Sains Malaysiana 46(7)(2017): 1017–1024

http://dx.doi.org/10.17576/jsm-2017-4607-02

Thermal Stability and Conductivity of Carbon Nanotube

Nanofluid using Xanthan Gum as Surfactant
(Kestabilan Termal dan Kekonduksian Bendalir Nano Karbon Tiub Nano
menggunakan Gam Xantan sebagai Surfaktan)

SABA RASHIDI*, RASHMI, W., LUQMAN CHUAH ABDULLAH, KHALID, M.,

FAKHRUL-RAZI AHMADUN & M.Y. FAIZAH

ABSTRACT
A nanofluid is a suspension of nano-sized particles dispersed in a base fluid. It is very much obligatory to know more
about stability and thermal characteristics of such a nanofluid for their further use in practical applications. In this
research, multiwalled carbon nanotubes (CNT) is dispersed in water. CNT dispersed in water is highly unstable and it
sediments rapidly due to the Vander Waals force of attraction. Therefore, to overcome this limitation, xanthan gum (XG)
was added which behave as a promising dispersant followed by 4 h water bath sonication. Experimental work includes
stability studies using UV Vis spectroscopy with respect to CNT concentration (0.01 and 0.1 wt. %) and XG concentration
(0.04 and 0.2 wt. %). The thermal conductivity of the most stable suspensions was measured using KD 2 Pro as a function
of temperature (25-70°C) and CNT concentration. The optimum XG concentration was found for each CNT concentration
studied. Thermal conductivity was observed to be strongly dependent on temperature and CNT concentration. The
dispersion state of the CNT-water nanofluid is further examined using scanning electron microscope (SEM). In short, CNT
nanofluids are found to be more suitable for heat transfer applications in many industries due to their enhanced thermal
conductivity property. This work provides useful insight on the behavior of CNT nanofluids.

Keywords: Carbon nanotubes; nanofluid; stability; thermal conductivity; xanthan gum

ABSTRAK
Bendalir nano ialah penggantungan zarah bersaiz nano dalam bendalir asas. Adalah sangat penting untuk mengetahui
lebih lanjut tentang kestabilan dan pencirian termal daripada bendalir nano tersebut bagi tujuan kegunaan praktik
selanjutnya. Dalam kajian ini, pelbagai lapisan karbon tiub nano (CNT) terserak di dalam air. Penyerakan CNT ini tidak
stabil dan endapan berlaku dengan pantas kerana adanya daya tarikan Vander Waals. Oleh itu, bahan sampingan gam
xantan (XG) telah digunakan dalam kajian ini sebagai agen serakan. Penyelidikan bagi mengkaji kesan kepekatan CNT
(0.01 dan 0.1 wt. %), kepekatan XG (0.04 dan 0.2 wt. %) dan masa sonikasi (4 jam) ke atas kestabilan bendalir nano telah
dijalankan. Bacaan kestabilan diambil dengan menggunakan spektrofotometer UV-Vis. Termal konduktiviti yang paling
stabil telah diukur sebagai fungsi suhu (25-70°C) dan kepekatan CNT. Bendalir nano didapati tidak stabil pada sonikasi
selama 4 jam dan kepekatan optimum XG didapati antara 0.04,0.2 % bt. dan 0.01,0.1 % bt. bagi julat kepekatan CNT
yang dikaji. Pemerhatian menunjukkan bahawa, konduktiviti termal amat bergantung kepada suhu dan kepekatan CNT.
Keputusan mendapati CNT bendalir nano adalah lebih sesuai untuk aplikasi pemindahan haba dalam pelbagai industri
kerana adanya peningkatan sifat konduktiviti termal. Kajian ini menyediakan maklumat mengenai sifat CNT nano bendalir.

Kata kunci: Bendalir nano; karbon tiub nano; kestabilan; konduktiviti termal; gam xantan

INTRODUCTION
can be used that contains dispersed nano sized particles
Several techniques have been suggested to increase the (Choi & Eastman 1995). Nanoparticles are very small
heat transfer performance of fluids in order to achieve particles (nanometer size) and based on the Stokes theory,
smaller heat transfer systems with improved energy nanofluids demonstrate higher stability than common
efficiencies and lower capital costs. Maxwell (1954) suspensions. In addition the transport fluids require less
suggested utilizing micro-sized suspensions instead of pumping power and erosion effects compared to common
common heat transport liquids due to higher thermal suspensions. Moreover, nanofluids show much higher
conductivity of solids compared to liquids. However, thermal conductivity compared to the base fluid and usual
micro-sized particles pose many difficulties, such as suspensions (Amrollahi et al. 2007; Choi & Eastman 1995;
higher pumping power requirement, sedimentation of Keblinski et al. 2002; Wang & Mujumdar 2007; Wang et
particles and erosion of transport equipment. In order al. 1999; Yu et al. 2008). There are many parameters that
to overcome these limitations, ‘Nanofluid’ suspensions affect the nanofluids behavior such as size and shape of
1018

the particles, property of the base fluid and particles which stable nanofluid samples. The thermal conductivity of
are detailed in several studies (Ding et al. 2007; Liu et al. nanofluids with the base fluid (water), XG solution and stable
2005; Zhang et al. 2007). However, the interactions among CNT nanofluids was investigated in this study.
the various parameters have been neglected.
Besides, the stability of CNT based nanofluids is
MATERIALS AND METHODS
another major concern before utilizing in heat transfer
equipment. It is reported that CNT based nanofluids are
prone to sedimentation due to its hydrophobic nature, the EXPERIMENTAL DETAILS
high tendency of nanoparticles to agglomeration and its Multi-walled carbon nanotubes (MWCNTs) having an
high aspect ratio (Garg et al. 2009; Hussein et al. 2013). average O.D of 20-30 nm, I.D of, 5-10 nm, length of 10-30
In addition, other researchers (Ghadimi et al. 2011), μm and purity of 95% are obtained from Lab. Scientific,
specified that a durable and stable nanofluid is a key factor Malaysia. XG is obtained from the R & M Marketing;
to achieve optimized thermal property performance. Ismail Essex, U.K. Distilled water is used in this research. Figure
et al. (2016) investigated the rheological performance of 1 shows the molecular structure of xanthan gum.
multi walled carbon nanotudes in drilling fluids. They
realized that applying xanthan gum with 0.2 wt. % as a
PREPARATION OF NANOFLUID
surfactant improved rheological performance significantly
(Ling et al. 2017) prepared non-Newtonian nanofluids by CNT of known mass is dispersed in water along with the
using xanthan gum (0.2 wt. %) and multi walled CNTs in measured amount of XG. The resultant suspensions were
order to enhance the shell-side heat transfer coefficient sonicated using water bath sonicator (Elma Transsonic
of the helical baffled heat exchanger. Interestingly, XG TI-H-15, USA) at 50°C temperature for 4 h, frequency
(0.2 wt. %) could improve heat transfer of multi walled of 35 KHz. The sonication provides enough energy to
carbon nanotubes. Also, Mahendran et al. (2012) reported detangle the CNT while the XG is adsorbed on the CNT
that there is a relationship between stability and thermal surface preventing agglomeration and sedimentation. The
conductivity of the carbon nanotube based nanofluids. diffusional rates and the frequency of collision between
Ponmani et al. (2014)xanthan gum (XG prepared copper the individual tubes and XG molecule are achieved
oxide and zinc oxide nanofluids with the use of Xanthan by sonication. It is important to know increased the
gum as a dispersant to enhance stability. They exhibited temperature of water bath up to 80°C may change the
that copper oxide in 0.4 wt. % of xanthan gum was more properties of nanoparticles (Fadhillahanafi et al. 2013;
stable than its counterpart. Ponmani et al. 2014). According to literature, the optimum
In this present study, the focus was to enhance both the duration to maximize the adsorption of dispersant on the
stability and thermal conductivity of CNT/water nanofluid. CNT is 4 h sonication time at 35 kHz (Rashmi et al. 2011).
The stability of nanofluids is evaluated through visual Also, reducing the aspect ratio of CNT and dislocation of
method for duration of 2 months and also using UV vis carbon structure can be obtained by Prolonging sonication
spectroscopy method to determine the relative sedimentation which will affect the thermal properties of CNT (O’Connell
with respect to time. XG is used as a surfactant to produce 2006).

FIGURE 1. Molecular structure of xanthan gum (Palaniraj & Jayaraman 2011)

 1019

CHARACTERIZATION obtained through the graph of CNT concentrations versus

sedimentation time.
STABILITY The stability studies were carried out for two months,
in order to investigate the most stable nanofluids. CNT
The stability of the Nanofluids usually has been determined concentration was measured with sediment time using
by using UV-VIS spectroscopy (Shimadzu UV -1800, UV-Vis spectrophotometer and stable nanofluids were
Japan). In this technique, after sonication of nanofluids, determined with respect to CNT and XG concentration.
approximately 3 mL of sample was transferred instantly
into the cuvette cells. Distilled water is used as blank
sample for baseline correction, while reference sample THERMAL CONDUCTIVITY
(water + respective XG) was used to measure the CNT The thermal conductivity was measured based on the
concentration with respect to time. Figure 2 clearly showed standard transient hot-wire method by utilizing a KD2-Pro
that the wavelength of CNT was 216 nm, which is in thermal analyzer (Decagon Devices, USA). The transient
concordance with the applicable wavelength of the cuvettes hot wire (THW) method is a transient dynamic technique
(210 to 900 nm). Figure 3 demonstrates the absorbance based on the measurement of the temperature rise of a
value to carbon nanotube at various concentrations through linear hot wire embedded in the tested material. The wire
the calibration curve. Based on the data in Figures 2 and (platinum) serves both as the thermometer and heating
3, the optimum XG concentration for each CNT can be element. For a good measurement, the KS-1 needle is

FIGURE 2. UV Vis absorption spectrum of CNT in water

FIGURE 3. Calibration curve of light absorption and CNT concentration at 216 nm

1020

immersed in a homogeneous medium with uniform initial a value of >0.95 which indicates a proper fit to the linear
temperature, heated with a constant heat flux per unit length regression line. This is indicative of validity and reliability
and then the temperature rise T (t) of the wire is measured. of stability results. Figures 4(a), 4(b), 5(a) and 5(b)
Before measuring the thermal conductivity, the device was demonstration the effect of XG concentration on stability
calibrated with glycerin. In order to avoid any convection of CNT dispersions. XG concentration is varied (0.04 and
errors and effects, it is essential to observe some important 0.2 wt. %) for each CNT concentration (0.01 and 0.1 wt.
points such as preparing a thermally and acoustically stable %) and the results are plotted for 4.0 h sonication time.
environment around the sample and dipping the probe From Figures 4(a), 4(b), 5(a) and 5(b), it is observed
vertically into the middle of the suspension. It is significant that the dispersant added to stabilize the suspension
to note that the KD2-Pro has the ability to indicate the plays a very important role. CNT concentration in the
quality of the measurement via an error factor. In order to suspension was measured with respect to sediment time to
have reliable thermal conductivity value the error should study the sedimentation rate of the nanofluids. Moreover,
be less than 0.01. All measurements were repeated 10 times stabilization of nanofluid required the optimum amount
then the average value was reported, in order to confirm a of XG concentration. By increasing the concentration of
precise measurement. 4 sets of nanofluid and XG solutions CNT the respective XG concentration of also increases
for each dispersant individually with different amount of to adsorb onto the hydrophobic site in order to fully
CNT, XG are prepared and shown in Table 1. separate the individual tube during sonication. The
optimum values of XG concentration were obtained for
TABLE 1. Amount of CNT, XG and water used all the CNT concentrations. The optimum values of CNT
in nanofluid preparation and XG concentrations are (0.01 wt. % and 0.1 wt. %)
and (0.04 and 0.2 wt. %), respectively. In addition, XG
Samples Contents
concentration below the optimum value was not adequate
1 Distilled water + 0.04 wt. % XG in exfoliating the thorough CNT agglomerates and hence
2 Distilled water + 0.2 wt. % XG caused sedimentation. It should be noted that, the additional
3 CNT 0.01 wt. % + 0.04 wt. % XG + Distilled water amount of dispersant caused in self-agglomeration and
4 CNT 0.1 wt. % + 0.2 wt. % XG + Distilled water form reverse micelles, therefore cannot adsorbed onto the
CNT (Choi et al. 2008; Qi 2006). This study demonstrates
that XG dispersant have ability to maintain the dispersion of
SCANNING ELECTRON MICROSCOPY (SEM)
CNT nanoparticles in the water by overcoming the Van der
In order to investigate the morphological structure of CNT Waals or attractive forces between the neighboring tubes
and its interaction with XG dispersant, the SEM (FEI Quanta through steric repulsion. Table 2 shows the optimum XG
400F, USA) test was carried out. A small amount of samples concentration for each CNT concentration studied.
(CNT 0.01 + XG 0.04 wt. %) and (CNT 0.1 + XG 0.2 wt. %)
were transferred into the petri dish and dried overnight in THERMAL CONDUCTIVITY MEASUREMENTS
an oven at 100°C before it is observed under SEM.
Thermal conductivity of the base fluid (water), XG solution
and stable CNT nanofluids have been measured at a CNT
RESULTS AND DISCUSSION concentration of 0.01, 0.1 wt. % and XG concentration of
0.04, 0.2 wt. % for temperature ranging from 25 to 70o C
It is recognized that CNT cannot be dispersed homogeneously
is shown in Figures 6 and 7, respectively.
in aqueous solution and thus form aggregation due to Van
The effect of temperature on CNT-XG nanofluid is
der Waals forces of attraction. Thus, the optimum amount
investigated with respect to XG and CNT concentration,
of dispersant plays vital role to stabilize the CNT in aqueous
respectively. Thermal conductivity of water/XG solution
solution. Studies on XG have been clearly showed that this
is shown in Figure 6. It is observed that by increasing
biopolymer has a great capability being used as a surfactant
temperature and XG concentration, the thermal conductivity
in preparation of nanofluids. In this study, XG behaves
of base fluid decreased. This phenomenon occurs
as a suitable dispersant in stabilizing the CNT in water
due to the lower thermal conductivity of XG (0.08 *
by supplying sufficient repulsive force and minimizing
10-1 W/mK) compared to the water (6 * 10-1 W/mK).
the aggregation effect. Meanwhile, the sonication time, According to Figure 7, by increasing temperature and
XG concentration and CNT concentration plays a key
CNT concentration, the thermal conductivity of the base
role in production of stable homogeneous nanofluids. fluid increased. This enhancement is more significant
Morphological and thermo-physical properties of CNT for higher CNT concentration (0.1 wt. %) at 50oC. This is
nanofluids are measured comprising thermal conductivity due to the Brownian motion of the nanoparticles where
and stability behavior. the nanoparticles are able to gain more kinetic energy at
higher temperature. The CNT with high energy content will
STABILITY MEASUREMENTS tend to move faster and bombard with each other, leading
From Figure 3 is can be seen that the R2 value for calibration to a substantial increase in the thermal conductivity of
curve which is defined as a determination coefficient, has nanofluids (Li et al. 2008). As Figures 6 and 7 demonstrated
 1021

XG 0.01 wt. % 0.04 0.08 0.12 0.16 0.18 0.2 (A)

(B)
FIGURE 4. Effect of xanthan gum (XG) concentration on the stability of CNT: 0.01 wt. % (a) sample images
after 800 h of standing at a different XG concentration and (b) CNT concentration vs sediment time

XG 0.01 wt. % 0.04 0.08 0.12 0.16 0.18 0.2 (A)

(B)
FIGURE 5. Effect of xanthan gum (XG) concentration on the stability of CNT: 0.1 wt. % (a) sample images
after 800 h of standing at a different XG concentration and (b) CNT concentration vs. sediment time
1022

TABLE 2. Optimum values of XG concentration

CNT concentration Optimum XG

(wt. %) concentration (wt. %)
0.01 0.04
0.1 0.2

FIGURE 6. Effect of temp on thermal conductivity of XG solutions

FIGURE 7. Effect of temp on thermal conductivity of CNT nanofluid 0.01 and 0.1 wt. %

that CNT have remarkable influency on enhancing of low concentration of surfactant was relatively rough
thermal conductivity of water compared to XG alone. which derived from the fact of nanoparticle nature
Rashmi et al. (2011) reported that Brownian motion of and also incapability of surfactant to provide a good
nanoparticles at the nanoscale and molecular level is a dispersity among nanofluids. As matter of the fact, due
key mechanism governing thermal behavior of nanofluids, to high surface-to-volume of nanoparticles, they have
which is also a strong function of temperature. Therefore, it a great capability to interact with their own molecules
is clear from these figures that dispersant added to stabilize leading to self-agglomeration phenomena. Moreover,
the nanoparticles in suspension does not have a significant low concentration of surfactant could not cover the
role in thermal conductivity enhancement. entire carbon nanotubes, consequently, rough surface
with aggregated nanoparticles observed in Figure 8(a).
However, further addition of surfactant not only decreases
SEM ANALYSIS
the self-interaction of nanoparticles but also cover entire
The surface morphology of multi walled carbon nanotubes nanoparticles; subsequently a smooth surface of nanofluid
coated with biopolymer xanthan gum was characterized with good dispersity of nanoparticles illustrated in Figure
through SEM. Figure 8(a) and 8(b) illustrates the stable 8(b). As a result, high concentration of surfactant was
nanofluids with low (0.04 wt. %) and high (0.2 wt. %) adequately ability to settle carbon nanotubes along with
concentration of biopolymer surfactant, respectively. xanthan gum, implying the surfactant concentration is
It can be clearly seen, the surface of nanofluid with directly proportional to stability of nanofluids. It means
 1023

(a) (b)
FIGURE 8. SEM images of nanofluids with difference concentrations of CNT, (a) 0.01 and (b) 0.1 wt. %

that, the increase in surfactant concentration leads to the Mechanical Engineering Congress and Exposition 66: 99-
increase in stability of suspension. 105. doi:10.1115/1.1532008.
Ding, Y., Chen, H., Wang, L., Yang, C.Y., He, Y., Yang, W., Lee,
W.P., Zhang, L. & Huo, R. 2007. Heat transfer intensification
CONCLUSION using nanofluids. KONA Powder and Particle Journal 25
(March): 23-38. doi:10.14356/kona.2007006.
This present study investigated the effects of surfactant
Fadhillahanafi, N.M., Leong, K.Y. & Risby, M.S. 2013. Stability
and nanoparticles concentrations on the stability as well as and thermal conductivity characteristics of carbon nanotubes
thermal conductivity of nanofluids. The UV-Vis and KD2- based nanofluids. International Journal of Automotive and
Pro methods used to determine the stability and thermal Mechanical Engineering 8: 1376-1384.
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stability of nanofluids achieved, when the concentration of & Annamalai, K. 2009. An experimental study on the effect
surfactant increased with the approval of SEM morphology. of ultrasonication on viscosity and heat transfer performance
In nanofluid samples with 0.01 and 0.1 wt. % carbon of MWCNT based aqueous nanofluids. International Journal
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0.04 and 0.2 wt. %, respectively, to obtain the maximum Ghadimi, A., Saidur, R. & Metselaar, H.S.C. 2011. A review
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Interestingly, nanoparticle concentration due to its nature
Hussein, A.M., Sharma, K.V., Bakar, R.A. & Kadirgama, K. 2013.
and also temperature raised the thermal conductivity.
Heat transfer enhancement with nanofluids - a review. Journal
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ACKNOWLEDGEMENTS doi:10.1017/CBO9781107415324.004.
One of the authors (Saba Rashidi) acknowledges the Ismail, A.R., Wan Sulaiman, W.R., Jaafar, M.Z., Ismail, I. &
Sabu Hera, E. 2016. Nanoparticles performance as fluid
financial support from Universiti Putra Malaysia and
loss additives in water based rilling fluids. Materials Science
MOHE, project no: UPM /700-2/1/FRGS/GSP/5524868.
Forum 864: 189-193. doi:10.4028/www.scientific.net/
MSF.864.189.
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