Accepted Manuscript

Thermo-physical properties of Cu-Zn-Al LDH nanofluid and its application in

spray cooling

Samarshi Chakraborty, Ishita Sarkar, Avinash Ashok, Iman Sengupta, Surjya

K. Pal, Sudipto Chakraborty

PII: S1359-4311(18)31500-X
DOI: https://doi.org/10.1016/j.applthermaleng.2018.05.114
Reference: ATE 12253

To appear in: Applied Thermal Engineering

Received Date: 8 March 2018

Revised Date: 27 May 2018
Accepted Date: 28 May 2018

Please cite this article as: S. Chakraborty, I. Sarkar, A. Ashok, I. Sengupta, S.K. Pal, S. Chakraborty, Thermo-
physical properties of Cu-Zn-Al LDH nanofluid and its application in spray cooling, Applied Thermal
Engineering (2018), doi: https://doi.org/10.1016/j.applthermaleng.2018.05.114

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Thermo-physical properties of Cu-Zn-Al LDH nanofluid and its application in

spray cooling

Samarshi Chakraborty a, Ishita Sarkar a, Avinash Ashok a, Iman Senguptaa, Surjya K. Pal
b
, Sudipto Chakraborty a*
a
Department of Chemical Engineering, Indian Institute of Technology Kharagpur, India.
b
Department of Mechanical Engineering, Indian Institute of Technology Kharagpur, India.

Abstract:

The current experimental investigation deals with the thermo-physical attributes of Cu-Zn-Al

LDH nanofluid its use in high temperature steel cooling. Here, authors used three metals

(Copper, Aluminium, and Zinc) having high thermal conductivity to synthesize a brand new

nanofluid for heat transfer application. Authors have achieved moderate increment (13.9%) in

thermal conductivity value compared to water. A section of this work also aims to maximize the

cooling rate which aids in improving mechanical properties of quenched steel plate. The

maximum cooling rate of 158.4oC/sec was attained at 160 ppm of nanofluid concentration which

is 18.5% higher than that attained by water. In addition to enhanced thermal conductivity,

nanoparticle deposition on the cooling surface also contributes to the heat transfer enhancement

by providing additional nucleation site. It is also to be considered that above an optimum

nanofluid concentration both thermal conductivity and cooling rate values decline. Such trend is

owed to several factors namely poor suspension stability, high agglomeration tendency and

formation of nanoparticle layer on steel surface which prevents contact between coolant and

surface.

Keywords: Cu-Zn-Al LDH, nanofluid, spray cooling, thermal conductivity, cooling rate,

average heat flux.

1
* Author to whom all the correspondence should be addressed
Sudipto Chakraborty,
Chemical Engineering Department, IIT Kharagpur,
Kharagpur-721302, West Bengal, India

Phone (office): +91 - 3222 -283942

Email: sc@che.iitkgp.ernet.in

1. Introduction:

In the past few decades with continuous growth in nanotechnology, synthesis of nanoparticle has

become a reality. In early 1990, an American scientist named Stephan U.S. Choi [1]first used

nanoparticle suspension as a coolant. The concept of particle suspension in base fluid is around

for an even longer time. However, in spite of giving higher thermal conductivity value than the

base fluid, the highly unstable nature of millimeter and micron sized particle suspension made it

undesired for heat transfer application. Poor stability of micron sized suspension gives rise to

higher sedimentation, higher erosion in heat transfer equipment, high pressure drop, increased

pipeline clogging, higher viscosity value and higher pumping cost etc. Therefore, there was a

need for a stable particle suspension which would also have a higher thermal conductivity value.

In order to achieve stable particle suspension, scientists have used nanoparticle and suspended it

in a basefluid. Basefluid having suspended nanoparticle is termed as nanofluid [1]. The

beneficial attributes of nanofluids over micron sized particle suspension has been discussed by

Das et al. and Li et al. [2, 3] in details. Due to several advantageous attributes, nanofluid has

been used for wide range of applications starting from the heat exchanger, electronic chips,

microchannel, automobile engine, refrigerators, chillers, and nuclear reactor etc. Among all the

attributes of nanofluids, high thermal conductivity value makes it research worthy and

specifically crucial for the current study.

2
The present study partially focuses on the high temperature steel plate cooling using nanofluid

aided pressurized spray cooling scheme. In steel manufacturing process, run out table plays a

decisive part in creating desired microstructure which is responsible for improved mechanical

properties (tensile strength). Manufacturing of high strength steel is also possible via a metal

alloying technique which is much expensive as compared to the cheaper alternative named ultra-

fast cooling[4]. Attainment of ultrafast cooling in the run out table (ROT) (Temperature range

900-600oC)is critical for obtaining desired microstructure (combination of austenite and

martensite, bainite and pearlite phase, etc.)[5]. When the product between cooling rate and steel

plate thickness goes above 800, and then ultrafast cooling is achieved. According to Zhang et

al.[6] by using conventional laminar jet cooling and conventional coolant (such as water)

attaining such a high cooling rate is difficult. The cooling rate achieved during jet or spray

cooling process (under ROT condition) is not only dependent on experimental flow parameters

and fluid properties but also on plate thickness and plate composition. To nullify the effect of

plate thickness, authors have used 6 mm thick steel plate for all the spray cooling experiments. In

order to attain desired cooling rate, both high mass flux spray cooling and advanced coolant are

needed. Nanofluid provides a suitable and more efficient alternative to any conventional coolant

due to its enhanced thermal properties. In this study, authors are focused on the high temperature

applications of nanofluid especially thermal treatment in the steel industry. Nanofluid based

cooling of high temperature steel plate is a relatively unexplored domain of research.

Chakraborty et al. [7] explored the potential of TiO2-water nanofluid as a coolant to cool down

high temperature steel plate by using jet impingement technique and found improvement in

cooling rate. Mitra et al.[8] also conducted laminar jet impingement cooling of hot steel plate by

using water-TiO2 and water-MWCNT nanofluids and found substantial augmentation in heat

3
transfer rates. Water based cooper[9]and alumina[10] nanofluids were also used by researchers

along with an air-atomized spray to cool down high temperature steel plate(>900oC).

Implementation of nanofluid for high temperature metal quenching are motivated by several

factors such as, 1) increase thermal conductivity of coolant, 2) better suspension stability with

limited increase in pumping cost and 3) suspended nanoparticle deposits on the heat transfer

surface and aids in surface roughness increase, it provides additional nucleation site and also

restricts vapor film formation which can hamper the heat transfer. The possible roadblock for

large scale industrial application of nanofluid is its possible environmental impact on aquatic life,

human body as well as other environmental impact. In one of the recent works, authors have

invented a new breed of nanofluid for heat transfer application which is layered double

hydroxide based nanofluid[11]. Layered double hydroxide (LDH) is a layered crystalline

material (anionic clay) which has positively charged metal hydroxide sheets compensated by

anionic counter ions in the gallery space. LDH is represented by the following chemical formula:

[M2+1-x M3+x(OH)2]x+(Am-)x/m x, yH2O, where divalent/bivalent , trivalent are represented by M2+

and M3+ ,respectively[12].Its dynamic chemical formula enables researchers to add multiple

metal ions in a single compound. LDH is naturally occurring clay minerals, made out of mostly

biocompatible materials[13]. LDH has found application in several field human life including

medical application, water treatment process and biological application (ATP, DNA, enzyme

intercalation with LDH to avoid degradation). Mg-Al LDH has found application as an antacid

and anti-pepsin agent[14]. Mg-Al LDH, Zn-Al LDH, Li-Al LDH and Fe-Al LDH has also been

used as a drug delivery agent[15].Above studies confirm the bio-compatibility nature of LDH

nanoparticle. Water-Cu-Al LDH[16] and water-Zn-Al LDH[17] nanofluids have already been

4
used as a coolant for jet quenching hot steel plate which gave significant augmentation heat

transfer rate compared to water.

In the current study, authors have combined three highly thermally conducting metal ions (Cu2+,

Zn2+, and Al3+) to form a novel nanofluid which is Cu-Zn-Al LDH nanofluid. No work reported

in the open literature has combined thermal attributes of three metal ions into a single nanofluid.

Present work centers on the consequence of Cu-Zn-Al LDH nanofluid loading on thermo-

physical properties as well as its heat transfer application. Implementation of this brand new

nanofluid for high temperature metal quenching application makes the present study worthy of

investigation.

2. Preparation of Cu-Zn-Al LDH nanofluid:

In the present study, Cu-Zn-Al LDH nanofluid was synthesized by co-precipitation methods

which uses three metal nitrate salts namely copper (Cu(NO3)2.3H2O), zinc (Zn (NO3)2·6H2O )

and aluminium nitrate(Al (NO3)3·9H2O) and sodium nitrate (NaNO3) in the molar ratio of 4

(Cu2+):1 (Zn+):1 (Al3+):2 (Na+). NaNO3 is used to increase NO3 - ion concentration in the solution

and to prevent CO2 intercalation. The aforementioned nitrate salts were dissolved in water and 2

M NaOH was added to the solution until the pH of the solution reaches 10.7. NaOH works as a

precipitating agent. The synthesis scheme used in this study was adopted from our earlier work

on Cu-Al LDH nanofluid[11]. Post titration, the solution is stirred for 16 hrs and the solution is

filtered to bring down the filtrate pH level up to 7. The precipitate is then used to prepare the

final nanofluid solution by further stirring it for 12 hrs and followed by 30 minutes of sonication.

Nanofluid concentrations were varied between 40 ppm to 240 ppm, to verify its impact on the

5
heat transfer properties. Nanofluid synthesis scheme used for this current study has been depicted

in Fig. 1.

Fig. 1.Graphical representation of Cu-Zn-Al LDH nanofluid synthesis method

3. Characterization of Cu-Zn-Al LDH nanoparticle and nanofluid:

Characterization of Cu-Zn-Al LDH nanoparticle includes X-Ray Diffraction (XRD), Field

Emission Scanning Electron Microscope (FESEM), and Transmission Electron Microscope

(TEM) analyses. XRD analysis of Cu-Zn-Al LDH nanoparticle was executed by Philips made X-

Ray Diffractometer (PW-3050/60, Netherlands) having a Cu Kα radiation wavelength, λ of

1.5406 Å. XRD analysis was conducted over a diffraction angle(2θ) range of 8o-70ohaving scan

speed of 0.5 sec-1and step increment of 0.05o. FESEM analysis (JEOL JSM 7610F, USA) was

performed for both particle morphology and nanoparticle deposition study. Energy dispersive

spectroscopy analysis was conducted for the elemental study. For particle size analysis, an FEI

6
made analytical TEM (TECNAI G2 20S Twin, USA) was used. The thermo-physical properties

of nanofluid include three main properties which are thermal conductivity, surface tension, and

viscosity. The thermal conductivity of all the samples was evaluated by using KD2 thermal

conductivity meter manufactured by Decagon Device (USA) which works on the principle of

transient needle probe method. The surface tension of nanofluids was measured by Jencon

(India) made du Noüy ring surface tensiometer. Static contact angle was measured by using a

goniometer (Rame-Hart 190-F2, USA). For viscosity measurement, authors have used a cone

and plate rheometer (Physica MCR 301, Austria). Viscosities of all the nanofluid samples were

measured at a fixed shear rate of 100 sec -1. All the thermo-physical properties were measured at

30oC.In order to sustain the temperature during thermal conductivity and surface tension

measurement, a temperature controlled water bath was used. However, in case of viscosity

measurement, liquid sample was kept for at least 5 minutes on a temperature controlled

rheometer plate (plate temperature: 30oC) prior to all the experiments. Stability of nanofluid is

one of the most crucial factors to be considered for industrial application. The stability of the

nanofluid was evaluated by taking sedimentation photograph (Nikon D7100 camera, Japan) and

zeta potential measurement of nanofluid samples at different time interval. Surface roughness

was measured for both prior and post nanoparticle deposition by using Mitutoyo surface

roughness tester (SJ-201 P/M, Japan).

3.1. XRD analysis

XRD patterns of nanoparticle provide its unique characteristics feature, the degree of

crystallinity, basal spacing, and crystal size. XRD analyses of Cu-Zn-Al LDH nanoparticles were

matched with JCPDS file (37-0629). JCPDS file contains characteristics peaks corresponding to

known Cu-Zn-Al LDH samples. The XRD patterns of Cu-Zn-Al LDH nanoparticle consists of

7
several distinctive peaks in the 2θ angle range of 8-70o (Fig. 2). From JCPDS file details, it was

found that nanoparticle is rhombohedral in character and its lattice is rhombo-centred. LDH is a

layered crystalline material which is made of metal hydroxide layers and anionic counter ions.

Nanoparticle sample was analyzed to determine basal spacing (Braggs Law) and crystal size

(Scherrer Law) of the nanoparticle[11, 18]. The basal spacing and crystal size data corresponding

to each characteristics peak are reported in Table 1.

Fig. 2. XRD pattern of Cu-Zn-Al LDH nanoparticle with varying diffraction angle

8
Table 1.Basal spacing and crystal size chart of Cu-Zn-Al LDH nanoparticleat different

diffracion angles.

Nanoparticle d 2θo Basal spacing, Crystal size, JCPDS file

(h k l) d (nm) L (nm) No

Cu-Zn-Al (0 0 3) 11.72 0.75 37 037-0629

LDH (0 0 6) 23.64 0.38 18

(1 0 1) 33.81 0.26 24

(0 1 2) 34.71 0.26 43

(1 0 7) 44.83 0.20 95

(1 0 10) 53.08 0.17 99

(1 1 0) 60.48 0.15 126

(1 1 3) 61.57 0.15 11

(1 1 6) 65.71 0.14 105

3.2. Morphology and elemental analysis

FESEM analysis was carried out on Cu-Zn-Al LDH nanoparticle which is layered crystalline

material. High magnification image of Cu-Zn-Al LDH nanoparticle clearly shows its layered

morphology. It also shows that metal hydroxide sheets (flakes) are stacked upon each other and

its thickness is well below 100 nm. It confirms that at least one of the particle dimensions is in

the nanometer range (See Fig. 3 (a)). This observation can be further varied in TEM analysis.

The layered morphology of layered double hydroxide has also been observed by other scientists

[19-21]. Nanoparticles were also tested for elemental analysis by using Energy dispersive

9
spectroscopy (EDS). EDS analysis established the existence Cu, Zn, Al, O, and N in the

nanoparticle.

Fig. 3 (a-b). Morphology and elemental analyses of Cu-Zn-Al LDH nanoparticle

3.3. Particle size analysis

TEM analysis was carried out to check the average particle size as well as the aspect ratio of Cu-

Zn-Al LDH nanoparticle. Fig. 4 shows that the particles possess a layered geometry (flake type

structure) which has a high aspect ratio (See Fig. 4(b)).Cu-Zn-Al LDH nanoparticles are stacked

upon each other which clearly match with its characteristic feature. According to several

scientists [22-24], higher the aspect ratio of nanoparticles greater will be its thermal conductivity

in a suspension. The average particle length was observed to be 49 nm whereas average width

was 7 nm (average of 12 data points). Therefore, the aspect ratio was 7 which are significantly

higher than that of any sphere shaped nanoparticles and making it more effective for heat

extraction. Particles with high aspect ratio provide longer heat conduction path and create a mesh

for faster transport of heat. The current findings are in line with our earlier finding with Cu-Al

10
LDH[11] and Zn-Al LDH[17] nanoparticle as well as with the work of other scientists worked

on different LDH[25].

(a) (b)

Fig. 4. Size analysis of Cu-Zn-Al LDH nanoparticle, a) TEM image and b) histogram plot

3.4. Thermo-physical property analyses

Thermo-physical properties (thermal conductivity, surface tension, and viscosity) of nanofluid

are critical while considering it for thermal application. Thermal conductivity is the most crucial

factor for any nanofluid because higher the thermal conductivity of the coolant better will be its

thermal performance. The surface tension of any coolant and contact angle it creates with the

surface determines its spreadability over the same. A lower value of surface tension and contact

angle is desired for greater contact area with the hot surface. Nanofluid viscosity is also a factor

to be considered for its industrial application as higher viscosity will increase pressure drop

(increase in pumping cost) and also influence its spreadability over the surface.

11
3.4.1. Thermal Conductivity

The main driving force for creating nanofluid was to produce a coolant which will have superior

thermal conductivity compared to any conventional coolant such as water, alcohol, transformer

oil etc. In the present study, the focus is to find the effect of concentration variation on thermal

conductivity of Cu-Zn-Al LDH nanofluid. Figure 5 shows that with growing particle

concentration thermal conductivity value increases and beyond an optimum concentration it

starts to decline. The maximum enhancement in thermal conductivity value was observed at160

ppm concentration of Cu-Zn-Al LDH nanoparticle which is 13.9% greater than that of water.

The responsible mechanism behind both increase and decrease in thermal conductivity can be

owed to combination of several critical factors such as particle concentration[2, 11], Brownian

motion of suspended particle[26, 27], degree of agglomeration and clustering [23, 28, 29],

dispersion stability[30-32], liquid layering effect[33], particle size[34, 35] and aspect ratio/shape

[22, 36, 37]etc. It is to be noted that for spherical nanoparticles, the mechanism of Brownian

motion can estimate the thermal conductivity more precision than in case of particles with high

aspect ratio where both translational and rotational diffusion reduces the effect of Brownian

motion. The complex behaviour of asymmetric nanoparticle in the base fluid makes thermal

conductivity prediction harder using basic micro-convection model as it does not include shape

factor and ordered layer thickness [38-40].However, the positive impact of high aspect ratio of

nanoparticles on the thermal conductivity of nanofluid has been reaffirmed by several researcher

[37, 41]. At high particle concentration, clustering tendency has a detrimental effect on thermal

conductivity. According to Ozerinc et al.[42], there exists an optimal clustering level above

which thermal conductivity value declines. Increase in thermal conductivity value with

increasing particle loading is a common phenomenon with nanofluids. In this study also authors

12
have observed similar trend up to a concentration of 160 ppm. The improved thermal properties

can be linked to Brownian motion, optimum clustering tendency, proper heat conduction path,

high aspect ratio and small size (length 49 nm and width 7 nm) of the nanoparticle etc.

However, it is also to be noted that at higher particle concentration due to increased Van der

Waal attractive force (agglomeration tendency), poor stability and undesired shape modification,

thermal conductivity value declines. A table has been added in this section to show the

comparison between the thermal conductivity increments attained by conventional nanofluids

and the newly developed Cu-Zn-Al LDH nanofluid (See Table 2).

Fig. 5.Effect of concentration on thermal conductivity variation of Cu-Zn-Al LDH nanofluid

13
Table 2.Comparative summary of thermal conductivity improvement achieved by different

nanofluids

Reference Nanofluid Maximum Augmentation in

Thermal Conductivity

Lee et al. Water- Al2O3, 10 % and 12 %

[43] Water- CuO
Ravikumar et al. Water- Al2O3 4%
[44]
Tiara et al. Water- Alumina 7.02 %
[45]
Chakraborty et al. Water-TiO2 8.3%
[46]
Jeong et al. Water- ZnO 18%
[41]
Chakraborty et al. Water- Cu-Al LDH 16.1%
[47]
Tiara et al.[48] Water- Zn-Al LDH 10.5%

Present Work Water- Cu-Zn-Al 13.9%

LDH

3.4.2. Surface Tension and Contact Angle

The surface tension of a coolant plays a vital role important in determining spreadability. Low

surface tension value of any coolant indicates better spreadability, low contact angle, and higher

contact area. Positive attributes of reduced surface tension on the heat transfer application have

been accepted by numerous researchers [9, 49-51]. Addition of nanoparticle can also play a role

in altering the surface tension value of nanofluid by changing the surface energy in the liquid-air

boundary. The increase and decrease in surface tension value of nanofluid samples depend on

14
three basic factors such as variation in the nanoparticle, base fluid, and concentration. It is also

observed that irrespective of nanoparticle and basefluid nature, at higher nanoparticle

concentration surface tension value tends to increase [52]. As the nanoparticle concentration

rises in the base fluid, large amount nanoparticles accumulates around the liquid surface. Due to

nanoparticle aggregation on the liquid-air interface, the cohesive force between each

nanoparticles increases which is responsible for increased surface tension value at higher

concentration[53, 54]. In addition to that increase or decrease in surface tension value of

nanofluid depends on electrostatic repulsion force and Van der Waal (VDW) attractive force

between suspended particles. At low nanoparticle concentration (40 ppm), slight reduction in

surface tension value is observed as repulsive force can dominate over the VDW attractive force

due to the charges present on the nanoparticle surface. However, with further increase

concentration, surface tension value rises up again due to over dominating VDW force. In the

current study, authors have observed both of these trends with varying nanoparticle

concentration (See Fig. 6). The current trend is in synchronous with the observation made by

Tanvir and Qiao[54] for MWCNT/DI water nanofluid. However, it is to be noted that alteration

in surface tension value for Cu-Zn-Al LDH nanofluid with varying concentration is insignificant

(surface tension variation ±1-1.3mN/m) as compared to that achieved by surfactant added

nanofluids[54, 55].

15
 Fig. 6. Effect of concentration on surface tension variation of Cu-Zn-Al LDH nanofluid

The importance of surface tension analysis is partly insignificant for this study because spreading

of impinging drops not only depends on liquid surface tension but also on the surface roughness

of steel. The surface roughness plays a crucial role in determining contact angle as well as the

spreadability of drop on the surface. With increase in surface roughness contact angle of reduces

for a fixed coolant. In order to validate our claim, contact angle was measured for different

nanofluid concentration at two different surfaces which includes steel plate prior to deposition

and steel plate post nanoparticle deposition. The result clearly shows that post particle deposition

as the surface roughness increases; it leads to lower contact angle value for all the nanofluid

concentration (See Fig. 7). The effect of nanoparticle deposition on reducing static contact angle

and improved surface wettability has also been observed by Kim et al.[56]. However, for a fixed

surface roughness increase in nanofluid concentration gives identical trend which is comparable

with the trend obtained during surface tension analysis.

16
 Fig. 7. Variation in static contact angle by varying nanofluid concentration and surface

roughness of the steel plate

3.4.3. Viscosity

Viscosity is one of the crucial parameters which impacts both flow properties as well as heat

transfer efficiency of the nanofluid. Viscosity can influence the heat transfer performance of any

system like thermal conductivity value. Here, in this study thermal conductivity of nanofluid

changes with the addition of nanoparticle concentration. Addition of nanoparticle increases the

viscosity of nanofluid which in turn increases the pressure drop and pumping cost. The

implementation of nanoparticle instead of a micron sized particle in base fluid is expected to

limit the viscosity rise significantly. High viscosity can also hinder the spreadability of coolant

over the hot surface. Several scientists have observed that with the increase in nanoparticle

concentration viscosity value also increases irrespective of nanoparticle nature such as metal

[57], metal oxide [58-61]and carbon based nanoparticle. The finding obtained in this current

study for Cu-Zn-Al LDH nanofluid also indicates towards the same conclusion. Figure 8 shows

17
increasing viscosity value with increasing particle concentration. When compared with the

viscosity of water increase in viscosity at 240 ppm concentration is 68.7%. It is also to be noted

that moderately high viscosity can be considered beneficial in some aspects as it increases the

residence time of the impinging drop on a solid surface. Hence, it can increase the contact time

between hot surface and coolant which indirectly influences the heat transfer rates [7].

Fig. 8. Effect of concentration on viscosity value of Cu-Zn-Al LDH nanofluid

3.5. Stability

Stability is one of the main parameters to be considered for nanofluid in order to use it

industrially. Stability analyses were conducted via sedimentation photography and zeta potential

value (See Fig. 9 and Table 3). Zeta potential values for different nanofluid concentrations were

reported at two different time interval (2 and 12 hours) to check the effect of time on nanofluid

stability. Table 3 clearly shows that nanofluid stability decreases slightly with increasing time

18
which true for all the samples reported here. It is also to be noted that even after 12 hours from

preparation the value remains above the desired zeta potential value of ± 30 mV.

Using sedimentation photography technique, it can be said that up to initial 12 hours, there is no

sign of sedimentation in all the samples. However, as the time progresses 120, 240 ppm solutions

start to show sedimentation after 12 hours. On the other hand, 40 ppm solution remained stable

up during the entire duration of the experiment. To give a clear idea on sedimentation,

photographs were taken after 24 hours from the bottom side which clearly shows no

sedimentation has taken place for 40 ppm solution whereas both 120 and 240 ppm solutions

show traces of sedimentation below the container. However, it is to be noted that Cu-Zn-Al LDH

nanofluid shows best stability within 2 hours from its preparation and it is preferred to be used

for application within that time frame.

Fig. 9. Sedimentation photography of Cu-Zn-Al LDH nanofluid at various concentrations and

time duration

19
Table 3. Zeta potential value of Cu-Zn-Al LDH nanofluid at different particle loading and time

interval

Nanofluid Concentration Zeta potential value (mV) Zeta potential value (mV)

(ppm) (after 2 hrs ) (after 12 hrs )

40 36.9 34.6

120 37.3 35.4

160 38.6 36.6

240 37.7 35.3

4. Spray cooling experimental setup & surface temperature calculation:

Detailed schematic diagram of spray cooling experimental setup is shown in Fig. 10. The

experimental setup contains several key components such as Lechler full cone spray nozzle,

pressure gauge, rotameter, centrifugal pump, coolant reservoir, solenoid valve, gate valve, muffle

furnace, insulating resting pad, data acquisition system and computer. The key objective of the

experiments is to check the effect nanofluid concentration on surface cooling rate. AISI 304

grade stainless steel plates were used for all experiments. The steel plate dimensions were 100

mm (length) ×100 mm (width) ×6 mm (thickness). An electrically powered muffle furnace

(Voltage 440V, Load 8/12 kW) which has a maximum heating range up to 1400oC was used to

heat up the steel plate. The test plates were heated up to 1050oC for spray cooling experiments. A

Lechler (Nozzle No: 460-843-17-CG) manufactured full cone water spray nozzle was used for

the cooling experiments. An insulating resting pad (made with fire brick) was fabricated to

ensure adiabatic boundary condition where the hot steel plate was kept during the experiment.

20
The transient temperature data during the experiments were collected by using 3 K-type

thermocouples which were connected to a National Instrument (USA) made data acquisition

system (NIcDAQ-9174 and NI 9211 card). The data acquisition system was then connected to a

computer for data storage. All the three thermocouples were placed at three specific locations to

capture the temperature variation across the steel. TC 1(x=20 mm, y= 3 mm; Distance from

spray/plate centerline = 30 mm) was placed farthest from spray/plate centre, TC 2 (x=50 mm, y=

3 mm; Distance from spray centerline = 0 mm) was placed right below the spray/place centre and

TC 3 (x= 70 mm, y= 3 mm; Distance from spray centerline = 20 mm) was placed on the opposite

side of TC1 and closer to the spray/plate centerline. Figure 10 also shows the position of the

three thermocouples and their coordinates. The thermocouples holes are drilled up to 50 mm in

the Z direction and the holes were sealed with a conducting paste to eliminate any air gap

between thermocouples and plate. In order to ensure that water does not fall on hot steel plate

until the spray is stabilized, a wooden board was used to prevent the spray impingement. The

board was only removed after the spray is stabilized and desired flow rate was attained. All other

details regarding the spray cooling experiments were given in Table 4.

Using the three subsurface thermocouple data, authors have calculated surface temperature

profiles by using a commercially purchased 2 D inverse heat conduction solver, INTEMP[62-

65]. For surface temperature distribution, calculations were done by transforming the entire

geometry in to two dimensions (x= 100 mm, y= 6 mm). The entire geometry is divided into 7781

nodes and 7500 elements (Δx= 0.0004 m, Δy= 0.0002 m). The transient thermocouple data is

taken as the input data. Only the top surface is considered of heat transfer as all other surface is

covered by insulating fire bricks. The boundary conditions for aforesaid 2 D computational

domain are as follows:

21
 T
For x = 0 mm and y = 0 to 6 mm, 0
x

T
For x = 100 mm, and y= 0 to 6 mm, 0
x

T
For y = 0 mm, and x= 0 to 100 mm, 0
y

T
For y = 6 mm, and x= 0 to 100 mm,  unknown
y

The principal equation for the computation of surface heat flux is given below:

  T    T  T
k  k   C p
x  x y  y  t
 2T  2T T
k 2  k 2  C p
x y t
  2T  2T   C p T
 2  2 
 x y  k t

Where, k (Unit: W/m.K), ρ (Unit: Kg/m3), and Cp (Unit: J/Kg.K) denotes the thermal

conductivity, density, and specific heat capacity of steel plate, respectively.

To calculate surface heat flux and surface temperature from internal thermocouple data, the

software takes a guess value of surface heat flux and computes temperature data for all the nodes

as typical heat conduction problem. Nonlinear optimization technique is used to re-modify the

guess value of heat flux for the purpose of error minimization (difference between measured

temperature value and INTEMP calculated temperature at the same node). The INTEMP

calculation proceeds and iteration takes place until the error value goes below the predefined

tolerance limit. Several researchers have used INTEMP for surface heat flux and temperature

calculation [66, 67]. For the current study, three thermocouples were used for temperature

22
recording. Based on the position of three thermocouples in steel plate, authors have divided the

top surface into three heat flux zones, a) Flux zone 1 (x= 0 to 36 mm, y =6 mm), b) Flux zone 2

(x= 36 to 64 mm, y =6 mm), and c) Flux zone 3 (x=64 to 100 mm, y=6 mm) having different

heat flux value. It is assumed that heat flux value within each zone is uniform.

Fig. 10. Experimental setup for spray impingement cooling using Cu-Zn-Al LDH nanofluid

23
Table 4. Experimental design for Cu-Zn-Al LDH nanofluid based spray cooling experiments

Parameter of Concern Operating Condition

Steel Plate Temperature 1050 oC

Zone of Interest (Temperature) 900-600oC

Coolant Temperature 30oC

Coolant Flow Rate 16 lpm.

Coolant Pressure 4 bar

Spray Impingement Height 6 cm

Spray Angle 45o

Nanofluid Water-Cu-Zn-Al LDH

Nanofluid Concentration 40, 80, 120, 160, 200 & 240 ppm

5. Results and Discussion:

Implementation of Cu-Zn-Al LDH nanofluid for heat transfer enhancement during steel

quenching process is the core of the current study. In this section, authors have focused on the

effect of varying nanofluid concentration on cooling rate and effect of nanoparticle deposition

behind the heat transfer mechanism.

5.1. Cooling curves and cooling rate

The transient surface temperature corresponding to three thermocouple locations was calculated

using INTEMP. Figure11(a-b) shows the variation of surface temperature with time during spray

cooling within a temperature range of 10500C to 2000C for pure water and 160 ppm Cu-Zn-Al

LDH nanofluid concentration. From the figure, it can be seen that both the curves follow an

24
identical trend with thermocouple TC2 showing the highest cooling rate.TC2 is located just

beneath the nozzle and hence the temperature declines faster as compared to other two

thermocouples. Based on its distance from the spray impingement zone, fastest temperature drop

was observed in TC2 which is followed by TC3 and TC1.Another distinctive feature observed in

all the graphs is the presence of two characteristic stages of temperature drop. Both the stages are

owed to different modes of heat transfer such as natural convection (first stage), forced

convection (second stage), and radiation (first stage). Temperature drop in the first stage is much

slower than the second stage as it only involves heat loss due to radiation and natural convection.

In Fig. 11, t= 0 sec is measured when the plate is removed from the furnace. The duration of the

first stage extends from the time when the plate is detached from the furnace and placed on the

fire brick till the time spray starts to fall on the hot steel plate. For the purpose of ensuring stable

and uniform spray impingement on a steel plate, a wooden board was used to prevent any spray

impingement until desired water flow rate; water pressure and uniform spray distribution are

attained. Once the wooden board is removed and spray impinges on the steel surface the

temperature profile starts to show rapid decline which is the onset point of the second stage.

From the slope of the transient temperature profile, both the stages can be easily identified.

25
 (a) Water (b) 160 ppm

Fig. 11 (a-b). Transient surface temperature profile for all three thermocouple

locations,(a) water, and (b) 160 ppm concentration of Cu-Zn-Al LDH nanofluid

Temperature drop in TC2 thermocouple is the fastest among all three thermocouples. Therefore,

from here onwards only data corresponding to TC2 thermocouple has been reported in the

manuscript. For the current study, cooling rate value attained (between the temperature zone of

900-600oC) for all the nanofluid concentration has been displayed in Fig. 12. It was observed

that on increasing LDH concentration up to 160 ppm, cooling rate increases and thereafter it

decreases. At 160 ppm, the maximum cooling rate of 158oC/s was achieved which lies in the

ultra-fast cooling region indicating that UFC can be achieved with Cu-Zn-Al LDH nanofluid

assisted spray cooling. An increase of 18.5% in cooling rate was found out for a concentration of

160 ppm as compared to water. Authors have achieved 15.6% reduction in coolant consumption

at 160 ppm concentration when compared with pure water (Supplementary Table 1). During the

spray cooling of nanofluid, nanoparticles get deposited on the steel surface which creates

additional nucleation sites and helps to rupture the insulating vapour layer formed on the steel

surface. As observed in contact angle analysis, nanoparticle deposition also helps in improving

26
surface wettability and effective heat transfer rate. However, too high nanofluid concentration

can also adversely affect the cooling rates because the entire steel surface gets covered with LDH

nanoparticle layer which acts as a hindrance for heat transfer between the coolant and the steel

surface. The current trend in cooling rate plot is owed to both surface roughness of steel (owed to

nanoparticle deposition) and thermal conductivity variation due to nanofluid concentration

change. The influence of particle deposition on heat transfer enhancement and the subsequent

decline has been clearly explained in section 5.4. To compare the cooling performance of the

current nanofluid with earlier reported nanofluids (at similar experimental condition), a

comparative table has been formulated (See Table 5).

Table 5. Comparison between cooling rate enhancement obtained by different nanofluid at

similar experimental condition

Reference Cooling Nanofluid % Increase in Cooling

Technique Rate than Base Fluid

Ravikumar et al. [9] Air-atomized Water-Cu Nanofluid 21.6%

spray
(without surfactant)

Ravikumar et al. Air-atomized Water-Al2 O3 Nanofluid 10.2%

[44] spray
(without surfactant)

Tiara et al.[68] Forced Jet Water-Al2 O3 nanofluid 16.1%

Ishita et al.[16] Forced Jet Water-Cu-Al LDH 41%

nanofluid

Tiara et al.[17] Forced Jet Water-Zn-Al LDH 29%

nanofluid

Present Study Spray Water- Cu-Zn-Al LDH 18.5%

nanofluid

27
 Fig. 12.Cooling rate alteration at different concentration of Cu-Zn-Al LDH nanofluid

5.2. Boiling curve

Surface heat flux variation with surface temperature (900 0–2000C) during cooling at various Cu-

Zn-Al LDH nanofluid concentrations has been shown in Fig. 13. A nonlinear variation of surface

heat flux with surface temperature was observed irrespective of the LDH concentration. Initially,

an insulating vapour layer forms due to the high temperature difference between coolant and

steel surface resulting in a low heat flux. The formation of vapour cushion due large temperature

gradient is called as the Leidenfrost effect [69]. As the temperature decreases during cooling, the

heat flux increases and attains a peak value termed as critical heat flux (CHF) due to the rupture

of insulating vapour layer and this region is termed as transition boiling regime.On further

cooling, nucleate boiling dominates where the surface heat flux value decreases after CHF due to

the reduction in thermal energy. The highest enhancement in critical heat flux was achieved for a

nanofluid loading of 160 ppm.

28
It was also observed that the average heat flux (taking the average of heat flux values between

900-600oC) value increases with LDH concentration up to 160 ppm, thereafter it decreases as

shown in Table 6. Reduction in thermal conductivity of nanofluid and formation of a thick layer

of particles on steel surface is responsible for the lowering of heat transfer at high nanofluid

concentrations.

Fig. 13.Variation in surface heat flux with surface temperature at different concentration of Cu-

Zn-Al LDH nanofluid

5.3. Heat transfer coefficient

Heat transfer coefficient, h (W/m2.K) of a coolant is found out by using the following equation.

Q
h (1)
Ts  Tc

29
Where, Q is the surface heat flux in W/m2, Ts is the surface temperature in K and T c is the

coolant temperature in K. Heat transfer coefficients for different nanofluid concentrations were

calculated and plotted against the surface temperature (9000-2000C) as shown in Fig. 14. It was

found out that irrespective of nanofluid concentration heat transfer coefficient values were

almost same at initial stages of cooling where the surface temperature was higher. However, heat

transfer coefficient value increases as cooling proceeds in all cases. This occurs due to the

rupture of insulting vapour layer during cooling. As cooling proceeds, nanoparticle deposition

increases leading to newer nucleation sites and thus enhances heat transfer. Heat transfer

coefficient value rises with nanofluid concentration up to 160 ppm, thereafter it decreases. Table

6 also shows that the highest average heat transfer coefficient (AHTC) value of 2.34 kW/m2K

was obtained for a nanofluid concentration of 160 ppm and in the surface temperature of the

range of 900-6000C. A maximum of 4.47% enhancement was observed at 160 ppm concentration

as compared to that achieved by pure water spray.

Fig. 14. Alteration in heat transfer coefficient value with surface temperature at varying

Cu-Zn-Al LDH nanofluid concentration

30
Table 6. Summary of average heat flux and heat transfer coefficient values obtained at different

nanofluid concentration

Nanofluid Concentration AHF (MW/m2) AHTC (kW/m2 K)

(ppm)

0 1.52
2.24
40 1.55
2.25
80 1.57
2.26
120 1.58
2.28
160 1.65
2.34
200 1.61
2.33
240 1.60
2.32

5.4. Effect of nanoparticle deposition on heat transfer mechanism

Presence of nanoparticle in the base fluid leads to increment in heat transfer rate by two ways

one is by elevating the thermal conductivity value of the coolant and secondly by increasing the

number of nucleation site via nanoparticle deposition. Effect of nanoparticle dispersion on

thermal conductivity value has already been discussed in thermal conductivity analysis section.

Therefore, in this section authors have mainly focused on the other aspect of heat transfer

enhancement which is nanoparticle deposition. During the steel quenching process, nanoparticle

suspended in water gets deposited on the steel surface which increases the surface roughness.

Enhanced surface roughness acts as an advantage in terms of the heat transfer aspects [16, 70].

The deposited particles act as additional nucleation sites. Increase in nucleation site by particle

31
deposition is considered to be one of the reasons behind improved cooling rate. The effect of

nanoparticle concentration on surface roughness has been displayed in Fig. 15. The figure shows

that with increasing particle concentration, surface roughness gradually increases up to 160 ppm

concentration, and then it starts to decline as the entire surface gets covered with the nanoparticle

layer. In order to explain the phenomenon, a schematic diagram (See Fig. 16) of nanoparticle

deposition with varying nanoparticle concentration has been added along with the actual FESEM

image to further validate the claim. FESEM image clearly shows that at concentration beyond

160 ppm, the steel surface gets covered by a layer of deposited nanoparticles which is

responsible for the reduced heat transfer rate. Nanoparticle layers hinder the contact between

impinging drops and the hot steel surface which in turn, reduces the cooling rates. Such

observation has also been made by few other researchers who have found similar attributes of

nanoparticle deposition on heat transfer performance [71-74]. Similar to current observation,

Chang et al.[74] also reported that at higher nanoparticle (Al2O3) loading, excess nanoparticle

deposition causes reduction in nucleation site and decline in convective heat transfer rate.

However, at lower concentration optimum particle deposition helps to improve both nucleation

site and heat transfer rate during spray cooling. The aforesaid observation is in sync with results

obtained in the present study.

32
Fig. 15.Influence of nanofluid concentration on deposition induced surface roughness

Fig. 16.Schematic diagram of nanoparticle deposition on steel plate

33
6. Measurement uncertainty:

The error analysis or uncertainty measurement is one of the key studies for any experimental

investigation. To ensure measurement accuracy and to acknowledge the system error, it is

important to go for uncertainty analysis. In this study, authors have used ASME recommended

test code for error analysis [75]. For ensuring measurement accuracy, all experimental data

reported in this study has been repeated multiple times to guarantee accuracy. All the parameters

from which uncertainties may arise have been reported in Table 7 along with their contribution.

Table 7.Measurement uncertainty for different parameters

Source of Error Error Type Maximum Error

Water Flow Rate Bias ±3%

Spray height Bias ± 0.1 cm

Temperature measurement Bias ± 4oC

Nanofluid Concentration Bias ± 3 ppm

Thermal Conductivity Precision ± 4.00 %

Surface Tension Precision ± 0.69 %

Viscosity Precision ± 6.55 %

Surface Roughness Precision ± 4.98 %

Cooling Rate Precision ± 8.64 %

Average Heat Flux Precision ± 8.18 %

34
7. Conclusion:

A new breed of nanofluid namely Cu-Zn-Al LDH has been synthesized by one step co-

precipitation technique. The current work focuses on the thermo-physical aspects of the

aforementioned nanofluid and its use in the spray cooling of hot steel plate (above 900oC).

Implementation of nanofluids aids in heat transfer enhancement during steel quenching via two

routes, firstly by enhancing the thermal conductivity of coolant and secondly by increasing the

number of nucleation site with nanoparticle deposition. The nanofluid concentration is varied in

the range of 40-240 ppm to check its impact on the thermo-physical property as well as its

thermal performance. The following summarized points are the key outcomes of the present

research,

1) Cu-Zn-Al LDH nanoparticles were rod shaped. The average Cu-Zn-Al LDH nanoparticle

size was found to be 49 nm which was measured by using TEM analysis.

2) The thermal conductivity of Cu-Zn-Al LDH nanofluid at 160 ppm was 13.9% higher than

that of water. Thermal conductivity increases with increasing particle loading upto 160

ppm concentration then it starts to decline again. Surface tension remains almost

unchanged with changing nanoparticle concentration. However, the viscosity value

increased with increasing particle concentration. Highest enhancement in viscosity was

attained at 240 ppm which is 68.7% higher than water.

3) The highest enhancement in surface cooling rate was reached at 160 ppm nanofluid

concentration which is 18.5% greater than what attained by pure water. The maximum

cooling rate of 158.43oC/sec was obtained at 160 ppm which is well above ultra-fast

cooling range (>133.3oC/sec for 6 mm plate).

35
 4) Other than the thermal conductivity value, nanoparticle deposition on steel plate also

plays a crucial role in heat transfer enhancement. With increasing particle concentration,

surface roughness value increases which in turn attributes in improving a number of

nucleation site. However, as the particle concentration is further increased steel surface

becomes entirely covered with particles and it prevents incoming drop contact with the

hot surface. As a result, the overall heat transfer performance declines beyond 160 ppm

concentration (See Fig. 12).

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List of Figures:

Fig. 1 Graphical representation of Cu-Zn-Al LDH nanofluid synthesis method

Fig. 2 XRD pattern of Cu-Zn-Al LDH nanoparticle with varying diffraction angle

Fig. 3 Morphology analysis of Cu-Zn-Al LDH nanoparticle

Fig. 4 Size analysis of Cu-Zn-Al LDH nanoparticle, a) TEM image and b) histogram

plot

Fig. 5 Effect of concentration on thermal conductivity variation of Cu-Zn-Al LDH

nanofluid

Fig. 6 Effect of concentration on surface tension variation of Cu-Zn-Al LDH nanofluid

Fig. 7 Variation in static contact angle by varying nanofluid concentration and surface

roughness of the steel plate

Fig. 8 Effect of concentration on viscosity value of Cu-Zn-Al LDH nanofluid

Fig. 9 Sedimentation photography of Cu-Zn-Al LDH nanofluid at various

concentrations and time duration

Fig. 10 Experimental setup for spray impingement cooling using Cu-Zn-Al LDH

nanofluid

Fig. 11 (a-b) Transient surface temperature profile for all three thermocouple locations,(a)

water, and (b) 160 ppm concentration of Cu-Zn-Al LDH nanofluid

Fig. 12 Cooling rate alteration at different concentration of Cu-Zn-Al LDH nanofluid

Fig. 13 Variation in surface heat flux with surface temperature at different concentration

of Cu-Zn-Al LDH nanofluid

Fig. 14 Alteration in heat transfer coefficient value with surface temperature at varying

46
 Cu-Zn-Al LDH nanofluid concentration

Fig. 15 Influence of nanofluid concentration on deposition induced surface roughness

Fig. 16 Schematic diagram of nanoparticle deposition on steel plate

List of Tables:

Table 1 Basal spacing and crystal size chart of Cu-Zn-Al LDH nanoparticle at different
diffracion angles
Table 2 Comparative summary of thermal conductivity improvement achieved by different
nanofluids
Table 3 Zeta potential value of Cu-Zn-Al LDH nanofluid at different particle loading and
time interval
Table 4 Experimental design for Cu-Zn-Al LDH nanofluid based spray cooling experiments
Table 5 Comparison between cooling rate enhancement obtained by different nanofluid at
similar experimental condition
Table 6 Summary of average heat flux and heat transfer coefficient values obtained at
different nanofluid concentration
Table 7 Measurement uncertainty for different parameters

Supplementary Table:

Supplementary Table 1 Variation in coolant consumption at different nanofluid concentration

Nomenclature:

Cp Specific heat capacity of steel plate

d Basal spacing

47
h Heat transfer coefficient

k Thermal conductivity of steel plate

L Crystal size

Q Heat flux

Ts Surface Temperature

Tc Coolant Temperature

Greek Letter:

ρ Density of the steel plate

θ X-Ray diffraction angle

λ X-Ray wavelength

Abbreviation:

AHF Average Heat Flux

AHTC Average Heat Transfer Coefficient

ASME American Society of Mechanical Engineers

CHF Critical Heat Flux

EDS Energy Dispersive Spectroscopy

FESEM Field Emission Scanning Electron Microscope

JCPDS Joint Committee on Powder Diffraction Standards

LDH Layered Double Hydroxide

48
TC Thermocouple

TEM Transmission Electron Microscope

UFC Ultrafast Cooling

VDW Van der Waal

XRD X-Ray Diffraction

49
Graphical abstract

50
Highlights

 Cu-Zn-Al LDH nanofluid was prepared and used for metal quenching.

 Nanoparticles are rod shaped having an average particle size of 49 nm.

 13.9% enhancement in thermal conductivity was achieved at 160 ppm loading.

 Nanofluid was used for spray cooling of hot steel plate (above 900oC).

 Maximum cooling rate of 158.4oC/sec was also achieved at 160 ppm concentration.

51