also decreases confirming the
lower number of ‘‘N” type of hydrogen due to the less number of
CH@CH groups, and consequently the relevant attached CH2
groups. In addition, a new small signal is observed at 2.20 ppm
which is assigned to the hydrogen atoms of tertiary carbon [33]
that can be produced through intermolecular connections
(Fig. 8a). It can be concluded that when the UV break downs the
carbon–carbon double bond, the polymerization is initiated
through the resultant carbon radicals and propagated with time.
This hypothesis is also supported by observing a poor solubility
of UV exposed oleic acid sample in anhydride toluene compared
to the fresh oleic acid which is completely dissolved in toluene.
Further, the signal of the hydrogen atom of COOH (‘‘E”) of both
oleic and stearic acid disappears after the UV exposure. This can be
due to the interaction between COOH groups and possible dimer-
ization via hydrogen bonding (Fig. 8b). Less change is observed in
the stearic acid H NMR spectra after the UV radiation (Fig. 7b).
However, the intensity of ‘‘A”, ‘‘B” and ‘‘D” is decreased compared
to the ‘‘C” peak. Again, this may be due to the interaction between
two acid molecules occurring as a result of the heat produced by
the UV lamp.
H NMR of the TiO2 nanoparticles treated with oleic or stearic
acid is also shown in Figs. 6c and 7c. The presence of hydrogen
atom signal of HC@CH at d = 5.7 ppm, together with the disappear-
ance of the signal at d = 11.90 ppm support the results previously
obtained by FTIR analysis. This suggests the occurrence of chemical
reaction between oleic acid and TiO2 nanoparticles. A comparison

Table 1
The 1H NMR peaks assignments.

Hydrogen type Oleic acida (ppm) Stearic acidb (ppm) Marked asa,b Ref.
CH3 0.90 0.90 D [31]
(CH2)n 1.25 1.25 C [31]
CH2 1.50 1.65 B [31]
CH2 1.97 – M [31]
CH2 2.72 2.50 A [31]
ACH@CHA 5.50 – N [31]
COOH 11.90 11.90 E [32]

b
 M.M. Jalili et al. / Advanced Powder Technology 27 (2016) 2168–2174
Fig. 9. UV–visible transmittance spectra of TiO2 nanoparticles treated with oleic
acid (a) in toluene, and (b) in CCl4, before and after 500 h UV irradiation.
between Fig. 6c and d suggest some significant differences in the
chemical structure of the oleic acid treated nanoparticles after
exposing to the UV irradiation. In addition of reduction in hydro-
gen atoms signal of HC@CH which was similarly observed in UV
degradation of the oleic acid modifier, the form and intensity of
those hydrogen atoms signal (‘‘B” in Fig. 6) are also changed after
500 h UV exposure which was not previously recorded for pure
oleic acid at the same conditions.
3.5. UV–visible studies
Fig. 9 shows UV–visible transmittance spectra of the TiO2
nanoparticles treated with oleic acid and dispersed in two different
non-polar solvents (i.e. toluene and CCl4) (before and after 500 h
UV irradiation). As can be seen from Fig. 9, only less than 30% of
the total incident light is transmitted through the sample of oleic
acid treated nanoparticles dispersed in either toluene or CCl4. Such
increase in light extinction suggests that the oleic acid treated TiO2
nanoparticles can be considerably dispersed into non-polar sol-
vents. However, the UV irradiation inversely influences the dis-
persibility of the treated nanoparticles into non-polar solvents,
causing an increase in the percentage transmittance (at approxi-
mately double). This phenomenon after UV exposure period can
be therefore justified by the photocatalysis behaviour of the ana-
tase TiO2 nanoparticles in UV irradiation condition and as a result
more degradation of the hydrocarbon chains in oleic acid. This
behaviour has been also reported by Hashimoto et al. [10]. They
measured the water contact angle of the oleic acid treated TiO2
before and after UV irradiation and discovered that the contact
angle of treated TiO2 decreases from 70° to 0° after UV irradiation,
which was even lower than that of non-treated TiO2 (i.e. 30°). This
finding suggests that highly hydrophilic surface can be produced
after UV irradiation.
Fig. 10 illustrates UV–visible transmittance spectra of the stea-
ric acid treated nanoparticles dispersed in toluene and CCl4 before
and after UV exposure. As seen, these modified nanoparticles can
only transmit less than 10% of the total incident light when dis-
persed in toluene, and scatter the incident light totally when they
are dispersed in CCl4. This indicates better dispersions are formed
with the stearic acid modified TiO2 nanoparticles rather than the
oleic treated ones. These quantitative results are in consistent with
what visually observed in the dispersion stability tests, indicating a
better performance for the stearic acid treated TiO2 nanoparticles.
2173
Fig. 10. UV–visible transmittance spectra of TiO2 nanoparticles treated with stearic
acid (a) in toluene, and (b) in CCl4 before and after 500 h UV irradiation.
Also, an increase in the level of transmittance is observed for the
nanoparticles treated with stearic acid after 500 h UV irradiation
(Fig. 10) similar to what reported for oleic acid treated particles.
It seems that after UV irradiation, two different types of photo-
effect have occurred on the TiO2 surface. One is the well-known
photocatalytic oxidation–reduction reaction which can decompose
organic compounds absorbed on the TiO2 surface. Another is the
highly hydrophilic conversion under UV light irradiation and is
attributed to the increase of the amount of OH groups on the
TiO2 surface [9,10,34]. The photocatalytic reactions break down
the carbon chains resulting in reducing the steric repulsion effect
of the hydrocarbon modifier attached to the TiO2 surface, and
decrease its dispersibilty. Moreover, the highly hydrophilic conver-
sion might also negatively affect the dispersiblity of the modified
TiO2 in the non-polar solvents.
It is also interesting to note that less changes in the transmit-
tance spectra of the stearic acid treated TiO2 nanoparticles after
UV irradiation are observed compared to those treated with oleic
acid. This is in a good agreement with the HNMR results, reassur-
ing better UV resistance for the stearic acid treated nanoparticles.
It is acknowledged that determining the particle and/or
agglomerate size distributions using scattering methods would
provide more information on the particle size distribution before
and after UV radiation, and it is suggested for future work.
4. Conclusions
This work describes the dispersion performance of TiO2
nanoparticles treated with oleic or stearic acid in non-polar sol-
vents. It was found that the adsorption of stearic acid onto TiO2
nanoparticles is more than oleic acid. The influence of the UV irra-
diation on the chemical structure as well as the dispersion beha-
viour of the oleic acid and stearic acid treated nanoparticles was
investigated and it was found that stearic acid provide better dis-
persion performance after UV irradiation.
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