Accepted Manuscript

Enhancement of solar energy collection with magnetic nanofluids

Zeyu Liu, Yuying Yan, Rong Fu, Mustafa Alsaady

PII: S2451-9049(18)30195-1
DOI: https://doi.org/10.1016/j.tsep.2018.08.015
Reference: TSEP 225

To appear in: Thermal Science and Engineering Progress

Received Date: 26 March 2018

Revised Date: 6 August 2018
Accepted Date: 19 August 2018

Please cite this article as: Z. Liu, Y. Yan, R. Fu, M. Alsaady, Enhancement of solar energy collection with magnetic
nanofluids, Thermal Science and Engineering Progress (2018), doi: https://doi.org/10.1016/j.tsep.2018.08.015

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 Enhancement of solar energy collection with magnetic nanofluids

Zeyu Liu1, Yuying Yan1,2*, Rong Fu1, Mustafa Alsaady1

1 Fluids & Thermal Engineering Research Group, Faculty of Engineering, University of Nottingham, United Kingdom
2 Fluids & Thermal Engineering Research Centre, University of Nottingham Ningbo, China
*corresponding: yuying.yan@nottingham.ac.uk

Abstract

Nowadays, energy crisis has caused widespread concerns about sustainable energy. Solar
energy, as sustainable, renewable energy, has attracted many attentions. Compared to other
solar energy utilizations, solar collectors are more efficient and commercial devices to collect
solar energy. In our present study, well-dispersed magnetic nanofluids (MNFs) are reported
that they exhibit excellent optical thermal conversion performance under the suitable magnetic
intensity and direction. In this work, the colloidal stability of MNFs was improved by
controlling pH within neutral value. One kind of surface modifications, oleic acid, was carried
out to enhance the interaction between particles and surfactants. The hydrodynamic diameter
was found to be very close to the real size of particle. Meanwhile, a highly efficient solar
collection system was built based on controlling the optical thermal performance of MNFs by
magnetic fields. The experimental results showed that the thermal efficiency of solar collectors
increased with MNFs. The thermal efficiency of MNFs is much higher than base liquid with
the concentration of only 0.05 vol. %. Moreover, in the presence of the external magnetic field,
the solar collector efficiency increases to the maximum, 25% higher than the conventional
parabolic trough and 12% higher than the selective surface absorber. The study indicates that
MNFs, even of low-content, have good absorption of solar radiation, and can improve the outlet
temperatures and system efficiencies. All these studies show the potential of MNFs in solar
thermal conversion applications.

Keywords: magnetic nanofluids, co-precipitation method, solar energy.

 1. Introduction

Environmental issues and energy shortages force researchers to explore a new generation of
green energy to replace the fossil fuels [1]. The utilization of solar energy has been paid many
attentions since it is sustainable, renewable and environmentally friendly [2]. The solar thermal
collection, as a more efficient and commercial method to harvest solar energy, absorbs solar
radiation and transfers heat to working fluids. In this way, solar energy can be converted into
internal energy by working fluids. And heated fluids can be used for heating or electricity
productions. The collection efficiency depends on the radiation absorption and heat transfer
efficiency of working fluids.

Concentrated solar power (CSP) can help working fluids absorb solar energy volumetrically[3].
Basically, CSP technology can be classified into four types, including parabolic trough systems,
parabolic dish systems, solar power systems and linear Fresnel systems[4]. Among them,
parabolic trough systems are technically studied and have been used in both power generation
and industrial process heat application[5, 6]. However, the cost of the parabolic trough systems
is much higher than that of the conventional ones. Therefore, many researchers are committed
to making them more cost competitive. The core issue needed to be solved is to enhance the
heat transfer performance of parabolic trough fundamentally. Some researchers have tried to
optimize the structure of the systems[7, 8], while others are upgrading working fluids to
improve the heat transfer performances[9, 10].

Nanofluids, liquids suspension with nano-scaled particles, have been proven to be excellent
thermal working fluids. The particles are made of metal, metal oxide or semiconductor [11].
The dispersed particles can help enhance the thermal conductivity of fluid significantly
compared to base liquid. Many efforts have been made to develop nanofluids-based solar
collection system [12-14]. It is found that the collection efficiency associates intimately with
the colloidal stability of nanofluids[12, 15]. Particle precipitations not only make worse heat
transfer performance of nanofluids, but also cause clogging and pipe corrosion. In addition,
particle aggregation augments the viscosity of nanofluids, which often leads to a larger pressure
drop[16].

MNFs is a special kind of nanofluids whose particles are superparamagnetic[17]. When the
magnetic field is applied, magnetic particles will react to the field, bringing impacts on the
magnetism and physical properties of the whole suspension. Many works showed that magnetic
nanofluids exhibited better thermal physical properties and heat transfer performance under a
magnetic field. Philip[18] reported that the thermal conductivity of MNFs whose particle
concentration was 6 vol. % increased to 300% by applying the external magnetic field. It was
found that intensity, direction, and arrangement of the applied magnetic field will all affect heat
transfer characteristics of MNFs. Li et al.[19] measured the convective heat transfer coefficient
of the aqueous magnetic fluid flow around a heated wire in both a uniform magnetic field and
a magnetic field gradient and found that heat transfer of MNFs was affected by both direction
and magnitude of external magnetic fields. Ghofrani and Dibaei[20] presented an experimental
investigation on forced convection heat transfer of aqueous MNFs with the presence of an
alternating magnetic field under a uniform heat flux. They investigated the effects of the
alternating magnetic field, volume fraction and the Reynolds number. The results showed that
the convection heat transfer was enhanced up to 27.6%. However, few works were carried out
to study the collection of solar energy by using MNFs.

In this work, colloidal stability of MNFs was creatively improved by controlling pH within a
neutral value. MNFs can keep 8 months with only tiny precipitation. Meanwhile, due to the
thermomagnetic property of MNFs, we innovatively introduced pH controlled MNFs to the
parabolic trough collection system with different magnetic field strengths. The experimental
results showed the contribution of external magnetic field to photothermal conversion, and
theoretically give a mechanism explanation.

2. Methodology

2.1 Preparation of MNFs

The magnetic nanofluids were synthesized by co-precipitation method. Typically, 13.5g

FeCl3·6H2O and 6g of FeCl2·4H2O were firstly dissolved in 150ml deionized water. The
solution was reacted at ambient temperature and bubbled with nitrogen for 15 minutes to
remove oxygen. 40 mL ammonium hydroxide was quickly added to the solution under vigorous
stirring. And then the mixture was heated to 60°C for 1 hour, and black precipitate was collected
at the bottom of the flask by using a magnet and washed with water several times until pH
value reached 7.

In the following, 50g wet precipitate was dispersed into 200mL distilled water with ultrasonic
treatment. The suspension was then transferred to a three-necked flask equipped with a stirring
paddle and nitrogen inlet. After adding oleic acid, the suspension was stirred at 80 °C under the
protection of nitrogen for 2 hours. The particles were then washed several times with ethanol
and hexane until the upper solution became transparent. After dumping the supernatant, oleic
acid modified Fe3O4 particles were obtained. Modified magnetic nanoparticles were then added
to 200ml water solution of sodium dodecyl sulfate (25 mg/mL). After the mixture was kept at
80°C for 2hours, particle-micelle solution was formed.

2.2 Characterizations

The morphology and size of nanoparticles were observed by a transmission electron

microscopy (TEM). The samples which used for TEM observation were prepared on a TEM
copper grid by dropping diluted particle dispersion and drying under a reduced pressure
overnight. TEM images were taken by a JEOL-2000 electron microscope operating at 200 kV
and equipped with a CCD camera. The size distribution was gained based on at least 300 of
particles or clusters.

The dynamic size and size distribution of magnetic nanoparticles was carried out by dynamic
light scattering (DLS) (Autosize Loc-Fc-963, Malven Instrument).

Acrystall ographic study of magnetic and composite particle powder was performed on an X-
ray diffract meter (D/MAX-IIIC, Japan). The X-Ray Diffraction (XRD) patterns were taken
from 20 to 90o (2θ) using Cu Ka radiation; scanning speed was kept at 15 o/min.

Thermogravimetric analysis (TGA) was carried out on a TGA-SDTQ600 thermogravimetric

analyser to measure the amount of stabilized attached on the particles surfaces. The modified
Fe3O4 nanoparticles were heated to 1000C under the protection of N2. The rate of temperature
increase was kept at 10oC/min.

The magnetic properties of the particles were measured by using a vibrating-sample

magnetometer (VSM, HH-15, China) at 298 K with a 12kOe applied the magnetic field.

2.3 Experimental set up

An experimental test bench was set up to investigate the photo-thermal performance of

magnetic nanofluids as shown in Figure 1. Respectively, the solar simulator contains three
tungsten halogen lamps, which are similar to natural sunlight, produce a very stable and smooth
spectral output. Therefore, it can be commonly used in solar beam experiments for solar
simulator application. Moreover, in terms of thermal radiation, the wavelength, ranging from
360nm to 2500 nm, is also very similar to sunlight [21]. Some experimental tests were carried
out for various distances of the light surface from the simulator surface to investigate the
unevenness of variations in light distribution. The absorber tube is made of borosilicate glass,
which allows MNFs to absorb radiation directly. Three solenoids fed by transistorized
regulated DC power supply were used to generate magnetic field parallel to the flow direction.
The intensity of the magnetic field was measured with a Gauss meter. A reflective mirror, with
1mm thick high impact polystyrene sheet, is used to concentrate the radiation to the absorber
tube. A pyranometer is used to measure the solar radiation, which is in a good agreement with
British standards for testing a solar simulator. The flow rate is measured by an ultrasonic flow
meter, FLOWNETIX 100. Two non-magnetic type T thermal couples are positioned to
measure the inlet and outlet temperature.

Solar simulators

Chiller

Thermocouple

Reflector

Electromagnetic coil

Container

DC power supply

Figure 1. Photograph of the experimental setup.

The schematic diagram of the test rig is shown in Figure 2. MNFs store in the container,
which can be pumped up to the test section by a positive displacement pump. MNFs
then flow back through a chiller, which can control the temperature of working fluids
irradiated by solar simulators. A water bath was used to control the inlet temperature of
fluids. Magnetic fields were parallel applied along the flow direction. At the beginning of each
test, the solar simulators were turned on firstly. They need 30 minutes to reach the maximum
intensity and keep stable. After that, inlet temperature of test section can be adjusted by water
bath and chiller to keep a stable condition.
 Figure 2. Schematic diagram of the test bench.

The parameters of the parabolic trough are shown in Table 1.

Table 1: Parameters of the parabolic trough and test conditions.

Parameters Values
Length of the receiver 500mm
Width of the aperture 250mm
Outer diameter of absorbers 15mm
Solar irradiance 1000 W/m2
Mass flow 0.02 kg/s
The useful heat absorbed by MNFs is calculated by Eq. (1)

QU = mfCp,f(Tout ‒ Tin) (1)

where mf is the mass flow of MNFs, Cp,f is the specific heat capacity of MNFs which is
calculated by Eq. (2)

Cp,f = (1 ‒ φ)Cp,w + φCp,np (2)

where Cp,wand Cp,np are specific heat capacity of water and nanoparticles, respectively. φ is
the volume fraction of MNFs. The heat capacity is affected by the temperature. Therefore, the
heat capacity at the mean temperature Tm can be calculated by Eq. (3)

Tin + Tout (3)

Tm =
2

The thermal efficiency can be calculated by Eq. (4)

 QU (4)
η=
IDAC

where η the efficiency of the parabolic trough is, ID is the direct solar radiation and AC is the
area of the collector.

The solar radiation uncertainty is less than 2%. The uncertainty of mass flow is less than 1%.
Uncertainties for inlet and outlet temperatures were less than 0.1 °C. Complex uncertainty was
calculated by Eq. (5) and was between 1% and 5.2%, which calculated by Eq. (5)

2 2 2 2
Uη = (∂mf
∂η
Um ) ( ) (
+
∂η
U
∂ID ID
+
∂η
U
∂Tout Tout ) ( +
∂η
U )
∂Tin Tin (5)

3. Results and Discussions

The stability of nanofluids is always one of the most significant issues. This is because
nanoparticles have great tendency to aggregate in base liquid caused by van der Waals
attractive force. To solve this problem, we synthesized MNFs by controlling pH value at a
neutral level. In this way, the surface potential of nanoparticles keeps strongest to ensure the
maximum repulsive force among particles. It also means that MNFs synthesised can keep the
maximum stability. Figure 3 shows the TEM image of oleic acid modified Fe3O4 nanoparticles.
The particles are sphere-like in shape. The average size is 10 nm. Since oleic acid is modified
on the surface of the nanoparticles, it is possible to make nanoparticles more dispersed in the
nanofluids, which is beneficial to two factors, namely steric effect and electrostatic repulsion.
The first one is the effects of large molecules that come from the fact that oleic acid occupies
space. When nanoparticles are put close to each other, this costs energy. The electrons around
the particles want to stay away from each other, which keep nanoparticles well-dispersed.
Meanwhile, the other factor is electrostatic repulsion, which relies on the electric repulsive
force arising between two particles possessing charges with the same sign. According to the
classic DLVO theory, increasing the surface charges of particles will enhance electric repulsive
force, thus reducing the particles’ tendency to aggregate. Part of them exhibits chain-like
aggregates without clumping in the centre of TEM image. It was reported that such chain-like
structure provides extra conduction paths for the enhancement of effective conductivity,
whereas large aggregates and clumps sediment will lead to the decline in conductivity.
 Figure 3: TEM image of Fe3O4 nanofluids formation and distribution.

DLS measurement was carried out to investigate the colloidal stability of the MNF. As shown
in Figure 4, the hydrodynamic diameter of the modified particles ranges from 3.2 to 10.2 nm,
which is matched by the TEM image in Figure 3. Therefore, the particles are well dispersed in
water due to formation of particle–micelle complexes.

Figure 4: The size distribution of Fe3O4 nanofluids.

Figure 5 gives the XRD pattern of dried sample of the nanofluids. The pattern presents the
characteristic peaks of cubic inverse spinel structure, indicating that the crystal structure of
Fe3O4 nanoparticles was also not changed after the modification of oleic acid and formation of
particle–micelle complexes.
 Figure 5: XRD characterization of modified Fe3O4 nanoparticles in the presence of sodium
dodecyl sulfate.

As shown in Figure 6, a 9.5% of weight loss occurred in the range of 200-400oC, which can be
attributed to decomposition of oleic acid and surfactant on the Fe3O4 nanoparticles. The result
suggests that sodium dodecyl sulfate is chemically bonded on the surface of the magnetite
nanoparticles and the weight ratio of oleic acid and surfactant to Fe3O4 nanoparticles reaches
to ration of 1:9.

Figure 6: TGA measurement of Fe3O4-CA.

The magnetization characterization is supplied in Figure 7. Due to the modification of oleic

acid, the saturation magnetization of the dried sample was about 33.54 emu/g (emu per gram
of nanoparticles (iron oxides) in the ferrofluid), which was lower than the saturation
magnetization of pure Fe3O4 nanoparticles with 50 emu/g. The hystersis loop is minute,
suggesting the modified particles exhibit superparamagnetism which is a form of magnetism
appearing in small magnetic nanoparticles. Therefore, nanoparticles inside form a regular
arrangement following the direction of applied magnetic fields. In our experiment, a magnetic
field parallel to the direction of fluid flow was applied. The magnetic field induced magnetic
nanoparticles inside to form the chain-like structures, which are able to accelerate more heat
transfer by optimizing heat transfer path and particle arrangement. With the increase of chain
strength, creating more bridges of thermal energy conduction along the magnetic field direction.

Figure 7: VSM analysis of the magnetic hysteresis in MNFs

Figure 8 shows the thermal efficiency of 0.05vol. % MNFs in the presence of external magnetic
fields in the laminar region. The instantaneous thermal efficiency relates the useful energy to
the total radiation incident on the surface of the collector as shown below.

𝜂𝑖 = 𝐹𝑅(𝜏𝛼) ‒ 𝐹𝑅𝑈𝐿(𝑇𝑖 ‒ 𝑇𝑎)/𝐺𝑇 (6)

where 𝜂𝑖 is the thermal efficiency, 𝑄𝑢 is the useful energy, 𝐴𝑐 is the surface area of solar
collector, 𝐺𝑇 is the global solar radiation to the solar collector, 𝐹𝑅 is heat removal factor of

collector, 𝑈𝐿 is the overall coefficient of heat losses, 𝑇𝑖 and 𝑇𝑎 are inlet temperature of
test section and ambient temperature respectively.

The experimental result shows that thermal efficiency enhances with increasing magnetic field
strength when the orientation of the magnetic field is parallel to the flow direction. Using a
glass tube to allow nanoparticles absorb solar radiation can achieve higher efficiency than
selective surface absorber which is 13% higher than the selective surface absorber. Moreover,
when the magnetic field is up to 10.47mT, thermal efficiency of MNFs in laminar condition is
13.4% higher than the experimental results of Ghofrani and Dibaei[20]. Many mechanisms are
put forward to explain the enhancement of heat transfer of nanofluids, including Brownian
motion induced micro-convection, the aggregation of nanoparticles, ballistic phonon transport
[20-24]. Lots of literature show that conduction path through agglomerates in one of the most
important factors for the quick enhancement [25-28]. Under the influence of magnetic field,
magnetic particles form the chain-like structure which accelerates the heat transfer in the
working fluids. With the enhancement of the magnetic field, the chain length also increases,
which creates more bridge of thermal energy conduction along the magnetic field direction
[29]. Meanwhile, chain-like structure improves the optical properties of MNFs as well, because
such structure allows less radiation to transmit through the fluid [30]. Higher heat transfer
performance will be reached if the solar radiation is completely absorbed by MNFs. For all
these reasons thermal efficiency of a solar collector with direct absorber tube increases by using
MNFs and becomes higher than a selective surface tube parabolic trough. Increasing the
magnetic field further will not affect the thermal efficiency because the particles reach to a
saturation magnetization. This work shows the capability of using MNFs in direct absorption
parabolic trough.

Figure 8. Thermal efficiency of MNFs and base liquid in the presence of magnetic field.

4. Conclusions

In this work, a highly efficient solar collection system is developed based on controlling the
optic thermal performance of MNFs by magnetic forces. MNFs prepared can keep the
maximum stability by controlling pH within a neutral value. The characterization shows
nanoparticles are uniform, and MNFs exhibit superparamagnetism. An experimental
comparison of thermal efficiency between base liquid and ferrofluids with different magnetic
strengths have been performed. The results show that the thermal efficiency of 0.05%
ferrofluids increases 6% than that of base liquid. Moreover, the thermal efficiency increases to
the maximum 41% when the magnetic field is up to 10.47mT, which is 13% higher than the
selective surface absorber. It is also showed that MNFs exhibit excellent thermal efficiency
compared to base liquid and selective surface absorber. Results showed that controlling pH
value can not only open the window to improve the stability of nanofluids, but also make
nanofluids more controllable in engineering fields. Meanwhile, MNFs also exhibit great
potential in photo-thermal conversion.

Further work needs to be carried out to make it applicable. The thermal and optical loss of the
current work needs to be reduced. Higher operation temperatures, higher concentration ratios,
larger glass tube with anti-reflection, using envelope to decrease the thermal loss, and a high-
quality reflector is required to compare the performance of MNFs parabolic trough solar
collector with the commercial parabolic trough. Some other important influencing factors,
magnetic directions and flow conditions also need to be considered for the further study.
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Conflict of interest
We confirm that we have no conflict of interest.
Highlights

 Apply magnetic nanofluids on parabolic trough solar collector to enhance the thermal
efficiency.
 The characterizations of MNFs are investigated to analyse different properties of MNFs.
 The thermal efficiency of MNFs can increase to 16%, which is roughly 5% higher than the
base liquid.
 The thermal efficiency of MNFs increases with magnetic field.