ISSN : 2454-9150 A Review on Change in Properties …ijream.org/papers/IJREAMV04I0743005.pdfthermal energy for low consumption and slow energy delivery system. One of the challenges

International Journal for Research in Engineering Application & Management (IJREAM)

ISSN : 2454-9150 Vol-04, Issue-07, Oct 2018

45 | IJREAMV04I0743005 DOI : 10.18231/2454-9150.2018.0894 © 2018, IJREAM All Rights Reserved.

A Review on Change in Properties of Phase Change

Materials (PCM) on Incorporating Additives

Vraj Mundra, Student-IV year, Medi-Caps Institute of Technology and Management, Indore,

India, [email protected]

Sourabh Mahajan, Student-IV year, Medi-Caps Institute of Technology and Management, Indore,

India, [email protected]

Bhupendra Singh Sikarwar, Assistant Professor, Medi-Caps University, Indore, India

[email protected]

Abstract: Latent heat energy storage and exchange system is emerging as an efficient alternative of storing extra

thermal energy for low consumption and slow energy delivery system. One of the challenges for latent heat storage

systems is the proper selection of the phase change materials (PCMs) for the targeted applications. The Phase change

materials in their native state display primitive heat storage and transition with discreet phase change properties,

melting and phase separation properties. To overcome these properties, doping or enhancement of the PCM is done,

quiet often which they differ is by the nature, structure or the fabrication of the composite displaying a myriad of

properties and their variation with change in additive’s structural matrix inside the composite, material of the additive

and their concentration inside the PCM. Furthermore, the nature of the bulk of PCM, display relatively distinct

properties as they may be organic or inorganic. This paper is a review based on the contemporary work done on

organic and inorganic PCM, their additives and effects of additives on the thermodynamic and phase change properties

of the composites, and gives an insight into potential uses and classification of the PCMs according to their properties

and ease of incorporation for industrial and domestic applications.

Keywords: PCM, Paraffin wax, embedded graphite, expanded graphite, Inorganic PCM, Metallic foam.

I. INTRODUCTION

The electrical/electronic goods are an integral part and

components in one‟s working life now-a-days. Abrupt rise

in the standard of living and the expansion of the

boundaries of what defines human comfort and luxury have

become necessities and this has been aided by rise in living

comforts, the affordability of electronics and rapid

industrialization. Therefore, the research is primarily

focused on miniaturizing the electronic components whilst

maintaining the computing power and efficiency of the

previous generation configurations of the system.

As of today, thermal management is the foremost concern

in developing and designing of new systems. Temperature

has been identified as the key factor in the performance and 1reliable operation of the electronic system. The traditional

methods of cooling, namely natural and forced convection

are no longer seen as sufficient alternatives for heat

exchange and subsequent cooling of high-performance

electronics. Alongside, PCM‟s have been widely

experimented and researched upon in civil engineering and

energy management domain, primarily as a backup latent

energy storage medium for smoothing out energy demand

fluctuations as well as acting as a passive heat/energy

release media in domestic heating/cooling applications.

PCM‟s have been also introduced as the cooling enhancer

in lithium ion batteries in electric vehicles and power

consuming battery operating devices.

The widespread potential uses and applications however are

not assisted or followed by a parallel rise in scientific

literature and research over the generalized industrial

potential of PCM and the effect of additives on their

properties, subsequent usage as well as their domain of

usability and fabrication. The cited works have been

extremely useful yet a bit myopic about the larger scope of

PCM in the widespread product design engineering and

industrial/civic application. Our work aims to comprehend

and distill the available works and findings of the research

work currently in progress as well as the past and provide a

brief and concise insight into the properties, fabrication as

well as the potential scope and spectrum of applications the

PCM can be put into practice.

A survey conducted by US air force noticed that the

temperature related failure in electronics exceeded in the

excess of 55% (E.M. Alawadhi and C.H. Amon [32]).

Manufacturing industry in communication systems expect a

reliability percentage of 99.99%, also called as 5 9‟s




principle. Which translated to roughly 5 minutes of total

down time in any year. These high expectations ensure that

the conventional cooling methods are inadequate for the job

demanded from them. It has been found that a 1 °C

decrement in a localized temperature may lower its failure

rate percentage by as much as 4% and about 10–20 °C

increment in temperature can increase its failure rate by

100% ( S.F.Hosseinizadeh et al. [33]).”

The cooling methods used are mainly active and passive in

nature. The active cooling designs work by direct contact,

like a metal surface with many fins incorporated. This heat

transfer is obtained through free or forced convection,

liquid cooling or any combinations of them possible in

practice. In forced convection, heat sinks‟ thermal

performance is increased by uplifting overall heat transfer

coefficient, usually by adding a fan to the system. Fans

improve the transfer of thermal energy from the heat sink to

the surrounding air by moving cooler ambient air between

the fins, the major disadvantage of the fan system being is

noise, life, size and vibration. Wherever there is some

improper functioning of fan, like imbalance and rotational

friction, the system fails to operate for longer duration due

to generation of more heat and vibrations. Hence in recent

years, passive cooling is gaining property in passive cooling

applications. PCM exhibit properties of high latent energy

of fusion and relatively small amount of volume change

during energy absorption. This demonstrates that high

amount of energy can be reliably stored in PCM during its

phase change battery, not unlike a slow charging

conventional battery.

The physical and thermodynamic properties of PCM with

additives, mixed/impregnated/expanded (Organic) or other

methods (Inorganic) have been studied and discussed about

in this paper. The common properties mentioned in all our

citations have valuable insights into the thermal

conductivity, thermal storage, latent heat, temperature

distribution, reliability, effect of temperature distribution on

thermal conductivity.

For ease of comprehension and reference the PCM are

classified on some discreet divisions with insignificant

overlap due to the nature of experiments carried out but

mainly divided on nature, additives and melting points of

the PCM composites. The studied PCM in this paper are

classified by nature additives and melting points.

Organic composites:

1) Paraffin:

i) Expanded graphite

ii) Embedded graphite nanofibers

iii) Porous graphite matrix

iv) High density Poly ethylene composite

v) Carbon foam and contrast with isolated

carbon foam

vi) Carbon fiber

vii) RT44HC paraffin with expanded graphite

viii) Embedded herringbone style graphite

nanofibers

2) 1-Octadecanol

i) Graphene

ii) Graphene sheets

3) Poly-ethylene Glycol

i) SiO2 composite

ii) Graphite-nano-plates/Poly-methyl

Methacrylate composite

4) MA-PA-SA

i) Expanded graphite

Inorganic composites:

1) Pristine silver epoxy, hybrid graphene FLG- Silver

epoxy

2) LiNO3-KCl, LiNO3-NaNO3, LiNO3-NaCl

impregnated with expanded graphite

3) PCM44 {Mg (NO3)26H2O–MgCl26H2O–NH4NO3}

with carbon fiber

4) NaNO3 in copper.

Melting Points (Binary classification):

1) High temperature PCM (melting points above 2000C )

2) Low temperature PCM (melting points below 2000C)

The objective of this paper is to recollect and encapsulate

data and conclusions from various sources and researches

to make a comprehensible and self-contained source of

information regarding the properties, fabrication and

potential applications of PCM in industry.

II. CONTEMPORARY STUDIES ON PHASE

CHANGE MATERIALS

1. ORGANIC MATERIALS

1.1 Thermal conductivity

H. Yin et al. [1] studied the effect on thermal conductivity

of paraffin by adding expanded graphite in it. It was known

that thermal conductivity of paraffin with 0% of expanded

graphite is 0.2697W/mK, but during experiments it was

seen that thermal conductivity of composite increases on

adding 6.25% of graphite in paraffin which is 4.676W/mK

& on further inclusion of graphite thermal conductivity

observes downward trend i.e. it decreases to 1.795W/mK at

90.9% of graphite in PCM. Therefore, there is an optimized

range of doping of expanded graphite in paraffin.

C. Lin et al. [2] conducted experiment on LiFePO4 battery

of size (length*breadth*height) 100*32*180 (mm) to check

the rise in thermal conductivity on adding expanded

graphite in paraffin. It was found that there is increase in

thermal conductivity of composite to 24 times as that of

pure paraffin as shown in Table I.

Table I: Thermal properties of Paraffin and Paraffin EG composite

[2]

https://www.sciencedirect.com/science/article/pii/S1359431111003905#!




Paraffin Paraffin and

expanded graphite

composite

Thermal conductivity

(W/mK)

0.16 3.95

Latent heat (kJ/kg) 174.4 132.6

Phase change

temperature oC

223.9-27.1 21.6-25.5

F. Yavari et al. [3] in their study studied the effect of

adding nano structured graphene in 1 – Octadecanol. It was

found that on insertion of 4% of graphene in 1-Octadecanol

there is 2.5 times rise in thermal conductivity of composite

from (0.38W/mK to 0.91W/mK). This increase in thermal

conductivity can be considered due to high thermal

conductivity network of filler material (graphene) and may

be large aspect ratio.

W. Wang et al. [4] conducted the study in which they form

a composite by blending polyethylene glycol, β -Aluminum

nitride powder and silica gel. Due to doping in pure PCM

there is rise in thermal conductivity of PCM. It is also seen

that as mass ratio of β-Aluminum Nitride increases, there is

increase in value of thermal conductivity which increase

from 0.3847 to 0.7661W/mK.

G. Xin et al. [6]in his work firstly forms a defect free

graphene then doped this defect free graphene into phase

change material. Fig. 1 shows the effect of mass loading of

GSs on thermal conductivity of pristine graphene/PCC

(PGPCC). It is known that measured thermal conductivity

of pure PCM is 0.22W/mK at ambient temperature. It is

seen that at loading from 0% to 10% Pristine GS there is

increase of thermal conductivity from 0.27 to 0.55W/mK.

Further TCE of PGSPCC is found to be 1.5 at 10% weight

of PGS.

Fig 1: Thermal conductivity and thermal conductivity enhancement

of pristine graphene/PCC (PGPCC)

at various mass loading fraction of GSs [6]

X. Yang et al. [7] performs an experiment in which they

measure the effect of expanded graphite on myristic acid–

palmitic-acid–stearic acid. Proportion of myristic acid–

palmitic-acid–stearic acid and EG was kept 13:1. On

comparison of thermal conductivities it was observed that

thermal conductivity of MA–PA–SA/EG composite PCM is

10.04 time higher than that of pure PCM.

W. Wang et al. [8] in his study forms a composite of

polyethylene glycol/silicon dioxide and studied its effect on

thermal properties. It was found that in table that with

increase in percentage of SiO2 there is increase in thermal

conductivity which reaches to 0.5124 W/mK but due to

constraint of heat storage mass percentage is optimized at

20% at which thermal conductivity is 0.3615 W/mK.

Table II: Thermal conductivity of the composite PEG (10,000)/SiO2 [8]

Samples Weight

percentage of

SiO2

Conductivity

(W/mK)

Increases

Percentage

1 0 0.2985 0

2 20 0.3615 21.0

3 30 0.4126 38.2

4 40 0.4783 60.2

5 50 0.5124 71.7

A. Trigui and M. Karkri [10] in order to determine apparent

thermal conductivity of liquid and solid of composite,

between up and down side of composite temperature

difference was applied until equilibrium condition. They

prepared two composite paraffin/epoxy resin/copper tube

(1) and paraffin/epoxy resin/brass tube (2). It was observed

that thermal conductivity of (1) sample without PCM was

0.270W/mK which increases to 0.280W/mK on in liquid

state on adding PCM. While thermal conductivity of sample

(2) without PCM was 0.214W/mK which increases to

0.218W/mK on adding PCM in liquid state.

A. Sari [13] in work forms a form stable composite

paraffin/high density polyethylene (HDPE). He used two

types of paraffin (P1 and P2) having different melting

temperature of 42 – 44oC and 56 - 58

oC respectively. In

order to increase thermal conductivity of composite, 3% of

expanded graphite is added in composite which changes

percentage of paraffin and HDPE to 74.7 and 22.3 w/w %

respectively. As result of inclusion of EG it is observed that

there is increase in thermal conductivity of P1/HDPE and

P2/HDPE by 14 and 24% respectively.

Z. Ling et al. [16] conducted the investigation in which he

forms a composite of RT44HC/expanded graphite (EG) to

check the change in properties of pure PCM on addition of

EG. It is seen that thermal conductivity at 35% of EG is

nearly 30 times more than that of 25% mass fraction of EG.

Further it is seen that packing density has great influence

over thermal conductivity. It is seen that with increase in

packing density there is increase in thermal conductivity. At

density of 300 kg/m3 thermal conductivity of 25% EG was

4.3W/mK which increase to 10.7W/mK at density of 900

kg/m3.

1.2 Latent Heat

C. Lin et al. [2] conducted the experiment in which they

investigate the effect of using paraffin with expanded




graphite in LiFePO4 battery. It was found that latent heat of

composite decrease to 132.6 kJ/kg as compared to that of

pure PCM which was 174.4kJ/kg. This decrease is due to

the impregnation of graphite in PCM. The Latent heat of

the composite is shown in Table I.

W. Wang et al. [4] in their experiment evaluated the change

in latent heat of polyethylene glycol, β –Aluminum nitride

powder and silica gel composite. In Fig. 2 two pointed

peaks were observed indicating solidification point and

melting point. Solidification point during cooling and

melting point during the

Fig 2: DSC Curve of the PEG/SiO2/ β –AlN composite PCM [4].

heat was 44.81 o

C and 60.93 o

C respectively, whereas latent

heat of solidification and melting process was 117.6 kJ/kg

and 137.7 kJ/kg respectively. Further the author calculated

latent heat, solidification and melting point of PCM at

various percentage of β – Aluminum Nitride and results are

shown in Table III.

From Table III it is seen that on increasing the percentage

of β-Aluminum Nitride there is a decrease in the value of

latent heat with a very insignificant change on crystallizing

and melting temperature respectively.

Table III: Thermal activities of the PEG/SiO2/β-AlN composite PCMs

[4]

AIN% Hm

(kJ/kg)

Tm (oC) Tc (

oC) Hc

(kJ/kg)

1 161.4 60.41 45.13 132.9

5 154.6 62.32 43.96 129.8

10 152.8 58.59 45.04 128.7

15 137.7 60.93 44.81 117.6

20 129.5 61.18 42.39 106.8

X. Yang et al. [7]in his experiment found that the melting

and freezing temperature of myristic acid–palmitic acid–

stearic acid and EG composite are 41.64oC and 42.99

oC

respectively and the melting and freezing latent heat to be

151.4 kJ/kg and 153.5 kJ/kg respectively.

Table IV: Comparison of thermal properties of the prepared

composite PCM with that of some composite PCMs in literatures. [7]

Composite

PCM

Meltin-g

point

(oC)

Freezin-g

point (oC)

Latent

heat

(kJ/kg)

Reference-s

Capric–myristic

acid (55

wt%)/expanded

perlite

21.70 20.70 85.40 A.

Karaipekli

and A. Sari

[25]

Capric–lauric

acid (66

wt%)/diatomite

16.74 – 66.81 M. Li et al.

[26]

Lauric acid (33.3

wt%)/activated

carbon

44.07 42.83 65.14 Z. Chen et

al. [27]

Stearic acid (47.5

wt%)/activated

montmorillonite

59.9 55.1 84.4 Y. Wang et

al. [28]

Stearic acid

(83%)/expanded

graphite

53.12 54.28 155.50 G. Fang et

al. [29]

Palmitic acid

(80%)/expanded

graphite

60.88 60.81 148.36 A. Sari and

A.

Karaipekli

[30]

Myristic–

palmitic–stearic

acid (92.86

wt%)/expanded

graphite

41.64 42.99 153.5 X. Yang et

al. [7]

G. Xin et al. [6] studied the influence on phase change

enthalpy of 1 – octadecanol on adding GS. It is seen that

phase change enthalpy of 1-octadecanol decrease on

addition of GS. There was minor reduction in enthalpy 225-

222kJ/kg at 55 oC of GSs loading, while at 10% reduction

in enthalpy of PGPCC and AGPCC reaches to 199kJ/kg

and 195kJ/kg respectively. This reduction is observed

because now volume of PCM decreases as some place of

PCM is occupied by GS which in turn do not contribute to

phase change.

Further it was seen TCE of 13.33 o

C is achieved at 15% of

loading fraction in PGPCC but it is still less than that of

AGPCC.

W. Wang et al. [8] checked the influence of SiO2 over

polyethylene glycol (PCM) and found that latent heat of

polyethylene glycol at temperature 61.8 o

C is 187.3 kJ/kg

which was slightly higher than that of composite which is

162.9 kJ/kg at temperature 61.61 oC, this indicates that there

is no reaction between PCM and silicon dioxide.

X. Fang et al. [11] compared predicted and measured latent

heat of fusion of eicosane – graphite nanofiber composite at

various loading of GNP in figure 3. It is known that latent

heat of fusion is approximately inversely proportional to the

loading. There is decrease latent heat of fusion in composite

as compared to that of pure PCM by 0.5%, 1.7%, 5.4% and

16% on loading of 1%, 2%, 5% and 10% respectively. At




loading of 10% composite has the thermal conductivity of

2W/mK and latent of fusion to be 220kJ/Kg.

Fig 3: Comparison of the measured and predicated latent heat of

fusion of the eicosane-based composite PCMs with various loadings of

the GNPs [11].

A.Sari [13] in his experiment found that on increasing

the percentage of paraffin or decrease in the percentage of

HDPE, there is an increase in the latent heat. At 50:50 ratio

paraffin and HDPE latent heat was 95.7 kJ/kg which get

rise to 192.8 at ratio of 100:0 of paraffin and HDPE. But on

decrease the percentage of HDPE there is decrease in

strength of PCM there percentage is optimized at 77% of

paraffin with 33% HDPE. At this ratio latent heat of

P1/HDPE and P2/HDPE is takes as 146.7 o

C and 162.2 o

C

respectively.

Z. Ling et al. [16] in his experiment on investigation found

that the phase change enthalpy of RT44HC/expanded

graphite (EG) composite with 25% EG is 168.1 kJ/kg while

on increase percentage of EG to 35% phase change

enthalpy decrease to 152.5 kJ/kg.

L. Zhang et al. [17] in their study found that at mass

fraction of 0% of GNP in form stable polyethylene

glycol/polymethyl methacrylate, theoretical latent heat of

melting and freezing was 125kJ/kg and 114kJ/kg

respectively which decrease to approximately to 117kJ/kg

and 113kJ/kg at mass fraction of 8% respectively. Same

was observed as that were observed with another

composites.

R. J. Warzoha et al. [18] investigated the relation between

latent heat of fusion of HGNF/PCM and peak melt

temperature. It is seen in Table V that with increase in

percentage on HGNF in paraffin there is decrease in latent

heat of fusion. Latent heat of fusion of pure PCM is 271.6

kJ/kg which decrease to 242.7kJ/kg at 11.4% of HGNF.

Further with increase in HGNF there is increase in peak

melt temperature from 327.75 K to 333.65 K at 0% to

11.4% respectively.

Table V: Peak melt temperature and latent heat of fusion values for

HGNF/PCM nanocomposites [18].

Sample Peak melt

temperature (K)

Latent heat of

fusion (kJ/kg)

IGI 1230A 327.75 271.6

2.8% HGNF 330.55 252.9

5.8% H-GNF 330.15 251.3

8.5% H-GNF 330.35 250.6

11.4% H-GNF

333.65 242.7

333.65 242.7 242.7

Z. Zhang et al. [19] in his experiment found that at paraffin

mass fraction of 92% latent heat of composite (paraffin and

expanded graphite) was 170.3 kJ/kg which was lower than

that of latent heat of pure paraffin which was 188.2 kJ/kg.

1.3 Temperature variation

H. Yin et al. [1] in his experiment investigated temperature

distribution of paraffin/expanded graphite curve over

different heat input. It is seen that the phase change of

composite PCM is reached in Line 4.

In Figure 4 at heat input 37.5W before that phase change

was not achieved. Further all curve follows same pattern

i.e. curve experience rise till power is supplied and after

that there is decrease when heat input is shutoff.

Fig 4: Temperature variation curves of composite PCM [1].

C. Lin et al. [2] in his experiment which he performed by

using expanded graphite and paraffin composite found that

phase change temperature of composite reduced to 21.6 –

25.5 oC which was 23.9 – 27.1

oC for pure PCM.

O. Sansui et al. [5] conducted an experiment in which they

impregnated GNF in paraffin. They evaluated a transient

temperature profile for various temperature profile. It was

observed that at constant mass/volume and power input,

there was change in heat flux due to change in aspect ratio

i.e. on supplying heat input of 500W at A.R. = 0.5 (q = 2.5

W/cm2), at A.R. = 1 (q = 5 W/cm

2) and at A.R. = 2 (q = 10

W/cm2). It was seen that solidification time of pure paraffin

at A.R. of 1 is 80 min which reduces to 69 min at A.R. of

0.5 and increase to 225 min at A.R. of 2. But when GNF is

embedded in PCM it is observed that solidification time at




A.R. of 0.5 and 2 changes. At AR. Of 0.5 there is reduction

of A.R. to 56 min of pure PCM which is 19% while

reduction of solidification time of A.R. of 2 is 39 min

which is 78% of time of pure PCM.

G. Xin et al. [6]in his experiment evaluated the temperature

response of phase change composite of annealed graphite

and PCM during heating and cooling.

Fig 5 (a) shows temperature response of phase change

composite during heating. To measure transient temperature

response samples of AGPCC, PGPCC both with loading

fraction of 10% and pure PCM is created of circular shape

and put into cylindrical mold which was kept hot isothermal

plate at 105 o

C. When approaching Tm, phase change takes

places and temperature of surface remain stable. Time

required to attain the phase change of 1-Octadecanl was

found to be highest that is 135s and final surface

temperature was found maximum of AGPCC which was

101 oC.

Fig 5(a): Temperature response of PCCs during heating [6]

The beginning temperature of AGPCC was maximum; 101

oC, due to its maximum thermal conductivity. It is clearly

being seen that as the time increases there is a rapid

decrease in temperature of AGPCC as compared to other

two. From their respective plateau length, it was seen that

AGPCC can store higher thermal energy at increased rate

during phase change.

Fig 5 (b): Temperature response of PCCs during cooling [6]

W. Wang et al. [8] in their study found that at 60 o

C PEG

was solid but as the temperature increases to 64 o

C some

part of PCM starts to melt and at 68 o

C there is complete

change of PEG into liquid state.

In contrary to this even at 110 o

C, there was minuscule

amount of volume change in composite of PEG/SiO2

showing that it is in solid state.

„A. Babapoor et al. [15] has his study on change of

properties of paraffin on insertion of carbon fiber. Fig. 6

shows local temperature versus time for composite having

0.46% wt mass fraction of carbon fiber at constant rate of

heat dissipation (2W) and fiber length of 2 mm. It is

observed from the graph that on increasing radial location

there is a decrease in local temperature. Maximum

temperature reaches to 47 0C at 7mm of radial location.

Fig 6: Local temperatures versus time at constant rate of heat

dissipation (2 W) for a composite containing 0.46% wt. carbon fiber

and fiber length of 2 mm [15].

Fig. 7. Time variation of the simulator surface temperature

vs different mass ratios of carbon fiber (fiber length = 1

mm). It is observed that with increase in time there is

increase in temperature battery. It was seen that when

system is enclosed it has its maximum temperature rise as

compared to pure PCM and composite. Temperature curve

can be break down in three portions. First prior to melting

phase when time is less then 50min. In this portion

temperature rise is maximum because of high latent heat. In

second portion time is between 50 min and 150min. where

rise in temperature is at slower rate as phase change occurs.

And in the last portion composites reaches temperature

stability at time greater then 150min. It was observed that

composite with 0.46% mass fraction of carbon fiber is the

most efficacious among all composites.




Fig 7: Time variation of the simulator surface temperature for

different mass ratios of carbon fiber (fiber length = 1 mm) where W1=

0, W2=0.32, W2=0.46, W3=0.56 and W4=0.69 are the mass ratio of

fiber [15].

1.4 Thermal Storage Performance

H. Yin et al. [1] studied the effect of expanded graphite on

the performance of paraffin. It was seen that time required

by pure paraffin to reach 66 o

C from 28.5 o

C is 1010s in

comparison to time for composite is only 350s which was

65.3% of pure PCM. Further time required for cooling of

the composite was 2620s which was 26.2 % lower than that

of pure paraffin.

W. Wang et al. [4] studied the change in thermal

performance of polyethylene glycol/ SiO2 – β AIN

composite. Fig. 8 shows the heat release and storage curve

of pure PCM and composite.

On investigation it was seen that PEG takes 577s to reach

80 oC from 28

oC in contrast to it time taken by composite is

265s to attain same temperature.

Further during solidification process, it was observed that

composite PCM crystallize rapidly as compared to that

PEG. It was seen that the composite takes 1225s to freeze

whereas time taken by PEG to freeze is 2720s.

Fig 8: Heat storage and release curves of PEG and PEG/SiO2/β-AlN

[4]

O. Sansui et al. [5] studied the effect on thermal

performance after the impregnation of GNF in paraffin. Fig

9 shows the relation between Stefan‟s number and time for

composite as well as pure PCM at power input of 4W/cm2

and 20 W/cm2. It is seen that at heat flux of 20W/cm

2 time

required for complete solidification of pure PCM is 52 min

which reduces to 20.5 min on addition of graphite nanofiber

in PCM which is approximately 60% reduction of

solidification time. It is very beneficial in electronic cooling

requires for more operating time, so that PCM can get

rejuvenate for next cycle.

Fig 9: St vs. time the 5.08 cm side length cubic TCU cube with paraffin

and GNF/paraffin [5].

While at a low heat flux of 4 W/ cm2 for pure PCM

solidification time was 27 min but when GNF is embedded

in PCM, it was noticed that there is not requirement of

solidification time because PCM‟s steady state is achieved

under melting time.

B. Wu and Y. m. Xing [9] perform the numerical study and

evaluated the temporal variation of heat transfer for carbon

foam‟s different porosities in organic PCM. On

investigation it was seen that the composite with porosity of

0.95% has heat transfer approximately 3 times greater than

that of heat transfer of pure PCM. It is well evident from

the graph that after some time graph experience negative

trend.

J. M. Marin et al. [12] studied the influence of graphite on

the properties of paraffin. Table VI shows the energy

storage and process time for the accumulator with and

without PCM. It is seen that time taken by system to reach

at zero heat exchange for PCM with graphite is 50% lower

that of pure PCM. Further effect of mixing of graphite in

PCM on energy stored is also very slight about 12% to 20%

reduction.

Table VI: Process time and energy stored for loading and unloading of

the accumulator for the PCM without and with a graphite matrix [12].

Type of

process

C

(m3/h)

Process

time (h)

RT-25

Process

time (h)

composite

Stored

energy

(kJ)

RT-25

Stored

energy

(kJ)

composite

Solidification 100 6.31 3.16 602 525




Solidification 150 5.47 2.55 600 510.75

Melting 100 7.34 2.83 591 476

Melting 150 6.32 3.47 592 475

W. G. Alshaer et al. [14] studied the effect of the two

different carbon foams (CF-20 and KL1-250), multi wall

carbon nanotube on paraffin (RT-65).

Fig. 10. Temperature histories of thermocouples at power

of 30W of different TM modules. It is seen from the graph

8(a) that time taken to reach 60 o

C is approximately 450s

for pure CF-20 whereas for CF-20+RT65 and CF-

20+RT65/MWCNTs is about 600s. Further to reach 80 o

C

time required is 1100s for CF-20 while CF-20+RF65 and

CF-20+RT65/MWCNTs observed time lag of 800s and

1700s respectively.

Fig 10: Temperature histories of thermocouples of different TM

modules (power = 30 W) [14].

Fig. 11. Heater temperatures for different thermal

management modules at different uniform power levels. It

is seen from all curves that with an increase in power

supply of heater there is increase in temperature of heater.

But in all scenario, it was observed that CF-

20+RT65/MWCNTs perform better as compared to CF-20

and CF-20+RF65.

It is seen that that for KL1-250 power supplied was 58W

while for CF-20 was 18W but approximately same steady

state temperature heater temperature is reached. His study

implies that power carrying capacity of KL1-250 is more of

CF-20. When RT65/MWCNTs is doped in KL1-250 steady

state temperature is 1.2 o

C lower than that of KL1-250

while KL1-250+RF65 which can lead to increase in thermal

conductivity.




Fig 11: Heater temperatures for different TM modules at different

uniform power levels [14].

Z. Zhang et al. [19] in their experiment studied the effect of

expanded graphite on thermal storage of paraffin. It is seen

that at 92% of mass fraction of graphite and time period of

123min, temperature remain constant at 68.5 o

C for

composite PCM in contrast to it at time period of 385min

temperature of pure paraffin was 66.8 o

C. This property of

the composite shows thermal conductivity of composite is

higher than that of pure paraffin.

1.5 Thermal Recycle Stability

G. Xin et al. [6] in their study of recycling stability of

composite of GS and organic PCM. Fig. 12 shows the

transient temperature response of PCC before and after

recycling. In order to check thermal stability transient

temperature responses of AGPCC has been compared (at

temperature of 2200 °C annealed GSs and with 10 wt. %

loading fractions) before and after melting-solidification

cycles. Phase change composite was melted till 105°C and

then cooled till 20°C continuously for 50 cycles. It was seen

that phase change enthalpy and thermal conductivity gives

excellent performance.

Fig 12: Transient temperature response of PCC before and after

recycling with temperature °C on y axis and time on x axis [6].

X. Yang et al. [7] studied the change on thermal properties

of myristic acid–palmitic acid–stearic acid and EG

composite after 500 and 1000 cycles. They found that after

500 cycle there is increase in 1.03°C in freezing

temperature which changes to 44.02°C while there is

decrease of 0.46°C in melting temperature which changes

to 41.18°C. Further they also observed change in latent heat

of freezing and melting which changes to 150.8 kJ/kg and

152.6kJ/kg, which is very slight. After 1000 cycle change

in solidification and melting temperature is 0.28°C and

0.48°C respectively, while that is latent heat of

solidification and melting is -1.32% and -1.62%

respectively.

1.6 Effect of temperature on thermal conductivity

G. Xin et al. [6] studied the impact on thermal conductivity

on change in temperature. Fig 13 shows relation between

annealed graphene/PCC (AGPCC) at 5 wt. % loading

fractions of GSs and various annealing temperatures.

It is found that with the anneal fraction of 5% thermal

conductivity increase from 0.7 W/mK to 1.32 W/mK with

temperature ranging between 1600 °C to 2200 °C. While at

this fraction increase in TCE from 2.18 W/mK to 5 W/mK.

This is due to elimination of lattice defect on Gs and of

oxygen functional group.

Fig 13: Thermal conductivity and thermal conductivity enhancement

factor of graphene-PCCs annealed graphene/PCC (AGPCC) at 5 wt

% loading fractions of GSs with various annealing temperatures [6].

X. Fang et al. [11] conducted the experiment in which they

added graphene nano platelets in organic PCM eicosane to

evaluated change in thermal conductivity as function of

temperature of composite as compared to that of pure PCM.

It is seen that at loading of 0%, 1% and 2% respectively

curves are nearly parallel to each other i.e. independence of

temperature but there is increase in thermal conductivity

with increase inn loading. At 10% loading a trough is

observed between 20-30oC having nadir at 25

oC. At 1%

loading value of thermal conductivity is approximately

2W/mK which was approximately 400 times higher than

that of pure eicosane. On comparison to thermal

conductivity of eicosane/CuO presented by Nabil and

Khodadadi much lesser even for 10% of composite than 1%

of eicosane/GnP composite.

Further they studied the change in thermal conductivity in

temperature range of 30 o

C to 35 o

C. It is observed from the

graph that there is minute increase in thermal conductivity

from 30 o

C to 31 o

C. But after that there is constant increase

in thermal conductivity at all loading. In few loadings there

is approximately 1.2W/mK increase in thermal conductivity

from 30 oC to 35

oC.

Z. Ling et al. [16] studied the temperature dependent

thermal conductivity of RT44HC/EG composite where

mass fraction of EG is 25wt%. It is seen that thermal

conductivity of composite increases up to 50-60% on

addition of EG to PCM. Further it is also observed that

thermal conductivity above 45 o

C and below 35 o

C is




approximately same. But within phase change temperature

range there is there is nearly double rise in thermal

conductivity i.e. at 42 o

C thermal conductivity of composite

with density 700kg/m3 is 14.7W/mK which approximately

double of thermal conductivity at 30 oC which is 30W/mK.

R. J. Warzoha et al. [18] studied the temperature dependent

thermal conductivity HGNF and paraffin composite. Fig.

14. (a) shows the temperature-dependent thermal

conductivity of HGNF/PCM composites, (b) variance ratio

(ratio of solid and liquid thermal conductivity).

From the figure it is seen that the thermal conductivity in

liquid phase is lower than that of thermal conductivity in

solid phase. It is seen that thermal conductivity is

dependent on temperature

But it cannot be considered as strong function of

temperature.

Fig 14: Temperature-dependent thermal conductivity of HGNF/PCM

composites, (b) variance ratio (ratio of solid and liquid thermal

conductivity) [18].

It is seen from 14(a) there with increase in percentage of

inclusion of HGNF from 0 to 11.4% & there is increase in

value of k/k base paraffin solid from 1 to 1.8 for solid phase. In

liquid phase region there is decrease in thermal

conductivity of 11.4% HGNF to nearly 1.

Further on evaluating ratio of thermal conductivity in solid

phase to that in liquid phase it is seen that at 8.5% of HGNF

ratio is highest nearly 2.4.

2. INORGANIC PCM COMPOSITES:

2.1 Thermal conductivity

V. Goyal and A. A. Balandin [23] performed an experiment

to evaluate the thermal conductivity of pristine silver

epoxy, hybrid graphene-FLG-silver-epoxy composites. It is

seen in Fig 15 that at 0% of graphene volume fraction

thermal conductivity of composite was 1.67WmK but it

was observed that with increase in percentage of volume

fraction there was drastically rise in thermal conductivity.

Fig 15: Thermal conductivity of the pristine silver epoxy, hybrid

graphene-FLG-silver-epoxy composites, and the reference silver

epoxy-carbon black composites as a function of the volume fraction f

of the graphene-FLG nano-micro-filler [23].

Further they also evaluated thermal conductivity of hybrid

graphene-FLG-silver-epoxy composites as a function of

temperature. It is observed that temperature has

insignificant effect over thermal conductivity of silver

epoxy graphene composite which was very beneficial.

Further in range of temperature from 0-75 o

C with rise in

volume fraction of graphene there was increase in thermal

conductivity but remain constant with increase in

temperature.

Fig 16: Thermal conductivity of the hybrid graphene-FLG silver

epoxy composite as a function of temperature for 1%, 3%, and 5% of

the volume fraction of graphene-FLG filler loading. Note that the

thermal conductivity almost does not change in the examined range,

which is important for TIM applications [23].

L. Zhong et al. [21] performed an experiment to study

change in thermal conductivity of three binary molten salts

(LiNO3–KCl, LiNO3–NaNO3 and LiNO3–NaCl) on

impregnation of expanded graphite. It is known that thermal

conductivity of expanded graphite is 7.34 W/mK and that

of molten salts are usually around 1 W/mK. Therefore, in

order to increase the thermal conductivity of PCM, higher

thermal conductive material is added. It is seen in fig 17

that thermal conductivity of composite is increased to 5-6

times that of their respective pure form PCM.




Fig 17: Thermal conductivity of the samples [21].

F. Frusteri et al. [22] performed an experiment to check the

influence of carbon fiber on the PCM 44 which is Mg

(NO3)26H2O–MgCl26H2O–NH4NO3. They observed the

enhancement of thermal conductivity at different length of

fiber. It is seen from the graph that thermal conductivity

increases with increase with increase in mass fraction of

carbon loading. Further it was also seen that thermal

conductivity of decrease with increase in size of carbon

fiber.

2.2 Phase change properties

L. Zhong et al. [21] performed an experiment to study the

influence of expanded graphite on LiNO3–KCl, LiNO3–

NaNO3 and LiNO3–NaCl. It is seen that melting

temperature of pure PCM is lower than that of composite

PCM (impregnated with expanded graphite). While other

properties such as latent heat of fusion, solidification

temperature and enthalpy of crystallization are higher for

pure PCM as compared to that of composite PCM. Further

all properties of LiNO3–KCl and its composites are lower

than that of LiNO3–NaCl and its composites.

2.3 Thermal energy system

Z. Li and Z. G. Wu [20] performed a numerical study to

study the thermal energy of NaNO3 in copper in steady

state an in unsteady state.

In steady state they found that total heat flux without

natural convection of pure PCM is 196 W/m2 which is very

less as compared to that of composite PCM. It was seen that

maximum heat flux is obtained at porosity of 0.90 and

30PPI which is 5656.9 W/m2 at 96.3 % mass fraction of

copper matrix struts. As compared to heat flux without

convection, heat flux in convection get significantly rise. It

was observed that heat flux of pure liquid PCM was 3793.0

W/m2

which increases to 11965 W/m2

at porosity of 0.90

and 5PPI with 78.9 mass fraction of copper matrix strut.

While in unsteady state it is seen that melting time of the

pure PCM is 739 s which get reduced to 29.9 – 38.7% and

20.6 – 29.0% with composite of porosity of 95 and 90%

respectively. Further melting time of composite with

porosity of 90% was 69-75% lower than that of composite

with porosity of 95%. The melting process is endothermic

process.

It was further seen that solidification time of pure PCM is

5406s which gets reduced to 213s with copper foam having

porosity of 0.90 and 30PPI. It was seen that total

solidification time for composite with porosity of 90% is

nearly half of that of composite with porosity of 95%.

III. Summary

S

No

Author PCM Used Nature of

PCM

Additives Result

1 H. Yin et al. [1] Paraffin Organic Expanded Graphite It is seen that when paraffin is absorbed in EG heat release period and

heat storage period is reduced by 26.2% and 65.3%

2 C. Lin et al. [2] Paraffin Organic Graphite Sheets It is seen that in thermal conductivity of composite reaches to 3.95W/mK

which 0.16W/mK of pure PCM was.

Further there is decrease in latent heat by 41.8 kJ/kg.

3 F. Yavari et al. [3] 1-

octadecanol

Organic Graphene Thermal conductivity rises to 140% on adding 4% of graphene and heat

of fusion decrease to 15.4%.

4 Wang et al. [4] PEG Organic Silica gel and β-

Aluminum Nitride

powder

It is observed that there is melting temperature does not change but there

is increase in thermal conductivity from 0.3847W/mK to 0.7661W/mK

5 O. Sansui et al. [5] Paraffin Organic GNF It is observed that GNF reduces solidification time by 61% over pure

paraffin at aspect ratio of 1

6 G. Xin et al. [6]

1-

Octadecano

l

Organic Graphene Sheet At 10% weight there is increase in thermal conductivity to 600% of

composite as compared to that of pure PCM




7 X. Yang et al. [7] Myristic

Acid-

Myristic

Acid-

Palmitic

Acid

Ternary

Eutectic

Mixture

Expanded Graphite Melting Temperature of composite 41.64oC

Freezing Temperature of composite 42.99 oC

Latent heat of melting and freezing are 153.5J/g and 151.4J/g

At 1000 thermal cycle latent heat changes 1.63% and 1.32% respectively.

8 Wang et al. [8] PEG Organic Silicon dioxide It is seen that there is decrease in latent heat to 162.2J/g from 187.3J/g

and thermal conductivity increase to 0.3615W/mK which is 21% of

thermal conductivity at 0% of silicon di oxide.

9 B. Wu and Y. m.

Xing [9]

Paraffin Organic Graphite foam With porosity of 0.95% heat transfer of composite is approx. 3 times of

pure PCM.

10 A. Trigui and M.

Karkri [10]

Paraffin Organic composite

paraffin/epoxy

resin/copper tube (1)

and paraffin/epoxy

resin/brass tube (2)

It was seen that thermal conductivity of composite PCM was higher in

liquid state than pure PCM. While thermal conductivity of sample (1) was

higher than sample (2)

11 X. Fang et al. [11] Eicosane Organic GNP At 10% of GNP thermal conductivity reaches to 400% of pure PCM at 10

oC.

12 J. M. Marin et al.

[12]

Paraffin Organic Graphite Time taken to reach zero heat exchange of composite is nearly 50% lower

than pure PCM

13 A. Sari [13] Paraffin Organic High density

Polyethylene

It is seen that maximum percent of PCM in composite without leakage

was 77%. Thermal Conductivity of P1/HDPE and P2/HDPE increase to

14% and 24% respectively.

14 W. G. Alshaer et al.

[14]

RT-65 Organic CF-20 and KL1-250

and MWCNT

It was seen that CF-20 was more effective as compared to KL1-250

15 A. Babapoor et al.

[15]

Paraffin Organic Carbon Fiber At 0.46% mass of Carbon fiber maximum temperature rise reduced to

45%

16 Z. Ling et al. [16] RT44HC Organic Expanded Graphite On increase in mass fraction of EG there is increase in thermal

conductivity up to 60 times

17 L. Zhang et al. [17] PEG/PMM

A

Organic GNP At 8% of GNP thermal conductivity increased to 9 times that of pure

PCM

18 R. J.

Warzoha et al. [18]

Paraffin Organic Herringbone style

graphite nanofibers

It was observed that HGNF /PCM thermal conductivity increase

exponentially in Paraffin solid phase.

19 Z. Zhang et al. [19] Paraffin Organic Expanded Graphite It was seen that there is decrease in latent heat on adding EG to paraffin.

Latent heat reaches to 170.3J/g as compared to pure PCM which was

188.2J/g.

20 Z. Li and Z. G. Wu

[20]

Sodium

Nitrate

Inorganic Copper matrix Doped NaNO3 shows 80% reduced melting time than pure NaNO3, heat

transfer coefficient increased by 28.1 times in solid phase.

21 L. Zhong et al. [21] Binary

molten salts

Inorganic Expanded graphite Thermal conductivity increased by 4.9-6.9 times when impregnated with

EG

22 F. Frusteri et al. [22] PCM44 Inorganic Carbon fiber Thermal conductivity quadruples at 7% of fiber loading wt%

23 C. Y. Zhao and Z.

G. Wu [24]

NiNO3 Inorganic Metal Foam/expanded

Graphite

It was seen that heat transfer can be increased with both metal foam and

EG, but metal foam gives maximum performance.

The findings from the summarized result indicate that the Graphene/Expanded graphite/GNF composites increase the thermal

conductivity in the range of 19-60 times their non-doped organic samples and decrease latent heat values; the dispersion of

heat channels inside the composite significantly lower the melting time and solidification time. The inorganic composites

however show improvement in the melting times and heat transfer coefficients, the conductivity increase being not as

significant as their organic counterparts are.

IV. Conclusion

On studying to conventional active cooling by forced

air/liquid convection which is cumbersome and complex,

the passive thermal management system based on phase

change materials shows highlights of high efficiency,

compactness, no extra power input and the very simplicity.

However, the phase change materials with proper phase

transition temperatures are useful in keeping the

temperature of electronic devices within the desired range

for a long duration. The low thermal conductivity of

traditional organic and inorganic phase change materials

thwart rapid heat liberation from electronic system to

phase change materials and the augmentation of heat cause

to an extra high temperature. On reviewing works on

PCM-based thermal energy storage system, it is seen

expanded graphite and metal foam has been to be

efficacious in enhancing the thermal conductivity and

controlling temperatures of phase change materials. The

thermal properties which extracted from various research

works are: thermal conductivity, latent heat, temperature

variation, thermal storage performance and thermal

recyclability. Thermal conductivity can be enhanced by




inserting expanded graphite matrix in to PCM matrix or by

inserting foam in PCM. Although PCMs have large

amount of latent heat, but it decreases on incorporating

additives. Application of the passive thermal management

system is not suitable for devices operating non-

periodically.

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https://www.sciencedirect.com/science/article/pii/S1359431111003905#!

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