Accepted Manuscript

Title: Performance investigation of CuO-Paraffin Wax

nanocomposite in Solar water heater during Night

Authors: Swaroop Kumar Mandal, Samarjeet Kumar,

Purushottam Kumar Singh, Santosh Kumar Mishra, Harish
Bishwakarma, Naresh P. Choudhry, Rajen Kumar Nayak,
Alok Kumar Das

PII: S0040-6031(18)30517-3
DOI: https://doi.org/10.1016/j.tca.2018.11.003
Reference: TCA 78139

To appear in: Thermochimica Acta

Received date: 12 July 2018

Revised date: 12 October 2018
Accepted date: 6 November 2018

Please cite this article as: Mandal SK, Kumar S, Singh PK, Mishra SK, Bishwakarma
H, Choudhry NP, Nayak RK, Das AK, Performance investigation of CuO-Paraffin
Wax nanocomposite in Solar water heater during Night, Thermochimica Acta (2018),
https://doi.org/10.1016/j.tca.2018.11.003

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Performance investigation of CuO-Paraffin Wax nanocomposite in Solar
water heater during Night

Swaroop Kumar Mandala, Samarjeet Kumara, Purushottam Kumar Singh*a, Santosh Kumar
Mishrab, Harish Bishwakarmab, Naresh P. Choudhrya, Rajen Kumar Nayaka, Alok Kumar Dasb
a
Department of Mechanical Engineering, BIT Sindri-828123, India
b
Department of Mechanical Engineering, Indian Institute of Technology(ISM) Dhanbad-826004, India

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*
Corresponding author Email: purushottam.singh07@gmail.com

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Highlights

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 Performance investigation of the presence of nano cupric oxide in Paraffin wax in
solar water heating during night.
 Characterization technique is done to show to the effect of nano cupric oxide in base


paraffin.
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Heat storing behaviour of base PCMs and CuO-PCM nanocomposite is calculated.
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 Heat transfer and maximum outlet temperature obtained is determined and made a
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contrast.
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Abstract

To overcome the limitation of power and energy, various strategies have been developed which focuses on the utilisation of
the renewable sources of energy. One of the techniques is to harness the solar energy in solar water heater for heating
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purpose. To enhance the effect and maximize utilization of solar energy as well as availability of warm water over night,
phase changing materials (paraffin wax) are used as a thermal energy reservoir. But the problem linked with Paraffin is that
it has low thermal conductivity and so to enhance it, nanoparticles are widely used. In this paper, the behaviour of nano CuO
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with varying concentration of paraffin has been examined and its effect in its performance has been studied. As the variation
in concentration of nano CuO particles in CuO-PCM nanocomposite increases, temperature of CuO-PCM composite, outlet
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temperature of water, and heat transfer decreases in solar water heater.

Keywords: PCMs; Paraffin wax; CuO-PCMs nanocomposite; FESEM

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1. Introduction

Nowadays, energy is the prime necessity for daily activities. Resources are limited but the requirement of energy is
paramount. Solar water heating [1-3] is one of the most attractive and environmental friendly technique to use solar
energy for heating requirements. In this regard, many researchers performed their work extensively on the use of solar
energy and its advancement. They used solar energy for heating purposes. For enhancement of heating effect, phase
changing materials (PCMs) are widely used as a thermal energy reservoir (TER) [4-6].Various PCMs used are
paraffin wax, sodium acetate, salt-hydrated PCMs, mixture of palmitic and stearic acid etc. Experimental study on
melting and solidification phase of PCMs using heat pipes was performed to examine its behaviour [7, 8]. Paraffin in
consideration as TER absorb thermal energy as heat during charging process over the day when solar energy is
available in sufficient amount and release the thermal energy overnight called discharging process [9,10]. During the
day time, when solar radiation is available, Paraffin wax absorbs the heat and stores it as a sensible and latent heat. In
this way the solar intensity increases and hence results in the increment in temperature and heat absorption of paraffin
wax. At a certain temperature, paraffin wax starts melting and changes its phase from solid to liquid absorbing more
heat. This latent heat was used to warm the water over night as paraffin wax undergoes discharging process by losing
heat and that heat was taken by water and its get heated up. Paraffin behaves isothermally with the atmosphere. The
utilisations of nanoparticles are meant to enhance the overall performance [11, 12]. The application of nanoparticles

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improves the heat transfer rate and also enhances the thermal conductivity [13].Various nanoparticles have been used
till now like aluminium oxide[14, 15], titanium oxides[16], copper [17] etc. There are several methods employed for

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synthesise of nanoparticles such as chemical reduction [18], co-precipitation [19], electron beam irradiation [20], sol–
gel processing [21, 22], microwave hydrothermal methods [23, 24], thermal reduction [25], solution combustion [26],

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reverse micelles [27], arc discharge process [28], flame spray pyrolysis [29], vacuum vapour deposition [30] and laser

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ablation [31]. After an extensive study of a large number of research papers, it has been observed that there are very
few reports available in literature related to nanoparticle synthesis through electrochemical spark erosion process.
Additionally, none of the aforementioned studies about parametrical effect of nano CuO for determining the

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performance and behaviour of PCMs is reported and there is no conclusive information available highlighting the
effect of gap between the absorber plate and the glazing in solar water heater. However in the further extension of
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their work, the behaviour of the nanodoped PCM in solar water heater during night has been considered in the present
work. In addition to this, a novel (electrochemical discharge) method has been employed for the generation of CuO
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nanoparticles. Notwithstanding all these methods currently applied in the preparation of CuO nanoparticles,
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electrochemical discharge method synthesis stands out on account of its versatility in strengthening morphological and
crystal structure of the generated nanoparticles. Its eco-friendly nature is another factor making it the most desirable
synthesis method among all the generation processes.
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2. Experimentation
2.1 Materials and Method section.
In this work, Cupric oxide (CuO) nanoparticles have been synthesized through electrochemical discharge machining
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(ECDM) process as shown in Fig.1. For this copper wire (1mm diameter) is used as cathode and copper sheet (50
mm× 50 mm× 0.3 mm) is considered as anode. Both the electrodes are dipped into the KOH alkaline solution which
acts as an electrolyte. KOH alkaline solution (0.5M concentration) have been prepared by using small pellets of
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potassium hydroxide dipped into the distilled water. For cleaning the electrodes acetone is used. The copper wire is
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made as positive terminal and the copper sheet is connected to the negative terminal. A transistor- based pulse
generator is used during the study which is capable of generating 150V output pulses across a resistive load at a pulse
frequency of 100Hz-10 kHz. ECDM works on the principle of erosive action under which high potential difference is
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maintained between the electrodes. By the application of threshold voltage (85V) between the electrodes using a
direct current supply, arc discharge takes place. Due to the formation of arc, heat is liberated above the melting
temperature of the copper and results in the formation of molten metal. This molten copper gets deposited in the
electrolyte solution. Nanoparticle-mixed electrolyte is centrifuged at 10000 rpm till the droplets of molten copper
metal settled down at the bottom of the test tube in the form of black precipitates. Then, the precipitates are washed
several times with distilled water and ethyl alcohol. Lastly, the precipitates are dehydrated in oven at about 80oC for
24 hours. In this research, magnetic stirrer is used to prevent agglomeration of nanoparticles which is rotated at 220
rpm for better results [32].

Then, the nano CuO-PCM composite has been generated using gravity die casting process. As the paraffin gets melted
completely, nano CuO has been introduced into it through a channel provided and stirred it for proper mixing and then
it is taken out for use. The physical properties of paraffin wax are provided in table 1 [33].

Fig.2 shows the block diagram representation of the experimental set-up. The setup consists of Aluminium absorber
plate, Copper pipe for flow of water and glazing. Paraffin are filled in the peripheral region of the copper pipes.

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Through natural process, water flows through the set up. Six temperature indicators are used to determine the
temperature at various locations.

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3. Results and discussion

3.1 Morphological analysis

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The physical structure of the produced nano powder, paraffin wax and nano CuO-PCM composite has been analyzed
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by FE-SEM technique developed by Zeiss apparatus having specifications (model: Supra 55, Germany). For the
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examination of the sample an operating voltage and current of 5 kV and 20nA have been used. Fig 3 shows FESEM
image of Nano CuO, base paraffin and Nano CuO-PCM composite. Fig 3 (a) indicates clearly that the nano CuO
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synthesised through ECDM process has got flower shape and its size in nanometer. Fig 3 (c) shows nano CuO-PCM
composite fine grains and grain boundaries as compared to base paraffin in Fig.3 (b). Base paraffin has granular shape
as observed in Fig.3 (b) whereas fine shape has been depicted in Fig. 3 (c).Fig. 3 (d) shows the EDAX result of CuO
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powder. Based on it, it is concluded that the sample consists of Oxygen atom and Copper in the form of CuO. In this
study, during FESEM characterization, carbon tape is used for holding the sample. So, the possibility is that it may be
this carbon tape or a portion of it whose carbon content is shown in the EDX. FE-SEM image of CuO-PCM
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nanocomposite with varying percentage of CuO is shown in Fig.4. Very fine grain structures are observed in case of
higher concentration of nano CuO shown in Fig. 4 (d) as compared to lower concentration.
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3.2 Effect of nano CuO PCM composite

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Fig.5 and 6show the temperature of energy storage material and the outlet water decreased in case of nano CuO-PCM
composite as compared to base paraffin. As the concentration of CuO nanoparticles increases, both the outlet
temperature as well as the temperature of energy storage materials decreases. Since the presence of nano CuO lowers
the melting and solidification temperature of paraffin and consequently leading to the decrement in the sensible heat
and latent heat respectively [34, 35]. Fig.7 shows that the heat transfer between water and energy storage materials is
lower in case of nano CuO-PCM as compared to PCM, due to the following reasons:
(i) Due to the presence of nanoparticle in the PCM, the melting and solidification temperature of the PCM gets
decreased. Nanoparticle behaves as a nucleation agent and leading to the decrement in the both (melting and
solidification) temperatures. Hence, it results in the decrement of the both the sensible and the latent heats respectively
[36]. Lower the sensible and latent heats mean lower the heat absorbing capabilities. Hence the composite starts
storing less thermal heat and accordingly the supply of heat in overnight is observed to be lower.

(ii) The presence of nanoparticle enhances the thermal conductivity of the paraffin upto a great extent. Due to high
thermal conductivity, thermal energy is being transferred at a much faster rate rather than storing in it during day
period. The presence of nano CuO decelerates the melting and freezing rates, energy storage capability and the heat
retaining capacity of composite as compared to that of pure wax. Additionally, the heat transfer coefficient during

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solidification gets increased as less thermal energy is being stored by CuO-PCM nano composite during day time and

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consequently they are not able to provide thermal energy overnight as compared to base paraffin wax. The presence of
nano particle thus permits transfer the more heat to the heat exchanger rather than being stored by the paraffin wax

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[37, 38].

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(iii)The presence of nanoparticles reduces the thermal resistance and increases the heat removal capacity during
charging process (day time) [39]. As a result, PCM used as thermal energy reservoir is unable to store energy within
itself and hence discharges the maximum thermal energy to the heat exchanger instead of holding it. Because of low

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absorption of heat during charging process, less energy is available during discharging process (at night).
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4. Conclusions
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The presence of nano CuO results in decrease in the outlet temperature of water and lowers the heat absorbing
capacity of paraffin wax for a longer time. Presence of Nano CuO enhances the heat transfer rate by increasing the
conductivity of paraffin. As nano CuO have large volume/surface area along with heat transfer area, which results in
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less absorption of thermal energy by paraffin wax, as it transfers the maximum possible thermal energy to the water
instead of absorbing it. Maximum thermal energy, 57.7 0C has been stored by base paraffin in the gap of 2 cm
between the absorber plate and the glazing.The heat transfer also decreased because of less heat capacity of CuO-
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PCM nanocomposite over base paraffin. By varying the concentration of nano CuO, the heat transfer, outlet
temperature and the paraffin temperature decreases. The grain structure also gets refined and become finer as the
percentage of nano CuO is increased as observed in FE-SEM image. Hence, the presence of nano CuO is not
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effective during night.

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DATA ACQUISITION
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MOTION CONTROL
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Tank with electrolyte
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Work peice

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Fig.1 Block Diagram of Electrochemical discharge set-up.

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Fig. 2 Block diagram of the experimental set up
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Fig.3 FE-SEM images of (a) CuO nanoparticles, (b) Paraffin wax, (c) nano CuO-Paraffin wax composite and (d) EDAX analysis of CuO
nano powder
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Fig 4. FE-SEM images of nano CuO-Paraffin wax composite (a) 0.25 wt. % nano CuO, (b) 0.50 wt. % nano CuO, (c) 075 wt. % nano CuO
and (d) 1.00 wt.% nano CuO.
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 (a) PCM
80 (b) 80
0.25 % Nano CuO doped PCM PCM
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0.50 % Nano CuO doped PCM 70 0.25 % Nano CuO doped PCM
0.75 % Nano CuO doped PCM 0.50 % Nano CuO doped PCM
60 1.00 % Nano CuO doped PCM 60 0.75 % Nano CuO doped PCM
Temperature (oC)

1.00 % Nano CuO doped PCM

Temperature (oC)
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Time (hr) Time (hr)

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Fig.5 Variation of temperature of paraffin wax with time under (a) 2cm gap, (b) 3 cm gap and (c) 4 cm gap
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(a) 46 (b) 0.25 % Nano CuO doped PCM
0.25 % Nano CuO doped PCM
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0.50 % Nano CuO doped PCM 0.50 % Nano CuO doped PCM
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0.75 % Nano CuO doped PCM 0.75 % Nano CuO doped PCM

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Outlet Temperature (oC)

Outlet Temperature (oC)

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SC
32 34

30 32

18:16 18:36 18:56 19:16 19:36 19:56 20:16 20:36 20:56 21:16 18:16 18:36 18:56 19:16 19:36 19:56 20:16 20:36 20:56 21:16
Time (hr)

U Time (hr)
N
PCM
A
0.25 % Nano CuO doped PCM
48 (c) 0.50 % Nano CuO doped PCM
M

46 0.75 % Nano CuO doped PCM

1.00 % NanoCuO doped PCM
44
Outlet Temperature (oC)

42
ED

40

38

36

34
PT

32

30
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E

Time (hr)
CC

Fig. 6 Variation of outlet temperature of water with time under (a) 2 cm gap, (b) 3 cm gap and (c) 4 cm gap
A
 (a)
PCM (b)
50
0.25 % Nano CuO doped PCM 55 PCM
0.50 % Nano CuO doped PCM
45 50 0.25 % Nano CuO doped PCM
0.75 % Nano CuO doped PCM
0.50 % Nano CuO doped PCM
1.00 % NanoCuO doped PCM 45
40 0.75 % Nano CuO doped PCM

Heat Transfer (KJ/min)

Heat Transfer (KJ/min)

40
35
1.00 % NanoCuO doped PCM
35
30
30
25
25

20 20

T
15 15

IP
10 10

5
5
18:16 18:36 18:56 19:16 19:36 19:56 20:16 20:36 20:56 21:16
18:16 18:36 18:56 19:16 19:36 19:56 20:16 20:36 20:56 21:16

R
Time (hr)
Time (hr)

SC
(c) PCM
80
0.25 % Nano CuO doped PCM
75
70
65
60
0.50 % Nano CuO doped PCM
0.75 % Nano CuO doped PCM
1.00 % NanoCuO doped PCM U
N
Heat Transfer (KJ/min)

55
50
45
A
40
35
M

30
25
20
15
10
ED

18:16 18:36 18:56 19:16 19:36 19:56 20:16 20:36 20:56 21:16

Time (hr)

Fig. 7 Variation of Heat transfer(KJ/min) with time under (a) 2cm gap, (b) 3 cm gap and (c) 4 cm gap
E PT
CC
A
Table 1: Physical properties of Paraffin wax

Melting point 56.06° C

Density of the PCM 775 kg/m3
(liquid Phase)
Density of the PCM 833.60 kg/m3

T
(solid phase )
Specific heat of solid 2.565 J/g °C

IP
(<30 °C)
Specific heat of liquid 2.439 J/g °C
(>65 °C)

R
Flash Point 199 °C

SC
U
N
A
M
ED
E PT
CC
A