Thermochimica Acta 671 (2019) 83–88

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Experimental investigation on thermal properties of Ag nanowire nanofluids T

at low concentrations
R. Carbajal-Valdéza, A. Rodríguez-Juárezb, J.L. Jiménez-Pérezb, , J.F. Sánchez-Ramírezc,
⁎

A. Cruz-Oread, Z.N. Correa-Pachecoe, M. Maciasd, J.L. Luna-Sánchezb

a
CONACYT, SENER-Instituto Tecnológico de Celaya, Antonio García Cubas 600. Col. Fovissste, Celaya, Guanajuato, Mexico
b
UPIITA-Instituto Politécnico Nacional, Avenida Instituto Politécnico Nacional No. 2580, Col Barrio la Laguna Ticomán, Gustavo A. Madero, Ciudad de México, C.P.
07340, Mexico
c
Instituto Politécnico Nacional-CIBA, Ex-Hacienda San Juan Molino Carretera Estatal Tecuexcomac-Tepetitla Km 1.5, Tlaxcala, C.P. 90700, Mexico
d
Departamento de Física, Centro de Investigación y de Estudios Avanzados del Instituto Politécnico Nacional-IPN, Av. IPN No. 2508, Col. San Pedro Zacatenco, 07360,
Ciudad de México, Mexico
e
CONACYT, Centro de Desarrollo de Productos Bióticos-Instituto Politécnico Nacional (CEPROBI-IPN), Carretera Yautepec-Jojutla, Km. 6, calle CEPROBI No. 8, Col. San
Isidro, Yautepec, Morelos, C.P. 62731, Mexico

ARTICLE INFO ABSTRACT

Keywords: New nanofluids containing Ag nanowires with different concentrations were prepared by chemical reduction
Nanowires method. The metallic nanowires were monodispersed and soluble in distilled water. Thermal properties of na-
Photothermal techniques nofluids containing Ag nanowires were obtained using photothermal techniques. The thermal-wave resonator
Thermal parameters cavity (TWRC) technique was used to obtain the samples’ thermal diffusivity. Open Photoacoustic Cell (OPC)
Nanofluids
technique was used to obtain the thermal effusivity of Ag nanowires. The thermal diffusivity and effusivity were
tHermal conductivity
obtained by fitting the theoretical expressions for each configuration as a function of the sample thickness and
frequency to the experimental data. The thermal properties of the nanofluids seems to be strongly dependent of
Ag nanowire concentration. It was observed an increase of thermal parameters when concentration of nanowires
increased. Thermal conductivity behavior of the nanofluids is explained. UV–vis spectroscopy, Scanning Electron
Microscopy (SEM), Energy-dispersive X-ray spectroscopy (EDS) and X-ray diffraction (XRD) techniques were
used to characterize the nanofluids.

1. Introduction volumetric fraction in an oil suspension. According to other investiga-

tions, different materials, sizes, shapes and concentrations of nano-
In recent years, nanofluids have attracted great interest in the in- particles were used to improve the thermal conductivity of nanofluids
dustry and in the scientific community. The most important applica- [1–5]. Among particles, metal nanoparticles have deserved special at-
tions of nanofluids are in heat transport and its thermophysical prop- tention because of surface electron oscillations caused by the surface
erties such as thermal conductivity, viscosity and dielectric constant plasmon resonance (SPR) effect. Of special importance are the silver
have been enhanced by the use different concentrations of nano- nanoparticles (Ag) because they have low production cost and are ea-
particles, nanowires or nanotubes [1]. However, the thermal efficiency sily available, being used for shape-controlled synthesis [1,6–7]. They
of natural fluids is not enough effective and can cause damage to ma- have been often used as thermal additives for preparation of nanofluids
chines where a cooling system is required, resulting in overheating. [8,9]. In many works, spherical silver nanoparticles have been studied,
This increase causes the thermal conductivity of the industrial fluids to however, the effect of low concentrations has been rarely considered
increase, hence, the fluids are in the spotlight in day-to-day industrial [10–13]. Nanostructures such as nanowires have been used in nano-
work. Current research has found that the addition of nanoparticles in fluids, due to the surface-volume ratio that increases the heat transfer
fluids can improve the efficiency of the thermal properties of the fluid, [14]. It is important to highlight that there are few researchers who
such as conductivity, diffusivity and thermal effusivity. An example of have added nanowires in fluids in small proportions in order to enrich
this, is the work of Choi et al. [2]. They found that the thermal con- this fluid from the point of view of Nanotechnology. On the other hand,
ductivity was improved by 160% by adding 1% of carbon nanotubes the evaluation on the thermal conductivity of nanofluids has not been

⁎
Corresponding author.
E-mail address: [email protected] (J.L. Jiménez-Pérez).

https://doi.org/10.1016/j.tca.2018.11.015
Received 11 July 2018; Received in revised form 23 September 2018; Accepted 18 November 2018
Available online 19 November 2018
0040-6031/ © 2018 Elsevier B.V. All rights reserved.
R. Carbajal-Valdéz et al. Thermochimica Acta 671 (2019) 83–88

accomplished. In this work, silver nanowires were added in distilled 2.3. Open photoacoustic cell (OPC)
water at low concentrations to study their thermophysical properties by
thermal-wave resonator cavity (TWRC) and open cell photoacoustic OPC technique, was used for the thermal effusivity measurements
(OPC) techniques with the purpose of producing more effective, stable [17]. In this technique, a laser beam is modulated by using a me-
and uniform nanofluids. It was found, that the heat transfer of the fluid chanical chopper, at an angular frequency ω = 2πf. The details of the
was improved, therefore Ag nanowire-based nanofluids could have cross section of the photoacoustic cell and experimental cell are shown
possible applications in heat transport to reduce the losses of heat in Figs. 2 and 3. In the OPC technique, the liquid sample is placed on an
transfer in industrial machines of high efficiency, in the field of cooling aluminum foil, of known thermal effusivity. An electret microphone
of electronic equipment, in solar energy systems, heat exchangers and connected to the cell detects the heat generated due to the temperature
machining processes. rise and then it diffuses into the photoacoustic (PA) gas chamber
modulating the pressure (acoustic waves) within the PA cell. A lock-in
amplifier interfaced with a data acquisition system measures the mi-
2. Theory
crophone-response signal.
For the calculation of the thermal effusivity the obtained photo-
Thermal diffusivity and effusivity of the nanofluids were measured
acoustic signal of each sample is normalized, by using the photo-
by using the TWRC and OPC techniques [15–18]. acoustic signal when the sample is air, and the following equation was
used [18]:
2.1. Thermal wave resonator cavity (TWRC)
l0 0 c0
es =
In this work different concentrations of nanoliquids were acquired IR (2)
and their thermal diffusivities measured by a cavity-length scan in the
where 0 is the density of the used aluminum foil (2.7 gcm−3), c0 is the
TWRC device.
specific heat of the aluminum foil (0.9 Jg-1 °C-1), l 0 is the thickness of
The temperature fluctuations at x = l, interface between sample and
the aluminum foil (16 μm), = 2 f being f the modulation frequency
pyroelectric (PE) detector, can be detected with the PE sensor as a
of the excitation beam in the sample, and IR is the slope of the nor-
function of the sample thickness. The PPE (photopyroelectric) signal is
malized photoacoustic signal, as a function of the square root of f. The
amplified by the lock-in amplifier, at the reference of the beam mod-
cell was calibrated with water in order to compare with the values
ulation frequency (f), where its PPE amplitude and phase are measured
reported in the literature. The obtained value for distilled water was
as a function of the sample thickness (l).
(e H2 O = 1487.05 ± 47 Ws1/2 / m2°C ) and the reported value is
For the situation in which the sample in the TWRC may be con-
e H2 O = 1570 Ws1/2 / m2°C [19]). It can be seen that the obtained value
sidered as thermally thick, i.e., |ql| > 1, where q = (2π f i/Ds)1/2, with i
was similar to the reported one.
= (−1) ½ and Ds the sample thermal diffusivity,
the PE sensor output voltage, is given by Eq. (1) [15,16].

V (l) = V0exp(−ql) (1) 2.4. Materials

where V0 is a modulation frequency-dependent factor.

For silver nanowires synthesis, the following reactants without
Eq. (1) is a complex equation because q is a complex quantity,
treatment were used: silver nitrate (AgNO3 99.6%, Aldrich), PVP (PM
contains the factor i = (−1) ½, then this equation can be represented in
55,000 g/mol, Aldrich), glycerol (C3H5(OH)3, 99.90%, J.T. Baker) and
polar coordinates, which have a module, related directly with the ex-
sodium chloride (NaCl, 99.0%, Meyer).
perimental amplitude data measured by the lock-in amplifier, and a
phase, related directly with the experimental phase data measured by
the same lock-in amplifier.
2.5. Preparation of silver nanowires (AgNWs)
Since the PE signal, for thermally thick samples, depends on the
sample thickness (ls) in a simple linear way, as is shown in Eq. (1), the
The procedure adopted for AgNWs synthesis was as follows: 0.6 g of
thermal diffusivity can be obtained from the slope of the natural
PVP were dissolved with 19 mL of glycerol during 36 h at room tem-
logarithm of the PPE signal amplitude or from the slope of the PPE
perature. Then, the solution was added into a round-bottom flask and
signal phase, as a function of l.
0.158 g of AgNO3 were added to the solution with vigorous stirring until
AgNO3 was fully dissolved. Afterwards, a solution of 5.85 mg of NaCl in
2.2. TWRC experimental setup 0.05 mL of H2O was prepared and 1 mL of glycerol was added. The last
solution was put into the flask and the reaction temperature of the
In the TWRC technique, a cavity consists of two parallel walls: one mixture rapidly raised to 220 °C (roughly with a heating speed of
wall acts as the thermal-wave generator and the other wall is a pyro- 2.75 °C/min) on a hot plate (Cornic model PC-4200) with magnetic
electric transducer as shown in Fig. 1. The experimental arrangement stirring at 50 rpm in aerated condition. When the reaction was stopped
consists of a diode laser whose beam was modulated by the internal and the flask cooled down to room temperature, deionized water was
oscillator of a lock-in amplifier at 4 Hz. The modulated light impinges added into the flask in a 1:1 vol ratio, and then the mixture was cen-
on a thin copper foil of 100 μm thick mounted on an automatic cy- trifuged at 7000 rpm until all visible products were collected. The
lindrical micrometer stage controlled by a PC. This stage allowed the transparent supernatant was discarded and the obtained AgNWs were
cavity length to vary with a 1 μm step resolution. The modulated light washed with water three times to remove the PVP residue.
was absorbed on the highly conducting thin copper foil, which acted as Then, the nanowires were dispersed in ethanol and again cen-
an optical-to-thermal power converter. The cylindrical module was trifuged at 4000 rpm for 10 min. The final product was dispersed in
dipped in the sample as showed in Fig. 1. Thermal waves conducted distilled water to obtain nanofluids containing AgNWs with different
across the liquid interface reached the PVDF pyroelectric sensor of concentrations and the thermal measurement and further character-
110 μm thickness. The PE signal generated in the sensor was amplified ization were done. The obtained dispersion did not contain any visible
by a lock-in amplifier. The complex Eq. 1 was adjusted in the amplitude solids and was stable for more than three months without significant
and phase to the experimental amplitude and phase data, as mentioned changes in the spectral pattern indicating that these nanofluids are
before. All measurements were performed at room temperature. highly stable (see Fig. 4).

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R. Carbajal-Valdéz et al. Thermochimica Acta 671 (2019) 83–88

Fig. 1. Thermal-wave resonant cavity (TWRC) experimental set-up.

Fig. 2. Open photoacoustic cell (OPC) experimental setup.

Fig. 4. UV–vis absorption spectra of nanowires nanofluids obtained (̶) im-

mediately after preparation and (—) after three months.

path length of 1 cm. The nanofluid was place in a quartz cell. Powder X-
ray diffraction (XRD) spectra of the AgNWs were obtained using a
PANalytical X-ray Diffractometer, Model X’pert, with a CuKα radiation
(λ = 1.transm5406 Å), 40 kV– 40 mA, 2θ/θ scanning mode. Data was
taken for the 2θ range of 30 to 90 ° with a step of 0.02 and speed of 2 s/
step.

3. Results and discussion

Silver nanowires were synthesized by polyol process. The polyol

process is based on reduction of an inorganic salt by a polyol at an
elevated temperature. A polyol is a compound with multiple hydroxyl
functional groups available for organic reactions. In the polyol method,
glycerol is used as both, solvent and reducing agent, PVP is used as
Fig. 3. Cross section of the open photoacoustic cell (OPC). stabilizing agent, and AgNO3 is used as Ag source.
The UV–vis absorption spectrum of the synthesized solution is
2.6. Characterization shown in Fig. 4. The plasmon absorption peak appeared at 378 nm as
indicative of AgNWs formation. A shoulder peak appeared at about
The AgNWs morphology was analyzed by Scanning electron mi- 350 nm and is an optical characteristic for bulk silver. Absence of ab-
croscopy (Vega©tescan SN: VG1540475MX) at 15 kV. UV–vis analysis sorption peak at wavelengths higher than 400 nm indicates that the
was performed on a GENESYS 10S UV–vis Spectrophotometer GD10S final product is thoroughly AgNWs [17]. Nevertheless, the wide peak
UV–vis from 300 to 600 nm with a slit wavelength of 2 nm and light may indicate that a small amount of other morphologies such as
spherical nanoparticles are present.

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R. Carbajal-Valdéz et al. Thermochimica Acta 671 (2019) 83–88

Fig. 5. AgNWs morphology: (a) SEM image of AgNWs (magnification 2750) and (b) normalized diameter size distribution of AgNWs; average diameter was cal-
culated from Gaussian fitting of the histogram.

SEM images of the synthesized AgNWs is shown in Fig. 5. From the nanowires were obtained under the present synthesis conditions. The
images, it can be observed that the AgNWs are very homogenous in intensity ratios of (111)/(200) and (111)/(220) peaks were 5.58 and
morphology. It is clearly shown that AgNWs with a length up to 10 μm 7.59 respectively, which were relatively higher than the conventional
have been synthesized with high yield. The diameter of the nanowires 2.5 and 4 values which are described by Li et al. [22]. Therefore, this
was 96.04 nm with a standard deviation of 13.67%, indicating that the would indicate that the {111} planes of silver tend to be preferentially
AgNWs are homogenous. oriented for the polyol method.
Fig. 6 shows the typical XRD pattern of AgNWs. The diffraction The PE signal amplitude is shown in Fig. 7, as a function of the
peaks occurring at 38.1°, 44.82°, 64.62°, 77.2°, and 81.56° are indexed cavity length from the AgNWs sample in the TWRC experiment. The
as (111), (200), (220), (311), and (222) facets, being consistent well solid line, represents the best linear fit of Eq. (1) to the experimental PE
with a face-centered-cubic (fcc) Ag crystalline structure which is in data of the ln(amplitude). From this fit, the obtained mean thermal
accordance with the literature presented by Yang et al. 2015 [20] diffusivity was (16.04 ± 0.17) × 10−8 m2 s−1 for the sample with
(JCPDS card number 87-0717). concentration of 7 × 10−4 Vol. %. Similar measurements were carried
The calculated lattice constants according to the spacing distance dg out to determine the thermal diffusivity for the other concentrations.
of the {111} planes and the equation: 1/ d2 = h2 + k2 + l2/a2 is 4.088 Å Resulting thermal-diffusivity values of the AgNWs are summarized in
[21] and it is in agreement with the literature value of 4.086 Å. No Table 1.
peaks for other crystal types are observed. The sharp diffraction peaks Fig. 8 shows the typical behavior of the normalized OPC signal, as a
indicated the sample having a high crystallinity. Therefore, pure silver

Fig. 7. Natural logarithm of the TWRC signal amplitude as a function of the

Fig. 6. XRD pattern of silver nanowires synthesized by polyol process. relative cavity length for AgNWs with concentration of 7 × 10−4 Vol. %.

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R. Carbajal-Valdéz et al. Thermochimica Acta 671 (2019) 83–88

Table 1 In order to compare the obtained results with reported values in the
Thermal diffusivity (D), effusivity (e), volumetric heat capacity (ρc), con- literature, it was found the value of thermal conductivity for water
ductivity (k) and thermal conductivity enhancement of the evaluated samples. (k = 0.613 W/m K [23]), thermal diffusivity (D = 14.0 × 10−8 m2/s
AgNws/water Diffusivity Effusivity Conductivity Conductivity [24]) and thermal effusivity (e = 1570 W s1/2/ m2 K [19]), that are very
(Vol. %) D(10−8 m2/s) e(Ws1/2/m2K) Knf (W/mK) enhancement near with the calibration obtained values in this study.
((knf – kbf) / From the results obtained in this work, it was found that the thermal
kbf)×100(%)
conductivity enrichment of the AgNWs (φ = 96 nm × 40 μm) was from
3.5 × 10−6 14.00 ± 0.18 1663 ± 32 0.622 ± 0.013 4 4 to 20.8 for volumetric fraction between 3.5 × 10−6 and 1.74 × 10-4
4.7 × 10−6 15.11 ± 0.20 1687 ± 26 0.656 ± 0.011 9.6 vol. %., as shown in Fig. 9. Thermal conductivity enhancement increase
7.0 × 10−4 16.04 ± 0.17 1688 ± 41 0.676 ± 0.017 13 in a non-linear way for low volume concentrations. Similar results were
1.36 × 10−4 16.58 ± 0.16 1694 ± 125 0.690 ± 0.051 15.2
reported for Ag spherical nanoparticles with 55 nm in size, with con-
1.74 × 10−4 17.75 ± 0.24 1716 ± 52 0.723 ± 0.023 20.8
centrations from 1 × 10-5 to 1.02 × 10-3 vol. % and thermal con-
where kbf = kwater = 0.61 W/ m K. ductivity enhancement from 4 to 21.0 Vol. %, respectively and also
with increase non-linear way for low Vol % [25]. The high thermal
conductivity enhancement of the AgNWs, can be related with the spe-
cific surface area of the nanowires compared with Ag spherical nano-
particles, layering at the liquid solid surface interface and also Brow-
nian motion may be responsible for enhancement. However, our results
are in good agreement with many research works [25,26] i.e., the
thermal conductivities of nanofluids increase as particle volume con-
centration increase.
It is interesting to note that the model by Patel et al. [26] quite
accurately match with the experimental data for silver-water nanofluids
which show a non-linear increase of thermal conductivity as a function
of concentration.
From the comparisons, due to there are few works related to
thermal conductivity of AgNWs at low concentrations to compare with
our experimental results, it is concluded, that further research is needed
to develop a suitable model to predict the anomalous increase of
thermal conductivity in nanofluids of which will take into account
several possible factors in enhancing the heat transfer performance of
Fig. 8. OPC signal, as a function of the f1/2(s−1/2) for Ag NWs with con- nanofluids [25,26].
centration of 7 × 10-4 Vol. %.
4. Conclusions

In summary, silver nanowires (AgNWs) were successfully prepared

using the polyol process. Subsequently, the physicochemical properties
of AgNWs were investigated by UV–vis spectroscopy, SEM and XRD.
Also, a complete thermal characterization of AgNWs was achieved by
using two different photothermal techniques. Thermal diffusivity and
thermal effusivity of the nanofluids were obtained at room temperature
using the TWRC and OPC, respectively. The thermal conductivity (k)
values were calculated from the definition of the thermal diffusivity (D
= k/ (ρc)) and thermal effusivity e = (kρc)1/2. AgNWs showed an ef-
fective thermal transport property for low concentrations, as seen ex-
perimentally. For 3.5 × 10−6 vol% of AgNWs in the fluid, and en-
hancement of 4% was achieved, while an enhancement of 20.8% in
thermal conductivity was found for 1.74 × 10-4 volume fraction of
AgNWs. However, more research and new thermal models are neces-
Fig. 9. Ag nanofluids thermal conductivity enhancement of for different con- sary to predict the thermal properties of nanofluids. This study is a
centrations of AgNWs.
promising way for the elaboration of nanowires which can be used in
heat transfer applications.
function of the f1/2(s−1/2), where f is the light modulation frequency
from the AgNWs (for the concentration sample of 7 × 10-4 vol%). The Acknowledgements
solid lines, in Fig. 8 shows the best fit of the Eq. (2) to the normalized
OPC data. From this fit the obtained thermal effusivity for this sample is Thanks to CONACYT, COFAA, CGPI-IPN, Mexico, and Red-
1688.00 ± 41 Ws1/2/m2K. Similar measurements were carried out to Nanofotónica, for their partial financial support.
determine the thermal effusivity of the AgNWs for the other samples.
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