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Parameters Influencing the Performance of Nanoparticles-laden Fluid-based

Solar Thermal Collectors: A Review on Optical Properties

Article in Renewable and Sustainable Energy Reviews · March 2018

DOI: 10.1016/j.rser.2017.12.007

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Parameters Influencing the Performance of Nanoparticles-laden

Fluid-based Solar Thermal Collectors: A Review on Optical Properties

Vishal Bhalla, Himanshu Tyagi*

School of Mechanical, Materials and Energy Engineering
Indian Institute of Technology Ropar
Rupnagar-140001, Punjab, INDIA
Email(s): vishal.bhalla@iitrpr.ac.in & himanshu.tyagi@iitrpr.ac.in
*Corresponding Author: Phone: 91-1881-242119; Fax: +91-1881-223395

1
Highlights

 Due to their small size the optical properties of nanoparticles are tuneable

 LSPR plays an important role in metallic nanoparticles

 Nanoparticle-laden fluid-based solar thermal collectors have high efficiencies

 Nanoparticle material, volume fraction, shape significantly affect its performance

 At optimum value of volume fraction, maximum collector efficiency is reached

Graphical Abstract

2
 Parameters Influencing the Performance of Nanoparticles-laden Fluid-based Solar

Thermal Collectors: A Review on Optical Properties

Vishal Bhalla, Himanshu Tyagi*

School of Mechanical, Materials and Energy Engineering
Indian Institute of Technology Ropar
Rupnagar-140001, Punjab, INDIA
Email(s): vishal.bhalla@iitrpr.ac.in & himanshu.tyagi@iitrpr.ac.in
*Corresponding Author: Phone: 91-1881-242119; Fax: +91-1881-223395

ABSTRACT

The continuous and increasing usage of fossil fuels is adversely impacting the environment and

also presents economical and geo-political challenges for policy makers around the world. Solar

energy is one of the forms of renewable energy resources which is freely and abundantly

available on the earths' surface and hence could be a very good potential alternative to fossil

fuels. Apart from directly generating electric power (using solar photovoltaic cells), more and

more attention is being paid to the use of solar thermal collectors for heating various fluids for

applications ranging from space heating/cooling, process heating, steam generation etc. Such

solar thermal collectors are generally are of conventional type, having a 'black' surface-based

absorption of solar irradiation. In order to improve the overall efficiency of such collectors, a

new type of direct absorption solar collectors (DASC) have been proposed recently. In DASC, a

nano-sized particle are added to the heat transfer fluid and due to these particles the optical and

thermo-physical properties of the fluid improves, and it is able to directly absorb the solar

irradiation, eliminating the need of a conventional 'black' surface. This review paper presents a

3
state-of-art of such nanoparticles-laden fluid-based solar thermal collectors, and focuses on

factors like volume fraction, material and shape of the nanoparticle and mass flow rate of the

fluid which affects the performance of the nanoparticles-laden fluid-based-solar thermal

collector. In particular, special attention has been given to the studies involving the effect of

using nanoparticles of various classes of materials - metallic, core/shell, graphite - on the overall

optical properties of the working fluid (nanoparticles-laden fluids).

KEYWORDS

Solar energy; nanoparticles-laden fluid; absorption; scattering; extinction; solar weighted

absorptivity

NOMENCLATURE

Symbols

A area (m2)

Am solar weighted absorptivity

AR aspect ratio

a,b,c semi axis (m)

C concentration

Cp specific heat (J/kg.K)

D diameter (m)

d diameter (m)

fv volume fraction
4
GT solar flux incident on solar collector (W/m2)

H height (m)

h height (m)

h heat transfer coefficient (W/ m2 K)

I intensity (W/m2)

K radiative coefficient (m-1)

L length (m)

l length (m)

mass flow rate (kg/s)

m complex refractive index (m=n+iκ)

n index of refraction

Q radiative efficiency

R radius (m)

r radius (m)

Re Reynolds number

S(x) spatial distribution of stored thermal energy

Sm(λ) spectral distribution of the solar intensity

T temperature (K)

V volume (m3)

W width (m)

x penetration depth (m)

Subscripts

Abs absorption

5
a aperture, absorption

ai ambient

c cutoff

e extinction

in inlet

m air mass

out outlet

r receiver

s scattering

Greek symbols

α absorption coefficient

η efficiency (%)

κ index of absorption

λ wavelength (µm)

ρ reflectance

τ transmittance

τH optical thickness

Abbreviations

ATO antimony-doped tin-oxide

BCCCT black chrome coated copper tube

BF base fluid

CB carbon black

CNT carbon nanotubes

6
C.R. concentration ratio

DAPTC direct absorption parabolic trough collector

DASC direct absorption solar collector

DLCA diffusion limited cluster agglomeration

DI deionized

EG ethylene glycol

EM electromagnetic wave

GMM generalized multi particle Mie solution

GNS gold nanoshell

GOR gained output ratio

KPS potassium persulfate

LSPR local surface plasmon resonance

MWCNT multi-walled carbon nanotubes

N nanoparticles

NCPSC nanofluid based concentrating parabolic solar collector

NIR near infrared

OP optical properties

RTE radiative transfer equation

SAC surface absorption-based collector

SAR specific absorption rate

SC solar collectors

SPR surface plasmon resonance

SR surface receiver

SWCNH single-walled carbon nanohorns

SWCNT single-walled carbon nanotubes

7
UV ultraviolet

Vis visible

VR volumetric receiver

TABLE OF CONTENTS:

1. INTRODUCTION 9

2. THERMAL PERFORMANCE OF NANOPARTICLES-LADEN FLUID-BASED 17

SOLAR THERMAL COLLECTORS

2.1 Nanoparticles-laden fluid-based non-concentrating collectors 17

2.2 Nanoparticles-laden fluid-based concentrating collectors 24

2.3 Comparison between surface absorption-based solar collectors and 30

nanoparticles-laden fluid-based solar collectors

3. OPTICAL PROPERTIES OF NANOPARTICLES-LADEN FLUIDS 40

3.1 Optical properties of base fluids 41

3.2 Effect of nanoparticle volume/mass fraction on the optical properties of 43

base fluids

3.3 Effect of nanoparticle material 56

3.3.1 Metallic nanoparticles 58

3.3.2 Core/shell nanoparticles 64

3.3.3 Graphite nanoparticles 69

3.3.4.Metal oxide nanoparticles 73

3.4 Effect of nanoparticle shape 74

3.5 Effect of nanoparticle stability 77

4 OVERALL SUMMARY OF SECTIONS 2 AND 3 78

8
5. FUTURE DIRECTIONS AND CHALLENGES 83

5.1 Water desalination 83

5.2 Vapor absorption refrigeration system 84

5.3 Energy efficient buildings 85

5.4 Solar selective direct absorption based solar collector 85

5.5 Challenges 87

1. INTRODUCTION

Energy is one of the essential needs for the functioning of society and the scale of its usage is

closely linked to the quality of life [1]. In sectors such as industry, transport, agriculture,

residential etc. the dependence on fossil fuels is very high [2]. Figure 1(a) shows the trend of

consumption of coal, gas, and oil over the last 40 years [3]. It can be seen from this figure that

their consumption is increasing year by year resulting in ever increasing carbon dioxide

emissions as shown in figure 1(b). Large emissions of carbon dioxide is believed to lead to

significant climate change [4] and is a serious global issue for a clean and sustainable

environment. Dincer [5] has discussed major environmental issues with the usage of non-

renewable resources where it is proposed that in order to resolve this serious issue, the usage of

renewable energy resources should be encouraged.

9
 60000 40000
(a) Oil
Gas
(b) Carbon dioxide emission
50000 Coal

Energy consumption TWh/y 30000

40000

Million Tonnes
30000 20000

20000
10000
10000

0 0
1970 1980 1990 2000 2010 1970 1980 1990 2000 2010
Years Years

Figure 1 (a) Annual consumption of non-renewable energy resources, and (b) annual carbon

dioxide emissions [3].

A variety of renewable energy resources like biomass, solar energy, wind energy, geothermal,

ocean thermal, hydroelectricity, wave, tidal and nuclear energy [6–8] are available and apart

from these resources, there are some new emerging technologies in the renewable energy like

enhanced geothermal energy, cellulosic ethanol, marine energy, artificial synthesis [9] which can

also become promising alternate of non-renewable energy resources.

There are some challenges with renewable energy resources like reliability of supply, difficulty

to generate in large quantity, large capital cost, and requirements of large tracts of land. On the

other hand, each of the renewable energy resource has its own benefits. For example, solar

energy is available everywhere, and in large amount. It is estimated that the amount of solar

energy reaching earth's surface annually is approximately 5.6 million exajoules, which is more

than 1000 times the world's total annual primary energy consumption of 570 exajoules [10]. As a

result of which, a lot of research activity is going on to efficiently harness solar energy.

10
Solar energy can be harnessed by two predominant techniques: (1) solar photovoltaic and (2)

solar thermal collectors. Solar photovoltaic cells are used for direct generation of electric power

[11–13], whereas solar thermal collectors are used for a wide variety of applications such as

space heating/cooling, process heating, steam generation, electric power generation etc. [14,15].

On comparing the installed capacities of solar photovoltaic and solar thermal collectors, it has

been clearly seen that the latter has much higher installed capacity and hence warrants greater

attention. For example, the total installed capacity of solar water heater, concentrating solar

thermal power and solar PV was 409 GWth, 4.3 GW and 177GW respectively in 2014 and 435

GWth, 4.8 GW and 227 GW respectively in 2015 [16].

The various types of solar thermal collectors that are currently in use are shown in figure 2. The

solar thermal collector is a special kind of a device in which the incident solar irradiation is

converted to useful thermal energy [17]. The solar thermal collector can be categorized

according to (a) the type of concentration of solar radiation on the receiver and (b) the

temperature rise of fluid in collector [18]. Concentration ratio is defined as the ratio of aperture

area to the receiver area (C = Aa/Ar) [17]. So, on the basis of concentration there are two types of

solar thermal collectors (i) non-concentrating collector, and (ii) concentrating collector [15]. In

non-concentrating collector (e.g. flat plate collectors, evacuated tube collectors) the receiver area

is equal to the aperture area, therefore C = 1. These collectors utilize the total solar irradiation

(i.e. both the beam and diffuse components of solar irradiation) and as a result of which they do

not require any tracking mechanism [18]. Further, as illustrated in figure 2 the concentrating

collectors are of two types (i) line focused and (ii) point focus. In line-focused collectors, the

incident radiation is focus on the line (e.g. parabolic trough collector and linear Fresnel

reflectors) whereas in point-focused collectors, the incident radiation is focus on a point (e.g.

11
power tower and dish type collector). The concentrating collectors can utilize only the direct

component of the solar irradiation; hence they required to be pointed towards the sun at all times.

For this purpose 1-axis (line focus) or 2-axis (point focus) tracking mechanisms are used.

Solar Thermal Collectors

Non- Concentrating Collector Concentrating Collector

Flat Evacuated Line Point

Plate Tube Focussed Focussed

Max. C.R. 300 to 1500

Collector Collector

Max. C.R. 212

C.R. 1
C.R. 1

Linear Fresnel Parabolic Dish

Reflector Reflector

50-90o C Parabolic Trough Power Tower

Collector

Solar rays Absorbing pipe

area
50-120 o C
Glazing
cover

Parabola
50 – 400 oC` aperture area 150-2000 o C

Figure 2 Various types of solar thermal collectors. (Concentration ratio has been abbreviated as

'C.R.').

According to the temperature rise of the working fluid these collectors can be categorized as (i)

low temperature (ii) medium temperature and (iii) high temperature solar collectors [19]. The

low temperature solar collectors (e.g. non-concentrating solar collectors) can provide

temperatures up to around 90oC, while medium temperature solar collectors (e.g. line-focused

solar collectors) can provide temperature up to around 400oC [20], while the high temperature

12
solar collectors (e.g. point-focused solar collectors) can provide temperature up to 1000oC

[19,21–23]. These solar thermal collectors have three main components (a) absorber plate, (b)

transparent cover (glass), and (c) insulation. The absorber plate is a solar selective surface which

absorbs the solar irradiation, converts it into thermal energy and transfers the thermal energy to

the working fluid by conduction and convection. The absorber plate is wavelength selective i.e. it

has maximum absorption below cut-off wavelength (λc ≤ 3 µm) and has minimum emittance after

cut-off wavelength (λc > 3 µm), as shown in figure 3(a) [17,24,25]. Glass is placed above the

absorber plate to reduce the convective losses from the absorber plate. Glass also helps in cutting

emission losses to the surroundings because it is transparent at short wavelength (λ ≤ 2.5 µm)

and opaque at long wavelength (λ ≥ 3 µm). The transmittance of a typical glass of 6-mm

thickness is shown in figure 3(b). Insulation is placed at the bottom to reduce the losses from the

working fluid through conduction. Figure 3(c) depicts the placement of absorber plate,

transparent cover, insulation and the working mechanism of the solar thermal collector.

(c) Solar Radiation

1.0
1.0 (a) (b) Transparent cover
Reflectance()

Transmittance, 

Absorber Plate
0.5
0.5

Convection Conduction
Currents
Working Fluid
0.0
λc 0 1 2 3
Wavelength () Wavelength, m Insulation

Figure 3 (a) Reflectance of selective surface at cut off wavelength [17], (b) spectral transmittance

of glass (for one iron oxide content) within solar spectrum for normal incident radiation [17], (c)

working mechanism of solar thermal collector.

13
Few challenges are associated with solar thermal collectors due to which their thermal efficiency

is limited. These are summarized as follows. Firstly, an inherent thermal barrier is present in

these solar thermal collectors in the form of conduction and convection resistance between the

absorber plate and working fluid. Secondly, to attain high utilization of these solar collectors, the

temperature of the working fluid needs to be high. So, high flux is allowed to concentrate on the

absorber plate which may damage the absorber plate (due to hot spots) and as a result of this

damage the performance of solar thermal collector may deteriorate over time. Thirdly, high

surface temperature of the absorber plate leads to high emission losses to the surroundings [26].

To overcome the aforementioned challenges, Minardi and Chuang [27] proposed that the solar

irradiation may be directly absorbed by the working fluid itself. To demonstrate this principle,

they conducted experiments with black ink (India ink). Hunt [28], Miller et al. [29] and

Abdelrahman et al. [30] added particles in the working fluid, where Abdelrahman et al. [30]

proposed that the carbon particles may be suitable for ideal absorption of solar irradiation.

Researchers have proposed various configurations for direct absorption of solar irradiation like

gas particle suspensions [31–34], liquid films [35,36] and metal foams [37].

The working fluid can be seeded with micron-sized particles for the absorption of the solar

irradiation [38], but there are some challenges with micron-sized particles like agglomeration of

the particles in the working fluid which may cause abrasion and clogging of pumps and valves.

These challenges are undesirable in many heating and cooling applications [39,40].

In order to overcome the aforementioned challenges with micron-sized particles, researchers

started using nanometre-sized particles (particle size ≤ 100 nm [41]). Literature suggests that

with the addition of small amount of such nanoparticles in the working fluid, the thermo-physical

14
properties and the absorption capability of the working fluid enhances significantly [19,42–46].

In the thermo-physical properties, main emphasis has been given on thermal conductivity,

density, viscosity, specific heat [47]. The thermal conductivity of the nanoparticles is affected by

factors such as layering, Brownian motion, agglomeration of the nanoparticles, ballistic, phonon

motion, thermal boundary resistance and the mass differences. Out of these factors mass

difference has an intense effect on the thermal conductivity [48]. Fluid containing metal

nanoparticles have higher thermal conductivity compared to metal oxide nanoparticles, due to

layering phenomenon around the nanoparticles [49]. The thermo-physical properties of the

nanofluid depends on the nanoparticle shape, nanoparticle size, volume fraction of the

nanoparticles, operating temperature, additives, pH and base fluid [50–53].The heat transfer

coefficient of the working fluid also increases with the presence of nanoparticles in the base fluid

and this depends on the volume fraction of the nanoparticles in the working fluid. The heat

transfer coefficient increases with the increase of volume fraction of nanoparticles in the base

fluid [54]. The nanoparticles absorb the solar irradiation, get heated and transfer the thermal

energy to the working fluid. This eliminates overheating of any internal components (such as the

absorber plate). The working mechanism of nanoparticles-laden fluid-based collector is as shown

in figure 4. The performance of such a nanoparticles-laden fluid-based solar collector depends on

several design parameters, which are length of the collector, height of the collector, mass flow

rate of the fluid, flux of incident radiation, volume fraction of nanoparticles, nanoparticle

material, size and shape of the nanoparticles, and optical properties of working fluid [14,55–65].

15
 Nanoparticle

Solar Irradiation

Air
h, T∞


H
m
Inlet Outlet
y
L
x

Figure 4 Schematic of nanoparticles-laden fluid-based solar thermal collector.

The objective of this review paper is to summarize the recent results on nanoparticles-laden fluid

used in solar thermal collector, with a focus on the optical properties of nanoparticle-laden fluid

affecting the overall performance of the collectors. Section 2 presents the summary of

experimental and numerical studies on the thermal performance of solar thermal collectors

utilizing nanoparticles-laden fluids. Section 3 describes in detail the optical properties of the

working fluid (first for base fluids and then later for nanoparticles-laden fluids), as well as the

effect of various parameters like - volume fraction, material, shape and stability of the

nanoparticles on the optical properties of working fluids. Section 4 presents the overall summary

of sections 2 and 3 and Section 5 describes the future direction of the nanoparticles-laden fluid-

based solar thermal collectors and the challenges associated with these collectors.

16
2. THERMAL PERFORMANCE OF NANOPARTICLES-LADEN FLUID-BASED

SOLAR THERMAL COLLECTORS

In this section, the thermal performances of nanoparticle-laden fluid-based solar thermal

collectors (both concentrating and non-concentrating solar collectors) that are available in

literature have been reviewed in detail. These findings have also been summarized in a form of a

table at the end of this section. Moreover, a detailed comparison between surface absorption-

based solar collector and nanoparticles-laden fluid-based solar collector has been carried out.

2.1 Nanoparticles-laden fluid-based non-concentrating collectors

As the name suggests, the non-concentrating collectors are those in which the solar irradiation is

not concentrated on the absorber area i.e. these collectors have the same intercepting and

absorbing areas. These collectors are mechanically simpler than the concentrating collectors

(they do not require any mechanism for tracking the sun) and are used where the temperature

requirement is low (generally below 100oC). Major applications for these collectors are solar

water heating, cooling, air heating, industrial process heating etc. [66–71]. This sub-section

presents the review of articles based on non-concentrated solar thermal collectors using

nanoparticles-laden fluids.

Tyagi et al. [72] have conducted numerical study of direct absorption based solar collector

(DASC), Aluminum nanoparticles (D = 5 nm) dispersed in water. The schematic of DASC is

shown in figure 5. Certain assumptions were made in this study by such as the bottom surface of

the collector is adiabatic and transparent, top surface of the collector is exposed to the ambient,

very low emission losses and no significant in-scattering by the nanoparticles.

17
Figure 5 Schematic of direct absorption solar collector (figure reprinted with permission from

Lee et al. [73]).

By considering the aforementioned assumptions, they have studied the effect of certain

parameters (height and length of the collector, particle size and volume fraction of nanoparticles)

on the collector efficiency, η, which has been calculated by using Eq. (1).

useful gain mC p (Tout  Tin )

  , (1)
available energy AGT

where is the fluid mass flow rate, Cp is the specific heat of the fluid, Tin and Tout are the mean

fluid inlet and outlet temperature, A is the top cover area and GT is the solar flux incident on the

solar collector. From the numerical study, they have made certain conclusions regarding the

efficiency which are as follow:

1) With the increase of height of the collector, the efficiency reaches an asymptotic value of

about 80%.

2) Length of the collector and the size of the nanoparticles have marginal influence on the

efficiency of the solar collector.

18
3) The volume fraction (fv) of the nanoparticles plays a crucial role on the efficiency of solar

collector and at an optimum volume fraction direct absorption based solar collector performs

well.

Otanicar et al. [74] have refined the numerical model used by Tyagi et al. [72] and have also

experimentally investigated the performance of micro-solar-thermal-collector for different

nanoparticles [graphite spheres (D = 30 nm), carbon nanotubes (D = 6 to 20 nm, L = 1000 to

5000 nm) and silver spheres (D = 20 nm and 40 nm) dispersed in water]. They have reported that

the volume fraction of nanoparticles play a significant role in the enhancement of collector

efficiency as there is more than 3% improvement in efficiency by using graphite sphere at

fv = 0.5% and about 5% improvement in efficiency by using 20 nm silver nanoparticles at

fv = 0.25% as compared to a black absorber surface. So, they have concluded that it is important

to use an optimum volume fraction of the nanoparticles to attain maximum efficiency from

nanoparticle-laden based solar collector. Gorji et al. [64] have conducted both experimental and

numerical study on low flux direct absorption solar collectors using graphite (D = 50 nm),

magnetite (D = 15 nm) and silver (D = 20 nm) nanoparticles dispersed in DI (de-ionized) water.

During the synthesis of nanoparticles-laden fluid they have performed surface modification of

the nanoparticles to improve the overall stability of nanoparticles in the base fluid. The

schematic of experimental setup is shown in the figure 6 where in the experiments they have

adjusted the distance between the lamp and the nanoparticle-laden fluid collector to get

variations in the incident irradiation (600, 800 and 1000 W/m2) and these fluxes are related to the

cloudy and partly cloudy, and sunny conditions. They have concluded that the thermal efficiency

of the system increases by increasing particles concentration and flow rate, and decreases with

incident irradiation. Further, they have observed the effect of material of the nanoparticles on the

19
thermal efficiency of the collector. On comparing different materials of the nanoparticles, they

have seen that at 40 ppm of magnetite nanoparticles (at = 10 ml/min, flux = 1000 W/m2), the

thermal efficiency of the collector is about 55% more than the base fluid. They have also

evaluated the exergy efficiency and from the exergy efficiency they have observed that at fv = 40

ppm, with magnetite nanoparticles (at = 2.5 ml/min, flux = 1000 W/m2) the exergy efficiency

is 20.3% more than the base fluid (water).

Figure 6 Schematic of the experimental set up (figure reprinted with permission from Gorji et al.

[64]).

In order to evaluate the performance of nanoparticles-laden fluid in outdoor conditions, the

studies should be conducted under sunlight. Han et al. [75] and He et al. [76] have extended the

experimental work from one receiver to four receivers and measured the temperature rise of the

nanoparticle-laden fluid directly under sunlight. They figured out that the maximum temperature

rise of the nanoparticle-laden fluid is achieved at an optimum volume fraction, and with further

addition of nanoparticles (i.e. increasing the volume fraction) the temperature starts decreasing.

He et al. [76] have studied the effect of pH on the temperature enhancement of nanoparticles-

20
laden fluid (for Cu nanoparticles dispersed in water), because pH also plays an important role in

the preparation of the nanoparticle-laden fluids. To demonstrate the effect of pH they prepared

samples with different values of pH (pH = 2, 4, 6, 8 and 10) and heated the nanofluids samples

under sunlight for approximately 25000 seconds. During experiments the temperature of

nanofluid rises, and has been shown in figure 7. This figure shows that the temperature

enhancement is maximum at pH = 8, and after pH = 8 the temperature starts decreasing (i.e. pH

= 8 is an optimum value of pH), which shows that the volumetric absorption solar collector

performs well at an optimum pH value.

Figure 7 Temperature curve of Cu-H2O nanoparticle-laden fluids with different pH values, Cu:

50nm, 0.1 wt%, Ta is the ambient air temperature, (figure reprinted with permission from He et

al. [76]).

Gupta et al. [56] have conducted the experiments in outdoor conditions with a full scale (gross

area 1.4 m2) direct absorption solar collector (DASC). In the experiments, they have used Al2O3

nanoparticles dispersed in water and compared the performance of nanoparticle-laden fluids

(having four different volume fractions 0.001%, 0.005%, 0.01% and 0.05%) with pure fluid

(distilled water). From the experimental study they concluded that thermal efficiency at fv =

21
0.005% is about 40% higher compared to pure fluid (water). Also, it is seen that fv = 0.005% is

an optimum volume fraction at which solar collector performs well, for the geometry considered

by them. Visconiti et al. [77] conducted experiments with Al2O3-distilled water and distilled

water only. From the experimental study, they have concluded that the thermal efficiency with

Al2O3-distilled water is 7% more than that of distilled water. Further, Colangelo et al. [65] have

numerically concluded that higher thermal efficiency (increase of 7.5%) with aluminum oxide

based nanoparticles-laden fluid is achievable as compared to bi-distilled water.

Literature also suggests that the shape of the nanoparticles plays an important part in the

nanoparticle-laden fluid-based solar collector, due to which the researchers are showing more

interest in core/shell type nanoparticles-laden fluid due to LSPR (Localized surface plasmon

resonance) effect. Lee et al. [78] have conducted numerical study for direct absorption solar

collector in which core/shell type nanoparticles [core: SiO2 and shell: Au, abbreviated as GNS

(Gold nanoshell)] have been used. In this numerical analysis they have solved radiative transfer

equation (RTE) and 2-D heat transfer equation simultaneously. Modeling heat transfer equation

between solids and fluids is important in many applications in engineering [79]. For solving the

radiative transfer equation they have used Monte Carlo algorithm in which they have treated the

drift process independent from scattering process. They have calculated the collector's thermal

efficiency with GNS and compared its thermal efficiency with aluminum nanoparticles. After

comparison they found that the collector efficiency with GNS reaches a maximum value of 70%

(in the 0.02% - 0.1% volume fraction range), while with aluminum nanoparticles the

corresponding collector efficiency is also about 70% however at much high volume fractions (at

fv = 0.7%).They have concluded that a very small amount of GNS is required to achieve high

efficiency as compared to metallic nanoparticles.

22
Jeon et al. [80] have experimentally and numerically evaluated the performance of blended

plasmonic nanoparticles-laden fluids (gold nanorods with three different aspect ratios dispersed

in water). From numerical study they found that high temperature gain can be achieved with

large channel depth and lower mass flow rate. In addition they have observed that increasing the

channel depth is no longer advantageous once the depth exceeds four times the penetration

depth.

In summary, the studies on such collectors (non-concentrated solar thermal collectors using

nanoparticles-laden fluids) have highlighted some important parameters, mainly that the volume

fraction of the nanoparticles plays an important role in determining the overall thermal efficiency

of the collector. Consequently, the collector performance may be enhanced by using optimum

volume fraction of the nanoparticles. Additional parameters which also play a significant role in

the direct absorption solar collectors are height, length of the collector and the mass flow rate of

the fluid.

For a low temperature solar collector, the thermal efficiency increases with increase of the height

of the collector. This is due to the fact that the spectral intensity of the incident radiation decays

along the depth of the collector resulting in greater attenuation. Due to which greater amount of

solar irradiation get absorbed by the nanoparticles-laden fluid, resulting in higher thermal

efficiency of the collector.

Further, the effect of collector’s length on the efficiency can be interpreted in this way that with

the increase of collector’s length the outlet temperature of the fluid increases due to an increase

in the fluid exposure time. However, with the increase of outlet temperature, the losses to the

environment increases, due to which the efficiency of the collector decreases slightly. So, it can

23
be concluded that the change in overall efficiency of a nanoparticles-laden fluid-based solar

collector is relatively less (compared to the change in its outlet temperature) [80].

The effect of mass flow rate on the collector efficiency can be interpreted in this way that at low

mass flow rates, the fluid will spend more time in the collector, due to which the temperature of

the fluid increases. When the temperature of the fluid increases, the losses to the environment

increase as well, which lead to a slight decrease in its overall efficiency. On the other hand, at

high mass flow rate, the fluid spends less time in the collector, due to which its temperature rise

is low, and consequently it will have slightly higher efficiency (due to low losses to the

environment.

2.2 Nanoparticles-laden fluid-based concentrating collectors

For many applications much higher temperatures (say > 150oC) are required which are not

possible to achieve with non-concentrating collectors. Higher fluid temperatures can be achieved

if the area (absorbing surface) from where the losses occur can be reduced, while the incident

solar fluxes remain high [81]. This can be achieved by introducing an optical device (such as a

reflecting surface or a lens) in between the source of radiation (in this case - sun) and the

absorbing surface. Also, an additional mechanism for tracking of solar position is required,

which adds to the complexity of the system. The concentrating solar collectors operate on this

principle. This sub-section presents the review of articles which have studied concentrated solar

thermal collectors using nanoparticles-laden fluids.

Taylor et al. [82] have conducted both numerical and experimental studies to understand the

performance of point-focused solar thermal collector (dish-type geometry). For the experimental

study they have used a laboratory scale nanoparticle-laden fluid-based dish-type solar collector

24
(nanoparticles used: graphite, base fluid: Therminol VP-1) and conducted experiments at a

constant mass flow rate i.e. ( is of the order of 10-4 kg/s). From the experimental study they

have observed that at the peak values of flux (~ 800-950 W/m2) around 34% solar to thermal

energy conversion is achieved (for the configuration using nanoparticles) and this efficiency is

about 20% higher than the other configuration (which uses only the base fluid - Therminol VP-

1). Further in the numerical study, they have studied the effect of volume fraction, material of the

nanoparticles, mass flow rate and solar concentration ratio for different configurations of

nanoparticle-laden fluids (nanoparticles: Al, Cu, graphite, Ag, base fluid: Therminol VP-1). They

observed that amongst all the nanoparticles, graphite has uniform extinction coefficient, which

makes it different from rest of the metallic nanoparticles. Numerically they have shown that for

nanoparticles an optimum volume fraction exists, at which the system will have maximum

thermal efficiency. They have shown that this optimum volume fraction occurs when 85-95% of

incident radiation has been absorbed by the fluid in its first pass. Further they have suggested

that absorbing the light away from the boundaries provides best results (by preventing thermal

losses from the surface).

Veeraragavan et al. [83] have presented an analytical model to predict the effects of various

operational parameters (such as nanoparticles volume fraction, solar concentration, and height of

channel) on the efficiency of nanoparticle-laden fluid-based receiver. From their model they

have concluded that the surface temperature of the nanoparticle-laden fluid is lower than the bulk

fluid temperature, which is advantageous (as it corresponds to lower emission loses). Further

numerically and experimentally the effect of solar concentration ratio, height of the nanoparticle-

laden fluid in the receiver and optical thickness on the performance of nanoparticle-laden fluid-

based (nanoparticles: carbon-coated cobalt, D = 28 nm, base fluid: Therminol VP-1) receiver has

25
been studied by Lenert et al. [84]. From the numerical study Lenert et al. [84] have concluded

that the efficiency of the receiver increases with increase of height, optical thickness and the

concentration of incident solar flux on nanoparticle-laden fluid based receiver. Their results are

shown in figure 8. In the experimental study, they have conducted experiments with different

optical thicknesses of nanoparticle-laden fluids (τH = 1, 2 and 4) and concluded that at high

optical thickness (i.e. τH = 4) heat generation is maximum near the top surface of the

nanoparticles-laden fluid, where maximum losses occur. Also they have predicted that if system

is connected with power cycle, optimum system efficiencies will exceed by 35% when C > 100

and H > 5 cm. The outcomes of numerical and experimental results provide an important

perspective to the usage of volumetric receivers in the concentrated solar application.

Figure 8 Parametric study of receiver efficiency with mean fluid temperature for variable (a)

optical thickness, (b) solar concentration, and (c) nanoparticle-laden fluid height (figure

reprinted with permission from Lenert et al. [84]).

The effect of solar concentration on the performance of different nanoparticle-laden fluid-based

receiver was also studied by Luo et al. [85]. They conducted experiments with different types of

nanoparticle-laden fluids (nanoparticles: C, TiO2, Al2O3, Ag, Cu and SiO2, base fluid: Texatherm

oil). In the experimental study, they have varied the intensity of irradiation from 1000 to 9000

W/m2 to analyze the effects of solar concentration on the thermal efficiency of the collector.

26
They have concluded that as the incident radiation intensity increases the outlet temperature of

the fluid increases as well, but this is accompanied by a decrease in the system efficiency (due to

increase of losses to the environment). They have also concluded that the performance of the

system depends on the material of the nanoparticles.

Khullar et al. [86] have used a similar setup/procedure as Lenert et al. [84] and conducted two

experimental studies with two different types of nanoparticle-laden fluids (amorphous carbon

nanoparticles dispersed in ethylene glycol, and MWCNT nanoparticles dispersed in distilled

water). The schematic of the experimental set up is shown in figure 9. From the experiments they

have concluded that the performance of volumetric absorption system depends on various

parameters such as - mass fraction, material of nanoparticles, magnitude of incident flux and the

geometry of the receiver.

Figure 9 Schematic of the experimental set up (figure reprinted with permission from Khullar et

al. [86]).

Menbari et al. [87] have conducted both numerical and experimental studies with direct

absorption parabolic trough collector (DAPTC) using copper oxide nanoparticles–laden fluid

(base fluid: water). They have studied the effect of volume fraction and mass flow rate on the

27
efficiency of DAPTC and have observed that the thermal efficiency of DAPTC highly depend on

these factors. They have showed that the thermal efficiency increases from 18% to 52% with a

little increase of volume fraction from 0.002 % to 0.008 %. They have also observed that at high

mass flow rates (100 l/h) approximately 8% more thermal efficiency can be achieved than 20 l/h

due to reduction in heat losses to environment. Menbari et al. [88] have extended their previous

DAPTC study from single material nanoparticle-laden fluid (copper nanoparticles) to the mixture

of nanoparticle-laden fluid [(γ-Al2O3-CuO) dispersed in different base fluids (water and water-

ethylene glycol mixture)], which they called binary nanoparticle-laden fluid. They have

suggested that the mixture of nanoparticles have been chosen because CuO nanoparticles have

high thermal conductivity and absorptivity, whereas Al2O3 has high specific heat capacity and

scattering properties. Due to which, the mixture of both nanoparticles are beneficial to use as

working fluid for the harnessing of solar radiation.

Muraleedharan et al. [89] conducted an experimental study under the sun with the nanoparticle-

laden fluid (nanoparticles used: aluminum oxide, base fluid: Therminol 55) using a line-focused

concentrated collector. For line focus concentration, instead of using a parabolic trough collector

they have focused the sunlight on the receiver with the help of linear Fresnel lens. Schematic of

the experimental set up has been as shown in figure 10. Experimentally, they measured the

temperature rise of the nanoparticle-laden fluids (having four volume fractions viz. 0.025; 0.05;

0.075 and 0.1 vol. %) and compared the temperature rise with pure fluid (Therminol 55). They

have concluded that with 0.1 vol. % nanoparticle-laden fluid has 44.7oC higher temperature than

base fluid. From the temperature rise they have concluded that with the increases of volume

fraction of nanoparticles in the base fluid the absorbance has been increased due to which

0.1 vol. % gives highest temperature.

28
Figure 10 Schematic diagram of the solar concentrator experimental test rig (figure reprinted

with permission from Muraleedharan et al. [89]).

In summary, some important points have been highlighted by the studies on such collectors

(concentrated solar thermal collectors using nanoparticles-laden fluids). It has been observed that

optical thickness (τH) has significant impact on the receiver efficiency and can be controlled by

varying volume fraction of the nanoparticles. At moderate optical thicknesses (τH = 2) the

incident radiation is absorbed completed within the volume of the sample. Whereas, at very high

optical thicknesses the receiver efficiency decreases with height of the receiver because of large

temperature difference in mean fluid temperature and surface temperature. Researchers have

shown that with these concentrated collectors, maximum fluid temperatures of around 250oC can

be achieved with graphite nanoparticles dispersed in Therminol-VP1.

2.3 Comparison between surface absorption-based solar collectors and nanoparticles-laden

fluid-based solar collectors

The literature suggests researchers are working on the various configurations of the nanoparticle-

laden fluid-based solar thermal collectors (different materials and shapes of nanoparticles,

different types of heat transfer fluids, different types of solar collectors e.g. flat plate type solar

29
collectors, parabolic troughs, compound parabolic troughs), where they have compared the

efficiency and temperature rise of the nanoparticle-laden fluid-based solar collector with the pure

fluid (e.g. water, ethylene glycol, Therminol-VP1 etc.). Moreover, some researchers have also

compared the thermal efficiency (numerically and experimentally) of the surface absorption-

based solar collectors (collector in which an absorbing plate has been used to absorb the incident

radiation) with the nanoparticle-laden fluid-based solar collectors. Reviews of articles which

contain such comparisons have been presented in this sub-section.

Tyagi et al. [72] have numerically compared the efficiency of direct absorption collector with the

conventional flat-plate type collector under similar working conditions. From the comparison

they have concluded that on an absolute basis the efficiency of direct absorption collector is

about 10% higher than the conventional solar collector. They have suggested that thermal

efficiency of the nanoparticle-laden fluid-based solar collector can be improved by optimizing

the volume fraction of nanoparticles (fv) and the height of the collector (H).

Taylor et al. [82] have compared the thermal efficiency of nanoparticle-laden fluid-based solar

collector (nanoparticles used are: graphite, aluminum, copper and silver dispersed in Therminol

VP-1) with Abengoa's PS 10 power tower installed in Seville, Spain. From the numerical

analysis, they have concluded that PS 10 produces about 55 MW thermal power (~ 11 MWe)

with 250oC steam at 40 bars which is roughly similar to the nanoparticle-laden fluid-based power

tower. While comparing the system efficiency of both systems, they have shown that graphite

nanoparticles based fluid is ~ 2% more efficient than PS 10 power tower due to which they

suggested that in a large-scale system with graphite nanoparticle is a good choice (especially

fv ≤ 0.001%).

30
Otanicar et al. [74] have experimentally compared the efficiency of direct absorption solar

collector with surface absorption based solar collector (for absorber plate a matte black paint is

applied to copper surface) and they have concluded that under similar working conditions, the

nanoparticle-laden fluid-based collector’s efficiency is about 5% higher than the conventional

collector (see figure 11).

Figure 11 Comparison of water (black back) with different nanoparticle-laden fluid at different

volume fractions (figure reprinted with permission from Otanicar et al. [74]).

Based on the numerical analysis, Otanicar et al. [90] have also suggested that by tailoring the

extinction profile as a function of depth can lead to momentous increase in efficiency over a

conventional surface absorption based solar collector. Khullar et al. [86] have experimentally

compared the temperature rise of amorphous carbon and MWCNT nanoparticles-laden solar

collector (base fluid: ethylene glycol) with a conventional commercial material (TiNOX® coated

copper substrate, represents the surface absorption-based solar collector). From the experiments,

they have concluded that in the absence of convective heat transfer the temperature rise of

nanoparticle-laden fluid is higher as compared to that of selective surface coating. Khullar et al.

[91] have also numerically studied the effect of solar insolation, incident angle and convective

31
heat transfer coefficient on the nanofluid-based concentrating parabolic solar collectors (NCPSC)

and conventional parabolic solar collectors (experimental results from Syltherm 800 in which

silicon-based heat transfer fluid is used). They have concluded that under similar operating

conditions the efficiency of nanoparticle-laden fluid-based concentrating parabolic solar

collectors is about 5-10% higher than the conventional parabolic solar collectors.

Bhalla and Tyagi [92] have experimentally compared the temperature rise of water dispersed

cobalt oxide nanoparticles with TINOX® selective surface coating. They have concluded that

under similar operating conditions the temperature rise with nanoparticle-laden fluid is about

14oC higher than selective coating (at very low mass fraction, 40 mg/l, of cobalt oxide

nanoparticles). Li et al. [93] have compared the thermal efficiency of black chrome coated

copper tube (abbreviated as BCCCT) with volumetric absorber (multi-walled carbon nanotubes

based solar thermal collector). They have concluded that under similar working conditions the

efficiency of volumetric absorber is 14% less than BCCCT (due to large thermal emissivity and

high optical losses from volumetric absorber). They have suggested that both receivers could

work well, but more research is needed on volumetric receivers. They commented that if the

challenges like loss mechanism in nanoparticle-laden fluid-based solar collector can be

overcome, then these volumetric receivers may provide an effective and low cost approach in

industrial heating and air-conditioning applications. Literature also shows that the radiative

losses in surface absorption-based solar thermal collectors are high due to which the performance

of these collectors degrades. Luo et al. [85] have numerically compared the radiative losses from

surface absorption-based solar collector with a nanoparticle-laden fluid-based solar collector. For

the surface absorption-based solar collector they used a high absorption film deposited on the

glass plate which has been placed on the top surface of the collector. The numerical results have

32
shown that in the surface absorption-based solar collector a large temperature difference exists

between the surface and the bulk fluid due to which the mean fluid temperature is low. From

their results they have concluded that since the highest temperature occurs on the absorption film

(top surface of the solar thermal collector), therefore high emission losses will take place which

will reduce the thermal efficiency of the solar collector. Lee et al. [73] have experimentally and

numerically compared the thermal efficiency of black chrome coated surface (abbreviated as SR)

and MWCNT nanoparticles based solar collector (abbreviated as VR). From the studies, they

have concluded that under similar working conditions the thermal efficiency of VR is about 10%

higher than SR.

To summarize, it is observed that the surface absorption-based solar collectors generally have

higher thermal losses compared to nanoparticles-laden fluid-based solar collectors.

Consequently, the nanoparticles-laden fluid-based solar collectors have high thermal efficiency

(about 5-10% higher). Also, it has been observed that, under similar operating conditions Co3O4

nanoparticles-laden fluid-based solar thermal collector have achieved about 14oC higher outlet

temperature as compared to surface absorption-based solar thermal collector.

Finally, the details of the experimental and numerical work of the nanoparticles-laden fluids used

in solar thermal collector have been summarized in Table 1. This table shows the highlights of

all the works that were discussed in these sections so far.

33
Table 1 Detailed summary of the nanoparticle-laden fluid-based solar collectors.

Investigator
(Type of
Details of
work)-
Solar Irradiation Nanoparticles (N) Fluid
Numerical
collector Receiver size source and and temp. Remarks
(N),
details flux (W/m2) Base fluid (BF) range
Experiment
(oC)
al (E) or
Both (B)

The direct absorption solar collector has

Tyagi et al. H = 1.2 mm,
N: Al (D = 5 nm) 35 to 10% more efficiency than the
[72], N L = 1m Sun, 1000
BF: Water 35.35 conventional flat plate collector on
absolute basis.
N:
C (D = 30 nm)
CNT (D = 6-20
SUPERPAR
nm & L = 1000- 5% improvement in the efficiency of
Otanicar et Lamp, Color 25 to 45
H = 150 µm 5000 nm) the solar thermal collector when
al. [74], B Temperature
Ag (D = 20 nm nanoparticles have been used
3158 K, 1000
and 40 nm)
BF: Water

34
 N:
C (D = 35 nm),
TiO2 (D = 10 nm),
Al2O3 (D = 20
nm),
Xenon Ag (D = 50 nm),
NON CONCENTRATING

The outlet temperature depends on the

W = 10 cm, Lamps, 1000 Cu (D = 50 nm), 27 to
Luo et al. incident radiation. The efficiency
H = 2.5 cm to 9000 SiO2 (D = 50 nm), 277
[85], B decreases because the increase of heat
L-CNT (D = 10-20
losses from the system.
nm, L = 10-30
COLLECTORS

µm),
S-CNT (D = 10-20
nm, L = 0.5-2 µm)
BF: Texatherm Oil

L = 60 mm,
Sun, 1000 N: TiO2/ Ag The temperature rise with TiO2/Ag is
Xuan et al. W = 60 mm, 30 to 80
Core/shell more than TiO2 nanoparticles.
[94], B D = 80 mm
BF: Water
The efficiency improves with the
Natural N: Silver (D = 49
increase of particle concentration and
D = 26.8 mm, sunlight and nm), ZnO and 26.5 to
Chen et al. with the increase of irradiation time both
L = 460 mm simulated sun TiO2, 60
[95], E the temperature and specific absorption
light, 450 BF: Water
rate (SAR) decreases.

N: Treated Carbon
No significant temperature rise of
D = 26 mm, Sun black
Han et al. 24 to 40 nanoparticle-laden fluid after optimum
H = 150 mm 1000 BF: Distilled
[75], E volume fraction of nanoparticles.
water

35
 N: Cu (D = 25 nm
D = 15 mm
He et al. Sun and 50 nm) 30 to 85 Temperature rise is highly dependent on
H = 150 mm
[76], E 1000 BF: Water the mass fraction of nanoparticles.

Up to 144% improvement in the stored

W = 400 mm, N: Silver (D = 10
Bandarra Sun thermal energy can be obtained at
L = 400 mm nm) 23 to 52
Filho et al. 905 maximum temperature for volume
D = 15 mm BF: DI water
[96], E fraction of 6.5 ppm.

N: Core/Shell,
Particle concentrations influence the
SiO2 (D = 20 to 50
L=1m Sun uniformity of solar energy absorption
Lee et al. nm) /Gold (D = 3 20 to 65
H = 1.5 mm 1367 and the temperature distribution within
[78], N to 10 nm)
the system.
BF: Water

With very low volume fraction

N: Graphite (D = (0.000025%) of nanoparticles, it is
L=1m Sun
Ladjevardi 30 nm) possible to absorb 50% of incident
H = 10 cm 836 --------
et al. [97], N BF: Water radiation, while with pure water only
27% of incident solar radiation can be
absorbed.
Solar
simulator, N: Gold (D = 10- Gold nanoparticles show remarkable
D = 3.5 cm,
Zhang et al. Newport Co. 30 nm), 20 to 40 performance in improving the photo
H = 3 mm
[98], E Oriel Xenon BF: DI water thermal conversion efficiency of base
Arc Lamp fluid at very low volume fraction.
1000

36
 N: CuO (D < 40
A = 60 × 60 nm), Collector efficiency directly
Karami et cm2, Sun BF: Water and 30 to 50 proportional to the mass flow rate and
al. [55], E H = 1 cm 700 Ethylene glycol volume fraction of the nanoparticles.
(70:30 in volume)

N: Graphene (D =
At an optimum mass flow rate (0.015
A = 60 × 60 2 µm, thickness 2
kg/sec) of nanoparticles-laden fluid, the
Vakili et al. cm2, Sun nm) 35 to 50
collector efficiency increases with
[99], E H = 1 cm 700 BF: Deionized
increase of weight fraction of
water
nanoparticles.
Solar
simulator
V = 50×50×48 (Jinzhou
N: Gold (D = 25, At low volume fraction (~0.000008%)
mm3 Sunshine
Chen et al. 33, and 40 nm) 20 to 32 of gold nanoparticles, the photo-thermal
V = 60×160×6 Metrological
[100], E BF: Water conversion characteristics of gold
mm3 Science Co.
nanoparticles are better than water.
Ltd., TRM-
PD1 type)
450
N:
Al, Cu, Graphite
W = 2 cm Sun The nanoparticles based dish collector
and Ag (D = 20
Taylor et al. H = 2 cm 800-950 has 10% increases in efficiency is
nm) ~ 250
[82], B D = 1 mm possible as compare to the base fluid
BF: Therminol
VP-1

37
CONCENTRATING 1.6 kW Solar
Simulator (SS The rate of radiative losses to the
N:
1600 W, fully environment increases with increase of
COLLECTORS
C-coated cobalt
Lenert and D = 6 cm, reflective, optical thickness and at maximum
(D = 28 nm) 20 to 50
Wang [84], H = 6.35 cm Science tech optical thickness (τH = 4), heat
BF: Therminol
B Inc.), generation profile gets localized at the
VP-1
2460+163 top surface of the receiver.

700 W solar
N: Graphene
simulator
BF: 1-hexyl-3
D = 10 cm, (SOLAREDG 27 to The rate of radiative losses to the
Liu et al. methylimidazoliu
H = 10 cm E 700, Perfect 327 environment increases with increase of
[101], B m-
light inc.) optical thickness.
tetrafluoroborate
2300

N: Amorphous
carbon (D < 50
nm)
Halogen MWCNT (D =
lamp, color 31.6 nm and L = The performance of direct absorption
H = 8 mm,
Khullar et temperature 1.25 µm) 30 to 70 system is highly dependent of volume
D = 8 mm
al. [86], E 3400 K BF: Ethylene fraction
4930 Glycol for
amorphous carbon
and distilled water
for MWCNT

50 × 20 mm
N: Copper Sulfate The efficiency of the collector drops
Vijayaragha Wall Sun
solution 30 to 80 with increase in temperature of working
van et al. thickness 2 900-1000
BF: Water fluid due to increased thermal losses.
[102], E mm

38
The overall review of thermal performance of nanoparticle-laden fluid-base solar thermal

collectors clearly shows that it is potentially advantageous to use such collectors due to their

higher efficiencies. The efficiencies of nanoparticles-laden fluid-base solar thermal collector can

be enhanced if these collectors are made ‘solar selective’ [103][104]. In these types of solar

thermal collectors, the main active component is the nanoparticle-laden fluid (which absorbs the

solar irradiation). Consequently, it is highly imperative to determine which nanoparticle-laden

fluid combinations (nanoparticles as well as base fluids) are suitable for the absorption of solar

irradiation. This can be identified by measurement of their optical properties. In the next section,

we will review the optical properties of the nanoparticle-laden fluids which can be used for the

harnessing of solar energy in solar thermal collectors.

3. OPTICAL PROPERTIES OF NANOPARTICLE-LADEN FLUIDS

Quantification of optical properties for any nanoparticles-laden fluid involves the estimation of

parameters such as extinction, absorption, scattering coefficients, dielectric constants of the

medium. For optical characterization within the solar spectrum, mostly UV-Vis spectroscopy is

used which refer to absorption or reflectance spectroscopy [105]. In this spectroscopy, when an

electromagnetic wave interacts with the medium, the radiation intensity gets attenuated either by

scattering or absorption or both and resulting in a unique optical signature. The scattering can be

of dependent or independent type. Prasher and Phelan [106] inferred that the multiple and

dependent scatterings are very dominant in nanoparticles-laden fluid and are significantly

dependent on the volume fraction of the nanoparticles in the base fluid. They suggested that

39
scattering increases with the increase of volume fraction of the nanoparticles [107] and due to

multiple and dependent scattering the density of state, phase velocity and group velocity of

photons gets modified [108]. The overall optical properties of the nanoparticle-laden fluids

depend on various factors like: base fluid, volume/mass fraction of the nanoparticles, material,

shape of the nanoparticle, and stability of the nanoparticles in the base fluid [59][109]. In the

subsequent five sub-sections (3.1 to 3.5), we will review each of the aforementioned factors one

by one.

3.1 Optical properties of base fluids

Most of the available base fluids (e.g. water, ethylene glycol, propylene glycol etc.) are

transparent in nature and with the addition of nanoparticles these base fluids can potentially

become good absorber of solar radiations. The suitable base fluid can be found out from the

optical properties of the fluid because from the optical properties we can ascertain the spectral

range at which the base fluids are either transparent or absorptive.

Otanicar et al. [110] have measured the transmittance of four transparent base fluids such as

water, ethylene glycol, propylene glycol and Therminol-VP1 with UV-Visible

spectrophotometer (Shimadzu UV-3600) within 0.2-1.5 µm range. For the measurement they

have used 10 mm path length and the measured transmittances are shown in figure 12. They have

observed that water; ethylene glycol and propylene glycol heat transfer fluids have strong

absorption bands at 950-1000 nm and again at 1200 nm; however after 1400 nm these fluids are

completely opaque. While Therminol-VP1 is completely opaque at 200-300nm, and have two

strong absorption peaks at 1050 nm and 1400 nm. To find out suitable base fluid, they have also

40
calculated the solar weighted absorptivity of these fluids and observed that water has maximum

13% solar weighted absorptivity and Therminol-VP1 has only 2% solar weighted absorptivity

which shows that these fluids are poor absorber of sunlight. Khullar et al. [111] have also

measured the optical properties of the transparent base fluids such as DI water, ethylene glycol,

propylene glycol, perfluorodecaline, silicone oil, paraffin oil (light) and paraffin oil (heavy)

within the UV-Vis-NIR range. They have showed that most of the heat transfer fluids are

transparent in visible to NIR region and these fluids have strong absorption bands in the mid-

infrared region.

Figure 12 Transmission spectrum of four base fluids (a) water (b) ethylene glycol (c) propylene

glycol and (d) Therminol VP-1 (figure reprinted with permission from Otanicar et al. [110]).

The aforementioned experimental results show that transparent base fluids are not suitable for

the harnessing of solar energy by themselves because their solar weighted absorptivity ranges

from about 2% (Therminol VP-1) to 13% (water), for a 10 mm sample. Hence, some additives

(nanoparticles) need to be added in these transparent base fluids in order to enable them to

41
absorb the solar irradiation. The subsequent sub-sections will represent the effect of addition of

nanoparticles on the optical properties in the base fluids.

3.2 Effect of nanoparticle volume/mass fraction on the optical properties of base

fluids

Volume/mass fraction is defined as the ratio of the volume/mass of the constituent of a mixture

divided by the volume/mass of all constituents of the mixture prior to the mixing [112]. The

volume/mass fraction of the nanoparticles play an important role in enhancing the performance

of the nanoparticles-laden fluid-based solar collectors because the absorption as well as

scattering of incident light depends on the amount of nanoparticles have been added in the base

fluid. The extinction of the incident light increases with an increase in volume/mass fraction of

the nanoparticles. The absorption mechanism of the incident light with volume fraction is shown

in figure13.

Incident Radiation
Incident Radiation

(a) Low Volume fraction (b) High Volume fraction

Figure 13 Absorption mechanism of the incident light with volume fraction. The length of the

arrows indicates the strength of the radiation intensity.

42
Figure 13(a) shows that, at low volume fraction, the incident radiation can reach to the bottom of

the solar collector. Because of low volume fraction less attenuation of the incident radiation take

place. On the other hand, at high volume fraction, maximum attenuation of the incident radiation

take place on the upper thin layer of the fluid in the vicinity to free liquid surface (see figure

13b). Due to this, the intensity is unable to reach to the subsequent layers of the nanoparticles-

laden fluid. The literature related to the effect of volume/mass fraction on the optical properties

of nanoparticle-laden fluids has been presented in this sub-section.

Taylor et al. [113] have experimentally measured the transmittance of nanoparticles-laden fluids

(graphite nanoparticles, D = 10 to 50 nm, dispersed in water) using a spectrophotometer (Jasco

V-670) and from the measured transmittance they have calculated the extinction coefficient of

the nanofluid (summation of absorption and scattering coefficient). For the measurements, they

have used five different volume fractions (0.00001, 0.0001, 0.0025, 0.1 and 0.5%) and suggested

that these volume fractions can be used in various configurations of solar collector geometry.

They have also calculated the extinction coefficient by using Maxwell-Garnett effective medium

approach (a numerical approach). The comparison of both experimental and numerical results

has been shown in figure 14 and it shows that the absorptivity of the nanoparticles-laden fluid is

significant up to a wavelength of 1 µm for fv = 0.00001% and up to a wavelength of 2 µm for

fv = 0.5%.

43
Figure 14 Modeled and experimental extinction coefficient for several concentrations of aqueous

graphite nanoparticles-laden fluids (figure reprinted with permission from Taylor et al. [113]).

Saidur et al. [114] have numerically studied the effect of volume fraction on the optical

properties of aluminum nanoparticle-based fluid (D = 20 nm and base fluid: water) within the

solar spectrum range (0.2 to 2.5 µm). They have calculated the absorption, scattering and

extinction coefficients by using Eqs. (2), (3) and (4) respectively.

6 f v  m 2  1   2 D 2  m 2  1  m 4  27 m 2  38  
K a  Im  2 1  2    , (2)
λ  m  2  15λ  m  2  2m 2  3
2
 

2
4 4 D 3 f v  m 2  1 
K s   2  , (3)
λ4 m 2

K e  K a  K s , (4)

where K a is the spectral absorption coefficient, K s is spectral scattering coefficient and K e is

spectral extinction coefficient, m is the complex refractive index of the nanoparticle, fv is the

volume fraction of the nanoparticle and D is the diameter of the nanoparticle. The calculated

coefficients (absorption, scattering and extinction coefficients) have been shown in figure 15.

Figure 15(a) shows that the absorption coefficient peak arises at around 0.3 µm and then there is

44
a decreasing gradient after 0.9 µm. They have suggested that this trend remains same even at

higher values of nanoparticle volume fractions. Figure 15(b) shows the scattering coefficient for

different volume fractions and it shows that the peak for scattering coefficient occurs at 0.2 µm

(UV region) and after that there has an abrupt decay in the scattering coefficient after 0.2 µm

which shows that scattering coefficient has very small contribution in the extinction. Further

figure 15(b) shows that the scattering coefficient decreases with the increase of volume fraction

of the nanoparticles. Figure 15(c) shows the calculated extinction coefficient which is the

summation of absorption and scattering coefficient. They have concluded that extinction

coefficient shows same trend as like absorption coefficient because the impact of scattering

coefficient is very small and does not play a significant role in the extinction.

(a) (b) (c)

Figure 15 Effect of nanoparticle volume fraction on (a) absorption coefficient (b) scattering

coefficient and (c) extinction coefficient (figure reprinted with permission from Saidur et al.

[114]).

Karami et al. [115] and Hordy et al. [116] have measured the optical properties of functionalized

carbon nanotubes (f-CNTs) and have shown the effects of volume fraction on the optical

properties of f-CNTs. The CNTs act as a black body due to high absorption coefficient [115], but

45
are hydrophobic and unstable in polar fluids (such as water, ethylene glycol, propylene glycol

etc) under normal conditions [116], due to which they get agglomerated. In order to avoid this

agglomeration and keep the CNTs stable in the fluid they have attached a functionalized group to

the CNTs. Karami et al. [115] have used seven different volume fractions viz. S1: 0; S2: 5; S3:10;

S4:25; S5:50; S6:100 and S7:150 ppm of the nanoparticles (f-CNT dispersed in water) and have

measured the transmittance using UV-Vis-NIR spectrophotometer (Perkin Elmer Lambda 1050).

The measured transmittances have been shown in figure 16, which shows that transmittance

decreases with increase of volume fraction of the nanoparticles (with transmittance reaching

almost zero, for S7 samples). Further, they have evaluated the extinction coefficient (shown in

figure 16b) by using the Beer Lambert Law,  (  )  e  K (  ) H .

(a) (b)

Figure 16 (a) Transmittance and (b) extinction coefficient for various volume fractions of f-CNT

(figure reprinted with permission from Karami et al. [115]).

Hordy et al. [116] have experimentally measured the transmittance of seven different

concentrations of nanoparticles. They have used a double beam UV-Vis spectrophotometer

(Carry 5000, 175-3300 nm) to measure the transmittance of the samples (10 mm path length).

They kept 200-1500 nm measurement range for water, ethylene glycol, propylene glycol because

these fluids have strong absorption bands in the IR region (so measurement above 1500 nm has

46
no significance), while for Therminol VP-1 they have conducted measurement up to 2300 nm

because absorption in IR region is not the case with Therminol VP-1. From the measured value

of transmittance they have calculated the extinction coefficient by using Beer Lambert’s law

(shown in figure 17a).

Figure 17(a) shows the extinction coefficient of different nanoparticles-laden fluids

(nanoparticle: MWCNT, base fluid: (1) water, (2) ethylene glycol, (3) propylene glycol and (4)

Therminol VP-1). Figure 17(a) shows that for all the samples the absorption peak is at 260 nm

followed by broadband absorption spectrum across the measured spectral range. They have

suggested that some noise is observed in the measurement above 1400 nm due to strong NIR

absorption bands of the base fluid. They have concluded that the extinction coefficient depends

on the volume fraction of the nanoparticles. They have also calculated the solar weighted

absorptivity (Am) of the nanoparticles-laden fluid using Eq. (5). The solar weighted absorptivity

is defined as the fraction of solar energy that is absorbed by the nanoparticle-laden fluid over a

given penetration distance, x, [117].

Am ( x, c ) 
S m ( ) 1  e  (  ,c ) x  d 
, (5)
 S m ( ) d 

where Sm (λ) is the spectral distribution of the solar intensity through an air mass m. The quantity

1  e (  ,c ) x represents the attenuation of energy of optical beam having wavelength λ by the fluid

having thickness of x.

Figure 17(b) shows the stored energy fractions for different concentrations of nanoparticles for

various penetration distances (0 to 10 cm). It can be seen from figure 17(b) that at low volume

fraction of the nanoparticles, the incident irradiation is able to reach the bottom of the samples.

47
On the other hand, at high volume fractions the irradiation gets absorbed within very small

penetration distance. They have concluded that the addition of nanoparticles has a significant

effect on the solar weighted absorptivity and it’s possible to adjust the volume fraction of the

nanoparticles to get 100% absorption for a given thickness of fluid sample.

Figure 17 (a) Extinction coefficients of MWCNT nanoparticles-laden fluid for (1) Water, (2)
ethylene glycol, (3) propylene glycol and (4) Therminol VP-1and (b) Stored energy fraction as a
function of penetration distance for various concentrations of MWCNTs for (1) Water, (2)
ethylene glycol, (3) propylene glycol and (4) Therminol VP-1 (figure reprinted with permission
from Hordy et al. [116]).

Sani et al. [118] have synthesized single walled carbon nanohorns (SWCNHs), which were

dispersed in ethylene glycol. SWCNHs consist of a single layer of graphene sheet wrapped into

irregular tubule with varying diameters of 2-5 nm and having a length of 30-50 nm. The tips of

48
the nanohorns are cone-shaped with an average angle of 20o corresponding to five pentagonal

carbon rings on the top of the tubule. They have used UV-vis-NIR spectrometer (Perkin Elmer

Lambda 900) to measure the transmittance of the various concentrations (g/l) of nanoparticles

(six concentrations of SWCNHs and three concentrations of carbon black (CB) nanoparticles).

The authors have labeled the six concentrations of SWCNH nanoparticles (ranging between 0 to

0.06 g/l) as G0, G1, G2 up to G6, and similarly the three concentrations of carbon black

nanoparticles (ranging between 0.01 to 0.12 g/l) as CB2, CB6, and CB7. They have measured the

transmittance of all the samples and calculated the extinction coefficient of both SWCNH and

CB which has been as shown in figure 18. Figure 18 shows that SWCNHs have broad-band

spectrum and has an extinction peak at around 260 nm. After this peak, the extinction coefficient

decreases constantly towards the infrared region, whereas CBs has almost flat spectrum for all

wavelengths. They have showed that extinction coefficient is directly proportional to the

concentration of the nanoparticles.

They have also calculated the spectral absorption coefficient of the nanoparticles-laden fluid and

the effect of volume fraction on the absorbed energy fraction, as shown in figure 18(b). From

figure 18(b), they have concluded that the absorptivity of both types of nanoparticles (carbon

black and SWCNH) is more than pure fluid (ethylene glycol). Further they have compared the

absorbed energy fraction of carbon black and SWCNHs and found that SWCNHs have higher

absorption than carbon black nanoparticles. So, small amount of SWCNHs are required as

compared to carbon black nanoparticles.

49
 (a)

(b)

Figure 18 (a) Transmittance spectra for suspension of SWCNH in ethylene glycol as a function
of the nanoparticle concentration, (b) Comparison of energy absorption capability of SWCNH
with carbon black suspension at same nanoparticles concentration (figure reprinted with
permission from Sani et al. [118]).

Gorji et al. [64] have measured the transmittance of nanoparticles-laden fluid (graphite,

magnetite and silver nanoparticles dispersed in DI water) by using double beam UV-vis

spectrophotometer (SPEKOL 2000) and have also calculated the solar weighted absorptivity of

these nanoparticle-laden fluids. They have considered three different volume fractions viz. 5

ppm, 22.5 ppm and 40 ppm. The measured results show that the 40 ppm sample has lowest

transmittance. On comparing the transmittance of these nanoparticles, they have concluded that

graphite nanoparticles have higher absorption than the other nanoparticles (magnetite and silver).

Literature also suggests that with mono-dispersion the absorption of the incident light is in a

small wavelength band, which can be increased if we mix such different types of nanoparticles.

Such a mixing of two different types of nanoparticles (to effectively increase the absorption

band) has been termed as a ‘binary-nanofluid’ or ‘hybrid-nanofluid’ [119] [120]. The thermo-

physical properties of the hybrid-nanofluid depends on the volume fraction of the nanoparticles

and on the operating temperatures [121] and review also suggests the thermo-physical properties

get enhanced due to hybrid nanoparticles [122]. Both Menbari et al. [123] as well as Chen et al.

[124] have conducted experiments with binary-nanofluids. Menbari et al. [123] have measured

the transmittance of binary-nanofluids (nanoparticles: γ-Al2O3-CuO, base fluid: ethylene glycol

and ethylene glycol/water mixture) with UV-Vis spectrophotometer (Jasco V-570, Jasco Corp.,

50
Japan) at room temperature. From the measured transmittance they have calculated the extinction

coefficients, as shown in figure 19. They have concluded that the extinction coefficient is

directly proportional to volume fraction of the nanoparticles, irrespective of the base fluid and

the extinction coefficient of binary nanofluid is higher than that of the individual nanoparticle-

laden fluids. So, they have suggested that it may be beneficial to use binary-nanofluid-based

solar collectors to further improve their efficiency.

(a) (b)

(c) (d)

Figure 19 Comparison of extinction coefficient of different nanoparticle-laden fluids at different

volume fractions (figure reprinted with permission from Menbari et al. [123]).

Chen et al. [124] have also studied the effect of various volume fractions (0.01, 0.05, 0.1, 0.2, 0.3

and 0.4 vol%) of binary nanofluids (copper (II) oxide (CuO) and antimony-doped tin-oxide

(ATO) nanoparticles, base fluid: water) on the transmittance and the solar weighted absorption

fraction of the nanoparticle-laden fluids. They have measured the transmittance of CuO, ATO

and the mixture of CuO and ATO with Lambda 750s spectrophotometer. From the measurements

they have found that CuO nanoparticles have good absorption in the visible range and very poor

absorption in NIR, while ATO has good absorption in NIR region and very poor absorption in

51
the visible region. They have stated that within the spectral distribution of solar energy, the

absorption with infrared region (NIR), and visible spectrum is about 42% and 53% of total

energy, respectively [125]. Therefore, to increase the absorption rate both nanoparticles should

be mixed in water, which they have done in a ratio of 4:6 i.e. 4 parts of CuO and 6 parts of ATO

(see figure 20a). Further they have calculated the solar weighted absorption fraction (Am) for all

nanoparticle-laden fluids (shown in figure 20b). This figure shows that for the solar weighted

absorptivity the ratio of 4:6 is an optimum ratio. And at 0.1% volume fraction and 1 cm

penetration depth, the solar weighted absorption was quite high (99.6%). For comparison, the

corresponding values for CuO/water and ATO/water samples individually are relatively lower

89.5% and 89.8% respectively. These results show that, the mixing of two different types of

nanoparticles can further improve the efficiency of the nanoparticles-laden fluid-based solar

collectors.

Figure 20 (a) Transmittance spectra of (1) CuO/water, (2) ATO/water, (3) CuO-ATO/water with
total volume fraction of 0.1% and (4) CuO-ATO/water with different volume fractions and (b)
dependence of solar weighted absorption fraction on the volume fraction and penetration depth

52
for (1) CuO/water, (2) ATO/water, (3) CuO-ATO/water with total volume fraction of 0.1% and
(4) CuO-ATO/water with different volume fractions (figure reprinted with permission from Chen
et al. [124]).

Zhang et al. [126] have measured the transmittance of carbon coated nickel nanoparticles (Ni/C)

dispersed in ionic liquid [HMIM][NTf2] with double beam UV-vis-NIR spectrophotometer

(PerkinElmer Lambda 950) within range of 200 to 2500 nm. From the measurements, they have

found that the samples containing carbon-coated Ni nanoparticles has lower transmittance and

higher extinction coefficient as compare to uncoated Ni nanoparticles having similar average

size. The radiative properties of Ni/C nanoparticles increase with the volume fraction of the

nanoparticles. It is observed that the overall solar weighted absorptivity reached around 100%,

when the nanoparticle volume fraction is 40 ppm (at 1 cm penetration depth).

In summary, it is observed that volume fraction of nanoparticles plays a very important role in

determining the overall optical properties of the fluid. The overall transmittance of the

nanoparticles-laden fluid decreases significantly with the increase of volume fraction of the

nanoparticles (due to significant increases in absorption, scattering and extinction coefficients).

Consequently, the volume fraction of the nanoparticles have a significant effect on the overall

solar weighted absorption of the fluid and in-principle the volume fraction of the nanoparticles

can be tailored to achieve 100% absorption for a given fluid thickness. Although for achieving

the overall higher efficiency of the solar collector, an optimum value of nanoparticle volume

fraction (usually less than 100%) could be utilized.

53
3.3 Effect of nanoparticle material

Due to the small size (0.2-100 nm), nanoparticles have remarkably different optical properties

compared to their bulk state. Moreover, the optical properties are very sensitive to the size, shape

of the nanoparticle material as well as the surrounding dielectric media. When the solid particle

absorbs the electromagnetic wave, it follows two mechanisms: lattice vibration and electronic

absorption. Table 2 explains the absorption mechanisms of different materials (metals,

semiconductors and dielectrics) over different regions of electromagnetic spectrum. It shows that

the presence of bound electrons, conduction electrons, lattice ions and permanent dipoles

dominate the absorption over the various regions of the spectrum, depending on the type of

material. In the metallic particles, the free conduction electrons dominate the absorption of

electromagnetic waves over the UV, visible, near infrared, infrared and in the far infrared

regions. The bound electrons also play a small contribution in absorption in the UV, visible and

near infrared regions.

Further, for the dielectric materials, the bound electrons play a vital role for absorption in the UV

region and lattice vibrations dominate the absorption in the infrared region. Most of the pure

dielectrics are opaque in the UV region. Also, dielectrics have transparent window somewhere

between the UV and the infrared regions.

Finally, semiconductors are hybrid case of both metals and dielectrics. In semiconductors the

absorption in the infrared region is dominated by lattice vibration and the semiconductors do not

have free electrons, due to which the semiconductors are unable to absorb in the visible region.

The optical properties of semiconductor properties are influenced by the electrons which can

emit and absorb the photons by changing the energy stated between valance band and conduction

54
band. In semiconductors, the transition of electrons in the conduction band side is unbounded,

due to which the electrons can emit or absorb photons of any frequency (as long as the photons

have sufficient energy). Due to this reason, the opaque electronic absorption is extended to

longer wavelength for the semiconductors, compared to dielectrics.

Table 2 Absorption mechanism of various materials [127].

Materials Metals Semi-Conductors Dielectrics

Wavelength
(µm)

electrons
Bound
Conduction electrons
Bound electrons
ultra-violet
Bound electrons

Conduction electrons

visible

near-infrared

Permanent dipoles
Permanent dipoles

Lattice ions
Lattice ions

infrared

far-infrared

The subsequent headings within this sub-section will discuss in detail the optical properties of

nanoparticle made from these four types of materials - metallic, core/shell, graphite and non-

metallic, and also discuss their potential for usage in solar collectors.

55
3.3.1. Metallic nanoparticles

When an electromagnetic wave is incident on the metal surface, the free electrons get displaced

from its equilibrium position. This polarization of charge on the surface induces a restoring force

in order to bring back the electrons to an equilibrium position. This restoring force is dissipative

in nature [128][129] and falls under two categories (a) radiative decay and (b) non- radiative

decay [130]. The radiative decay is responsible for the scattering of the electromagnetic wave

(EM) and due to non radiative decay absorption of the electromagnetic wave (EM) happens. In

metallic nanoparticles the non- radiative decay dominates which make them highly efficient

absorber [131] and when the frequency of the incident electromagnetic wave is near to the

resonant frequency of the metallic nanoparticle the absorption efficiency escalates. This

collective oscillation of the electrons is known as Surface Plasmon Resonance (SPR) [132][133].

The peak arises in metallic nanoparticle depending on the dielectric constant of the surrounding

media (solvent or the base fluid) as well as the free charge present on the surface of the

nanoparticle [134]. Mahmoud et al. [135] have shown the effect of the surrounding media

(solvent) on the extinction peak for Au nanocubes, whereas Link and El-Sayed [136] have

further shown that this plasmonic peak depends on the size of nanoparticles (Au nanoparticles)

and this effect is as shown in figure 21.

Figure 21 UV-Vis absorption spectra of gold nanoparticles dispersed in water (figure reprinted

with permission from Link and El-Sayed [136] Copyright (1999) American Chemical Society).

56
Taylor et al. [113] have demonstrated the effect of various metallic nanoparticles (Al, Ag and

Cu, having average particle size in the range of 10 to 50 nm, dispersed in water and Therminol

VP-1) on the optical signatures of the overall fluid sample. They concluded that these

nanoparticles have inherent peaks which depend on the material of the nanoparticles. They have

showed that for Ag nanoparticles plasmonic peak occurs at around 0.4 µm, whereas for Al, Cu

nanoparticles the plasmonic peak occur at around 0.3 µm. On comparing the extinction

coefficients they have found that Ag nanoparticle has higher extinction value than Al and Cu

nanoparticles. They have also suggested that the extinction coefficient also depend on the

diameter of the nanoparticle and it increases with nanoparticle diameter. He et al. [76] have

measured the transmittance of nanoparticles-laden fluid (Cu nanoparticles dispersed in water)

using UV-Vis-NIR spectrophotometer (PerkinElmer Lambda 950) at room temperature for

various nanoparticle weight fractions (0.01, 0.02, 0.04 and 0.1 wt %). From their measurements,

they have shown that the transmittance is almost zero within the band ranging from 300 nm to

500 nm and after 500 nm the transmittance starts increasing. The nanoparticles-laden fluid has

three peaks after 500 nm at wavelengths of 900 nm, 1100 nm and 1250 nm and after 1500 nm the

nanoparticles-laden fluid is completely opaque. From the measured transmittance they have

calculated the extinction coefficients (using Beer Lambert law) and compared the experimentally

calculated extinction coefficients with the extinction coefficient found from numerical model

(Rayleigh model). From comparison they have concluded that the numerical results are not

matching with experimental results below 1370 nm wavelength. For this mismatch they have

proposed two possible reasons which are as follows (a) an oxide layer may have occurred on the

surface of nanoparticles due to which the metal nanoparticles have different properties than bulk

material, and secondly (b) during experimentation, an agglomeration of the nanoparticles may

57
have taken place. In conclusion, they suggested that Cu-H2O based fluid has good solar

absorption ability and can effectively enhance the solar absorption ability.

Kameya and Hanamura [137] have measured the transmittance of Ni nanoparticles dispersed in

alkyl naphthalene using JASCO, V-670 spectrophotometer. They have found that the absorption

coefficient of Ni nanoparticles is much higher than the base fluid within the visible to near

infrared region (shown in figure 22). They have concluded that since the particles are well

dispersed in the base fluid therefore they have higher absorption coefficients than the base fluid.

Figure 22 Absorption coefficient verses wavelength for Ni nanoparticles and base fluid (figure

reprinted with permission from Kameya and Hanamura [137]).

Chen et al. [95] have quantified the transmittance of various volume fractions (20.24, 40.47 and

90.94 ppm) of synthesized silver nanoparticles dispersed in water using the UV-Vis

spectrophotometer (PerkinElmer Lambda 900). From the measured transmittance values they

have calculated the absorption efficiency and showed that at 20.24 ppm and 40.47 ppm, only one

peak occurs for Ag nanoparticles (at wavelength of 400 nm), while at 90.94 ppm two absorption

peaks occur (at 490 nm and 650 nm) as shown in figure 23. They have suggested that

agglomeration of the particles may be the reason of the occurrence of these two peaks at 490 nm

58
and 650 nm. The agglomeration of the nanoparticles in the base fluid can be studied

mathematically. Monte Carlo simulation, Brownian dynamic simulation and population balance

methods are few of the mathematical models used to study the agglomeration of the

nanoparticles [138]. Du and Tang [139] have also theoretically investigated the effects of

agglomeration on the extinction coefficient of nanoparticle-laden fluid (Ag nanoparticles

dispersed in water) by using diffusion limited cluster aggregation (DLCA) and generalized multi

particle Mie solution (GMM) techniques. They have concluded that due to particle

agglomeration the extinction coefficient increases at long wavelengths, while there is a small

reduction in absorption at shorter wavelengths.

Figure 23 (a) The absorbance spectrum of silver nanoparticle-laden fluids at different mass
concentrations (figure reprinted with permission from Chen et al. [95]) and (b) Experimental
absorbance spectra of Au, Ag nanoparticle-laden fluids and their blended mixture comparing
with solar radiation spectral intensity (figure reprinted with permission from Chen et al. [140]).

Chen et al. [140] have measured the transmittance of synthesized Ag and Au nanoparticles-laden

fluid (base fluid: water) using UV-Vis spectrophotometer (Pgeneral TU1901). They have used

different volume fractions for Ag/H2O and Au/H2O (0.5 ppm and 2.5 ppm respectively). They

observed that for Ag and Au nanoparticles the absorbance peaks occur at wavelengths of 408 nm

and 521 nm respectively. Additionally they have blended both Au and Ag nanoparticles and

measured the absorbance of the blended solution (within the solar spectrum). They have

59
concluded that with the blended nanoparticles-laden fluids two absorption peaks arises at around

400 nm and 550 nm (see figure 23b) and proposed that these two peaks are beneficial for the

harnessing of solar energy and also that these plasmonic peaks can be adjusted accordingly and

therefore would be helpful in improving the efficiency of direct absorption based solar collector.

Chen et al. [141] have measured the absorbance spectra of synthesized gold nanoparticles

dispersed in water at different values of particle volume fraction (0.5, 1.0, 1.5 and 2.5 ppm) and

have reported that for gold nanoparticles the absorption peak occurs at around 524 nm (shown in

figure 24a). They have further observed that the absorbance depends on the volume fraction of

the nanoparticles and with the increase of volume fraction no blue or red shift of the plasmonic

peak was observed. They have also shown that a linear relationship exists between the peak

absorbance peak and the nanoparticle volume fraction (figure 24b).

(a) (b)

Figure 24 (a) Absorption spectra of Au nanoparticles at different volume fractions and (b)

relationship between the peak absorbance and nanoparticles volume fraction (figure reprinted

with permission from Chen et al. [141]).

In summary, a review of literature has shown that in the metallic nanoparticles the plasmonic

peak arises due to surface plasmon resonance (SPR), due to which maximum absorption of

incident solar irradiation take place at a wavelength. The SPR depends on the size, material of

60
the nanoparticle and the dielectric constant of the base fluid. The SPR for Ag nanoparticles peak

arises at about 400 nm and for Au nanoparticles the plasmon peak arises at about 520 nm. On the

basis of the absorption of solar irradiation Ag nanoparticle has more absorbance than Au

nanoparticle because Ag has higher plasmonic strength.

3.3.2. Core/shell nanoparticles

The nanoparticles can be synthesized with a single material or with the combination of two or

three materials which are known as composite materials. The core/shell nanoparticles are a

special type of composite material in which core (inner portion) is made of one material and shell

(outer portion) is of another material [142]. These core/shell materials may consists of different

combinations like inorganic/inorganic, organic/inorganic, organic/organic and inorganic/organic

materials [143]. According to the shape these core/shell nanoparticles have different classes as

shown in figure 25 and apart from these different shapes the spherically-shaped core/shell

nanoparticles are the ones most commonly used [143]. Researchers are gaining interest in the

core/shell nanoparticles because the optical properties of these nanoparticles can be suitably

altered, and these particles exhibit high stability and dispersion in the base fluid [144]. Moreover

these nanoparticles are significantly cheaper than precious material nanoparticles (Ag, Au etc.)

because a thin layer of precious material can be coated over an inexpensive material.

Figure 25 Different core/shell nanoparticles (a) Spherical core/shell nanoparticles (b) hexagonal
core/shell nanoparticles (c) multiple small core materials coated by single shell material (d)

61
nanomatryushka material (e) movable core within hollow shell material (figure reprinted with
permission from Chaudhuri et al. [143] Copyright (2012) American Chemical Society).

Lee et al. [78] have shown numerically that the core/shell nanoparticles are very useful for the

harnessing of the solar energy and the optical properties of these nanoparticles can be easily

tuned according to the requirement. They calculated the absorption and scattering coefficients of

water based core/shell nanoparticles in which the core is of SiO2 and shell is of gold. They have

shown the effects of core size (diameter of the core) and shell thickness on the absorption and

scattering coefficients and have also compared these coefficients with the absorption and

scattering coefficients of Al nanoparticles (r = 2.5 nm). For such comparisons they have used

different geometric parameters for the core/shell nanoparticles (GNS1, GNS2, GNS3 and

GNS4). These four sets of nanoparticles have the following values of SiO2 core radius, Au shell

thickness, and relative volume fraction, respectively - GNS1 (20 nm, 10 nm, 20%), GNS2 (30

nm, 5 nm, 15%), GNS3 (45 nm, 5 nm, 25%), GNS4 (55 nm, 3 nm, 40%). They showed that for

Al nanoparticle the absorption and scattering coefficient peak arise at about 200 nm (UV region),

while for GNSs (Gold nanoshell particles) the absorption and scattering peaks are at 610 nm, 750

nm, 860 nm and 1110 nm for GNS1, GNS2, GNS3 and GNS4 respectively. They have

concluded that the wavelengths corresponding to the absorption peak can be controlled by

varying the core radius and shell thickness.

Lv et al. [145] have numerically evaluated the extinction coefficients of water-based core/shell

nanoparticles for different shell materials (Au, Ag, Cu and Al) while keeping the same core

material (Si). On comparing the extinction coefficients for aforementioned nanoparticles, they

have found that extinction coefficient for Al shell nanoparticle fits well with the solar spectrum

62
as extinction peak due to SPR effect is in the visible region. For comparison, they have also

shown that if the geometry of core/shell is kept identical while the size ratio (core radius to shell

thickness) is increased, then red shift of the extinction coefficient takes place. They have also

evaluated the solar weighted absorptivity of these fluids and concluded that the solar weighted

absorptivity Cu and Al core/shell nanoparticles is nearly equal to Au core/shell nanoparticle, so it

can be used for direct absorption based solar collector, which is beneficial from a cost point of

view.

Otanicar et al. [146] have observed the effect of temperature on the optical signatures of

core/shell based nanoparticle-laden fluids. They have measured the temperature-dependent

transmittance spectra of SiO2-core/Au-shell nanoparticles dispersed in water and ethylene glycol

and found that a blue-shift of the absorption peak takes place at higher temperatures. This is

because the refractive index of the base fluids decreases with temperature. Xuan et al. [94] have

calculated the absorption efficiency of TiO2-core and Ag-shell nanoparticles and compared the

absorption efficiency with TiO2 nanoparticle. They have shown that two plasmon resonance

peaks arises at 360 nm and 630 nm (see figure 26a). They have also evaluated the effects of core

radius on the absorption efficiency (Qabs) and concluded that a red-shift occurs as core radius is

increased. From their calculations they found that R1/R2 = 20/30 nm is optimum core/shell ratio

where maximum solar energy can be absorbed (shown in figure 26b).

(a) (b)

Figure 26 (a) Absorption efficiency of TiO2/Ag (R1/R2 = 20/30) nanoparticle and TiO2 (R =
30nm) nanoparticle (b) absorption efficiency of TiO2/Ag nanoparticles with different core sizes

63
(figure reprinted with permission from Xuan et al. [94] Copyright (2014) Royal Society of
Chemistry).

Lenert and Wang [84] have measured the absorption coefficients of carbon-coated cobalt

nanoparticles dispersed in Therminol VP-1 at very small volume fractions (0.93 ppm to 4.3

ppm). They have observed that absorption coefficient depends strongly on nanoparticle volume

fraction. Zhang et al. [126] have measured the transmittance of Cu, Ni and carbon-coated Ni

nanoparticles (D = 40 nm) dispersed in an Ionic liquid ([HMIM][NTf2]) using double beam UV-

Vis-NIR spectrophotometer (PerkinElmer Lambda950). For the measurements, they have used

spherical morphology of the nanoparticles and the measured values of transmittance are shown

in figure 27. They have shown that base fluid has almost 100% transmittance from 300 nm to

1050 nm and Cu nanoparticles have 90% transmittance in the same wavelength range, whereas,

with Ni nanoparticles, this transmittance has been decreased by 50-60%. Furthermore, with Ni/C

nanoparticles, the transmittance decreased by 70% for same volume fraction (10 ppm). They

have proposed that coating a layer of carbon on Ni nanoparticle has improved the overall

absorption due to predictable broadband spectrum of carbon in the visible-NIR region.

Figure 27 Transmittance verses wavelength for different types of nanoparticles having same
volume fraction 10 ppm (figure reprinted with permission from Zhang et al. [126]).

To summarize, researchers have shown that the absorption peak of core/shell nanoparticles can

be tuned by changing the geometric parameters of the nanoparticle (core radius and shell

64
thickness) and this tunability can be easily engineered for the effective solar thermal absorption.

The core/shell nanoparticles are cheaper than metallic nanoparticles because in these

nanoparticles a small layer of metal (shell) has been used on the non-metal (core). The extinction

coefficient of the nanoparticles-laden fluid largely depends on the material of the shell. A red-

shift of the plasmonic peak is generally observed with the increase of the core radius.

3.3.3. Graphite nanoparticles

Graphite is a natural occurring mineral which is a form of carbon. Graphite is a common material

so it’s very cheap and possesses excellent thermal, mechanical and optical properties. The

graphite nanoparticles also have high surface area and exhibit excellent dimensional stability.

Due to which, graphite nanoparticles are increasingly being considered by researchers for

various applications including their use as absorbers of solar irradiation. Arai et al. [38] have

suggested that small size black particles in the fluid (such as graphite and silicon carbide) has

higher absorption than white particles (like silicon dioxide). Various carbon-based particles like

carbon nanotubes (CNT), multi walled carbon nanotubes (MWCNT), carbon nanohorns, carbon

nanoballs, graphene have been used by the researchers for the direct absorption of sunlight. So, it

becomes essential to quantify the optical properties of the graphite nanoparticles. Otanicar et al.

[74] have theoretically shown the benefit of graphite nanoparticles (D = 30 nm) by comparing

the solar energy absorbed and reflected by a given depth of nanoparticle-laden fluids over a

surface absorber (black painted metal plate). They have shown that graphite-based nanoparticle-

laden fluid has strong absorption and weak reflectance as compared to the conventional surface-

based absorption system. Taylor et al. [82] have calculated the extinction coefficients of graphite

nanoparticles (D = 20 nm) dispersed in Therminol VP-1 and observed that graphite

65
nanoparticles-laden fluids have wide broadband spectra over Vis-NIR range due to which a large

amount of solar irradiation can be absorbed.

Sani et al. [147] have measured that the transmittance of functionalized single walled carbon

nanohorns (dispersed in water) and showed that the transmittance of nanoparticles-laden fluids is

inversely proportional to volume fraction of the nanoparticles. Further, they have calculated the

spatial distribution S(x) of the stored thermal energy within the fluid bulk by using Eq. (6) and

the calculated distribution has been shown in figure 28. From figure 28 they have concluded that

at high nanoparticle volume fractions, the thermal energy is stored near to the surface and inner

layers do not get heated which results in strong distribution gradient (see curve ‘A7’ in figure

28). As the nanoparticle volume fraction decreases, the stored thermal energy penetrates more

deeply within the sample, resulting in a more uniform profile in the inner layers of the fluid.

max


 I ( ). ( ).e (  ) x d 
S ( x)  min
max
, (6)

min
I ( ) d 

where I (λ) is the incident solar irradiance, λmax = 2300 nm, λmin = 300 nm, α(λ) = extinction

coefficient.

Figure 28 Spatial distribution of stored energy along the light propagation direction (figure

reprinted with permission from Sani et al. [147] Copyright (2010) The Optical Society).

66
Apart from spherical shaped graphite nanoparticles, some researchers have also studied different

shapes of graphite nanoparticles like nanoplatelets and carbon nanotubes (CNT). Graphite

nanoplatelets are a type of nanoparticles consisting of a small stack of graphene layers and have

diameters in nanometer range. Whereas, CNTs are allotropes of carbon, and are one-dimensional

cylinders with one or multiple layers of carbon (one dimension of the CNT is in nanometer range

[148]). Vakili et al. [99], Ahmadi et al. [149], and Khosrojerdi et al. [150] have studied the

optical properties of graphene nanoplatelets. They have shown that graphene nanoplatelets have

strong absorption within the 250 to 380 nm wavelength range. Vakili et al. [99] have shown that

with graphene nanoplatelets, a strong absorption band exists at 250-300 nm and again at 1400-

1500 nm. Beyond a wavelength of 1850 nm the nanoparticle-laden fluids are completely opaque

for the solar irradiation because of water, whose absorption is very high in this range.

Khosrojerdi et al. [150] have calculated the solar weighted absorptivity of graphene oxide

nanoplatelets and have concluded that at 0.045 wt% concentration almost 99.6% of incident solar

radiation can be absorbed (for a sample thickness of 3 cm).

Hordy et al. [116], Shende et al. [151] and Mesgari et al. [152] have measured the optical

properties of Multi-Walled Carbon Nanotubes (MWCNTs). Shende et al. [151] have measured

the optical properties of nitrogen-doped functionalized MWCNTs (base fluids: DI water and

ethylene glycol). From the optical properties they have observed that the spectral absorption

depends on the base fluid because the spectral absorption in DI water is higher than ethylene

glycol.

As the nanoparticle-laden fluids have to operate at very high temperature in the solar thermal

collectors, their performance and stability also need to be evaluated at high temperatures. Due to

which some researchers have tested the stability of the nanoparticle-laden fluids with cyclic
67
heating. In order to see whether the nanoparticles are stable or not in the fluid, the optical

properties were measured before and after cyclic heating. Mesgari et al. [152] functionalized the

MWCNTs with KPS (K2S2O8) and dispersed them in Therminol 55. They observed that such

MWCNTs are thermally stable at very high temperature (250oC). In order to ensure the stability,

they measured the optical properties after cyclic heating and observed little or no sedimentation

of the nanoparticles in the base fluid. Hordy et al. [116] have also conducted thermal cyclic

experiments with plasma functionalized multi-walled carbon nanotubes (f-MWCNTs) dispersed

in water, ethylene glycol, propylene glycol and Therminol VP-1. They have heated the water and

glycols based samples (nanoparticle: f-MWCNT and base fluid: water, ethylene glycol and

propylene glycol) from 85oC to 170oC, while for Therminol-VP1 based samples were heated up

to 220oC. These heating temperatures were chosen according to the boiling point of the base

fluid. From the optical property measurement they have suggested that water and glycol based

samples do not show any agglomeration after cyclic heating while Therminol VP-1 has shown a

little agglomeration at 220oC after heating for approximately 2-3 hours. They have shown that

this agglomeration increases with the increase of MWCNT concentration and number of thermal

heating cycles. Gorji et al. [153] have compared the thermal stability and agglomeration of

functionalized single walled carbon nanotubes (f-SWCNT) with pristine SWCNT and concluded

that f-SWCNT are much more stable than pristine SWCNT even at 90oC thermal cycling.

To summarize, graphite nanoparticles are insignificantly cheaper than metallic nanoparticles and

they have strong absorption within 250 to 380 nm wavelength range. Since graphite

nanoparticles have broadband spectrum, they are very effective in absorbing solar irradiation. It

is also observed that f-MWCNT are highly stable in various base fluids, such as Therminol 55,

68
water, ethylene glycol and propylene glycol even at very high temperature (250oC), hence can be

considered good candidate for usage in solar thermal applications.

3.3.4. Metal oxide nanoparticles

Metal oxides play an important role in many areas of chemistry, physics and material science

[154–157]. Metal oxides have less density than the metal, which results in less agglomeration of

these nanoparticles in the base fluid [158]. Although their optical properties (absorptivity) are not

expected to be very conducive to absorption of solar irradiation, nevertheless a few researchers

have performed studies using metal oxide nanoparticles. Milanese et al. [159] have measured the

optical properties of several oxide materials (Al2O3, CuO, TiO2, ZnO, CeO2 and Fe2O3 dispersed

in water) using Agilent UV-vis-NIR Carry 5000 spectrophotometer. During the measurements

they have taken samples having same nanoparticle volume fraction for each type of metal-oxide

material. They concluded that compared to other nanoparticles, CuO and Fe2O3 nanoparticle-

laden fluids exhibit relatively higher absorption properties. They have also observed that Al2O3

nanoparticles do not have suitable absorption characteristics, even though they are some of the

cheapest nanoparticles available. Milanese et al. [160] have also demonstrated that absorption

coefficient of ZnO, Fe3O4 and CeO2 nanoparticles dispersed in chloroform does not change

significantly in the temperature range from 25oC to 500oC. Said et al. [161] and Leong et al.

[162] have showed that TiO2 nanoparticles-laden fluid has higher absorptivity than Al2O3

nanoparticles, but Al2O3 has more stability than TiO2. So, they have concluded that if the

stability of TiO2 can be improved then they are more beneficial for the harnessing of solar

energy. Zhu et al. [163] have measured the absorbance of various types of nanoparticles (ZnO,

69
AlN, ZrC and TiN) dispersed in water and showed that ZrC and TiN nanoparticle-laden fluids

have relatively higher solar radiation absorption compared to AlN and ZnO.

3.4 Effect of nanoparticle shape

The shape of the nanoparticles has a large impact on its optical properties. This is because with

the change of shape of the nanoparticle, electric field density on the surface also changes which

further results in change in the oscillation frequency of electrons. This results in different cross

sections for absorption and scattering of electromagnetic waves [129]. The examples for

different shapes of the nanoparticles are nanorods, nanoellipsoids, nanosheets, nanodisks,

triangular nanoparticles etc. [128] . In the recent times, nanorods have attracted a lot of attention

because they are easy to prepare, have high monodispersity, and have direct control on the aspect

ratio, which is primarily responsible for the change of optical properties. Nanorods show two

plasmon resonances, (a) transverse oscillation, and (b) longitudinal oscillation of the electrons on

the surface of the nanoparticles. The longitudinal oscillations occur on the longer wavelengths of

the spectrum. In the anisotropic nanoparticles, the transversal oscillation does not depend on the

aspect ratio of the nanoparticles. For the transversal oscillation, the peak will rise at the same

wavelength as that of sphere. Whereas, for the longitudinal oscillations the surface plasmon

resonance depends on the aspect ratio and it will increase with increase of aspect ratio[129].

Jeon et al. [164] have experimentally studied the optical properties of gold nanorods (have

different aspect ratios) and from the optical properties they concluded that gold nanorods have

good absorption in visible and near infra-red (NIR) spectral region. They have further concluded

that by enlarging the aspect ratio of the nanorods the peak position of LSPR (local surface

70
plasmon resonance) has showed red shift. Rativa et al. [165] has theoretically investigated the

optical property of gold and silver nanoellipsoids with Maxwell-Garnett models. They have

concluded that the LSPR of nanoellipsoid can be tuned by changing the aspect ratio of the

nanoellipsoid. They have showed that with Gold ellipsoid (D = 2.5 nm and AR = 4) high solar

weighted absorption can be obtained under ideal conditions.

Du et al. [166] have theoretically evaluated the optical properties of gold nanorods (h > d), gold

ellipsoids (a > b = c) and gold nanosheets (l/h) by using discrete dipole approximation

(schematics of nanorods, nanoellipsoid and nanosheet are shown in figure 29a). From the

calculations they have concluded that the absorption efficiency of nanoellipsoid and nanorods

depends on the aspect ratio and with the increase of aspect ratio red shift of LSPR occurs which

has been shown in figure 29b. They have suggested two reasons for the red shift a) transversal

oscillation mode and b) longitudinal oscillation mode. The transversal oscillation mode plays an

important role in spherical nanoparticles, whereas longitudinal oscillation mode is responsible

for dipole moment. In general, longer distance between polarized atoms will bring a larger

absorption peak due to longitudinal LSPR. So, longitudinal oscillation mode dominates the

absorption by nanoellipsoid and nanorods due to which the absorption efficiency of gold

nanorods is higher than gold ellipsoids, as shown in figure 29b. They have also found the

absorption peak for gold nanosheets by changing the l/h ratio. After comparing the absorption

peaks, they showed that nanosheets have higher absorption peak than ellipsoids and nanorods.

But with the change of aspect ratio, the absorption peak does not show any red-shift like

nanorods and nanoellipsoids.

71
Figure 29(a) Schematic of (1) nanoellipsoid (2) nanorod and (3) nanosheet and (b) absorption
efficiency verses wavelength for (1) nanoellipsoid and (2) nanorods, at different aspect ratios
(figure reprinted with permission from Du et al. [166]).

3.5 Effect of nanoparticle stability

The stability of the nanoparticles plays a vital role in the optical properties of the nanoparticles-

laden fluids. In the agglomerated nanoparticles-laden fluid, the particle size distribution is a

critical factor which affects the optical properties of the fluid. In the nanoparticles-laden fluid,

when the particle size is smaller, then the absorption coefficient is larger [167], which means that

when the particles are stable in the base fluid, then the nanoparticles are able to absorb

significantly more irradiation. Whereas, when the nanoparticles get agglomerated they tend to

settle down, which results in decrease of absorption by the nanoparticles-laden fluid [111,116].

The stability of the nanoparticles can be achieved by physical and chemical methods. In the

physical method, sonication or magnetic stirring methods are used to break the agglomeration of

the nanoparticles. Whereas, in the chemical method agglomeration can be prevented either by

adjusting the pH of the suspension or by modifying the surface of the nanoparticles. The pH of

the dispersion plays an essential role in the stability of the nanoparticles. When the pH of the

isoelectric point of the nanoparticles carries no charge, then there are no repulsive forces in

between the particles, due to which the particles may agglomerate. So, it is seen that greater the

72
difference between the pH of nanoparticles-laden fluid and isoelectric point, better will be the

dispersion of the nanoparticles [171–173]. The surfaces of the nanoparticles can be modified by

exerting similar charges on the nanoparticle and due to similar charges repulsive forces will

exert. These repulsive forces can be attained either with the surfactant or by attaching a

functional group on the nanoparticle. Surfactants which are also known as ambiphile contain two

ends, one end is hydrophilic end and the other end is hydrophobic end (either head or tail). The

head/tail group mainly interacts with the medium and as a result of which nanoparticles get

dispersed in the dielectric medium (base fluid). Commonly used surfactants across the

nanoparticles-laden fluid community are sodium dodecylsulfate (SDS),

cetyltrimethylammoniumbromide (CTAB), Sodium dodecylbenzenesulfonate (SDBS), dodecyl

trimethy- lammoniumbromide (DTAB), polyvinylpyrrolidone (PVP), Polyethylene glycol (PEG)

and Gum Arabic [168].

The other promising method in terms of stability of nanoparticles-laden fluid is the

functionalization of nanoparticles. For the functionalization of nanoparticles, plasma deposition

process has been found to be very effective method especially for carbon nanotubes

[116,169,170]. The surface of the CNTs can be modified by acid and potassium persulfate (KPS)

and the treatment with KPS showed very good thermal stability in a non-polar solvent

(Therminol-55) at very high temperature (250oC) [152]. Researchers have also showed that the

functionalization of the metal oxide nanoparticles (Al2O3) is possible even with polar or non

polar functionalized groups [89].

73
4. OVERALL SUMMARY OF SECTIONS 2 AND 3

To summarize, sections 2 shows that the performance of nanoparticles-laden fluid-based solar

collectors depend on various parameters such as height and length of the collector, incident

intensity, mass flow rate of the fluid in the collector. Furthermore, an elaborate review, related to

the comparative study between commercially available and nanoparticles-laden fluid-based solar

collector, has been provided. It highlights the benefits of nanoparticles-laden fluid-based solar

collector over commercially available solar collectors. In the nanoparticles-laden fluid-based

solar collectors, the optical properties of the fluid (base fluid and nanoparticles-laden fluid) also

play a critical role.

The overall review of section 3 (optical properties of nanoparticles-laden fluid) shows that the

optical signatures are dependent on various parameters such as, nanoparticle material, volume

fraction and shape. Different materials (metallic, graphite, oxides) of the nanoparticles can be

used for harnessing solar energy and each material has unique optical signature. Further the

optical properties are mainly dependent on the volume fraction of the nanoparticles, and the

overall absorption by the nanoparticles-laden fluid generally increases with increasing volume

fraction. The optical signatures can also be tuned by altering the shape (aspect ratio) of the

nanoparticles, for example by the use of nanorods, nanohorns and nanosheets.

Finally, the details of previous review studies related to nanoparticles-laden fluids have been

summarized in table 3. This table highlights the differences between the current review article

with the previous review articles.

74
Table 3: Summary of review papers related to optical properties and thermal performances of the direct absorption based solar

collector

Applications
Sr. Solar Collectors (SC)
Authors Year Summary
No. or
Optical Properties (OP)
1. Mahian et al. 2013 SC:  Various volume fractions should be tested to
[172] 1. Solar collectors and solar water heaters find an optimum volume fraction of the
2. Photovoltaic/thermal (PV/T) collector nanoparticles.
systems  Collector efficiencies should be tested with
3. Solar ponds different nanoparticle sizes.
4. Solar cells
5. Thermal energy storage
6. Solar stills
2. Phelan et al. 2013 SC:  Direct absorption solar collectors have good
[19] Nanoparticles-laden fluid-based potential in the harnessing of the solar
1. Low-temperature systems energy due to high solar energy absorption
2. Medium-temperature systems capability.
3. High-temperature systems
3. Hossain et al. 2014 OP:  The optical properties of metallic and non-
[181] 1. Rayleigh scattering approach metallic nanoparticles-laden fluid shows
2. Maxwell-Garnett effective medium improved attenuation of the light.
approach
3. Lambert-Beer approach
4. Mie and Gans approach
5. TL & I-scan method (Based on Fresnel
approximation)
6. Discrete dipole approximation (DDA
approach)
4. Suman et al. 2015 SC:  The performance of the solar collector can

75
 [182] Solar thermal collectors be enhanced by using extended surface, ribs,
corrugations, and with the addition of
nanoparticles in the working fluid.
5. Kasaeian et 2015 SC:  The reduction in the agglomeration leads to
al. [46] 1. Concentrating type high thermal efficiency of the solar
2. Non-concentrating type collector.
3. Evacuated solar collector
4. Photovoltaic thermal system
5. Thermal energy storage
6. Solar thermoelectric devices
7. Solar cells
6. Leong et al. 2015 Both SC and OP:  Various challenges like stability of
[109] 1. Rayleigh Scattering Approach nanoparticles, effective cost and use of
2. Maxwell-Garnett effective medium direct absorption based solar collector for
approach heating are still need to address.
3. Lambert-Beer approach
&
Solar thermal collectors
7. Verma and 2015 SC  The thermal efficiency of
Tiwari [45] Solar collectors photovoltaic/thermal (PV/T) can be
enhanced with the use of nanoparticles.

8. Ahmed 2016 SC:  More efforts are needed on the reliability of

Kadhim 1. Flat plate solar collector
Hussein [40] 2. Direct absorption solar collector
3. Parabolic trough solar collector
4. Wavy solar collector.
9. Muhammad 2016 SC:
et al. [15] Nanoparticles-laden fluid-based
1. Flat plate solar collector
2. Evacuated tube solar collector
3. Direct absorption solar collector
nanoparticles from environmental and
economic point of view.
 Future research should be in the
manufacturing of non-toxic and low cost
nanoparticles.
 Challenges like agglomeration of the
nanoparticles, instability of nanoparticles
and increase of viscosity of the nanoparticles
need to address.

76
10. Ahmad et 2017 OP:  Absorption, scattering and extinction
al.[59] Optical properties of nanoparticles-laden coefficients are dependent of volume
fluid fraction and the particle size.
1. Metallic
2. Non-metallic
3. CNTs
4. Graphene and Graphite

77
5. FUTURE DIRECTIONS AND CHALLENGES

A lot of research is going on the use of nanoparticles-laden fluid-based solar collector, especially to

explore various applications in which they can be used. The previously conducted studies reveal that these

collectors have good potential for harnessing of solar energy and hence can be used for various

applications. A few of those applications are discussed in this section.

5.1 Water desalination

The demand of fresh water is very high in the arid and semi-arid regions of the world. There is

good availability of sea water on the earth’s surface, but sea water is not drinkable. In order to

make the sea water drinkable, salt and water need to be separated and this separation require

energy which is usually provided by the burning of fossil fuels. To avoid the burning of fossil

fuels (which damages the environment), solar energy can be used for this purpose. There are

many thermal based technologies available for the desalination of the saline water, e.g. solar

stills, multi-stage flash desalination, multistage distillation, thermal vapor compression,

mechanical vapor compression, humidification and dehumidification [174]. For the operation of

these technologies thermal energy is required, which may be provided by solar energy. The solar

energy based desalination units are of two categories (a) direct collection system and (b) indirect

collection system. The basic difference in both the systems is the production and collection of the

pure water, like in the indirect collection system two units have been used, one for the power

generation and the other one is for the desalination. In these systems, for the power generation

nanoparticles-laden fluid-based solar collector can be used. Since the literature shows that the

thermal efficiency of these collectors is slightly higher than the commercially available surface-

78
based absorption systems, therefore higher GOR (Gained output ratio) can potentially be

achieved.

5.2 Vapor absorption refrigeration system

The concept of usage of nanoparticles-laden fluid-based solar collector for the vapor absorption

refrigeration is very new topic, hence relatively less literature is available on this topic. In past

many techniques like waste heat, fuel combustion etc. have been used for powering the vapor

absorption refrigeration systems [175]. The vapor absorption cooling system is a thermal driven

technique in which the heat is used to produce the refrigerant vapors through the heating of

binary fluid such as LiBr-H2O or NH3-H2O. In the solar-driven vapor absorption refrigeration

systems, the main components are absorber, condenser, evaporators and generator. In

conventional solar-driven vapor absorption refrigeration system the generator has two units. One

unit is for the heating of the working fluid (water, oil etc.) by using solar collector, whereas, the

second unit is the heat exchanger used for extracting heat from working fluid to the binary fluid.

By adding nanoparticles to the binary fluid, it may be possible that the mixture of binary fluid

and the nanoparticles will flow though the solar collector directly and get heated. This could

eliminate the heat exchanger unit in the generator (which is used in the conventional solar driven

vapor absorption refrigeration system). Gulati et al. [176] have performed numerical simulations

to show that amorphous carbon based nanoparticle-laden fluid could be used in such a system.

79
5.3 Energy efficient buildings

The direct absorption based solar thermal collector can be used to make the buildings energy

efficient (by heating or cooling the building using solar energy). The schematic for the heating of

the buildings with the direct absorption solar collector is shown in figure 30. In such a system,

the nanoparticles-laden fluid-based collector will be placed on the roof of the building, where the

solar collector’s working fluid (nanoparticles-laden fluid) will absorb the solar irradiation, and

get heated. Inside the building this heated fluid will transfer the heat to the room air through a

heat exchanger.

Building

Figure 30 Schematic for the heating of the buildings with the direct absorption solar collector

5.4 Solar-selective direct absorption based solar collector

Literature suggests most of the studies have been conducted on enhancing the solar absorption

and overlooked the radiative losses from the nanoparticles-laden fluid-based collectors. Due to

the radiative losses, the performance of the nanoparticles-laden fluid-based collectors degrades

and the aspect of making these collectors ‘solar-selective’ is yet to explore. The solar selective

80
design requires two conditions: (a) high absorptivity in the short wavelength (solar spectrum

region, λ < 2.5 µm) and (b) low emissivity at high wavelengths (typically in the mid infrared

region λ = 2.5 to 10 µm) [177][178]. When the temperature of the nanoparticles-laden fluid

increases, the radiative losses will occur and the radiative losses will be fourth power to the

absolute temperature of the fluid (i.e. T4). So, by controlling these losses, the performance of the

nanoparticles-laden fluid-based collectors will get improved. Bhalla et al.[179] have proposed

that the radiative losses from nanoparticles-laden fluid can be reduced with a layer of liquid

[silicone oil (Sigma Aldrich, viscosity 50 cST at 25oC)] above the nanoparticles laden fluid

[Amorphous carbon (Sigma Aldrich, < 50 nm particle size, granular) dispersed in water]. They

have proposed that the silicone oil layer will act like a thermal barrier to the radiative losses. The

mechanism of energy absorption and losses to the environment is as shown in figure 31.

(a) (b)
Incident Radiation Incident Radiation
Convection Radiative losses Convection

Radiative losses Silicone Oil Conduction

Nanoparticles-laden fluid Nanoparticles-laden fluid

Figure 31 Schematic of energy absorption and losses to the environment for (a) nanoparticles-
laden fluid-based solar collector without silicone oil and (b) nanoparticles-laden fluid-based solar
collector with silicone oil.

Figure 31 shows that, radiative and convective losses occur at the top surface of the

nanoparticles-laden fluid as shown in figure 31(a), which results in reduction of the overall

performance of the solar collector. In order to overcome these losses and make a nanofluid solar

selective, a stratified fluid (silicone oil) has been used in which a thin layer of silicone oil has

81
been placed on the top surface of the nanofluid as shown in figure 31(b). In this stratified fluid

case, when the nanofluid will get heated and will emit the radiations to the environment, the

layer of silicone oil will absorb the emitted infrared radiations. Due to which the silicone oil will

act as a barrier to the radiative losses from the nanofluid because of its thermo physical and

optical properties. In order to test the stratified fluid, they have conducted an experimental study

with nanoparticles-laden fluid-based solar collector without silicone oil and nanoparticles-laden

fluid-based solar collector with silicone oil. From the experimental study, they have concluded

that with a 3 mm layer of silicone oil on the nanoparticles-laden fluid, there has 5oC more

temperature rise with nanoparticles-laden fluid-based solar collector with silicone oil than

nanoparticles-laden fluid-based solar collector without silicone oil.

5.5 Challenges

The prospects for the use of nanoparticles-laden fluid based solar collectors for industrial and

domestic heating purposes are quite bright. However, before their widespread usage, there are

some challenges that need to be overcome. Some of these challenges are summarized as follows

[172]

1) Instability and agglomeration of nanoparticles.

2) High capital cost of nanoparticles-laden fluid-based systems.

3) Difficulties in the manufacturing of nanoparticles.

4) Erosion and corrosion of the components (such as pumps, pipes, bends).

5) Increased viscosity of the nanofluid (leads to high pumping power).

82
In summary, a lot of research has been carried out on the synthesis and use of the nanoparticles-

laden fluid, however some challenges still exist. The stability of the nanoparticles at high

temperature is one such issue. More work needs to be done to develop simple, scalable and

environmentally acceptable nanoparticles-laden fluids that can meet the specifications of various

applications [180].

CONCLUSION

 The review of various numerical and experimental studies shows that the thermal

performance of direct absorption based solar thermal collectors (DASC) is better than the

surface absorption based collectors (SAC).

 The performance of direct absorption based solar thermal collector (DASC) depends on

the volume fraction, material and shape of the nanoparticle.

 The volume/mass fraction of the nanoparticles play an important role in enhancing the

performance of the nanoparticles-laden fluid-based solar collectors because the

absorption as well as scattering of incident light depends on the amount of nanoparticles

have been added in the base fluid. It is not beneficial to use higher volume fraction of the

nanoparticle, rather at an optimum volume fraction the efficiency of the collector will be

high. Any subsequent increase in the nanoparticle volume fraction leads to a degradation

in the performance.

 The optical signatures are dependent of various parameters such as, nanoparticle material,

volume fraction and shape. Different materials (metallic, graphite, oxides) of the

nanoparticles can be used for the harnessing of solar energy and each material has unique

83
 optical signature. Further the optical properties are dependent on the volume fraction of

the nanoparticles, and the overall absorption by the nanoparticles-laden fluid generally

increases with increasing volume fraction. The optical signatures can also be tuned by

altering the shape (aspect ratio) of the nanoparticles, for example by the use of nanorods,

nanohorns and nanosheets.

 LSPR plays an important role in the metallic nanoparticles and it has been seen that the

resonance peak depends on the material and size of the nanoparticle. The core-shell

nanoparticles play a significant role in the enhancing the optical properties of the

nanoparticle-laden fluids and with these nanoparticles a wide range of the spectrum can

be covered. It has been seen that with binary nanoparticles the broad band range of the

spectrum can also be covered.

 It is beneficial to make the direct absorption based solar collectors as ‘solar-selective’. By

making them solar selective, the overall performance of the DASC get improved.

Enveloping the nanoparticles-laden fluid with a thin layer of silicone oil ensures high

performance of direct absorption based solar collector.

Overall, it is seen that the optical signatures of nanoparticle-laden fluids are largely influenced

by parameters such as, nanoparticle material, volume fraction and shape. Different materials

(metallic, graphite, oxides) of the nanoparticles can be used for the harnessing of solar energy

and each material has unique optical signature. Further the optical properties are dependent on

the volume fraction of the nanoparticles, and the overall absorption by the nanoparticles-laden

fluid generally increases with increasing volume fraction. The optical signatures can also be

tuned by altering the shape (aspect ratio) of the nanoparticles, for example by the use of

nanorods, nanohorns and nanosheets.

84
ACKNOWLEDGMENTS

The authors wish to acknowledge the support provided by School of Mechanical, Materials and

Energy Engineering at IIT Ropar and the support provided by Indo-US Science and Technology

Forum (IUSSTF).

CONFLICT OF INTEREST

None

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LIST OF FIGURES

Figure 1 (a) Annual consumption of non-renewable energy resources, and (b) annual carbon

dioxide emissions [3].

Figure 2 Various types of solar thermal collectors. (Concentration ratio has been abbreviated as

'C.R.').

Figure 3 (a) Reflectance of selective surface at cut off wavelength [17], (b) spectral transmittance

of glass (for one iron oxide content) within solar spectrum for normal incident radiation [17], (c)

working mechanism of solar thermal collector.

Figure 4 Schematic of nanoparticles-laden fluid-based solar thermal collector.

Figure 5 Schematic of direct absorption solar collector (figure reprinted with permission from

Lee et al. [73]).

Figure 6 Schematic of the experimental set up (figure reprinted with permission from Gorji et al.

[64]).

Figure 7 Temperature curve of Cu-H2O nanoparticle-laden fluids with different pH values, Cu:

50nm, 0.1 wt%, Ta is the ambient air temperature, (figure reprinted with permission from He et

al. [76]).

Figure 8 Parametric study of receiver efficiency with mean fluid temperature for variable (a)

optical thickness, (b) solar concentration, and (c) nanoparticle-laden fluid height (figure

reprinted with permission from Lenert et al. [84]).

108
Figure 9 Schematic of the experimental set up (figure reprinted with permission from Khullar et

al. [86]).

Figure 10 Schematic diagram of the solar concentrator experimental test rig (figure reprinted

with permission from Muraleedharan et al. [89]).

Figure 11 Comparison of water (black back) with different nanoparticle-laden fluid at different

volume fractions (figure reprinted with permission from Otanicar et al. [74]).

Figure 12 Transmission spectrum of four base fluids (a) water (b) ethylene glycol (c) propylene

glycol and (d) Therminol VP-1 (figure reprinted with permission from Otanicar et al. [110]).

Figure 13 Absorption mechanism of the incident light with volume fraction

Figure 14 Modeled and experimental extinction coefficient for several concentrations of aqueous

graphite nanoparticles-laden fluids (figure reprinted with permission from Taylor et al. [113]).

Figure 15 Effect of nanoparticle volume fraction on (a) absorption coefficient (b) scattering

coefficient and (c) extinction coefficient (figure reprinted with permission from Saidur et al.

[114]).

Figure 16 (a) Transmittance and (b) extinction coefficient for various volume fractions of f-CNT

(figure reprinted with permission from Karami et al. [115]).

Figure 17 (a) Extinction coefficients of MWCNT nanoparticles-laden fluid for (1) Water, (2)

ethylene glycol, (3) propylene glycol and (4) Therminol VP-1and (b) Stored energy fraction as a

109
function of penetration distance for various concentrations of MWCNTs for (1) Water, (2)

ethylene glycol, (3) propylene glycol and (4) Therminol VP-1 (figure reprinted with permission

from Hordy et al. [116]).

Figure 18 (a) Transmittance spectra for suspension of SWCNH in ethylene glycol as a function

of the nanoparticle concentration, (b) Comparison of energy absorption capability of SWCNH

with carbon black suspension at same nanoparticles concentration (figure reprinted with

permission from Sani et al. [118]).

Figure 19 Comparison of extinction coefficient of different nanoparticle-laden fluids at different

volume fractions (figure reprinted with permission from Menbari et al. [123]).

Figure 20 (a) Transmittance spectra of (1) CuO/water, (2) ATO/water, (3) CuO-ATO/water with

total volume fraction of 0.1% and (4) CuO-ATO/water with different volume fractions and (b)

dependence of solar weighted absorption fraction on the volume fraction and penetration depth

for (1) CuO/water, (2) ATO/water, (3) CuO-ATO/water with total volume fraction of 0.1% and

(4) CuO-ATO/water with different volume fractions (figure reprinted with permission from Chen

et al. [124]).

Figure 21 UV-Vis absorption spectra of gold nanoparticles dispersed in water (figure reprinted

with permission from Link and El-Sayed [136] Copyright (1999) American Chemical Society).

Figure 22 Absorption coefficient verses wavelength for Ni nanoparticles and base fluid (figure

reprinted with permission from Kameya and Hanamura [137]).

110
Figure 23 (a) The absorbance spectrum of silver nanoparticle-laden fluids at different mass

concentrations (figure reprinted with permission from Chen et al. [95]) and (b) Experimental

absorbance spectra of Au, Ag nanoparticle-laden fluids and their blended mixture comparing

with solar radiation spectral intensity (figure reprinted with permission from Chen et al. [140]).

Figure 24 (a) Absorption spectra of Au nanoparticles at different volume fractions and (b)

relationship between the peak absorbance and nanoparticles volume fraction (figure reprinted

with permission from Chen et al. [141]).

Figure 25 Different core/shell nanoparticles (a) Spherical core/shell nanoparticles (b) hexagonal

core/shell nanoparticles (c) multiple small core materials coated by single shell material (d)

nanomatryushka material (e) movable core within hollow shell material (figure reprinted with

permission from Chaudhuri et al. [143] Copyright (2012) American Chemical Society).

Figure 26 (a) Absorption efficiency of TiO2/Ag (R1/R2 = 20/30) nanoparticle and TiO2 (R =

30nm) nanoparticle (b) absorption efficiency of TiO2/Ag nanoparticles with different core sizes

(figure reprinted with permission from Xuan et al. [94] Copyright (2014) Royal Society of

Chemistry).

Figure 27 Transmittance verses wavelength for different types of nanoparticles having same

volume fraction 10 ppm (figure reprinted with permission from Zhang et al. [126]).

Figure 28 Spatial distribution of stored energy along the light propagation direction (figure

reprinted with permission from Sani et al. [147] Copyright (2010) The Optical Society).

111
Figure 29(a) Schematic of (1) nanoellipsoid (2) nanorod and (3) nanosheet and (b) absorption

efficiency verses wavelength for (1) nanoellipsoid and (2) nanorods, at different aspect ratios

(figure reprinted with permission from Du et al. [166]).

Figure 30 Schematic for the heating of the buildings with the direct absorption solar collector

Figure 31 Schematic of energy absorption and losses to the environment for (a) nanoparticles-

laden fluid-based solar collector without silicone oil and (b) nanoparticles-laden fluid-based solar

collector with silicone oil.

112
 LIST OF TABLES

Table 1 Detailed summary of the nanoparticle-laden fluid-based solar collectors.

Table 2 Absorption mechanism of various materials [127].

Table 3: Summary of review papers related to optical properties and thermal performances of the

direct absorption based solar collector

113

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