Article

pubs.acs.org/JPCC

Influence of Ionic-Liquid-Tethered Al2O3 Nanoparticle on the

Nonisothermal Cold Crystallization in Ionic-Liquid-Based Nanofluids
Debalina Deb and Subhratanu Bhattacharya*
Department of Physics, University of Kalyani, Kalyani, Nadia 741235, West Bengal, India
*
S Supporting Information

ABSTRACT: A series of ionic-liquid-based nanofluids (ion-

anofluids) has been prepared by dispersing different wt % of
alumina (Al2O3) nanoparticles, covalently tethered with 1-n-
butyl-3-(3-(trimethoxysilyl)propyl)imidazolium bis-
(trifluoromethanesulfonyl)imide [b((MeO)3Sip)im][NTf2],
in 1-decyl-3-ethylimidazolium bis(trifluoromethanesulfonyl)-
imide [Deim][NTf2] ionic liquid (IL) host. Thermophysical
properties of the pure-IL and its nanofluids have been studied
using transmission electron microscopy, differential scanning
calorimetry (DSC) and vibrational spectroscopy. The tethered
nanoadditives are dispersed uniformly within the IL host to
form stable nanofluids over the entire range of nanoparticle weight fraction studied. Analysis of the heating rate dependent DSC
data illustrates that the phase transition and fragility of the nanofluids can be effectively tuned by varying the content of the
[b((MeO)3Sip)im][NTf2]-tethered Al2O3 nanoparticles. Moreover, the crystallization and melting transitions of the host can be
completely avoided by dispersing merely 10 wt % of the nanoadditives. Analysis of the vibrational spectroscopy data reveals that
the guest nanoadditives significantly affect both the relative orientation and the separation of the anion within the host IL
through strong intermolecular interactions. The nonisothermal cold crystallization kinetics of the host IL and its nanofluids has
been studied using different existing models. The concave downward temperature dependence of the effective activation energy,
estimated from the isoconversional analysis of the crystallization data, has been successfully analyzed by standard nucleation-
based kinetic model in combination with a power law model. The parameters evaluated from the combined analysis indicate that
the tethered nanoparticles within the nanofluids act as heterogeneous nucleation agent, reducing the free energy barrier to
nucleation. However, simultaneous large enhancement in diffusion contribution to the nucleation dominates and shifts the
process toward higher temperature.

■ INTRODUCTION
Interest in dilute suspensions of nanometer-sized particles in
fluids (nanofluids) has grown in tremendous response to their
excellent promise for applications in numerous fields of
technology.1 It has been well established that even a small
amount of nanoparticle dispersion significantly enhances
energy transport process of the base fluid.2 Noble metal
nanoparticles such as gold, silver, etc. or ceramic oxide
nanoparticles are the most popular nanophases that are used
in nanofluids. Recently, multiwalled carbon nanotubes3
(MWCNTs) and graphene4 have also been adopted as the
nanoadditive to prepare stable nanofluids with application
potentiality. On the contrary, water, synthetic oil, glycols, and
polyolefins have been traditionally considered as the base fluids
for the suspension of those nanophases.
Recently, room temperature ionic liquids (RTILs), compris-
ing bulky organic cations and inorganic or organic anions, have
received considerable attention as the base fluid to form
nanoparticle dispersed stable nanofluids (ionanofluids). Ionic
liquid as a dispersion medium for nanoparticles provide a
number of advantages over molecular liquids because of their
many attractive physicochemical properties, including ultralow
vapor pressure, high dielectric constant and electrochemical
stability with broad electrochemical potential windows over a
wide temperature range. The large interface area and the
combination of properties of both nanoparticles and ILs, thus
obtaining flexible and desirable materials with synergies
properties for a wide range of potential applications such as
heat-carrier fluids, pigments for solar batteries, electrolytes in
batteries, capacitors, magnetic fluids, and so on.2,5,6
Designing nanofluids for a given application, it is essential to
understand their thermophysical properties and thermody-
namic phase behavior. Specifically for the nanofluids, the
defining characteristics are their melting point and crystallinity.
However, the thermochemical behavior of IL is not so simple.
Some IL may supercool without melting transition. Some of
them show freezing transition, crystal formation upon cooling
and a melting transition upon heating. Furthermore, some of
them do not show any tendency to crystallize upon cooling;
however, upon heating, they exhibit cold crystallization. It is
Received: November 24, 2016
Revised: March 8, 2017
Published: March 9, 2017

© 2017 American Chemical Society 6962 DOI: 10.1021/acs.jpcc.6b11845

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The Journal of Physical Chemistry C
Scheme 1. One-Pot Synthesis of [Deim][NTf2] Room Temperature Ionic Liquid Host with the Corresponding 1H NMR
Spectrum
Scheme 2. Surface Modification of Al2O3 Nanopartcles by the IL Precursor [b((MeO)3Sip)im][NTf2]a
a
The 1H NMR and the 29Si NMR of the Al2O3-tethered IL precursor are also shown.
worthy to mention that the desirability of crystallinity for a
nanofluid depends upon the effective temperature window of
the specific properties of the material. A recent study on the
thermal properties of nanofluids created by dispersing 1-
( t r i m e t h o x y s i l y l ) p r o p y l - 3 - m et h y l im i d a z o l i u m b i s -
((trifluoromethyl)sulfonyl)imide [Spimim][NTf2]-tethered
SiO2 nanoparticles in a 1-butyl-3-methylpyrrolidinium bis-
((trifluoromethyl)sulfonyl)imide [Bmpyr][NTf2] host has
shown that the addition of the SiO2-SpmImNTF2 particles
dramatically alters the thermal properties of the IL host at low
and high particle loadings.7 The increases in concentration of
nanoparticles up to 40 wt % transformed the IL host from a
plastic crystalline material into a simple liquid with superior
mechanical properties, with no observed melting transition.7
Thus, fundamental understanding of the crystallization
phenomena of nanofluids and to get insight into the factors
that tune it (e.g., suppression or retardation) is extremely
important to support emerging applications of this class of
material. However, there has been no report so far in the
literature dealing with the mechanisms and kinetics of
crystallization of nanofluids.
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In this research a series of stable nanofluids is prepared by
dispersing different wt % of covalently tethered alumina
(Al2O3) nanoparticles in an imidazolium-based ionic liquid
host. Thermal stability, vibrational properties, and dispersion of
nanoparticles within the nanofluids have been studied using
conventional thermal gravimetric analysis (TGA), transmission
electron microscopy (TEM), and vibrational spectroscopy. To
probe the influence of the covalently tethered nanoparticles to
the nucleation, phase transition, and crystal growth within the
host IL, nonisothermal cold crystallization kinetics of the
nanofluids have been studied using differential scanning
calorimetry (DSC). It has been observed that the dispersion
of as little as 0.5 wt % of tethered nanoparticles dramatically
influences the crystallinity of the IL host by slowing down the
conversion rate. Moreover, for the nanofluid containing merely
10 wt % of tethered guest the crystallization and melting
transition could not be observed during heating from its
supercooled state. The differential isoconversional technique of
Friedman8 has been implemented to evaluate the temperature
dependent effective activation energy for the nanofluids at
different degree of conversion. The observed temperature
dependence of the activation energy has been analyzed using
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the Fisher−Turnbull nucleation-based kinetic model9 in All spectra were externally referenced to liquid tetramethylsi-
combination with a power law model10 to assess the lane (TMS) at 0 ppm. The spectrum shows (inset) a sharp
contribution of diffusion in the overall crystallization process. peak at δ (ppm) = −108.8 and a shoulder at δ (ppm) = −91.2

■ EXPERIMENTS
Synthesis of Ionic Liquid Host. All chemicals used for the
corresponding to the Q3 and Q2 siloxane, respectively, similar
to the earlier reports of Mijatovic et al.12 Q3 and Q2 describe
the possibilities of anchoring of the (MeO)3Si part of the (3-
synthesis of nanofluids were procured from Sigma-Aldrich and chloropropyl)trimethoxysilane to the negatively charged surface
were used without further purification. The ionic liquid host for of the Al2O3 nanoparticles (shown schematically). The
the nanofluids, 1-decyl-3-ethylimidazolium bis- significantly higher intensity of Q3 as compared to that of
((trifluoromethyl)sulfonyl)imide, [Deim][NTf2] was synthe- Q2 resembles that the maximum anchoring of the silane groups
sized using the general one pot synthesis procedure11 (Scheme to the Al2O3 surface occurs by the Q3 mode.
1) and is designated here as “pure-IL”. 1H NMR (400 MHz, Preparation of Nanofluids. Different wt % (x = 0.5, 1.0,
DMSO-d6) (inset of Scheme 1): δ (ppm) = 9.165 (s, 1H), 2.5, 5.0, 7.5, and 10) (corresponding relative volume
7.792−7.775 (m, 2H), 4.216−4.123 (m, 4H), 1.786 (t, J = 7.2 percentages are included in Table 1) of purified and vacuum-
Hz, 2H), 1.424 (t, J = 7.2 Hz, 3H), 1.242 (s, 14H), 0.856 (t, J =
4.0 Hz, 3H). The as-synthesized IL was dried at a temperature Table 1. Preparation of Different Nanofluids with Relative
of 100 °C for 24 h under a dynamic vacuum and stored in an Weight and Volume Percentages of the Components
argon-filled glovebox. [Deim][NTf2] [b((MeOSi)3p)im][NTf2]-Al2O3
Surface Modification of Al2O3 Nanoparticles by IL
wt % vol % wt % vol % name
Tethering. The surface modification of the alumina nano-
particles by covalent tethering of ionic liquid to their surfaces 100 100 0 0 pure-IL
was performed in two steps. Initially, the IL precursor 1-n- 99.5 99.582 0.5 0.418 0.5 Al2O3-IL
butyl-(3-(trimethoxysilyl)propyl)imidazolium chloride [b- 99.0 99.163 1.0 0.837 1.0 Al2O3-IL
((MeO)3Sip)im][Cl] was prepared according to the previously 97.5 97.902 2.5 2.098 2.5 Al2O3-IL
reported procedure7 (Scheme 2). Briefly, (3-chloropropyl)- 95.0 95.786 5.0 4.214 5.0 Al2O3-IL
trimethoxysilane and 1-butylimidazole were refluxed under a N2 92.5 93.653 7.5 6.347 7.5 Al2O3-IL
atmosphere at 120 °C for 2 days. After cooling to room 90.0 91.501 10.0 8.499 10 Al2O3-IL
temperature, a honey-like orange viscous liquid [b-
((MeO)3Sip)im][Cl] was obtained. Any unreacted chemical dried [b((MeOSi)3p)im][NTf2]-functionalized Al2O3 nano-
was removed from the product by column chromatography. 1H particles were dispersed in the [Deim][NTf2] IL host to
NMR (inset of Scheme 2) (400 MHz, DMSO-d6): δ (ppm) = form different stable nanofluids designated as “xAl2O3-IL” in
10.796 (s, 1 H), 7.568 (t, J = 1.8 Hz, 1 H), 7.45 (t, J = 1.2 Hz, 1 the manuscript.
H), 4.334 (dt, J = 4.2 Hz, 4 H), 3.571 (s, 9 H), 1.872−2.075 Characterizations. The thermal stabilities of the pure-IL
(m, 4 H), 1.352 (dt, J = 8.1 Hz, 2 H), 0.967 (t, J = 7.5 Hz, 3 H), and its nanofluids were evaluated by TGA (Netzsch TG 209 F3
0.616−0.672 (m, 2H). Tarsus) at a heating rate of 10 °C/min under a nitrogen
The excess amount (1.5 times) of as-prepared [b- environment. The samples were scanned from room temper-
((MeO)3Sip)im][Cl] was allowed to react with the desired ature to 600 °C. Fourier transform infrared (FT-IR) experi-
amount of deionized water dispersed γ-Al2O3 nanoparticles ments of the samples were performed on a Shimadzu IR affinity
(<50 nm (TEM), >40 m2/g (BET)) under a N2 atmosphere. 1S FT-IR spectrometer, equipped with a single-reflection
The reaction proceeded for 12 h under continuous stirring at diamond attenuated total reflection (ATR) sampling module.
100 °C, and subsequently, absolute ethanol was added to the The spectra were acquired using 64 scans and 4 cm−1
mix. Eventually, the surface-functionalized alumina nano- resolution within a spectral range of 4000−400 cm−1. The
particles were collected by repeated washing and high speed Raman spectra were measured with a Bruker RFS 27,
centrifugation. The [b((MeO)3Sip)im][Cl]-Al2O3 were con- multiRAM standalone FT-Raman spectrometer with a reso-
verted to the [b((MeO)3Sip)im][NTf2]-Al2O3 system by the lution of 2 cm−1. Samples were excited by the 1064 nm
simple anion exchange reaction. In a typical reaction, 10 g of radiation of a Nd:YAG laser with 100 mW output power.
[b((MeO)3Sip)im][Cl]-Al2O3 was dispersed in 300 mL of DI Transmission electron microscopy (TEM) was performed on a
water to form a clear dispersion. Eight grams of lithium JEOL JEM-2100, 200 kV microscope in high resolution mode.
bis((trifluoromethyl)sulfonyl)imide (LiNTf2) salt dissolved in The nonisothermal cold crystallization kinetics of the nano-
50 mL of DI water was then added to that clear solution under fluids were studied using a Netzsch DSC 214, Polyma
vigorous stirring. Immediately after the addition, [b- differential scanning calorimeter (DSC) under a nitrogen
((MeOSi)3p)im][NTf2]-functionalized Al2O3 nanoparticles atmosphere with temperature calibrated by indium. In practice,
were separated from the water phase and settled to the bottom ∼10 mg of the sample was encapsulated in concave aluminum
due to the hydrophobicity of the NTf2 anion. The organic crucibles covered by lids. The sample was first heated to 120 °C
viscous part was collected by centrifuging and washed several at 10 °C/min and kept there for 10 min to eliminate any
times with DI water and acetone to take out the remaining thermal history. The sample was then rapidly cooled (100 °C/
untreated Cl-anion-tethered nanoparticles. Finally, the IL- min) to −100 °C and isothermally kept there for 10 min.
tethered nanoparticle gel was dried at a temperature of 100 Afterward, the supercooled liquids were heated at different
°C for 24 h under a dynamic vacuum and stored in an argon- heating rates up to 30 °C.
filled glovebox.
29
Si NMR spectra of the dried IL-tethered nanoparticle gel
was recorded in DMSO-d6 on a Bruker Avance III 500 MHz
■ RESULTS AND DISCUSSION
Thermal Stability. Thermal stabilities of Al2O3-[b-
spectrometer operating at 500.1 and 99.35 MHz, respectively. ((MeOSi)3p)im][NTf2], pure-IL, and its three nanofluids
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have been compared in Figure 1. Respective derivative
thermogravimetric (DTG) curves for pure-IL and nanofluids
Figure 1. Comparison of the thermal decomposition behavior of
different nanofluids with host IL and Al2O3-[b((MeOSi)3p)im][NTf2].
The derivative thermogravimetric (DTG) curves for pure-IL and
different nanofluids are shown at the inset.
are also included in the inset. The absence of any weight loss
below 390 °C for each of the samples rules out the possibility of
any solvent or unreacted small molecules within them. As
observed, Al2O3-[b((MeOSi)3p)im][NTf2] shows better ther-
mal stability than others. From the TGA trace for the Al2O3-
tethered [b((MeOSi)3p)im][NTf2] the grafting density of the
ligand to the nanoparticle surface has been estimated by ∑ =
NA(1 − Wnano)/(Wnano × anano × ρnano)/(6Mligand) and is found
to be ∼0.71 ligand/nm2 and a spacing of around 0.23 nm
between the IL chain tethered to the Al2O3 nanoparticle
surface.
The thermal stability of nanofluids increases at higher
nanoparticle loading and the DTG curves depict a systematic
shift in the decomposition onset temperature and the
temperature range of the nanofluids with respect to host IL
with increasing guest loading. From the residual of the
decomposed 2.5, 5, and 10 wt % nanoparticle-loaded nanofluids
the percentage of nanoparticles has been estimated as 2.3%,
4.8%, and 8.6%, respectively. Such a close agreement to the
above two percentages indicates the uniformity of dispersion of
the nanoparticles within the nanofluids.
Figure 2. TEM micrographs of (a) [b((MeO)3Sip)im][NTf2]-tethered Al2O3 nanoparticles. The inset shows the high resolution image and
corresponding SAED pattern. (b) Dispersion of nanoadditives within the 5.0Al2O3-IL nanofluid.
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Morphology of Tethered Nanoparticles and Nano-
fluids. Surface functionalization of the Al2O3 nanoparticles and
their distribution within the IL host play the key roles to alter
the properties of the host. Both of these have been analyzed by
TEM imaging, as shown in Figure 2a,b for the [b((MeO)3Sip)-
im][NTf2]-tethered Al2O3 nanoparticles and 5.0 Al2O3-IL
nanofluid, respectively. Figure 2a along with the high resolution
image (inset) clearly shows the effectiveness of [b-
((MeO)3Sip)im][NTf2] to functionalize the surface of the
Al2O3 nanoparticles that limits their aggregation. The
corresponding SAED pattern (inset) demonstrates the
diffraction spots of tethered γ-Al2O3 nanoparticles. Figure 2b
indicates that the nanoparticles are uniformly dispersed within
the host IL to form stable nanofluid.
Differential Scanning Calorimetry and Phase Tran-
sition. The effect of uniformly dispersed, surface-functionalized
nanoparticles at different loading on the thermodynamic phase
transition of the host IL has been observed by differential
scanning calorimetry (DSC). DSC has been used to measure
the glass transition temperature (Tg), cold crystallization
temperatures, and melting temperature (Tm) of pure-IL and
its nanofluids during heating at different heating rates from the
supercooled states of the systems. Parts a−e of Figure 3 depict
the nonisothermal cold crystallization thermograms for pure-IL
and its nanofluids at various heating rates (φ). The endotherms
of pure-IL and different nanofluids at a fixed heating rate of 5
°C/min have been compared in Figure 4. Each of the plots
shows a glass transition temperature, an exothermic event
attributed to the cold crystallization followed by an
endothermic event corresponding to the melting of the
crystallites.
The glass transition temperature (Tg) the onset (Tocc), peak
(Tpcc), and end (Tecc), temperature of cold crystallization and
corresponding melting temperature Tm at different heating
rates are collected in Table 2. Parts a−c of Figure 5 depict the
variation of Tg, Tpcc, and Tm of different samples as the function
of φ. With increasing heating rate, the time for nucleation and
growth of the crystallites decreases. Subsequently, the process is
appreciably shifted to higher temperature. The respective glass
transition (Tg) and melting peak (Tm) are also shifted toward
higher temperature, but at a slower rate (Figure 5 and Table 2).
Above a particular heating rate the crystallization and melting
curve tend to merge. With increasing Al2O3 loading, this
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Figure 3. Nonisothermal cold crystallization endotherms of (a) pure-IL and (b)−(e) different nanofluids.
Figure 4. DSC thermograms of pure [Deim][NTF2] IL and different
wt % of [b((MeO)3Sip)im][NTf2]-tethered Al2O3 nanoparticles
dispersed in nanofluids during heating at 5 °C/min from the
supercooled state.
overlapping occurs at a substantially lower heating rate, as can
be observed from Figure 4. It is worthy to observe from Figure
4 that at a fixed heating rate the cold crystallization temperature
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of the nanofluid containing as little as 0.5 wt % of
functionalized Al2O3 nanoparticles has substantially shifted to
higher temperature. Furthermore, both the enthalpy change
due to crystallization from the supercooled state and
corresponding melting transition is considerably reduced. For
the nanofluid containing 10 wt % of nanoadditives, both the
crystallization and the melting transitions almost disappear and
the material exhibits only a glass transition temperature. The
temperature range for nonisothermal cold crystallization ΔTcc =
Tecc − Tocc and the corresponding difference between the
crystallization and melting peaks ΔT = Tpcc − Tm for different
samples are plotted in Figure 5e as the function of φ.
As can be observed, with increasing heating rate, ΔTcc for
nanofluids significantly increases with respect to the pure-IL.
However, that follows a sharp decrease in corresponding ΔT
value.
Moreover, at a particular heating rate, with increasing
nanoparticle loading, ΔTcc gradually widens with a simulta-
neous narrowing in ΔT. Relatively higher Tpcc and wider ΔTcc at
any heating rate for the nanofluids with respect to the pure-IL
imply the requirement of a higher amount of energy for the
relaxation of the amorphous fraction within these, inhibiting the
cold crystallization process. Consequently, at a 5 wt % loading,
the crystallization and melting phenomena can sustain only up
to φ ≤ 5 °C/min (Figure 5d). These clearly indicate that at
higher nanoparticle loading (10 Al2O3-IL), even at a very low
rate of heating the time for crystal growth between the
beginning of cold crystallization and corresponding melting
becomes so short that the materials do not get any chance to
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Table 2. Nonisothermal Crystallization Kinetic Parameters for Pure-IL and Its Nanofluids
xAl2O3-IL φ (°C/min) Tg (°C) Tocc (°C) Tpcc (°C) Tecc(°C) Tm (°C) t1/2 (min)
1.5 −87.1 −64.8 −60.9 −55.7 −14.5 2.62
2.5 −86.0 −63.5 −58.7 −54.0 −14.3 1.84
0.0 5.0 −84.7 −61.7 −55.3 −51.0 −13.8 1.27
10 −83.3 −59.0 −52.0 −45.2 −13.2 0.70
15 −82.6 −54.9 −47.7 −40.0 −12.5 0.46
20 −81.8 −50.8 −43.1 −31.2 −12.0 0.39
1.5 −86.3 −64.7 −60.7 −57.1 −14.4 2.64
2.5 −85.1 −63.2 −58.5 −53.8 −14.2 1.88
0.5 5.0 −83.9 −60.3 −53.8 −47.6 −13.3 1.30
7.5 −83.4 −56.6 −49.5 −42.0 −12.4 0.85
10 −82.8 −52.8 −45.0 −36.0 −11.8 0.79
15 −82.4 −43.3 −32.4 −23.9 −11.3 0.59
1.5 −84.6 −64.4 −60.4 −57.0 −14.0 2.66
2.5 −84.0 −58.3 −52.8 −50.0 −13.5 2.12
1.0 5.0 −83.4 −53.2 −44.3 −37.0 −12.7 1.74
7.5 −82.8 −46.7 −36.4 −22.8 −12.0 1.38
10 −82.3 −43.2 −32.1 −19.5 −11.3 1.12
1.5 −83.9 −59.6 −53.9 −49.6 −13.8 3.81
2.5 2.5 −83.4 −56.0 −49.0 −44.8 −13.1 2.80
3.5 −83.2 −50.2 −41.6 −35.0 −12.8 2.53
5.0 −82.8 −47.6 −38.0 −29.7 −12.1 1.93
1.5 −83.5 −59.0 −53.1 −48.6 −13.7 3.96
5.0 2.5 −83.1 −55.4 −48.4 −43.4 −13.5 2.84
3.5 −82.8 −50.5 −41.6 −33.5 −13.2 2.55
5.0 −82.5 −40.8 −29.9 −22.0 −12.0 2.19

recrystallize. All these observations designate that Al2O3
nanoparticles with a [b((MeO)3Sip)im][NTf2]-functionalized
surface play a retardant role in the cold crystallization process,
which might be ascribed to the nature of interactions between
the functionalized Al2O3 particles and the host IL. Similar
phenomena were also observed earlier for [Bmpyr] [NTf2] IL-
hosted nanofluid at a much higher loading (40 wt %) of
[Spimim][NTf2] IL-grafted SiO2 nanoparticles.7 Thus, the
covalently tethered Al2O3 nanoparticles are found to be
effective to tune the thermodynamic phase transition of the
[Deim][NTF2] IL-hosted nanofluids.
Glass Transition and Fragility. The variation of Tg with
heating rate manifests the kinetic nature of the glass transition.
To characterize the temperature dependent dynamics of the
nanofluids at their supercooled state near the glass transition,
subsequent determination of the fragility parameter is
important. Fragility (m) is a measure of the thermal sensitivity
of the liquid structure and is described as the rate at which the
structure of a supercooled liquid around the glass transition
temperature relaxes with heating.13 It is an important concept
to measure the magnitude of deviation from conventional
Arrhenius kinetics for supercooled liquids and glasses.
Accordingly, glass forming liquids can be classified as their
position between two extremes; the so-called strong/fragile
pattern.14 Strong liquids that show almost Arrhenius behavior
have small m values (m ≈ 16), whereas fragile liquids with
larger m values (m > 100) collapse under weak perturbations,
leading to fast dynamical rearrangement and non-Fickian
diffusion, giving rise to non-Arrhenius behavior.14 Fragile
liquids have been extensively studied because of their unusual
relaxation behavior. However, what exactly makes a liquid
fragile is still unclear. The fragility is often obtained from the fit
of the data to the Vogel−Fulcher−Tammann (VFT)
equation15−17 for viscosity (η) written as
6967
η = η0 exp[DT0/(T − T 0)] (1)
where η0, D, and T0 are adjustable parameters, and small D
indicates large fragility. However, if the range of viscosity data
corresponding to far above Tg are used in that fitting, it may
yield T0 values higher than Tg, which is unphysical.
The more reliable measure is the fragility determined from
the slope of the Tg-scaled Arrhenius plot for viscosity as18
m = [d logη /d(Tg /T )]T = Tg
= −Eg (Tg)/(RTg) ln 10
= 16 + 590/D (2)
where Eg is the glass transition activation energy or the
activation enthalpy for structural relaxation, assuming a value of
10−4 poise for η0.18
The activation energy Eg is determined using the theory
developed by Moynihan19 on the basis of the glass transition
kinetics and structural relaxation to a high degree of
approximation as
d ln(φ)/d(1/Tg) = −Eg /R (3)
Another method used to find the glass transition activation
energy is the Kissinger method,20 and the equation for it is
given as20
d ln(φ /Tg 2)/d(1/Tg) = −Eg /R (4)
Parts a and b of Figure 6 depict the activation plots
corresponding to Moynihan and Kissinger method ln(φ) and
ln(φ/Tg2) as a function of 1000/Tg for all the samples,
respectively.
The activation energy values (calculated from the slope of
the activation plots according to eqs 3 and 4) and the respective
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Figure 5. Variation of (a) Tg, (b) Tpcc, and (c) Tm with φ for different samples. (d) Heating rate dependent variation of ΔTcc = Tecc − Tocc and ΔT =
Tpcc − Tm for pure-IL and its nanofluids.
heating rate dependent fragility index (m) are depicted in
Figure 6c,d, respectively. As observed from Figure 6c,d, both
methods provide similar and almost identical results for the
activation energy and fragility index, respectively. Furthermore,
it is interesting to notice that with increasing Al2O3 content
within the host IL, the fragility of the resulting nanofluids
significantly enhances. This may be attributed to the develop-
ment of strong intermolecular interactions21 between the host
IL and tethered Al2O3 within the nanofluid medium that
actually perturbs both the local and global dynamics of host IL
chain matrix. This perturbation essentially leads to an increase
of the particle relaxation time relative to the host in a “layer”
about the particles,22 resulting in a gradual increase in both Tg
and fragility of the nanofluids with increasing nanoparticle
dispersion.
Intermolecular Interactions. The observed variation in
phase transition and higher fragility index of the nanofluids
clearly indicate the possibility of strong intermolecular
interaction between the host and guest. To investigate the
nature of intermolecular interactions, vibrational spectra,
including both infrared and Raman of different samples have
been analyzed in different spectral regions. Parts a and b of
Figure 7 depict the ATR-FT-IR spectra of pure-IL and three
different nanofluids in two different regions, viz., 3215−2820
and 1650−1020 cm−1, respectively. The high frequency region
(Figure 7a) represents the IR impressions of C−H vibrational
bands of aliphatic (below ∼3000 cm−1) and aromatic (above
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Article
∼3000 cm−1) groups, whereas the one in the lower frequency
region (Figure 7b) corresponds mostly to the IR pattern of the
conformational isomerism of NTf2 anion. Within the spectral
region 3215−3050 cm−1, the spectra of pure-IL and its
nanofluids are deconvolated (Figure 7c−f) using a Gaussian
function into four Voigt profiles with maxima at ∼3179 ,
∼3154, ∼3123, and ∼3100 cm−1, respectively. The pair of
bands at the higher wavenumbers are assigned to the symmetric
C(4)−H and antisymmetric C(5)−H stretching of the
imidazolium ring, while those at the lower wavenumbers are
attributed to the C(2)−H stretching modes of the ring and
Fermi resonances of the C−H stretching vibrations with
overtones of in-plane ring deformations.23
The deconvolated spectra (Figure 7c−f) clearly illustrate that
there is a direct interactions between IL and the oxide
nanoparticles within the nanofluids, which significantly
influences the characteristic CH···anion H-bonding modes
between the imidazolium cations and NTf2 anions.23,24 It has
been established earlier that in the imidazolium-based IL
system the C(2)−H and C(4,5)−H modes can either form
isolated ion pairs by hydrogen boding with the anion or form
larger networks where cation can be completely H-bonded via
C(2)−H and C(4,5)−H.23−26 In the latter case the H-bonds
are weaker than those in isolated ion pairs because of the
anticooperative charge transfer within the imidazolium ring.24
As the stronger H-bonded species give larger vibrational
intensities, the deconvulated spectrum of pure-IL (Figure 7c)
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Figure 6. (a) Moynihan and (b) Kissinger plots to estimate the glass transition activation energy (Eg) for pure-IL and different nanofluids. (c)
Composition variation of Eg obtained from different method. (d) Heating rate dependent fragility index (m) for pure-IL and different nanofluids.
clearly indicates the presence of significant amount of ion pairs
within it.
With tethered Al2O3 nanoparticle loading, although the
frequency envelope of the higher wavenumber bands does not
change in energy, a significant blue shift in the lower wave
bands can be observed. Furthermore, a variation of the relative
intensities of the bands can also be observed with increasing
Al2O3 nanoparticle content. The observed blue shift in C(2)−
H stretching bands and simultaneous increase in intensities of
the C(2)−H and C(4,5)−H vibrational bands of the network
structure clearly designate a gradual weakening of the strong
isolated ion pair H-bonds and simultaneous transformation of
the ion pairs to larger H-bonded network configuration.24 Apart
from the above bands, the intensity of the peaks at the
frequency ∼2960, ∼2940, ∼2900, and ∼2855 cm−1, corre-
sponding to the fundamental C−H stretching vibrational bands
of the alkyl chain of cation bound to the nitrogen atoms of the
imidazolium ring are also gradually diminished with increasing
concentration of Al2O3 within the nanofluids.
The observed changes in the delicate balance between
Coulombic attraction and H-bonding within the nanofluids are
also associated with simultaneous changes in the conformation
of the NTf2 anion, which has been demonstrated by the
infrared spectra within 1650−1020 cm−1 range in Figure 7b.
The NTf2 anion within the IL can adopt two different
conformations viz. the cisoid (cis or C1) and the transoid
(trans or C2), which differ only by a few kJ/mol in energy.25
The absorption bands corresponding to these conformations
are assigned as follows.27,28 The band around 1061 cm−1
corresponds to the antisymmetric SNS stretching mode of
the NTf2 anion, which is strongly coupled to the symmetric
stretch of the CF3 group. The absorption around 1138 cm−1
with a shoulder at 1143 cm−1 occurs due to coupled
asymmetric CF3 stretching of different phases. Specifically,
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the shoulder at 1143 cm−1 corresponds to either the out-of-
phase asymmetric CF3 stretch of the trans conformer or the
asymmetric stretch on only one side of the cis conformer. It
evolves with significantly higher absorption intensity for the cis
conformation than that of the trans. The intense peak at 1216
cm−1 corresponds to asymmetric CF3 vibration, which couples
strongly to the symmetric SO2 stretching mode. The shoulder
associated with the above band around 1230 cm−1 is assigned
to the symmetric CF3 stretch mode. The doublet feature at
1333 and 1359 cm−1 is allocated to the out-of phase
asymmetric SO2 stretch of the trans conformer or to the
asymmetric stretch of only one side of the cis conformer. In the
trans conformation the absorption intensity of the 1359 cm−1
band is substantially higher than cis. Finally, the absorption
bands around 1578 cm−1 is attributed to the vibrations of the
CC double bond overlapping with the vibrations of the NCN
group.
In Figure 7b, the spectrum of pure-IL stipulates the
dominating feature of the energetically stable trans-anion
conformation. In the trans conformation the NTf2 preferably
displaces slightly and establishes more specific interactions with
the C(2,4,5)−H sites (in particular with C(2)−H) favoring the
ion pair formation within the pure-IL. However, with increasing
tethered Al2O3 dispersion, the intensity of the absorption bands
exclusive to the cis-NTf2 conformation increases with
simultaneous suppression of the corresponding exclusive
trans-vibration bands. For the nanofluid containing 10 wt %
nanoparticles, the intensity of trans-vibration bands significantly
reduces and the cis conformation dominates.
The issue of intermolecular interaction has been further
addressed by employing Raman spectroscopy. In Figure 8a, the
Raman spectrum of the pure-IL and its nanofluids are shown
within 250−800 cm−1. The spectral range shown here contains
useful information on both the strength of interaction
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Figure 7. FT-IR spectra of [Deim][NTF2] IL and different wt % of [b((MeO)3Sip)im][NTf2]-tethered Al2O3 nanoparticles dispersed nanofluids in
the regions (a) 3215−2820 cm−1 and (b) 1650−1020 cm−1, respectively. (c−f) Deconvoluted spectra of bulk IL and different nanofluids
respectively, in the region 3215−3050 cm−1.

experienced by the NTf2 anion (expansion−contraction mode
at 740 cm−1) and its conformational state (240−450 cm−1).
The vibrational mode at 740 cm−1 has been assigned to the
most characteristic Raman signature for the NTf2 anion.29 It
has been demonstrated earlier that the 740 cm−1 feature is the
sum of two components arising from both the cisoid (C1) at
738 cm−1 and the transoid (C2) at 741 cm−1.12 It is interesting
to observe that, with increasing nanoparticle loading, this mode
gradually shifts toward lower frequencies, indicating the
increasing proportion of the C1 conformer than C2 within
the nanofluids.
It has been reported earlier that the series of interaction
independent deformation Raman modes centered within the
6970
low frequency range ∼250−450 cm−1 (Figure 8b) are the best
candidates to investigate the conformational isomerism of the
NTf2 anion within the aprotic ionic liquids.29 The vibrational
bands found within the above-mentioned range have previously
been assigned to the twisting (τ) and rocking (ρ) modes of the
SO2 and CF3 groups of the NTf2 anion.29 The bands at around
408, 333, 326, and 310 cm−1 are the best indicators for the C1
conformation, whereas the C2 conformer can be suitably
recognized by the bands near 398, 339, 314, and 297 cm−1.
Furthermore, the shoulder at 351 cm−1 is also due to the C1
conformer.12,29 As shown in Figure 8b, the spectrum of pure-IL
mainly contains the modes corresponding to the trans (C2)
form (see arrows). However, with increasing nanoparticles the
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Figure 8. (a) Raman spectra of pure-IL and its nanofluids in the spectral range 250−800 cm−1. The inset shows the enlarged portion of the strongest
Raman mode (∼740 cm−1) corresponding to the NTF2 anion. (b) Low frequency NTF2 anion sensitive Raman signature of different samples.
Arrows indicate the band position corresponding to different anion conformations.

Figure 9. Conversion (Xt(T)) with increasing temperature within (a) 1.0 Al2O3-IL nanofluid recorded for various heating rates and within (b)
different samples at a particular heating rate. Corresponding temperature variation of the rate of crystallization (dXt(T)/dt) are depicted in (c) and
(d), respectively.

intensity of the modes associated with the cisoid (C1) form
increases with respect to those of the transoid (C2). For the 10
Al2O3-IL nanofluid, the modes corresponding to the C2 form
almost diminish and the spectrum shows the characteristics of
the C1 form only. A similar trans to cis transformation was also
observed during adsorption and desorption of 1-butyl-3-
methylimidazolium bis(trifluoromethylsulfonyl)imide ionic
liquid on the of Al2O3/Ni Al(110) surface.27,30
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From the above discussion it is clear that the [b-
((MeO)3Sip)im][NTf2]-tethered Al2O3 nanoparticles within
the nanofluids significantly affect both the relative orientation
and the separation of the anion from the imidazolium ring,
which hinders the ion-pair formation and induces the NTf2
anion to gradually rearrange and establish a conformational
equilibrium different from that in the host. Both of these
rearrangements gradually alter the thermophysical properties
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Figure 10. Plots of log φ vs log t from Liu’s method for the nonisothermal cold crystallization of pure-IL and different nanofluids.
such as phase transition and fragility of the nanofluids as
compared to the case for the host.
Kinetics of Crystallization. To further investigate the
influence of the IL-tethered nanoadditives to the nucleation and
growth of the crystallites within the IL host, the kinetics of the
cold crystallization for different samples have been studied. As
the crystallization and melting endotherms for the 7.5Al2O3-IL
nanofluid coincide at φ ≤ 5 °C/min, the data for the nanofluids
up to 5.0Al2O3-IL are considered for the kinetics study. In the
dynamic crystallization mechanism, it is generally considered
that the development of crystallinity is linearly proportional to
the evolution of heat released during the crystallization. On the
basis of the above consideration, the thermal growth of mass
fraction of crystalline state in the sample i.e., the degree of
conversion as a function of temperature Xt(T), is defined as the
ratio of crystallinity at any arbitrary temperature to the
crystallinity as the temperature approaches infinity and can be
expressed as
ΔH T ⎛ dHc ⎞ T∞ ⎛ dH ⎞
X t (T ) = = ∫T ⎜ ⎟ dT / ∫T ⎜ ⎟ dT
c
ΔH∞ o
cc
⎝ dT ⎠ o
cc
⎝ dT ⎠
where dHc/dT is the rate of heat evolution, ΔH is the total heat
evolved at any arbitrary temperature T, and ΔH∞ is the heat
evolved at ultimate crystallization temperature T∞ (at t = ∞).
Tocc is the initial (at t = 0) crystallization temperature. In the
nonisothermal experiments the crystallization time is related to
the cooling rate φ as
t = |Tcc0 − T | /φ
Figure 9a illustrates the degree of conversion Xt(T) with
temperature at different heating rates for a representative
nanofluid. Similar Xt(T) vs T plots for other nanofluids are
depicted in Figure S1. The compositional variations of
temperature dependent Xt(T) at a particular heating rate (ϕ
= 5 °C/min) are shown in Figure 9b. All the curves have the
Article
same sigmoid shape, indicating that only the heating rate
dependent retardation effect in relaxation of the amorphous
fraction separates them from each other.
The transformation from temperature to time is performed
using eq 6 for different heating rates. Figure S2 shows the
variation of Xt with the crystallization time for pure-IL and
different nanofluids at different heating rates. The temperature
changes of the crystallization rate dXt(T)/dt in a representative
nanofluid, calculated for various φ, are presented in Figure 9c.
As can be seen, the rate of crystallization increases significantly
with φ. Figure 9d compares the temperature dependent
crystallization rates for different samples at a specific heating
rate. With increasing Al2O3 nanoparticle dispersion, the rate of
crystal growth within the nanofluids significantly diminishes as
compared to that of the pure-IL. Thus, at a specific heating rate,
higher temperature is necessary to achieve same degree of
crystallinity within the nanofluids.
The half cold crystallization time (t1/2), defined as the time
taken to reach the relative crystallinity at the value 50%, can be
obtained from the Xt vs t curve (Figure S2), as summarized in
(5) Table 2 at different heating rates. The t1/2 value gradually
decreases with increasing heating rate, as the crystallization
proceeds faster. However, higher t1/2 for the nanofluids with
respect to the pure-IL at any particular heating rate again
indicates the decelerating effect of the guest nanoadditives to
the overall crystallization process.
In isothermal crystallization kinetics, the degree of
crystallinity Xt(T) is usually described in terms of the Avrami
model31 as
(6)
X t(T ) = 1 − exp( −Ztt n) (7)
where n is the Avrami constant, associated with the nucleation
mechanism and the geometry of crystal growth, and Zt is the
overall (macroscopic) rate constant involves both nucleation
and growth rate parameters. To describe nonisothermal
crystallization kinetics in the experiment with constant heating
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rates ϕ, the Avrami model was generalized by Ozawa32 and Liu significantly with increasing Al2O3 content within the IL host.
and co-workers.33 This again confirms that the crystallization rate of nanofluids
In the Ozawa32 model, the nonisothermal conditions were gradually becomes slower with increasing Al2O3 content and
considered as the result of an infinite number of isothermal the tethered nanoparticles essentially retard the overall
steps and the following equation was proposed crystallization process.
Effective Activation Energy for Cold Crystallization.
1 − X t(T ) = exp[−K (T )/φm] (8)
To characterize the nonisothermal cold crystallization kinetics
where K(T) is a function of temperature, which relates to of the pure-IL and different nanofluids from their supercooled
nucleation style, nucleation rate, and crystal growth rate, and m state determination of the effective activation energy (EX), the
is the Ozawa exponent, which depends on the dimensions of energy required to transport molecular segments to the
the crystal growth. However, the Ozawa model was found to be crystallization surface is very essential. In this regard, the
inadequate to properly explain the nonisothermal crystallization reaction model independent isoconversional methods are
kinetics for different materials34−36 as the secondary crystal- advantageous as compared to the other methods.37 The
lization and the impingement of spherulites has been neglected isoconversional methods also enable us to evaluate the
in this model.32 dependence of the EX on conversion and temperature, which
Liu et al.33 combined the Avrami and Ozawa equations to is quite helpful in detecting and elucidating complex kinetics
give a relationship between Zt, K(T), and t as and crystal growth mechanism in any system.37 Among the
different existing isoconversional methods the differential
log Zt − m log φ = log K (T ) + n log t (9) method of Friedman8 and the advanced integral method of
Thus, a new equation for a description of crystallization Vyazovkin37 are most appropriate and in the current
appears investigation the method of Friedman has been used to
evaluate EX for different samples.
log φ = (1/m) log[Zt /K (T )] − (n/m) log t In the cold crystallization process above the glass transition,
the supercooled glassy material relaxes and turns into its
= log F(T ) − λ log t (10)
metastable liquid form. As the temperature continues to rise,
1/m the molecular mobility increases, promoting nucleation and
where the kinetic parameter F(T) = [Zt/K(T)] represents
the necessary value of heating rate per unit crystallization time crystallization of the supercooled liquid. Cold crystallization
to reach the systems at a distinct degree of crystallinity, i.e., the normally occurs below a certain temperature Tmax up to which
parameter that specifies the polymer crystallization rate, and λ is the nucleation rate increases with increasing temperature.
the ratio of the Avrami exponent (n) to the Ozawa exponent Above Tmax, as the process is solely diffusion controlled, a
(m). As shown in Figure 10a−e, the linear dependence of log φ dramatic decrease of the nucleation rate occurs.37 On the basis
vs log t is obtained for each degree of crystallinity for each of of the energetics involved in the nucleation process, the
the samples, indicating that the observed crystallization is a maximum rate of nucleation can be expressed according to the
well-defined process for all φ applied in the experiment. Fisher and Turnbull model as9
The values of λ and F(T) estimated from the slope and
w(T ) = w0 exp( −ΔG*/RT ) exp(−E D/RT ) (11)
intercept of the linear fitting are summarized in Table 3. F(T) is
where ΔG* and ED are considered as the free energy barrier to
Table 3. Dynamic Crystallization Kinetic Parameters at nucleation and the activation energy for diffusion across the
Different Degrees of Crystallinities by the Liu Method phase boundary, respectively. The product of these two
Xt (%)
exponential terms yields a temperature dependence that
demonstrates a maximum in the nucleation rate.9 The free
sample parameters 20 40 60 80 energy barrier is infinity near the glass transition temperature,
pure-IL F(T) 3.71 5.24 7.24 9.93 but quickly decreases with heating as
λ 1.67 1.69 1.72 1.73
0.5 Al2O3-IL F(T) 4.23 6.60 9.21 13.1 16πσ 3T0 2 A
ΔG* = =
λ 1.80 1.81 1.87 1.89 3(ΔHf )2 (ΔT )2 (ΔT )2 (12)
1.0 Al2O3-IL F(T) 6.03 9.72 15.4 24.5
λ 2.04 2.14 2.31 2.51 where σ is the surface energy, ΔT = T0 − T (T0 is the
2.5 Al2O3-IL F(T) 7.53 11.6 17.9 30.1 temperature where nucleation is zero), ΔHf is the heat of
λ 1.93 2.05 2.21 2.33 fusion, and A is a constant. Equations 11 and 12 can be used to
5.0 Al2O3-IL F(T) 13.8 23.1 40.2 62.1 predict a variation in the effective activation energy with
λ 2.11 2.21 2.41 2.47 temperature.37 By definition, the effective activation energy is
determined by the logarithmic derivative of the rate constant
considered as a parameter that indicates the cold crystallization with respect to the reciprocal temperature:
rate. A lower F(T) value corresponds to the higher ∂ ln w(T )
crystallization rate under nonisothermal crystallization. Con- E X = −R
stant λ together with F(T) growing with Xt(T) rules out the ∂T −1 (13)
appearance of any extra crystallization in the experiment and it Combining eqs 11 and 12 give the following equation
further indicates that at a particular crystallization time, to
achieve a higher degree of crystallinity a higher heating rate is ⎛ A ⎞ ⎛ E ⎞
w(T ) = w0 exp⎜ − 2⎟
exp⎜ − D ⎟
necessary. ⎝ RT (ΔT ) ⎠ ⎝ RT ⎠ (14)
It is worthy to observe from Table 3 that for an identical
degree of crystalline transformation the value of F(T) increases Substitution of eq 14 into eq 13 yields
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Figure 11. (a) Effective activation energies, obtained using the differential isoconvertional method, as a function of conversion for cold crystallization
of pure-IL and its nanofluids (open symbols) along with corresponding variation of average temperature (solid symbols). (b) Dependence of the
effective activation energy on average temperatures, for different samples. The solid lines represent best fits to eq 20.

Table 4. Nucleation and Diffusion Parameters for Different Samples Obtained from the Fitting of the Temperature Dependent
EX Data Using Eq 20
samples ED (kJ mol−1) T0 (K) A (K2 kJ mol−1) ε (kJ mol−1) n ED + ε (kJ mol−1) ΔG* (at Tc) (kJ mol−1)
pure-IL −68.3 183 7423.3 30.7 9.0 −37.6 6.16
0.5 Al2O3-IL −38.7 190 3811.6 35.4 4.6 −3.3 4.46
1.0 Al2O3-IL −16.3 199 1389.2 28.4 3.5 12.1 1.57
2.5 Al2O3-IL −4.9 203 165.9 26.9 2.5 22.0 1.36
5.0 Al2O3-IL 3.5 211 15.3 24.3 2.0 27.8 0.40

⎛ 2T 1 ⎞ nature (Figure S3). The values of EX for each sample, obtained

E X = ED − A⎜ − ⎟ from the slopes of the straight lines achieved for each
⎝ (ΔT )3
(ΔT )2 ⎠ (15) conversion and for different φ are plotted in Figure 11a as a
As the crystallization occurs on heating ΔT < 0, the value in function of Xt(T). Temperature variation of the average relative
the parentheses of eq 15 is negative and increases asymptoti- crystallinity for the respective samples is also included in the
cally to zero with increasing temperature. Thus, for cold figure. The EX dependencies for all the samples have a similar
crystallization the value of EX should be positive and expected concave downward shape, and its value is always positive
to decrease monotonically throughout the process.37 irrespective of conversion, which is in line with the Turnbull
The dependence of EX upon the conversion Xt(T) can be and Fisher crystal nucleation model (eq 15) up to a certain
obtained using the isoconversional principle, which states that extent. With increasing tethered nanoparticle dispersion, the EX
at a constant extent of conversion, the reaction rate is a value for a particular conversion substantially decreases with
function only of the temperature.10 Thus, the rate of the respect to pure-IL. However, it is worthwhile to notice that for
nucleation driven crystallization can be expressed by the basic each of the sample that above a certain conversion the value of
rate equation as EX shows a reverse trend. Such an increase in EX in the later
stages of crystallization may be attributed to the changing
d X t (T ) conditions of diffusion within the materials during heating.
= w(T ) f (x)
dt (16) Figure 11b depicts the average temperature dependence of the
activation energy for different samples. With increasing
where f(x) is the reaction model. The isoconversional activation nanoadditives the temperature range of crystallization process
energy can be estimated as10 widens and gradually shifts toward higher temperature.
⎡ ∂ ln(dX t(T )/dt ) ⎤ Furthermore, the diffusion controlled region, i.e., the region
E X = −R ⎢ ⎥ where EX varies inversely, gradually increases. Such a strong
⎣ ∂T −1 ⎦X (17) Xt(T) dependence of EX clearly indicates that the consideration
t
of constant activation energy for diffusion (ED) in eq 15 is
According to the differential isoconversional method of inadequate to demonstrate the complete crystallization process
Friedman,8 using eqs 16 and 17, different effective activation and should be replaced by a conversion dependent function
energies (EX) can be determined for each degree of conversion as37,38
as
⎛ d X (T ) ⎞ ε(X t ) = E D + εX t n (19)
EX
ln⎜ t ⎟ = ln(A X t f (x)) −
⎝ dt ⎠ X , i RTX ti (18) where ε are the activation energies of diffusion after complete
t
conversion (Xt = 1) and n determines the strength of the
where the subscript i is used for different heating rates. The contribution of diffusion in the crystallization process.38
variations of dXt(T)/dt at a specific Xt(T) for different heating Replacing ED with ε(Xt) in eq 15 the expression for the
rates (φ) with the corresponding crystallization temperature activation energy with contribution of both nucleation and
(TXti) for Xt(T) within 0.2−0.98 are found to be Arrhenius in diffusion becomes
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The Journal of Physical Chemistry C
⎛ 2T 1 ⎞
E X = E D + εX t n − A ⎜ 3
− ⎟
⎝ (T0 − T ) (T0 − T )2 ⎠ (20)
The parameter A designates the contribution of the
nucleation process to the temperature dependent conversion,
which is effective at a lower contribution of diffusion, i.e., within
the region of decreasing EX dependence upon T. The increasing
portion of the dependence resembles the strong diffusion
contribution that is represented by the parameters ε and n.
Solid lines in Figure 11b show that eq 20 simulates the
experimental data reasonably well with parameters given in
Table 4. The steady decrease in the value of both A and free
energy barrier to nucleation at respective onset of crystallization
Tocc (Table 2) (ΔG* = A/(T0 − Tocc)2) with increasing tethered
nanoparticle dispersion indicates the heterogeneous nucleating
effect of the nanoparticles. However, a simultaneous significant
increase in ε + ED, which reflects the total diffusion effect,
corresponds to the hindrance effect of the guest toward the
diffusion across the phase boundary during nucleation. These
two complementary effects essentially shift the process toward
the higher temperature (increasing T0). The constantly
decreasing value of n further indicates that cumulative
nanoparticle dispersion enhances the diffusion contribution in
the crystallization process. The observed feature directs that for
the nanofluid containing higher content of tethered nano-
particles (>10 wt %), the diffusion contribution may become so
large that the required temperature for the initiation of
nucleation supersedes the melting temperature of the
crystallites. That circumvents the process and a transition
from hard, glassy supercooled state to a soft rubbery
amorphous liquid state occurs.
■
CONCLUSIONS
The effects of the cumulative dispersion of IL-tethered Al2O3
nanoparticles to the thermophysical properties, crystallization,
and phase transition of [Deim][NTf2] IL-hosted nanofluids
were studied using TGA, vibrational spectroscopy, and
differential scanning calorimetry. TEM and DSC analysis
confirmed the uniform dispersion of the tethered nanoparticles
within the host IL to form stable nanofluids with different
thermophysical properties as compared to the host. For the
nanofluid containing more than 10 wt % of nanoadditives, the
crystallinity was completely suppressed with significantly higher
fragility as compared to that of the host IL. The observed
alteration of the thermophysical properties of the nanofluids
with respect to their host was corroborated by strong
intermolecular interactions between the host and guest, as
evidenced by vibrational spectroscopy including both ATR-FT-
IR and Raman. This intermolecular interaction was found to
affect both the relative orientation and the separation of the
anion from the imidazolium ring, intervening the ion-pair
formation with a simultaneous increase of the cisoid forms
relative the transoid forms of the anion within the nanofluids.
Analysis of nonisothermal cold crystallization kinetics data by
different models identified that the tethered nanoparticles
considerably retard the overall crystallization process within the
nanofluids. The effective activation energy for conversion was
obtained from the isoconversional technique at different
temperature. The nucleation model of Fisher and Turnbull
was found to be inadequate to represent the complete
temperature dependence of the nucleation rate within the
nanofluids and a modified model comprising the contribution
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Article
of both nucleation and diffusion was used to estimate different
nucleation parameters. The variation of the estimated
parameters with the wt % of tethered nanoparticles
demonstrated that in the presence of the nanoadditives,
although the free energy barrier within the nanofluids was
substantially reduced, it progressively enhanced the diffusion
contribution to the overall nucleation process. This diffusion-
mediated hindrance effect essentially delayed the process
toward higher temperature, and for the nanofluid containing
higher nanoadditives the conversion could not be occurred.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.6b11845.
Degree of conversion with temperature and time for
different samples, and Arrhenius plots of Friedman
differential isoconversional method for different samples.
(PDF)
■
AUTHOR INFORMATION
Corresponding Author
*S. Bhattacharya. Phone: (+91 33) 2582 0184. Fax: (+91-33)
2582 8282. E-mail: subhratanu1@gmail.com.
ORCID
Subhratanu Bhattacharya: 0000-0001-9601-034X
Author Contributions
The manuscript was written through the contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Funding
Council of Scientific and Industrial Research, Government of
India.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Authors thankfully acknowledge the Council of Scientific and
Industrial Research (Govt. of India) for the financial support
under the Extra Mural Research Scheme No: 03(1327)/14/
EMR-II Dated 03.11.2014. Also, the authors thankfully
acknowledge the DST-FIST scheme of the Department of
Physics, DST-SAIF and University of Kalyani for providing the
instrumental facilities.
■ REFERENCES
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Lv, W.; Rosengarten, G.; Prasher, R.; Tyagi, H. Small Particles, Big
Impacts: A Review of the Diverse Applications of Nanofluids. J. Appl.
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6976 DOI: 10.1021/acs.jpcc.6b11845

J. Phys. Chem. C 2017, 121, 6962−6976