Mya Mya Khin M.eng Thesis

ENCAPSULATION OF PHASE CHANGE MATERIALS (PCMS)
FOR HEAT STORAGE
MYA MYA KHIN
(B.E., Yangon Technological University)
A THESIS SUBMITTED
FOR THE DEGREE OF MASTER OF ENGINEERING
DEPARTMENT OF CHEMICAL & ENVIRONMENTAL ENGINEERING
NATIONAL UNIVERSITY OF SINGAPORE
2003
Acknowledgement
ACKNOWLEDGEMENT
I wish to express my thanks to the following institution and persons, without whose
assistance and guidance this thesis would not have been possible.
To the National University of Singapore, for the postgraduate research
scholarship, without which I would not be able to continue my higher degree
studies.
To my supervisors, Associate Professor M.S Uddin and Associate Professor
M.N.A Hawlader for their constant guidance, kindness, forgiveness, care, concern
shown throughout the project and time taken to read the manuscript.
To all the technical and clerical staff in the Chemical & Environmental
Engineering Department for their patience and help.
To Dr Zhu Haijun for giving me some informations and literature for this project.
To all my colleagues from E4A-07-07 especially Mr. Peng Zanguo for their help
on different occasions, discussion and for their encouragement during my tenure at
NUS.
To my parents and family members and my best friend Miss Thin Thin Aye for
their continuous love and encouragement throughout the study.
Last but not least, my thanks to all who have contributed in one-way or another to
make this thesis possible.
i
TABLE OF CONTENTS
ACKNOWLEDGEMENT i
TABLE OF CONTENTS ii
SUMMARY v
LIST OF FIGURES viii
LIST OF TABLES xi
CHAPTER 1 INTRODUCTION 1
1.1 General background 1
1.2 Objective and scope of thesis 4
CHAPTER 2 LITERATURE REVIEW 6
2.1 Thermal energy storage 6
2.2 Thermal energy storage techniques 7
2.3 Candidate heat storage materials 15
2.4 Factors affecting the energy storage capacity of PCM 20
2.5 Encapsulation of phase change materials 20
2.6 Methods of microencapsulation 25
2.7 Thermal cycling test for encapsulated PCM 30
2.8 Heat transfer of PCMs 31
2.9 Scope of the present work 34
CHAPTER 3 MATERIALS AND EXPERIMENTAL 34
METHODS 36
3.1 Materials 36
ii
3.2 Characteristics of core and coating materials 37
3.3 Experiments 40
3.3.1 Complex coacervation 40
3.3.2 Spray drying 42
3.4 Characteristics and performance of microcapsules 44
3.4.1 Energy storage and release capacities 44
3.4.2 Thermogravimetric analysis 45
3.4.3 Surface morphology and characterization of inner 46
structure
3.4.4 Microencapsulation efficiency 47
3.4.5 Estimation of core to coating ratio 47
3.4.6 Chemical structure stability evaluation 48
3.5 Accelerated test process 48
3.6 Fluidized bed heat exchanger for microencapsulated PCM 51
CHAPTER 4 RESULTS AND DISCUSSION 54
4.1 Encapsulation efficiency 54
4.2 Estimation of core to coating ratio 63
4.3 Thermal performance 64
4.4 Surface morphology and inner structure characterization 68
4.4.1 Surface morphology 68
4.4.2 Inner structure 69
4.5 Thermogravimetric analysis 70
4.6 Thermal cyclic test 75
iii
4.7 Structural stability 88
4.8 Thermal performance of microencapsulated PCM in 91
fluidized bed heat exchanger
4.8.1 Temperature profiles 91
4.8.2 Total heat storage and release 94
CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS 96
5.1 Conclusions 96
5.2 Recommendations 99
REFERENCES 100
APPENDICES 113
iv
SUMMARY
Microencapsulated PCMs are micron size phase change materials enclosed in a protective
wrapping. The microcapsule prevents the leakage of the material during its phase change.
It also provides larger heat transfer area per unit volume of heat storage vessel. It could
be used in solar energy storage, waste heat utilization, and space heating and cooling.
This study investigated the use of complex coacervation and spray drying methods for
microencapsulating paraffin wax by polymeric materials (gelatin and acacia) in an
aqueous system. Experiments on operational variables to select suitable conditions were
carried out for complex coacervation. Encapsulation efficiency was found to be higher
when the products had lower core to coating ratios. The optimum condition for various
core to coating ratios was found to be 10 minutes homogenizing time and the amount of
cross-linking agent 6~8 ml. Non-linear regression was used to correlate the encapsulation
efficiency and the parameters studied. In spray-drying method, decrease in encapsulation
efficiency with increase in the ratio of core to coating was observed. The optimum core to
coating ratio was found to be 1:2.
In the studies on thermal performance analysis by Differential Scanning Calorimetery
(DSC), the effect of core to coating ratio on energy storage/release capacities was
investigated. The higher paraffin wax content in the sample gave the higher energy
storage/release capacities. The energy storage/release capacities of the coacervated
microcapsules were higher than those of the spray-dried samples. Energy storage/release
v
capacities were found to be in the range of 91-239 J/g for microencapsulated PCMs
prepared under different conditions.
Further characterization for both coacervated and spray-dried samples focused on surface
morphology and inner structure by using microtone and Scanning Electron Microscopy
(SEM). SEM analysis showed that spray-dried samples were more regular and spherical
in shape compared to coacervated samples. Both samples contained a few small globules.
Size of coacervated particles ranged from 3.3 to10.5 µm. Spray-dried microcapsules had
a diameter ranging from 1.3-10.1 µm. The inner structure characterization showed that
both coacervated and spray-dried samples consisted of a polymeric matrix surrounding
numerous globules.
The thermal stability of both coacervated and spray-dried samples was estimated by using
Thermogravimetry (TG) analysis. Thermal decomposition temperatures of core and
coating materials were determined from TG output curves. The decomposition
temperature of paraffin wax existed between 200 and 300°C, and the decomposition
temperature of polymer network (gelatin and acacia) was observed between 300 and
400°C. The TG output curve for spray-dried samples had two peaks between 300 and
400°C. The second extra peak showed the decomposition temperature of unreacted
coating materials.
Thermal stability of microencapsulated PCMs was also checked through accelerated
thermal (melt/freeze) cyclic tests. Both samples were subjected to thermal cycle tests up
vi
to 2000 cycles. DSC analysis was carried out to measure energy storage/release
capacities, melting temperature and specific heat capacity after specific number of cycles.
Both the coacervated and spray-dried samples showed good thermal stability throughout
cycling process. Fourier Transform Infrared Spectophotometery (FTIR) analysis also
confirmed distinct chemical stability of both samples throughout thermal cycling.
Finally, the thermal performance of the PCM was carried out in as fluidized bed heat
exchanger. Heat transfer between the spray-dried encapsulated PCM and air was studied
during heating and cooling process. It was found that the time taken for charging and
discharging the capsules was about 760 and 600 seconds, respectively. Total energy and
release amount were found to be 2953 and 2431 J. Therefore, it was observed that it was
efficient heat exchange system.
vii
LIST OF FIGURES
Figure 2.1: Areas of research in thermal energy storage system 8
Figure 2.2: Thermal energy storage strategies 9
Figure 2.3: Various forms of capsules 21
Figure 3.1: Molecular structure of paraffinic hydrocarbons 37
Figure 3.2: Molecular structure for gelatin 38
Figure 3.3: Schematic representation of the coacervation process 41
Figure 3.4: Photograph of mini spray dryer used in microencapsulation of 43

paraffin wax
Figure 3.5: Schematic diagram of thermal cyclic system 50
Figure 3.6: Actual thermal cyclic system in laboratory 51
Figure 3.7: Schematic diagram of experimenatal set up for fluidized bed 53
Figure 4.1: Effect of homogenizing time and the amount of cross-linking 58

agent on encapsulation efficiency at 2:1 core to coating ratio (HCHO)



agent on encapsulation efficiency at 2:1 core to coating ratio
(CH3CHO)

(CH3CHO)

(CH3CHO)
viii
Figure 4.7: The output curve of DSC for spray-dried sample 2:1 67
Figure 4.8: The output curve of DSC for coacervated sample 2:1 67
Figure 4.9: SEM profile of the coacervated samples 68
Figure 4.10: SEM profile of the spray-dried samples 68
Figure 4.11: Inner structure of spray-dried samples (fresh) 71
Figure 4.12: Inner structure of spray-dried samples (cycled) 71
Figure 4.13: Inner structure of coacervated samples (fresh) 72
Figure 4.14: Inner structure of coacervated samples (cycled) 72
Figure 4.15: TG thermogram of coacervated microcapsules 74
Figure 4.16: TG thermogram of spray-dried microcapsules 74
Figure 4.17: DSC output curve for 1:1 coacervated sample after 500 cycles 79
Figure 4.18: DSC output curve for 1:1 coacervated sample after 2000 cycles 79
Figure 4.19: DSC output curve for 2:1 spray-dried sample at 0 cycle 80
Figure 4.20: DSC output curve for 2:1 spray-dried sample after 1500 cycles 80
Figure 4.21: DSC measurement of melting temperature of microencapsulated 84

paraffin wax (spray-dried 1:1) after 500 cycles


paraffin wax (coacervated 2:1) at 0 cycle

paraffin wax (coacervated 2:1) after 2000 cycles
Figure 4.25: DSC measurement of specific heat capacity of microencapsulated 86

paraffin wax (spray-dried 1:2) at 0 cycle

ix

Figure 4.29: FTIR output curve for spray-dried samples with 1:1 core to 90
coating ratio
Figure 4.30: FTIR output curve for coacervated samples with 1:1 core to 90
coating ratio
Figure 4.31: Temperature profiles during heat storage stage 93
Figure 4.32: temperature profiles during heat release stage 93
Figure 4.33: Heat storage with time during heat storage stage 95
Figure 4.34: Heat release with time during heat release stage 95
x
LIST OF TABLES
Table 2.1: Comparison of various heat storage media 13
Table 2.2: Physical properties of some PCMs 16
Table 2.3: Comparison of organic and inorganic materials for heat storage 19
Table 2.4: Important characteristics of energy storage materials 19
Table 2.5: List of published encapsulated PCM systems 24
Table 3.1: Materials used in the microencapsulating of paraffin wax 36
Table 3.2: Operating conditions for spray drying microencapsulation 44
Table 4.1: Encapsulation efficiency of coacervated capsules 55
Table 4.2: Encapsulation efficiency of coacervated capsules with 36% 55

formaldehyde
Table 4.3: Encapsulation efficiency of coacervated capsules with 50% 56

gluteraldehyde
Table 4.4: Non-linear regression analysis of encapsulation efficiency using 62

formaldehyde
Table 4.5: Non-linear regression analysis of encapsulation efficiency using 62

gluteraldehyde
Table 4.6: Encapsulation efficiency of spray-dried samples 63
Table 4.7: Comparison of experimentally measured core to coating ratio 64

with designed values
Table 4.8: Energy storage and release capacities for coacervated and spray-dried 66
microencapsulated paraffin wax
Table 4.9: Energy storage and release capacities for microencapsulated 77

paraffin wax (2:1 coacervated sample)


xi
paraffin wax (2:1 spray-dried sample)


Table 4.15: Thermophysical properties of microencapsulated paraffin 82

wax (coacervated 2:1) with test cycles



wax (spray-dried 2:1) with test cycles


xii
Chapter 1 Introduction
CHAPTER 1
INTRODUCTION
1.1 General background
Renewable energy has been used over the last two decades to save the costs and adverse
environmental pollution effects of fossil fuel (Klass, 2003). Today, use of the renewable
energy provides electricity and it has been used to improve solar water heating and space
application of an advanced power system over the past few years (Fath, 1995). However,
the main problems for renewable energy are:
(1) Solar radiation is intermittent by its nature; its total available value is a factor of
time, weather condition and latitude.
(2) Energy sources and the demands, in general, do not match each other.
Therefore, scientists investigated technically to solve these problems. Finally, they found
that energy storage is one of possible solutions for energy conservation and leveling of
energy demand patterns. Thermal energy storage (TES) is considered by many to be one
of the energy storage technologies (Dincer and Dost, 1996). TES contains a thermal
storage mass, and can store heat or cool. Basically, it can be classified as latent, sensible
and thermo-chemical energy. Among these energy storage types, the most attractive form
is latent heat storage in phase change material (PCM) because of the advantages of high
storage capacity in a small volume and charging/discharging heat from the system at a
nearly constant temperature (Abhat, 1983).
1
In a latent heat energy storage system, one of the main elements is the PCM and its
selection criteria. Most investigations were focused on salt hydrates, paraffin, non-
paraffin organic acids, clathrates and eutectic organic and inorganic compounds (Lane,
1986). Among those materials, paraffin wax offers more desirable properties such as non-
poisonous, chemically stable, self-nucleating, negligible supercooling, low vapor pressure
in the melt, no phase segregation and commercially available at reasonable cost (Abhat,
1978). Therefore, in this study, paraffin wax was emphasized.
The application of conventional paraffin wax for heat storage has some limitations. They
are as follows:
(1) paraffin wax has low thermal conductivity approximately 0.18 W/m K (Abhat and
Malatids, 1981) that leads to low heat transfer;
(2) energy withdrawn from paraffin wax during cooling is limited by the fact that the
storage medium begins to solidify on the surface of heat exchangers, the layer of solid
material can act as insulating material;
(3) large volume change during phase transition;
(4) if heat transport medium is air, oxidation of paraffin wax produces complex
compounds, aldehydes, ketones, etc. that can lead to toxic to our environment (Lane,
1986);
(5) conventional particles of paraffin waxes are slightly sticky and can stick together to
form large lumps, clogging occurs in a heat storage system, resulting in failure to
circulate heat transport fluid through the system (Winsters, 1991). These limitations can
result in decreasing in energy storage capacity.
2
In order to overcome these problems, Patel (1968), Patenkar (1980), Fouda et al. (1984),
Garg et al. (1985) and Yanadori et al. (1989) have identified heat transfer enhancement
concepts such as the use of agitators, scrapers and slurries in heat exchangers. The
disadvantage of their heat exchanger development is increasing the cost and complexity
of thermal energy storage devices. In order to solve these problems, both material
investigation and heat exchanger development should be performed. Therefore, the
studies focused on both cases were investigated (Hawlader et al., 2000). They observed
and reported that PCM should be bounded within a secondary supporting structure and
the application of a packed/fluidized bed heat exchanger is a better way of heat transfer
enhancement.
Therefore, the progress in latent heat storage systems mainly depends on heat storage
material investigations and on the development of heat exchangers that assure a high
effective heat transfer rate to allow rapid charging and discharging. The required heat
transfer surfaces should be large to maintain a low temperature gradient during these
processes (Banaszek et al., 1999).
Microencapsulation refers to a process where droplets of liquids, solids, or gases (core)
are coated by thin films (coatings) that protect the core material (Sheu and Rosenburg,
1995). The National Cash Register for commercially applying in carbonless copy paper
started encapsulation process at 1930 (Green and Schleicher, 1956). Recently,
encapsulation processes have been developed in various fields such as pharmaceutical
industry, food industry, biomedical field, coating of PCMs for better heat storage system
and so on. The advantages of using microencapsulated paraffin wax in fluidized bed heat
3
exchanger are that it provides large heat transfer area per unit volume and provides higher
heat transfer rate due to low thermal resistance between the heat transfer fluid and the
PCM and high convective heat transfer by heat transfer fluid in a fluidized bed (Hawlader
et al., 2000).
1.2 Objective and scope of thesis
For many applications, encapsulated PCMs were produced by researchers. Inaba et al.,
1997 prepared encapsulated paraffin wax by using interfacial polymerization and
integrated the samples with building materials to reduce overheating in summer and to
take effect storage discharge by ventilation. Xiao et al., 2000 prepared matrix type
microcapsules (paraffin wax) by using interfacial polymerization and used them as latent
heat storage materials for thermal storage units. Hawlader et al., 2002 prepared the
microcapsules by using complex coacervation method and studied thermal performance in
packed bed heat exchanger.
All preliminary studies showed that encapsulated paraffin wax was prepared by interfacial
polymerization and complex coacervation methods. However, not much work was
reported on the inner structure of the microcapsules, thermal cycles test on microcapsules
and the thermal performance of the encapsulated PCM in fluidized bed heat exchanger.
The overall objective is to synthesize microencapsulated paraffin wax and to evaluate
thermal performance of microencapsulated paraffin wax in fluidized bed heat exchanger.
The scope encompasses the following aspects of work:
4
(1) preparation of microencapsulated paraffin wax
(2) characteristic evaluation of encapsulated paraffin wax
(3) to study the effects of thermal cycling on the thermal properties of
(4) to study heat transfer behavior in fluidized bed exchanger.
This thesis is presented by organizing five chapters including introduction, Chapter 1. In
chapter 2, literature review on the renewable energy and its application, thermal energy
storage techniques and materials are presented. Furthermore, literature review on
encapsulation of PCMs, encapsulation techniques and heat transfer development for
PCMs are also presented in this chapter. Chapter 3 lists the materials used in this
experiment, the experimental detail procedures, the evaluation techniques and the
equipments used for characterization of microencapsulated paraffin wax. Chapter 4
presents experimental results and discussion on characterization of microencapsulated
paraffin wax, the effect of thermal cyclic test on thermal properties and heat transfer in
fluidized bed heat exchanger. Chapter 5 summarizes the conclusions of the present work
and recommendation for future work.
5
Chapter 2 Literature Review
CHAPTER 2
LITERATURE REVIEW
In this chapter, literature review on the most challenging techniques of thermal energy
storage and the advantages and disadvantages of each storage techniques are presented.
Moreover, the study of heat storage materials, encapsulation of PCMs and encapsulation
techniques, laboratory test of freeze-melt behaviour of recent researches on heat transfer
enhancement of PCMs has been included.
2.1 Thermal energy storage
Renewable energy is an intermittent energy source. For example, intermittence of solar
energy is caused by day-night cycles, seasons and weather conditions. Similar problems
arise for waste heat recovery systems, where the waste heat availability and utilization
periods are different. Therefore, thermal energy storage (TES) is an essential technique for
thermal energy utilization to solve the intermittence problems and levelling energy supply
and demand. A large volume of TES materials can store the entire daily and annual energy
requirement. The optimum size is mainly dependent upon meteorological conditions,
storage temperature, storage heat losses, economic viability of storage medium, collector
area and efficiency. (Rosen, 1992).
Irrespective of their sizes, all TES system must satisfy certain characteristics. The desired
characteristics of TES are as follows:
compact, large storage capacity per unit mass and volume;
heat storage medium with suitable properties in the operating temperature range;
6
capability to charge and discharge with largest heat input/output rates but without
large temperature gradients;
able to undergo large number of charging/discharging cycles without loss in
performance and storage capacity;
small self-discharging rate i.e. negligible heat losses due to surroundings;
long life;
inexpensive.
The research areas for TES systems are shown in the Figure 2.1. New TES concepts and
improvements required in the performance of TES system, the design of compact TES
systems, and the use of TES in practical energy applications are outlined. Research on
TES has been broad based and productive, and directed towards the resolution of specific
TES issues and new TES material.
2.2 Thermal energy storage techniques
For thermal energy storage, there are two alternatives:
sensible heat utilization;
latent heat utilization.
An overview of major TES techniques is presented in Figure 2.2. The storage techniques,
materials and their advantages and disadvantages are described in the following section.
7
Thermal energy storage
Materials research Heat exchanger development
Selection of materials in appropriate Selection of type of exchanger and

range parameters
Thermal analysis
Thermal storage material Construction of material
Simulation
Thermophysical Compatibility of
property data materials
Experimental
Melting-solidifying research
characteristics DSC
(Differential Scanning
Laboratory models
Calorimetry)
TA (Thermal
Analysis)
Prototypes
Short term behavior

Pilot Plants
Long term behavior Incorporation

into
heating/cooling
systems
Field tests
Thermal cycle
Useful life Final cost analysis
Commercial product
Figure 2.1 Areas of research in thermal energy storage systems (Zalba et al., 2003)
8
Thermal energy
storage
Thermo-
chemical Sensible heat Latent heat
Gas-liquid Solid-gas
Solid-liquid Solid-solid
Organics Inorganics
Eutectics single Mixtures Eutectics single Mixtures

temperature temperature temperature temperature
interval interval
Paraffins Fatty acids Hydrated

(alkanes salts
mixtures)
Commercial Analytical
grade grade
Figure 2.2 Thermal energy storage strategies (Zalba et al., 2003)
9
Sensible heat storage
Sensible heat storage medium is carried out by adding energy to a material to increase its
temperature without changing its phase. The amount of heat released or absorbed (Q), as
the medium is cooled or heated between temperatures T1 and T2, can be mathematically
illustrated by Equation 2.1.
T2
Q = ∫ mcpdT (2.1)
T1
Q = the amount of heat released or absorbed (J)
m = the mass of heat storage/release material (g)
cp = specific heat capacity of heat storage/release material (J kg-1°K-1)
T1 and T2 = initial and final temperatures of heat storage medium (°C)
Sensible heat storage media can be classified on the basis of storage media as (1) liquid
storage media (water, oil-based fluids, molten salts, etc.) and (2) solid media storage
(rocks, metals and others) (Duffy and Beckman, 1989).
Water as storage material has the advantages of being inexpensive and readily available,
of having excellent heat transfer characteristics. Hot water is required for washing,
bathing, etc. and it is commonly employed in radiators for space heating. Water also can
be used as storage and as a transport medium of energy in a solar energy system.
Consequently, it is the most widely used storage medium today for solar based warm
water and space heating applications. However, its major drawbacks include difficulties:
(1) system corrosion and leakage, (2) due to its high vapor pressure, it requires costly
10
insulation and pressure withstanding containment for high temperature applications and
(3) large size and large temperature swing during the addition and extraction of energy
(Wyman et al., 1980).
The most commonly proposed substitutes for water are petroleum based oils and molten
salts. The heat capacities are 25-40% of that of water on a weight basis. However, these
substitutes have lower vapor pressure than water and are capable of operating at high
temperatures exceeding 300°C. However, it can be limited due to stability and safety
reasons and high cost. In addition, it is highly corrosive, and there is a difficulty in
containing it at high temperatures (Hasnain, 1998).
For a low as well as high temperature thermal energy storage, solid materials such as
rocks, metals, concrete, sand and bricks etc. can be used. In this case, the energy can be
stored at low or high temperatures, since these materials will not freeze or boil. The
difficulties of high vapor pressure of water and the limitations of other liquids can be
avoided by storing thermal energy as sensible heat in solids. Moreover, solids do not leak
from the container.
The pebble bed or rock pile consists of a bed of loosely packed rock material through
which the heat transport fluid can flow. The thermal energy is stored in the packed bed by
forcing heated air into the bed and utilized again by recirculating ambient air into the
heated bed. The energy stored in a packed bed storage system depends, apart from the
thermophysical properties of the material, on several parameters, including rock size and
shape, packing density, heat transfer fluid etc.
11
Probably more important than rock size is uniformity of size. If there is too much
variation, the smaller stones will fill in the voids between the larger stones, thus increasing
air blower power requirement. When those types of rock tend to scale and flake, the
resulting dust will be picked up by the heat transfer air and either clogs the furnace filters
and, if the furnace is by-passed, dust is blown directly into the heating area (Hasnain,
1998).
Latent heat storage
The term “latent heat storage” can be generally described as the storage of heat in the form
of latent heat of fusion, vaporization and sublimation that can undergo phase separation at
a desired temperature level. The heat storage process using such a phase-change medium
can be represented mathematically, by the following Equation 2.2.
Tm T2
Q= ∫
T1
mcpdT + m∆Hfusion + ∫ mcpdT
Tm
(2.2)
Q = total amount of heat storage/release (J)
m = mass of heat storage material (g)
cp = specific heat capacity of heat storage material (J kg-1 °K-1)
Tm = melting temperature of heat storage material (°C)
T1 and T2 = initial and final temperatures of heat storage medium (°C)
∆H fusion = heat required to change from solid phase to liquid phase (J/g)
12
In a latent heat storage system, the sensible component of the heat storage is kept low.
This enables the system to be operated at low temperature resulting in high efficiency of
the solar energy collection system in renewable energy application. As shown in Table
2.1, latent heat storage media (PCMs) can store large quantity of heat in a smaller weight
and volume of material in comparison with sensible heat storage media. Therefore, latent
heat storage media offers the following advantages: (1) it provides high-energy storage
capacity, (2) it can operate at narrow range of temperature and (3) heat store for phase
transition is significantly greater than sensible heat.
Table 2.1 Comparison of various heat storage media (stored energy = 106 KJ,
∆T = 15 °K) (Hasnain, 1998)
Sensible heat storage media Latent heat storage media
Property rock water organic PCM inorganic PCM
Storage mass 67, 000 16, 000 5, 300 4, 350

for storing
106KJ
(kg)
Storage volume 30 16 6.6 2.7
for storing
106KJ
(m3)
Solid-solid, liquid-gas, and solid-liquid transformations can be found in PCM. Heat can be
stored as the heat of crystallization, as the substance is transformed from one solid phase
to another solid phase in solid-solid PCM. Relatively few solid-solid PCMs have been
identified that have heats of crystallization and transition temperatures suitable for thermal
energy storage applications. Liquid-gas PCMs usually have high heats of transformations,
however, due to the large volume change during transformation, they are not usually
13
considered for practical applications. Therefore, solid-liquid transformation is commonly
utilized and the energy stored could be discharged at a constant crystallization
temperature.
Basic technology for latent heat storage system design should be considered. Any latent
heat thermal energy storage system must possess at least the three following basic
components:
(1) a heat storage substance that undergoes a solid-to-liquid phase transition in the
required operating temperature range and where the bulk of heat added is stored as
the latent heat of fusion;
(2) a container for holding the storage substance;
(3) a heat exchanging surface for transferring heat from the heat source to the PCM
and from the later to heat sink.
The type of the heat-exchanging surface plays an important role in the design of the
system, as it strongly influences the temperature gradients for charging and discharging of
the storage. Therefore, the development of a latent heat thermal energy storage system
involves two essentially diverse subjects:
(1) screening of heat storage materials (PCMs);
(2) heat exchangers for better heat transfer (Abhat, 1983).
A large number of organic and inorganic substances are known to melt with a high heat of
fusion in any required temperature range, e.g. 0-120°C. However, for their employment as
heat storage materials in latent heat thermal energy storage systems, these phase change
materials must exhibit certain desirable thermodynamic, kinetic and chemical properties.
14
Moreover, economic considerations of cost and large-scale availability of the materials
must be considered.
2.3 Heat storage materials
Within operating temperature range of 0-120°C, candidates PCMs are grouped into two
subfamilies: organics and inorganics. Organic families include paraffin and non-paraffin
organics. Paraffins are substances having a waxy consistency at room temperature.
Paraffins contain in them one major component called alkanes, characterized by CnH2n+2;
the n-alkane content in paraffin waxes usually exceeds 75% and may reach 100%. The
melting point of alkanes increases with the increasing number of carbon atoms; alkanes
containing 14-40 carbon atoms possess melting points between 6 and 80°C and are
generally termed as paraffins. Commercial waxes, on the other hand, may have a range of
about 8-15 carbon numbers. Table 2.2 lists thermophysical data for some technical grade
paraffin wax materials, which are paraffin mixtures and are not completely refined of oil,
some fatty acids and salt hydrates. Physical properties are also included in this table.
Paraffins qualify as heat-of fusion storage materials due to their availability in a large
temperature range and their reasonably high heat of fusion. Furthermore, they are known
15
Table 2.2 Physical properties of some PCMs (Abhat, 1983)
Distri- Oil Freez- Heat of fusion Density at Specific Thermal

bution content ing heat at conduc-
of C- (%) point 100°C tivity
atoms range (KJ/kg) (KJ/m3) (solid
(°C) (KJ/kg K) phase)
(kg/m3) (W/m K)
C16- 5 42– 44 240 146 0.912 (20°C) 2.1 0.21
C28 0.769 (70°C)
C20 – <0.5 48-50 244 145 0.915 (20°C) 2.1 0.21
C33 0.790 (70°C)
C22- 4 58-60 189 150 0.930 (20°C) 2.1 0.21
C45 0.830 (70°C)
Caprilic - 16.5 149 128 1.033 (10°C) - 0.148
acid 0.862 (80°C)
Palmitic - 63 187 159 0.847 (80°C) - 0.165
acid
CaCl2.6 - 29.7 171 256 1.710 (25°C) 1.45 (s) -
H2O 1.496 (l)
MgCl2.6 - 116.0 165 239 1.57 (20°C) 1.72 (s) -

H2O 1.442 (78°C) 2.82 (l)
- data not available, s-solid, l-liquid
16
to freeze without supercooling. Due to cost considerations, however, only technical grade
paraffins may be used as PCMs in the latent heat stores.
Fatty acids are organic compounds characterized by CH3(CH2)2nCOOH with heat of
fusion values comparable to that of paraffins. Fatty acids are known to possess a
reproducible melting and freezing behaviour and freeze with little or no supercooling.
They, hence, qualify as good PCMs. Their major drawback, however, is their cost, which
is 2-2.5 times higher than that of paraffins (Lane and Glew, 1975).
Salt hydrates, characterized by M.nH2O, where M is an inorganic compound, form an
important class of heat storage substances due to their high volumetric latent storage
density. In fact, their use as PCMs has been propagated as early as 1947 (Telkes, 1952).
The major problems in using salt hydrates as PCMs is the most of them melt
incongruently, i.e. they melt to a saturated aqueous phase and a solid phase which is
generally a lower hydrate of the same salt. Due to density differences, the solid phase
settles out and collects at the bottom of the container, a phenomenon is called
decomposition. Unless special measures are taken, this phenomenon is irreversible, i.e.
during freezing, the solid phase does not combine with the saturated solution to form
original salt hydrate.
Another serious problem with salt hydrates is their poor nucleating properties resulting in
supercooling of the liquid salt hydrate prior to freezing. Supercooling deteriorates thermal
performance of inorganic salt hydrate. Suitable measures must be adopted to eliminate
17
supercooling or reducing it to a minimum. Typical methods suggested in the literature for
this purpose are
(1) addition of nucleating agents that have a crystal structure similar to that of the
parent substance (Telkes, 1952)
(2) using a “cold finger” in the PCM (Lorsch et al., 1975)
(3) promoting heterogeneous nucleation by using (rough) metallic heat exchanging
surfaces in contact with salt hydrate (Abhat et al., 1981).
A comparison of the advantages and disadvantages of organic and inorganic materials is
shown in Table 2.3. It can be concluded from the information complied that the main
characteristics required of phase change materials are those indicated in Table 2.4.
Organics have more advantages than inorganics, however, most of organics also present
some problems, which limit their practical use. Organic paraffin wax has low thermal
conductivity, therefore, during the discharging process, as a material solidifies onto heat
transfer surface, high thermal resistance is offered. Hence, during heat exchanging,
diffusion of heat transfer fluid is limited. Large volume change during phase transition is
another problem with some PCM such paraffin wax. In addition, most conventional
paraffin waxes are slightly sticky and can stick together to form large lumps, clogging
occurs in heat storage system. The above limitations can result in decreasing of energy
18
Table 2.3 Comparison of organic and inorganic materials for heat storage (Zalba, 2003)
Organics Inorganics
Advantages Advantages
No corrosiveness Greater phase change enthalpy
Low or none undercooling
Chemical and thermal stability
Disadvantages Disadvantages
Lower phase change enthalpy Undercooling
Lower thermal conductivity Corrosion
Inflammability Phase separation
Phase segregation
Lack of thermal stability
Table 2.4 Important characteristics of energy storage materials (Zalba, 2003)
Thermal properties Physical properties Chemical properties Economic properties
Phase change Low density Stability Cheap and abundant

temperature fitted to variation
application
High density No phase separation
High change of
enthalpy near Small or no Compatibility with
temperature use undercooling container materials
Non-toxic, non-
High thermal flammable, non-
conductivity in both polluting
liquid and solid
phases (although not
always)
19
storage capacity. Attempts have been made to address the problems by several
researchers. To overcome these problems, all preliminary studies show that paraffin wax
should be bound within secondary supporting structure by means of microencapsulation
(Hawlader et al., 2000). They reported that microencapsulated paraffin wax provides
matrix type capsule in which paraffin wax is homogeneously distributed. This could lead
to prevention in loss of heat storage capacity.
2.4 Factors affecting the energy storage capacity of PCM
Oxidation of PCMs (e.g. paraffin wax) results in formation of toxic compounds such as
aldehyde, ketones, carboxylic acid, that can dissolve in pure PCM forming PCM solution.
Thus, oxidation of PCM leads to reduction in energy storage capacity, decrease in phase
change temperature and broaden transition temperature range. So it can be concluded that
coating materials are required to prevent oxygen diffusion.
Most inorganic salt hydrates and water-soluble organic PCMs are hygroscopic substances,
so they can absorb moisture easily forming higher hydrates resulting in decrease in energy
storage capacity at its phase transition temperature. Therefore, they need protective
coating to reduce moisture gain. Recently, encapsulation of PCMs has been developed to
solve the above mentioned problems.
2.5 Encapsulation of phase change materials
The encapsulation of the PCM has developed interest in several researchers (Zalba, 2003).
Microencapsulated PCM means techniques in which the coating of the core PCM with
compatible coating materials forming sealed capsules. Various types of microcapsules are
20
presented in the Figure 2.3. Encapsulation can be of many different forms such as a simple
coating, a wall of spherical or irregular shaped, a multiwall structure with walls of the
same or varying compositions or numerous cores agglomerate within the same walled
Simple
Irregular
Multi-wall
Multi-core Matrix
Figure 2.3 Various forms of capsules (Gibbs et al., 1999)
structure. The matrix type of capsules contains matrix microparticles resembles that
of a peanut cluster where the core materials are buried into varying depths inside the wall
material. The matrix or capsule provides all the requirements of a container such as
moisture barrier and physical containment (Johnson, 1984; Langer et al., 1969).
Coating materials used in the encapsulation of PCMs should meet the following
characteristics:
Have high strenth, flexibility and thermal stability;
Stable to UV exposure, barrier to moisture, air, etc;
Stable to environmental conditions;
21
Capable of being used safely;
High thermal conductivity;
Not corrosive to container materials;
No migration of PCMs into coating materials;
No reaction between PCMs and coating materials.
The advantages of heat storage with encapsulated PCM are the following:
Heat storage does not absorb heat energy directly, so the shape of storage is
arbitrary, temperature gradient is more favorable, and longer PCM lifetime;
Bound PCM is always “dry” product and liquid handling is consequently
eliminated as the phase change occurs within the coating material;
Air is directly taken into heat exchange surfaces, no additional media is needed;
Large heat transfer area is provided for effective heat transfer;
Large quantities of thermal energy can be stored and released at a relatively
constant temperature without significant volume changes. Sufficient free space
exists within the supporting structure and size remains constant;
Meet the various needs for energy storage and suitable containment systems;
No expansion system is needed as the PCM propagate and contract directly in the
microcapsules;
The microcapsules’ embedment in heat storage is simple;
PCM with different melting temperature could be used;
Avoid problems such as supercooling and phase separation.
22
Successful utilization of encapsulated PCM heat storage media depends on developing
means of containment. Published encapsuletd PCM systems are summarized in Table 2.5.
Most research efforts have centered on “microencapsulation”, the packaging of a mass of
a PCM in a sealed container, which itself serves as the heat exchange surface. Different
encapsulant materials were examined for suitability (Lane, 1977). The most promising
film was a laminate consisting of inner film of heat-sealable polyethylene, a foil of
aluminium, and outer film of PET polyester. The plastic-aluminium foil laminate was not
suitable for the organic PCMs tested. Typically, the heat-sealed seam was attacked by the
organic material. It was also unsuitable for temperatures above about 70°C (Lane et al.,
1978). For inorganic PCMs operating below this temperature, it seemed applicable.
Organic heat storage compositions were also rejected in the case of plastic as
encapsulants. Those tested migrated into plastic (Lane, 1980).
For many applications, PCMs are microencapsulated, and have been studied and
developed by many researchers. However, studies on encapsulated paraffin wax are
extremely limited in scope, and the potential use of microencapsulated paraffin wax in
various thermal control applications is not widely available. Sanjay (1991) reported the
existence of limitations in the formation of encapsulated PCMs due to leakage problem
23
Table 2.5 List of published encapsulated PCM systems
Investigators Core materials Coating materials Methods Types of Applications

and year used capsules
Lane, 1980 Eutectic Polyester Sealing with macrocapsules Preheating
Mg(NO3)2. polyester film domestic water
6H2O- in a tank filled
MgCl2.6H2O with
encapsulated
PCM
Morikama et Inorganic salt Polyester Interfacial Matrix type Thermal
al., 1985 hydrate polymerization microcapsules control in the
buildings
Feldman et al., Organic PCM Polyester resin Interfacial Floor, wall, Storing off-
1989 30% wt, polymerization ceiling tiles as peak electricity
gypsum, composite in home
cement, materials
sawdust, sand
and water
Inaba et al., Paraffin wax High density Interfacial Matrix type Integrating
1997 polyethylene polymerization microcapsules with building
materials to
reduce
overheating in
summer and to
take effect
storage
discharge by
ventilation
Brown et al., octadecane and polymethylene- Interfacial Microcapsules Gas-fluidized
1998 paraffin urea, cross-linked polymerization bed
nylon, and gelatin
Salyer, 1999 Eutectic PCM Polyester resin Interfacial Matrix type Insulation
polymerization microcapsules materials for
using in
clothing or
bedding
articles
Xiao et al., Paraffin wax Styrene- Interfacial Matrix type Latent heat
2000 butadiene-styrene polymerization macrocapsules storage
copolymer materials for
thermal storage
units
Hawlader et Paraffin wax Gelatin and acacia Complex Matrix type Packed bed
al., 2000 and coacervation microcapsules heat exchanger
Hawlader et
al., 2002
24
after 100 thermal cycle test runs (Bo et al., 1979; Hart and Thorton, 1982; McMahon,
1982; Colvin, 1986; Colvin 1989). Limited reports have been published on encapsulated
paraffin wax.
2.6 Methods of Microencapsulation
Various techniques are used for encapsulation (Dziezak, 1988). In general, three steps are
involved: formation of the wall around the material, ensuring the leakage does not occur,
and ensuring that the undesired materials are kept out. The following encapsulation
methods will be discussed in the following sections: air suspension, coacervation-phase
separation, solvent evaporation technique, spray-coating, interfacial polymerization and
dip coating.
Air Suspension
This method known as the Wurster process or fluidized bed coating involves dispersing
solid particulate core materials in a supporting air stream and the spray coating of
suspending materials. The design of the chamber and its operating parameters effect
recirculating flow of the particles through the coating zone of the chamber, where a
coating material, usually a polymer solution, is sprayed onto the fluidized particles. The
cyclic process is repeated till the desired coating thickness is obtained. The process is
generally considered to be applicable to the encapsulation of solid core materials.
Extensive research has been carried out using this method of encapsulation (Zarn, 1995).
25
Coacervation-Phase Separation
Encapsulation by coacervation is one of the more popular methods commonly studied.
Coacervation is the separation of a macromolecular solution into two immiscible liquid
phases: a dense coacervate phase, which is relatively concentrated in the macromolecules,
and a dilute equilibrium phase. The general outline of the process consists of three steps
carried out under continuous agitation.
Step 1 – The core material is dispersed in a solution of coating polymer
Step 2 – Deposition of the coating, accomplished by controlled, physical mixing of the
coating material and the core material in aqueous phase.
Step 3 – Rigidization of the coating by thermal, cross-linking or desolvation techniques, to
form self-sustaining microcapsules.
There are two types of coacervation: simple and complex. Simple coacervation involves
the use of only one colloid, e.g., gelatin in water, and involves removal of the associated
water from the dispersed colloid by agents with a greater affinity for water, such as
various alcohols and salts.
Simple coacervation is induced by a change in conditions such as the addition of non-
solvent, the addition of microions or a temperature change resulting in molecular
dehydration of the macromolecules. Complex coacervation is driven by electrostatic
interaction between two or more macromolecules.
26
Complex coacervation is a common method of microencapsulation. Burgenberg de Jong
and Kruyt (1929) showed that the solid particles could also be entrapped in coacervated
systems. On phase separation by complex coacervation, tiny coacervate droplets are
formed which coalescence and sendiment to form a separate coacervate phase. If a core
material is present in a polyion system prior to complex coacervation, then the coacervate
will deposit on and coalesce around those particles. Agitation of the coacervate system by
stirring or other means can prevent coalescence and sedimentation of the coacervate
droplets. The coacervate droplets can be crosslinked to form stable microcapsules by
addition of a crosslinking agent, such as gluteraldehyde, or the use of heat.
Complex coacervate formation is dependant on a number of factors such as pH, ionic
strength, macromolecular weight, concentration and mixing ratio. Charge is the most
significant factor for complex coacervation. Complex coacervation system includes
gelatin-acacia, carbopol-gelatin, pectin-gelatin, gelatin-gelatin, sodium
carboxymethylcellulose-gelatin.
Although successful coacervate microencapsulation systems have been done at specific
pH, they require stabilization by the use of cross-linking agent or heat and the extent of
crosslinking determines the retention of encapsulant. Gluteraldehyde and formaldehyde
are commonly used as crosslinking agents for protein-polysaccharide complex coacervate
systems such as gelatin-acacia. A condensation reaction occurs between the amino groups
of the protein and the aldehydes. Since the core materials are microencapsulated while
being dispersed in aqueous phase, subsequent drying operations are usually required
(Luzzi & Gerraughty, 1964).
27
Solvent Evaporation Technique
The process is carried out in a liquid manufacturing vehicle. The coating material is
dissolved in a volatile solvent immiscible with the liquid manufacturing vehicle phase.
The core material to be encapsulated is dissolved or dispersed in the coating polymer
solution. With agitation, the core coating material mixture is dispersed in the liquid
manufacturing vehicle phase to obtain the appropriate microcapsule size. The mixture can
be used in suspension form, coated onto substrates or isolated as powders (Risch, 1988).
Spray Coating Process
Spray Drying
Spray drying can be used for microencapsulation, even though traditionally it has been
mainly associated with drying of materials. Spray drying is the transformation of feed
from a fluid state into a dried particulate form by spraying the feed into a hot drying
medium. The feed can either be a solution, suspension or paste (Newton, 1966).
Spray drying consists of four process stages. They are
Atomizing of feed into spray;
Spray-air contact (mixing and flow);
Drying of spray (moisture evaporation);
Separation of dried product from the air.
High rates of moisture evaporation enable the temperature of the product to be
considerably lower than that of the drying air leaving the drying chamber. The product is
thus not subjected to high temperatures and heat degradation (Masters, 1979).
28
Spray Congealing
Spray congealing is similar to spray drying in that it involves dispersing the core material
in a liquefied coating substance. Coat solidification is accomplished by congealing the
molten coating material or by solidifying a dissolved coating material by introducing the
coating-core material mixture into a non-solvent. Removal of the non-solvent is then
achieved by sorption, extraction or evaporation techniques. Waxes, fatty acids and
alcohols, polymers and sugars, which are solids at room temperature but meltable at
higher temperatures, are applicable to spray congealing methods (Blenford, 1986).
Interfacial Polymerization
Interfacial polymerization involves the reaction of various monomers at the interface
between two immiscible liquid phases to form a film of polymer that encapsulates the
disperse phase. Usually two reactive monomers are employed, one dissolved in the
aqueous disperse phase containing a solution or dispersion of the core material, and the
other dissolved after the emulsification step in the non-aqueous continuous phase. The
water-in-oil emulsion formed requires the stabilizer. The monomers diffuse together and
rapidly polymerize at the interface between the phases to form a thin coating, and the by-
product of the reaction is neutralized by alkaline buffer. The degree of polymerization can
be controlled by the reactivity of monomers chosen, their concentration, the composition
of either phase vehicle, and by the temperature of the system . The reaction between
monomers is quenched by depletion of monomer, which is frequently accomplished by
adding excess continuous phase solution to emulsion (Fanger, 1974).
29
Dip Coating
The process is an apparently simple means of encapsulation involves single or repeated
dipping of cores into a coating solution, allowing the excess to drain off and drying.
However, because of the static nature of the process, the major difficulty encountered is
damaged to the coating as cores separate from contact with each other and the mechanical
support used to hold them while being coated (Bodor and Dokuzovic, 1992).
2.7 Thermal cycling test for encapsulated PCM
An ideal PCM must have the following features: appropriate phase change temperature,
high latent heat, low cost, ready availability, non-toxicity, non-flammability and uniform
phase change characteristics, such as no subcooling or phase separation. Besides these
features, it must have a long life with regards to its thermal reliability depending on the
number of thermal cycles. So, the changes of latent heat values and of phase transition
temperatures for a PCM after a large number of melting and solidification processes must
be as low as possible (Sari and Kaygusuz, 2002). In this sense, an accelerated thermal
cycle test of a PCM should be conducted to study the changes in latent heat of fusion and
melting temperature and specific heat capacity of PCM before using it as a latent heat
storage material in an actual thermal energy storage system. And thermal cycling test also
gives the compatibility of PCM-encapsulant (Lane, 1980). Because of expansion and
contraction of the PCM during melting and freezing, some non-rigid encapsulants are
continually flexed. In the case of laminated film pouches filled with then heat sealed, the
encapsulant seemed to conform well to the PCM. On extended testing, however, some
packages failed in the seam area, apparently because occasionally expansion stresses were
concentrated in that area. In the case of HDPE sealed PCM, after melting PCM, thermal
30
cycling resulted in some stress cracking of polyethylene after many cycles. This could
probably prevented by changing of polymers. Sharma et al. (2002) have conducted 1500
accelerated thermal cycle test to study the changes in latent heat of fusion and melting
temperature of commercial acetamide, stearic acid and paraffin wax. They concluded that
paraffin and acetamide have shown reasonably good thermal stability for melting
temperature and variations in latent heat of fusion during the cycle process. A number of
studies have been carried out on thermal cycling of coacervated samples (Hawlader et al.,
2002). They reported that encapsulated paraffin kept its energy storage capacity even
after 1000 cycles of operation. Limited data for thermal stability of coacervated samples
are available in the literature.
2.8 Heat Transfer of PCMs
For usability of microencapsulated paraffin wax in energy storage, it can be clearly
explained that they generally have desirable thermophysical, thermodynamic and kinetic
characteristics for low temperature latent heat storage applications. Moreover, before
using a microencapsulated PCM for an actual energy storage application, establishment of
thermal performance criteria and heat transfer characteristics of the microencapsulated
PCM is an important necessity. The thermal performance can be assessed in terms of:
(1) temperature distribution within the storage medium;
(2) the storage charging time/discharging time;
(3) the energy charging/discharging capacity.
The latent energy storage heat exchanger must fulfill the following requirements:
31
it should provide for a high effective heat transport rate to allow rapid charging
and discharging of the storage;
it should permit only small temperature gradients for charging and discharging of
the storage. This effect may be achieved by providing a substantially large heat
transfer surface and small heat transfer paths in the storage medium.
Therefore, the researchers started to investigate the feasibility of using slurry of
microencapsulated PCM as a heat transfer fluid. Besides the benefit of additional thermal
capacity, no special equipment for generating PCM particles is needed because the PCM
is always separated from the suspending fluid (Colvin and Mulligan, 1986; Hart and
Thorton, 1982; Telkes (1980); Yamagishi, 1999). In the case of microencapsulated phase
change slurry, the phase change material is encapsulated and suspended in heat transfer
fluid to form phase change slurry. They found that the heat transfer rate per unit volume to
and from the material in the particles is high since the ratio of surface area to volume of
small particles. In addition, encapsulating of phase change material in separate, small
enclosures is expected to eliminate the problem of incongruent melting (Telkes, 1980).
Yamagishi et al. (1999) studied the characteristics of microencapsulated PCM slurry as
heat transfer fluid. In their experiment, the particles consist of octadecane and melamine-
formaldehyde resin wall and they used water as heat transfer fluid that flowed through
encapsulated PCM slurry in circular tube with uniform flux. They observed that heat
transfer performance was not good for laminar slurry flow with incomplete melting of
slurry in the test section although reduction of pressure drop was found. Ozawa (1985)
used shell-and-coil type heat exchanger, and microencapsulated PCM within polyethylene
32
was put in the shell. To enhance the heat transfer between PCM and heat transfer fluid
flowing in the coil for charge and discharge, the PCM was agitated. The agitation was
effective to enhance the heat transfer between PCM and heat transfer fluid. Serious
problem discovered is adherence of powders in the charged state to the walls of shell and
the coil when the agitation is insufficient. High heat transfer coefficients at the storage
have been reported by several workers (Edie et al., 1979; Fouda et al., 1980; Fouda et al.,
1984). They have studied the heat transfer coefficient characteristics of phase change
material contained in small capsules which were packed in the container. The heat transfer
medium was then circulated through the packed capsules. Hart and Thorton (1982) tested
slurry of 30% wax capsules in oil in a prototype solar collector pump system. They found
that the effective specific heat of the slurry was about two times greater than the pure oil at
the temperature range of 212-248°C. McMahon (1982) studied the slurries of n-
heptadecane and n-octadecane in ethylene glycol. They carried out thermal performance
test of the slurries as cooling fluids for protective garments and reported specific heat
increase of 20 percent. Brown et al. (1998) studied thermal performance of
microencapsulated octadecane with coating material gelatin in gas-fluidized bed heat
exchanger. They observed that the heat transfer rates of encapsulated PCM enhanced due
to increasing heat transfer coefficients in a fluidized bed with specific heat of the
particulate phase. They observed that enhancement of heat transfer was less than estimated
value due to the shortest residence time in fluidized bed.
In previous work, efforts have been made to manufacture microencapsulated paraffin wax
by complex coacervation method (Zhu, 2000). A promising application using
microencapsulated paraffin wax as a storage medium and air as heat transfer fluid in
33
packed bed heat exchanger has been proposed. He presented experimental and simulation
results and the potential benefits of microencapsulated paraffin wax. Literature review
shows that one study has been reported for thermal performance of encapsulated PCM in
fluidized bed heat exchanger. In addition, a few studies has been done for thermal
performance of encapsulated paraffin wax. So in the present study, fluidized bed was
applied for testing thermal performance of encapsulated paraffin wax.
2.9 Scope of the present work
In the present work, paraffin wax is selected as a phase change material for energy
storage. All preliminary studies showed that microencapsulated PCM was prepared by
using interfacial polymerization and complex coacervation. Here, complex coacervation
and spray drying encapsulation methods have been examined and their effectiveness is
compared. A number of investigations have been made for thermal performance and
characterization of encapsulated paraffin wax. The present work is concerned with
encapsulation efficiency, the recovery of core and coating materials, energy storage and
release capacities, surface morphology and inner structure for both coacervated and spray-
dried samples. The comparison data for energy storage/release capacities of the capsules
prepared by different methods is fairly well established. Therefore, another goal in
planning experimental work is to compare thermal performance for capsules prepared by
complex coacervation and spray drying. A comprehensive knowledge of thermal
reliability of the microencapsulated paraffin wax as functions of repeated heating and
cooling cycles is essential for assurance of the long-term performance and economic
feasibility of a latent heat storage system. In this regard, this study aims at determining the
change of energy storage/release capacities, melting temperature and specific heat
34
capacities of both coacervated and spray-dried samples after 2000 melt/freeze cycles.
Since the limited data available on the effect of thermal cycling on thermal performance of
microencapsulated paraffin wax prepared by complex coacervation method, this study is
an effort to provide some expanded experimental results. Researchers proved the
effectiveness of PCM by practical applications such as finned tube heat exchanger, spiral
heat exchanger and packed-bed heat exchanger. There is a lack of experimental work
deals with fluidized bed heat exchanger by using microencapsulated paraffin wax. So this
research work focuses on evaluation of thermal performance of microcapsules by using
fluidized bed heat exchanger.samples in fluidized bed exchanger.
35
Chapter 3 Materials and Experimental Methods
CHAPTER 3
MATERIALS AND EXPERIMENTAL METHODS
In this chapter, the materials used in the preparation of encapsulated paraffin wax are
presented. Detail experimental procedures of complex coacervation and spray drying are
also presented. Characteristics of core and coating materials, characterization techniques
and equipments are explained in detail.
3.1 Materials
Materials used in preparation of microencapsulated paraffin wax are listed in Table 3.1.
Table 3.1 Materials used in the microencapsulating of paraffin wax
Core material paraffin wax, melting point: 60-62°C and non-caking

granular type, Merck.
paraffin wax, melting point: 50-55°C, Acros organics,
U.S.A.
Coating material gelatin powder from porcine skin, laboratory grade, Sigma.
acacia powder, laboratory grade, Aldrich chemical company
Inc.
Emulsifier tween 80 (Polyoxyethylen-sorbitan-monoleate) laboratory
grade, Aldrich chemical company Inc.
Cross-linking agent 30% (w/w) formaldehyde, analysis grade, Merck.
50% (w/w) gluteraldehyde, analysis grade, Merck
Solvents absolute ethanol 99% (v/v), analysis grade, Merck
toluene, 99.7% (v/v), analysis grade, Merck
Miscellaneous chemicals sodium hydroxide, analysis grade, Merck
99.9% (w/w) acetic acid, analysis grade, Merck.
36
3.2 Characteristics of Core and Coating Materials
3.2.1 Paraffin wax
Paraffins/waxes are saturated hydrocarbon mixtures, normally consisting of a mixture of
numerous alkanes. They are sourced from crude oil, where they are contained within
fractions arising from the production of lube oils. They are organic materials; after the
refining process they are odourless, tasteless and non-toxic. These saturated hydrocarbons
occur in the form of simple straight chains, normal-paraffinic hydrocarbons or branched
chains, iso-paraffinic hydrocarbons (Figure 3.1) (Warth, 1965). For thermal energy
storage applications, the paraffin wax containing normal paraffin wax should be used due
to their higher storage capacity (Warth, 1965).
CH3-(CH2)n-CH3
(a)
CH3-CH2-CH-(CH2)n-CH3
CH2
CH3
(b)
Figure 3.1 Molecular structure of paraffinic hydrocarbons (a) normal paraffin

(b) isoparaffin
37
3.2.2 Coating Materials
3.2.2.1 Gelatin
Gelatin is isolated from animal skin and bones with dilute acids. A typical structure of
gelatin is as shown in the Figure 3.2. Gelatin consists of extended left-handed proline
helix conformation in single or multi-stranded polypeptides, each containing between 300
- 4000 amino acids. Solutions undergo coil-helix transition followed by aggregation of the
helices by the formation of collagen-like right-handed triple-helical
proline/hydroxyproline rich junction zones. Higher levels of these pyrrolidines results in
stronger gels. Chemical cross-links can be introduced, to alter the gel properties, forming
firm gels. (Carroll, 1931).
Measurable properties of gelatin include: bloom strength; gel strength and viscosity. The
properties of gelatin layer comprise melting point; scratch resistance, resistance to
abrasion during processing ("mushiness") and swelling. (Carroll, 1931).
CHOH
CH2
CH2 CH2 CH2 CH2
CH2 N CH NH CH2 NH N-CH
CH-CO-NH CO CH-CO CO
CO
CO
CO-NH
R R
Glycine Proline Y Glycine X Hydroxyproline
Figure 3.2 Molecular structure for gelatin
38
3.2.2.2 Acacia
Acacia is prepared from the stems and branches of the acacia tree. Acacia is a complex
and variable mixture of arabinogalactan oligosaccharides, polysaccharides and
glycoproteins. Acacia consists of a mixture of lower molecular weight polysaccharide and
higher molecular weight hydroxyproline. Because it is a mixture and the material varies
significantly with source, the exact molecular structures are still rather uncertain. Its
glycoprotein is a high molecular weight hydroxyproline rich arabinogalactan (~2% protein)
containing a repetitive and almost symmetrical 19-residue consensus motif -ser-hypa-hypa-
hypa-thr-leu-ser-hypb-ser-hypb-thr-hyp-thr-hypa-hypa-hypa-gly-pro-his- with contiguous
hydroxyprolines (a) attached to oligo-α-1,3-L-arabinofurans and non-contiguous
hydroxyprolines (b) attached to galactose residues of oligo-arabinogalactans combining a
β-1,3-galactopyran core with rhamnoglucuronoarabinogalactose pentasaccharide side
chains (Chaplin, 2002).
Acacia is a useful if rather expensive hydrocolloid emulsifier, texturizer and film-former,
widely used in the drinks industry to stabilize flavors and essential oils, for example in
soft drink concentrates. The simultaneous presence of hydrophilic carbohydrate and
hydrophobic protein enables its emulsification and stabilization properties. Emulsification
is particularly enhanced due to molecular flexibility which allows greater surface
interaction with the oil droplets. Gum arabic is used in confectionery such as traditional
hard (wine) gums, pastilles and as a foam stabilizer in marshmallows (Duke, 1983).
Acacia possesses a flexible but compact conformation. It is readily soluble to give
relatively low viscosity Newtonian solutions even at high concentrations (20-30 % wt/wt).
39
However, and rather confusingly, molecular aggregation can cause both shear thinning
and time-dependent thickening behavior at low shear.
Both gelatin and acacia possess wettability and hydrophilicity. By dispersing the
hydrophilic polymers in appropriate solvents, they can be applied as coating form in many
purposes, such as drug coating, food material coating, coating of medical devices, etc.
3.3 Experiments
To prepare encapsulated paraffin wax, two methods were used in this study. The two
methods were complex coacervation and spray-drying. Detail experimental procedures of
the two methods are described in the following sub-section.
3.3.1 Complex coacervation
All experiments were carried out under identical experimental conditions. In all
experiments, 10% (w/v) gelatin and 10% (w/v) acacia solutions were prepared by
dissolving separately the solid powder in distilled water. These solutions were allowed to
hydrate at least 12 hours before being used. Coacervation process is shown by schematic
diagram in Figure 3.3.
First, 100 ml of 10% gelatin solution was adjusted to pH 8.5 by using 0.1 N NaOH as at
this pH, the gelatin solution carried positive charge. Then, the solution was heated to 65°C
in hot water bath at 70°C. A known weight of the solid paraffin wax was dispersed in the
gelatin solution with gentle stirring. At 65°C temperature, paraffin waxes became coated
with gelatin. After all paraffin wax melted in the gelatin solution, the emulsifier (tween 80)
was added by 2% (w/v) with stirring.
40
Then, the suspension was homogenized for a certain period of time by using IKA T-18
Laboratory Homogenizer (IKA Works Inc., U.S.A) at 10,000 revolution per minute.
During homogenization, 100 ml of 10% acacia solution was added into the suspension.
The temperature of the suspension was maintained at 65°C throughout the process. After
10% acacia
Dispersion Homogenizing Cooling

and melting at 10, 000 rpm
Reduce the
Paraffin wax suspension to
+ 10% pH 4 + 0.1 N
gelatin (pH- acetic acid
8.5) +
emulsifier
Separation of
2 phases
Addition of
Drying Washing with Filtration cross-linking
in alcohol agent
vacuum
oven
Microencapsulated paraffin
wax
Figure 3.3 Schematic representation of the coacervation process
homogenization, the pH of suspension was reduced to 4 by using 0.1 N acetic acid. At
this pH, the positive charge on the gelatin neutralized the negative charge of the acacia
forming a complex coacervate of the colloids. Then 400 ml deionized water was added to
the suspension and the suspension was cooled down to room temperature. The cooling
process promoted not only the deposition of coacervate droplets around the core particles
41
but also the separation of two phases such as the coated solid particles and unreacted
solution of coating materials. The coating materials on the paraffin wax were then
hardened by the addition of a suitable amount of cross-linking agent, formaldehyde or
gluteraldehyde. Elevation of pH to 9 by using 0.1 N NaOH and temperature to 50°C was
made to complete the curing of capsule walls. Hardening process was carried out for 12
hours. Finally, the microcapsules were recovered by filtration, followed by washing with
absolute ethanol and drying in vacuum oven. Microcapsules were produced at different
core to coating ratios under varying homogenizing time (10, 20 and 30 minutes) and the
amount of cross-linking agent (0, 3, 6 and 9 ml.).
3.3.2 Spray drying
Sample preparation
Two coating material solutions, one containing 10% gelatin (w/v) and another with 10%
acacia (w/v) were prepared by dissolving solid powder in distilled water. A known weight
of core material, paraffin wax was dispersed and melted in 100 ml of gelatin solution with
constant stirring. After that, the solution was homogenized for 10 minutes by using IKA
T-18 laboratory homogenizer at 10,000 revolution per minute. During homogenizing, 100
ml of 10% (w/v) acacia solution was added. Then the pH of the suspension was reduced to
4 by using 0.1N acetic acid. The temperature of the suspension was maintained at 65°C
through out the process.
42
Spray drying process
Figure 3.4 shows the photograph of the spray dryer used. The hot emulsified suspension
(65°C) was continuously stirred and delivered into the nozzle head of a laboratory spray
dryer (Model: BUCHI B-191) at 9 ml per minute using a peristaltic pump. After that, the
suspension was atomized into spray droplets into the glass chamber (height 560 mm,
diameter 135 mm) by a centrifugal atomizer operated at 25,000 rpm. The hot gas was
supplied into the chamber to provide the latent heat of vaporization required to remove
water from the spray droplets. A two fluid pressure nozzle with a cone-shaped spray
pattern of angle 18-20° emerging from the nozzle orifice was used. The flow type was
concurrent with the internal mixing of air and liquid within nozzle head. After evaporation
of the solvent, the coarse dried product which was collected in the chamber outlet and the
fines were recovered from the cyclone separator. The operating conditions used are shown
in Table 3.2.
1. Feed Pump
2. Atomizing Nozzle
3. Drying Chamber
4. Cyclone Separator
5. Product Container
Figure 3.4 Photograph of mini spray dryer used in microencapsulation of paraffin wax
43
Table 3.2 Operating conditions for spray drying microencapsulation
Inlet air temperature 140°C

Outlet air temperature 80°C
Aspirator output 100%
Peristalsis pump 30%
Compressed air pressure 5 bar
for spray flow
Feed Spray Rate 9 ml/min
Drying Air Flow Rate 800 ml/min
Atomizing Pressure 1 kgf/cm2
Spray Nozzle Type 0.7 mm, complete, 04364
3.4 Characteristics and performance of microcapsules
The characteristics and performance of encapsulated paraffin wax prepared by both spray
drying and complex coacervation methods were evaluated by various techniques as
discussed in the following sections:
3.4.1 Energy storage and release capacities
The Differential Scanning Calorimeter (DSC) (Model: TA 822 Mettler Toledo GmbH)
was used for microthermal analysis of thermodynamic characteristics of the
microencapsulated paraffin wax. In this evaluation, DSC was used to measure heat
capacities and melting temperature of the samples.
A small amount of sample (3~20mg) placed in a small aluminium vessel was used for
DSC analysis. An empty vessel was used as a reference. After putting samples in
aluminium vessel, sample and reference vessels were hermetically sealed and a small hole
was made on the cover before being placed on the calorimeter sample chamber. The
sample space was purged with nitrogen at a constant flow during the experiments. When
44
the sample was heated at a constant heating rate of 5°C per minute from room temperature,
23°C to 80°C, any kind of change in its calorimetric properties caused a temperature
difference between the sample and the reference (empty aluminium crucible). The
measured temperature difference was controlling the electrical power to the sample and
the reference in order to keep them at the same temperature. In this technique the
difference in power supply to the sample and reference was recorded. The peak area from
the output recording directly corresponded to the heat consumed by the sample.
Then, the sample was kept at isothermal condition after it reached 80°C for 10 minutes.
After that, the sample was cooled down to 19°C at a constant cooling rate of 5°C per
minute. Liquid nitrogen was used as cooling medium. The area between the straight line
and that deviated curve represented the energy released for phase change, cooling, which
was integrated numerically by a program built in the DSC.
3.4.2 Thermogravimetric analysis
Thermogravimetry analysis (TGA) is a powerful technique for the characterization of
decomposition or weight loss properties of materials. The technique provides the
following information:
- Deposition temperature
- Thermal degradation properties
- Oxidative degradation characteristics
- Quantitative weight losses
- Long term stabilities
45
- Rates of degradation.
Here, thermal stability of core material, paraffin wax and the coating materials, gelatin and
acacia were investigated by using thermogravimetry analyzer (Model: NETZSCH TGA
2050). With the TGA approach, the microencapsulated paraffin wax was generally heated
at a constant rate 10°C per minute and the resulting temperatures and the degradation rate
were measured as a function of time or temperature. Nitrogen purging, furnace heating
and air-condition cooling were used in this experiment.
3.4.3 Surface morphology and characterization of inner structure
The most widely used procedures to visualize microparticles is scanning electron
microscopy (SEM). This technique can be used to determine the shape and outer structure
of microparticles. Sample capsules were mounted on copper stubs with dark double-sided
adhesive tape and vacuum-coated with platinum film (Ion Sputtering Device), and then
examined by SEM (Model: JEOL JSM-T 330 A) and photographed.
SEM and conventional microscope do not permit the visualization of internal structure of
objects at all. So mechanical sectioning for microparticles by using microtone cutter
(Model: Leica CM 3050, GmbH) was allowed inspection of core material and deposition
of wall materials involved in embedded particles. Before cross-sectioning,
microencapsulated paraffin wax was mixed with Jung Tissue Freezing Medium (Germany)
to bind samples to specimen blocks and to surround and encase specimens. After
mechanical sectioning, SEM was used as a characterization tool for inner structure of the
particle.
46
3.4.4 Microencapsulation Efficiency
Microencapsulation efficiency, as defined by Young et.al. (1993a), Mandan et al. (1974)
Albin (1976) and Haijun (2001) was determined as follows: 1 gram of dry capsule was
weighed into a separating funnel, and 25 ml. of toluene was added. The separating funnel
was shaked for the extraction of non-encapsulated and partially encapsulated paraffin wax.
The extraction was carried out for 15 minutes at 25°C. The mixture was poured through
the filter, the solvent was evaporated and the solvent free residue was dried and weighed.
The amount of non-encapsulated or partially encapsulated paraffin wax was determined
gravimetrically. The microencapsulation was calculated as follows:
[(original weight – residue weight)/ (original weight)] * 100.
3.4.5 Estimation of core to coating ratio
The wall material was recovered from the microencapsulated paraffin wax by extraction
of paraffin wax with toluene. The dried, encapsulated material was treated briefly with
toluene to dissolve any uncoated or partially coated particles. The washed and dried
microcapsules were extracted with toluene for at least 30 minutes. Forty milliliters of
toluene was used for each gram of microcapsules. This treatment completely extracted and
dissolved paraffin wax, leaving undissolved wall material. After separation by filtration
and further washing with toluene, the wall material was dried and weighed. As a check on
completeness of extraction, the weight of the paraffin wax extracted was determined after
evaporation of the toluene washing and filtrate (Mandan et al., 1974).
47
3.4.6 Chemical structure stability evaluation
This experiment provided information on the stability of functional groups in the molecule.
Paraffin wax contains long chain hydrocarbons, and can oxidize when it contacts with
transport medium, air. After 0, 500, 1000, 1500 and 2000 thermal cycling, chemical
structure stability of microencapsulated was examined by using Fourier transform infrared
spectrophotometer (Model: SHIMADZU, DR-8001). Both coacervated and spray-dried
samples were pressed to form pellets by mixing with pure and dry crystalline KBr for
FTIR instrumental analyses.
3.5 Accelerated test process
Thermal stability or the reliability of thermal performance of microencapsulated PCM and
the compatibility of coating materials over a long period-application are very important
criteria for successful thermal energy storage applications. Therefore, experiments were
conducted to study the changes in melting point, energy storage and release capacities and
specific heat capacities after a repeated number of melt/solidify cycles. The experimental
set-up for accelerated thermal cyclic process is shown in Figure 3.5. The actual set up for
thermal cycling in laboratory is shown in Figure 3.6. It consisted of long tunnel dryer with
both heater and air-conditioner. Required air was generated by the blower, which was
installed at the end of the tunnel dryer. The heater was placed inside the tunnel dryer after
by-pass duct. The power source of the heater was controlled by on-off controller. On-off
condition for the controller was adjusted by the microprocessor. Microprocessor was
equipped with a temperature programmer in order to carry out controlled thermal cycling.
48
For this experiment, two thermocouples were located in the test chamber. One
thermocouple from the test chamber was connected to the controller to monitor and ensure
the actual temperature of air in the test chamber. Another thermocouple from the test
chamber was connected to data logger, which could provide instantaneous analog and
digital outputs. The data logger had recorder in order to record the temperature
distribution of air with time. The recorder had an accuracy of ± 0.05% of the reading
0.5°C, and a resolution of 0.1°C for the measurements of T-type thermocouple.
About 10 grams of microencapsulated paraffin wax were filled in the petridish and set into
the thermostatic test chamber equipped with a temperature controller. The blower was
switched on to generate the required airflow to the heater. The airflow rate was measured
by the digital anemometer. The on-off control program in the microprocessor controlled
the power supply of controller which directly controlled the heater. Microencapsulated
paraffin wax was heated above the melting temperature, 70°C and then allowed cooling
under room condition 23°C. For the repeated thermal cycling, the hot air temperature was
regulated at constant temperature of 70°C to melt the paraffin wax. The required
heating/cooling time was set in the microprocessor. After heating, a solidification cycle
was realized with shutting off the controller. A thermal cycle consisted of melting and
solidification process had duration of 3 minutes each. This procedure was performed
consecutively for 500, 1000, 1500 and 2000 thermal cycles. The samples were subjected
to 2000 accelerated melt/solidify cycles. In order to measure melting temperature and
specific heat and estimate the energy storage and release capacities, about 1 gram of
material was withdrawn after the number of melt/freeze test cycles mentioned above. The
49
DSC analysis technique was used to evaluate the melting temperature, specific heat
capacity and energy storage/release capacity of the uncylced and cycled encapsulated
PCM. The following operational sets of values were used in thermal cycling:
Air velocities – 5m/s;
Controller set temperature - 70°C;
Cycle duration time – 6 min (3 min heating – ON, 3 min cooling – OFF).
Figure 3.5 Schematic diagram of thermal cyclic system
50
Figure 3.6 Actual thermal cyclic system in laboratory
3.6 Fluidized bed heat exchanger for microencapsulated PCM
In this study, the overall performance of heat storage and release capacity of the
microencapsulated paraffin wax prepared by spray-drying microencapsulation method in a
fluidized bed were evaluated.
Test facility
A schematic diagram of the experimental set-up is given in Figure 3.7. The system
consisted of a fluidized bed, air heating system (thermostatic water bath), thermocouples
and data acquisition system. A 33 cm long and 2.54 cm internal diameter glass column
was used as the fluidized bed. Compressed air was used as the heat transfer fluid and its
flow rate was measured by calibrated rotameter. Temperature of air was measured at inlet,
outlet and three different axial positions (10, 65 and 100 mm from the distribution plate).
T-type thermocouples were used for the temperature measurement. Hydra data logger was
51
used for data acquisition. A stainless steel wire mesh of opening size 100 µm was used to
support the PCM capsules. A similar wire mesh was used at the top section of the column
to stop the carry over of the capsules.
Test Procedure
40 g of spray-dried PCM capsules were used in the fluidized bed. The average size of the
capsules was about 300 µm. Minimum fluidization velocity was calculated to be 0.064
m/s (calculation is shown in Appendix F). An airflow rate of 10 L/min with superficial
velocity of 0.32 m/s was used. The melting point of paraffin wax was 53°C. During
heating inlet air was heated to 60°C. To achieve this temperature the water bath
temperature was set to 90°C. Firstly, the compressed air line was opened and let the air
pass through the coil immersed in water bath for heating from room temperature to 60°C.
Once, the inlet air reached the steady temperature, the air line to the fluidized bed was
opened and the heating experiment was started. All the five temperatures were recorded
continuously in the data acquisition system. At the end of heating process, when the outlet
air temperature has reached a constant value, the hot air line to the column was closed and
the cold air was passed through the bed and heat release experiment was started. The
temperatures were again recorded during the cooling stage.
52
Compressed air line

T/C
Fluidized T/C
bed H/E TC2
T/C
T/C
Sieve
support
Flow T/C
meter
By-pass
Hot line
Water Flow
Bath meter
Data Logger
PC
T/C: thermocouple
Figure 3.7 Schematic diagram of experimental setup for fluidized bed
53
Chapter 4 Results and Discussion
CHAPTER 4
RESULTS AND DISCUSSION
In this chapter, the results of test conducted to determine the characteristics and
performance of microencapsulated paraffin wax prepared by complex coacervation and
spray drying methods are presented.
4.1 Encapsulation efficiency
The characteristics of microencapsulated paraffin wax prepared by complex coacervation
and spray-drying methods under different core to coating ratios were evaluated in terms of
encapsulation efficiency. Encapsulation efficiency of coacervated samples prepared with
varying homogenizing time and the amount of cross-linking agent at different core to
coating ratios were also investigated. Two kinds of cross-linking agent were used. They
were 36% formaldehyde and 50% gluteraldehyde. Homogenization time, ranging from 5
to 30 minutes, and the amount of cross-linking agent, ranging from 0 to 9 ml were added
to 200 ml suspension. Spray-dried samples were obtained under different core to coating
ratios, keeping the other experimental conditions constant (homogenizing time- 10
minutes, air inlet and outlet temperatures-130 and 80°C, feed rate-30% and aspirator-
100%). Results of these experiments are summarized in Tables 4.1-4.4.
A non-linear regression and variance package (Wolfram, 1993)) was used to analyze the
54
Table 4.1 Encapsulation efficiency of coacervated capsules

[x=homogenizing time (minutes) and z = encapsulation efficiency (%)]
Core to coating ratios

1:2 1:1 2:1
x z x z x z
5 72.60 5 70.53 5 66.73
7 77.16 7 74.62 7 69.92
10 86.58 10 85.53 10 83.66
Table 4.2 Encapsulation efficiency of coacervated capsules with 36% formaldehyde:

Experimental design and results [x = homogenizing time (minutes), y = the amount of
36% formaldehyde (ml), z = encapsulation efficiency (%)]
Core to coating ratio

1:2 1:1 2:1
x y z x y z x y z
10 0 86.58 10 0 85.53 10 0 83.66
3 92.67 3 91.14 3 90.04
6 94.89 6 93.98 6 91.84
9 91.40 9 90.33 9 89.15
20 0 84.36 20 0 83.66 20 0 81.28
3 89.11 3 88.01 3 86.86
6 93.18 6 92.04 6 89.82
9 89.02 9 87.92 9 87.02
30 0 82.32 30 0 81.42 30 0 80.08
3 88.55 3 87.45 3 86.37
6 89.78 6 88.81 6 87.65
9 87.01 9 85.98 9 83.20
55
Table 4.3 Encapsulation efficiency of coacervated capsules with 50% gluteraldehyde:

Experimental design and results [x = homogenizing time (minutes), y = the amount of
50% gluteraldehyde (ml), z = encapsulation efficiency (%)]
Core to coating ratio

1:2 1:1 2:1
x y z x y z x y z
10 0 86.58 10 0 85.53 10 0 83.66
3 92.33 3 92.01 3 90.28
6 95.68 6 94.08 6 91.98
9 90.48 9 89.02 9 87.42
20 0 84.36 20 0 83.66 20 0 81.28
3 89.62 3 88.14 3 87.76
6 93.21 6 92.38 6 89.83
9 89.62 9 88.38 9 86.05
30 0 83.11 30 0 82.01 30 0 80.42
3 88.62 3 87.73 3 86.55
6 89.98 6 88.82 6 87.29
9 86.38 9 85.44 9 82.21
56
effect of process parameters on encapsulation efficiency and optimize the process
conditions in the complex coacervation of paraffin. Typical 3-D diagrams for 2:1, 1:1 and
1:2 core to coating ratios by using 36% formaldehyde are shown in Figures 4.1-4.3,
whereas Figures 4.4-4.6 represent 3-D diagrams for microcapsules at different core to
coating ratios by using 50% gluteraldehyde.
Results show that the extent of paraffin wax encapsulation is closely related to the ratio of
core to coating used. It was observed that microencapsulation efficiency decreases as the
ratio of core to coating increases. A lesser amount of coating materials tended to result in
incomplete coating on core materials. Therefore, the amount of coating materials
determined the effective encapsulation of the core material.
Homogenization includes three steps: (1) dispersion of paraffin liquid droplets in a
continuous phase (coating material solution), (2) deformation and disruption of large
droplets to small droplets and (3) the stabilization of emulsion. It was found that the
encapsulation efficiency increases as the homogenizing time increases (Table 4.1). The
prolonged homogenization led to a more efficient emulsification, resulting in efficient
incorporation of paraffin wax droplets into the coacervate and less non-encapsulated
paraffin wax. When the homogenizing time was beyond a critical value, 10 min, the
encapsulation efficiency decreases (Tables 4.2 and 4.3, Figures 4.1-4.6). The results were
consistent for all the coacervated samples. For longer homogenizing time, the dispersed
paraffin wax droplets may coalesce which may lead to destabilization of the emulsion
57
90
z 85 8
80 6
10
4
15
20 2 y
x 25
30 0
Figure 4.1 Effect of homogenizing time and the amount of cross-linking agent on
encapsulation efficiency at 2:1 core to coating ratio[x-homogenizing time
(minutes), y-the amount of formaldehyde (ml) and z-encapsualtion
efficiency (%)]
92.5
90
z 87.5 8
85
82.5 6
10
4 y
15
2
20
x 0
25
efficiency (%)]
58
95
90
8
z 85
6
10
4
15 y
20 2
x 25
30 0
efficiency (%)]
90
85 8
z
80 6
10
4
15 y
20 2
x 25
30 0
(minutes), y-the amount of gluteraldehyde (ml) and z-encapsualtion
efficiency (%)]
59
90
8
z 85
6
10
4
15
20 2
y
x 25
x 30 0
efficiency (%)]
95
z 90
8
85
6
10
4
15 y
20 2
x 25
30 0
efficiency (%)]
60
resulting in poor encapsulation.
The role of cross-linking agent is important for hardening of the coating materials.
Carboxylate (gelatin) reacts with formaldehyde or gluteraldehyde molecule, activating
carboxylic to nucleophillic attack for cross-linking. This hardening reaction is catalyzed
by OH- group(alkaline condition). It was observed that increasing the amount of cross-
linking agent led to an increase in the encapsulation efficiency. However, the results
indicated that above 6~8 ml of cross-linking agent (from Figures 4.1-4.6), encapsulation
efficiency decreased as the amount of cross-linking agent is increased. This may be due to
the alteration of mechanism or increase of reaction between individual polymer molecules
and inability to integrate into proper network structure even after the addition of excess
amount. Therefore, the hardening reaction reached equilibrium condition with
approximately at 6~8 ml cross-linking agent for 200 ml of feed suspension. The two
different types of cross-linking agents (30% formaldehyde and 50% gluteraldehyde) did
not have significant difference on the effect on encapsulation efficiency and this might be
due to the similarity in structure of the compounds.
Therefore, the above experimental results on microencapsulation efficiency suggested the
optimum conditions for encapsulation under coacervation method as:
Core to coating ratio = 1:2;
Homogenizing time = 10 minutes (at 10,000 rpm);
Cross-linking agent = (6-8) ml for 200 ml of feed suspension. In addition, our results
for microencapsulation efficiencies for coacervated samples are comparable with the
61
results reported by Hawlader et al. (2000). They found that the microencapsulation
efficiencies of coacervated samples lie between 80 and 96%.
Non-linear regression analysis was used to correlate the encapsulation efficiency with the
emulsification time and cross-linking agent concentration. The regression equations for
different core to coating ratios and different cross-linking agents are presented in Tables
4.4 and 4.5.
Table 4.4 Non-linear regression analysis of encapsulation efficiency using formaldehyde
Core : Coating Regression equation R2

2:1 z = 86.12-0.27x+0.001x2+0.00003x3+3.07y- 0.911
0.31y2+0.004y3
1:1 z = 94.91+0.60y+0.94y2-0.20y3+0.01y4- 0.951
3.85log[x]
1:2 z = 94.95+0.49y+0.77y2-0.14y3+0.006y4- 0.934
3.63log[x]
z = encapsulation efficiency (%), x = homogenizing time (minutes) and y = the amount of
formaldehyde (ml)
Table 4.5 Non-linear regression analysis of encapsulation efficiency using gluteraldehyde
Core : Coating Regression equation R2

2:1 z = 86.31-0.30x+0.002x2+0.00003x3+2.94y- 0.900
0.22y2-0.006y3
1:1 z = 87.50-0.17x-0.002x2+0.00004x3+2.39y- 0.805
2
0.07y -0.01y 3
1:2 z = 95.74+0.59y+0.93y2-0.19y3+0.01y4- 0.912
3.91log [x]
z = encapsulation efficiency (%), x = homogenizing time (minutes) and y = the amount of
gluteraldehyde (ml)
62
The results of encapsulation efficiency for spray-dried samples at different core to coating
ratios are shown in Table 4.6. It was evident that increasing the paraffin wax load
decreased the encapsulation efficiency. This was because of increase in viscosity of
disperse phase increased the interfacial viscosity and then broke down the emulsion
stability. Increase in core to coating ratio will make thinner wall material for the
microcapsules. This led to a decrease in encapsulation efficiency.
It was also observed that the encapsulation efficiency of spray-dried samples was less than
that of coacervated samples (homogenizing time-10 minutes without cross-linking agent)
for all different core to coating ratios. Partial phase separation in the feed solution during
spray drying could be the main reason for lower encapsulation efficiency.
Table 4.6 Encapsulation efficiency of spray-dried samples
Core to coating ratio Encapsulation efficiency (%)

1:2 82.92
1:1 75.60
2:1 71.00
4.2 Estimation of core to coating ratio
Actual core to coating ratio was experimentally determined for coacervated and spray-
dried samples prepared at different core to coating ratios. The results were compared with
the designed values in Table 4.7. The measured core to coating ratio was found to depend
on the relative quantities of the two materials used in the preparation of encapsulated
PCM, i.e. designed core to coating ratio. Higher the core material concentration, higher
63
was the measured core to coating ratio. The encapsulation efficiency as reported in section
4.1 represented loss of core and coating materials as a result of incomplete encapsulation
Table 4.7 Comparison of experimentally measured core to coating ratio with designed
values
Coacervated sample Spray-dried sample

Designed core to Measured core to Designed core to Measured core to
coating ratio coating ratio coating ratio coating ratio
0.5 (1:2) 0.422 0.5 (1:2) 0.375
1.0 (1:1) 0.872 1.0 (1:1) 0.713
2.0 (2:1) 1.805 2.0 (2:1) 1.436
whereas the results presented in Table 4.7 reflected on the relative loss of core and coating
materials. The measured core to coating ratios were lower than the designed value. This
indicated that more paraffin wax was lost in comparison to coating material during
encapsulation. For coacervated samples, higher paraffin wax concentration in capsule
preparation decreased the relative loss of paraffin wax in microcapsules. However, such
behaviour was not clearly observed in spray-dried samples. Higher loss of core material
was observed in spray-dried samples in comparison to coacervated samples. During
spray-drying, phase separation for liquid paraffin wax might have occurred, creating
deposits of solidified paraffin wax in various parts of spray-dried unit. Possibly, this
might be the reason for lower actual core to coating ratio obtained.
4.3 Thermal Performance
Thermal performance of both coacervated and spray-dried samples were evaluated by
their energy/storage and release capacities at various core to coating ratios. Energy
storage/release capacities of both samples were measured by DSC. A typical set of DSC
64
diagrams are shown in Figures 4.7 and 4.8. These figures show the DSC data
characterizing the melting and freezing behavior of both spray-dried and coacervated
microencapsulated paraffin wax at scanning rate of 5 °C per minute from 24°C through
80°C and from 80°C through 24°C. Two sharp peaks in the phase change temperature
range were observed. These two peaks signify a solid-to-liquid transition and a liquid-to-
solid transition. Sharp peaks for discharging mode showed no supercooling in the phase
transition temperature range 59.5-44.5°C and 59.5-45°C for spray-dried and coacervated
samples, respectively. At these temperature ranges, the samples transformed to the
crystalline phase. Melting has occurred between 50-67.5°C for coacervated samples and
between 49.5-64.5°C for spray-dried samples. The phase change temperature ranges of
spray-dried samples were of nearly equivalent width, which means there was not
difference between their phase temperature ranges where as a slight difference was
observed for the phase change temperature ranges for coacervated samples.
All the results of energy storage and release capacities for both samples are summarized
in Table 4.8. High energy storage and release capacities were found for all the capsules.
Comparable heats of fusion and solidifying were obtained with high thermal efficiency of
98% and above for both samples. These were considered high-energy storage and release
capacities in comparison to pure paraffin wax. Experimental measurement for pure
paraffin wax gave energy storage and release capacities of 298.6 J/g and 296.0 J/g,
respectively. It was found that the experimental results for both samples at different core
to coating ratios were more than the actual results calculated from the mass percentage of
paraffin in the samples. This might be due to the sensible heat of the coating materials in
65
the phase change temperature range. Paraffin wax used was of narrow-cut, highly
crystalline, high normal paraffin wax content, and encapsulated within highly conductive
coating materials. All these factors provided high latent heat storage capacities over
narrow range of temperature. Higher values of core-to-coating ratios increased the heat
charging and discharging capacities. The microcapsules obtained by the spray drying
method had a lower heat capacity compared to the coacervated samples. The reason could
be due to the presence of unreacted coating materials dried along with the encapsulated
particles. Based on experimental results, it is suggested that the higher paraffin wax
content should be used for storing high amount of energy. Zhu (2000) reported
experimental values of heat storage/release capacities of encapsulated paraffin wax
prepared by complex coacervation method (86, 42 and 28 J/g for 2:1, 1:1 and 1:2 core to
coating ratios). The lower values of heat storage could be due to the paraffin wax used of
different melting point and purity.
Table 4.8 Energy release and storage capacity for coacervated and spray dried
Coacervated ∆Hfusion ∆Hsolidifying TE Spray- ∆Hfusion ∆Hsolidifying TE

sample (J/g) (J/g) (%) dried (J/g) (J/g) (%)
sample
2:1 239.4 239.6 100 2:1 216.3 216.2 99
1:1 167.3 165.2 99 1:1 156.4 156.0 98
1:2 106.6 104.4 98 1:2 93.3 91.5 98
∆Hfusion = energy storage capacity, ∆Hsolidifying = energy release capacity, TE = thermal
efficiency = ∆Hfusion / ∆Hsolidifying * 100
66
59.5°C 44.5°C
64.5°C
49.5°C
Figure 4.7 Output curve of DSC for spray-dried sample 2:1
45°C
59.5°C
50°C 67.5°C
Figure 4.8 The output curve of DSC for coacervated sample 2:1
67
4.4 Surface morphology and inner structure characterization
4.4.1 Surface morphology
Two different methods, complex coacervation and spray-drying were used for
microencapsulation. Surface morphology of microcapsules obtained from the two
methods were studied by using a scanning electron microscope (SEM). Coacervated
Figure 4.9 SEM profile of the coacervated samples
Figure 4.10 SEM profile of spray-dried samples
68
samples had wider size range and screened for SEM analysis. Samples less than 20 µm
are used. No size screening was done for spray-dried samples. Figures 4.9 and 4.10
display the SEM profile of coacervated and spray-dried samples respectively. It was
observed that both caocervated and spray dried samples were globular in shape. Spray-
dried samples were found to be more spherical in shape compared to coacervated samples.
Larger spray-dried samples were slightly deformed from spherical shape. Size of both
samples from photo-micrographs were determined by Smile View Software. The
coacervated samples had a diameter ranging from 3.3-10.5 µm with mean diameter is 6.4
µm whereas the spray-dried samples had a diameter ranging from 1.3-10.1µm with mean
diameter is 4.5 µm. Size distributions for both samples were also measured by using
particle analyzer (Model: Coulter Counter, size range 1-4000 µm). The results are shown
in Appendix H1 and H2.
4.4.2 Inner Structure
The inner structure of microcapsules prepared by complex coavervation and spray drying
methods was examined by using microtone for cross-sectioning of particles and SEM for
visualization. As particle size less than 50 µm could not be used for cross-sectioning,
larger size particles ranging between 100-300 µm were used. The larger size particles
were prepared by using the different experimental conditions [airflow rate 400 ml/min and
aspirator 80%, feed pump 20%, inlet temperature 160°C and outlet temperature 80°C] for
spray drying. For complex coacervation method, the larger size particles were prepared by
using lower homogenizing speed of 6000 rev. per minute.
69
Both fresh capsules and capsules after repeated heating and cooling tests were used for
inner structure measurement. Figures 4.11 and 4.13 show the inner structures fresh spray-
dried and coacervated samples whereas Figures 4.12 and 4.14 show the structures after
thermal cycling tests. Spray-dried capsules were more spherical in shape compared to
coacervated samples. In both cases the coating material was found to form the capsule
wall and a matrix like inner structure. The core PCM was found as discrete particles
embedded in the inner matrix of the coating material. The inner structures of fresh and
cycled samples did not show any significant change, which confirmed that the discrete
particles were paraffin wax and did not coalesce during heating and cooling process.
Some cavities were also found the inner structure particularly for spray-dried samples.
These cavities were either empty voids created due to evaporation of water during drying
or due to loss of PCM particles from the coating material matrix during mechanical
sectioning of the samples. The structure showed that the PCM particles were distributed
more uniformly in spray-dried samples than coacervated one. The size of PCM particles
were about 2 µm and more spherical in shape for spray-dried capsules compared to
coacervated samples. Thus the inner structures of both spray-dried and coacervated
samples were composed of compact network of coating material where PCM particles
were distributed as discrete phase.
4.5 Thermogravimetry analysis
In order to use microencapsulated PCMs as thermal energy storage, the coating materials
have to keep up with requirements for high thermal resistance. TGA was performed on
microencapsulated paraffin waxes to find their decomposition temperature. Figures 4.15
70
Figure 4. 11 Inner structure of spray dried samples (fresh)
Figure 4.12 Inner structure of spray-dried samples (cycled)
71
Figure 4.13 Inner structure of coacervated samples (fresh)
Figure 4.14 Inner structure of coacervated particles (cycled)
72
and 4.16 show TGA test results of coacervated and spray dried microencapsulated
paraffin wax.
In TGA thermograms (Figures 4.15 and 4.16), the blue curves show the residual weight
percent of the sample as a function of temperature. The weight loss for the microcapsules
prepared by both methods started at near the melting point of core material, paraffin wax.
Microcapsules showed initial weight loss about 10 % from 50°C to about 200°C, and a
subsequent higher weight loss up to about 800°C. The violet lines show the derivative of
mass change (dm/dT) with respect to temperature T. The area under the derivative
thermogravimetry (DTG) curve is directly proportional to the mass change; the height of
the DTG peak gives the rate of mass change at that temperature. The TG thermograms
obtained for the two samples showed that two highest peak corresponding to maximum
degradation rate at temperature Tmax. The first highest peak corresponded the peak
decomposition temperature of core material, paraffin wax around (200 ~ 300°C), the
second highest peak showed the decomposition temperature of coating materials around
(300 ~ 400°C). The high decomposition temperature evidently indicated high thermal
stability of microcapsules. In addition, this decomposition temperature also determined
the upper limit of temperature that sample could be heated. Furthermore, the
decomposition temperature of the coating materials was significantly higher than that of
core material so that the coating materials could withstand the phase change process of the
core material, paraffin wax. The most reasonable explanation of this phenomenon was the
formation of network by two kinds of polymer chains. TG thermogram of spray-dried
73
Figure 4.15 TG thermogram of coacervated microcapsules
Figure 4.16 TG thermogram of spray-dried microcapsules
74
samples showed two peaks of thermal degradation between 300 ~ 400°C. Most probably,
first peak corresponded to the maximum rate of thermal decomposition for gelatin-acacia
network and the second peak represented the decomposition of unreacted coating
materials. TG diagram of coacervated samples did not show two peaks for coating
materials. After the final cross-linking step in the coacervation process the capsules were
washed with ethanol to remove all unreacted coating materials and thus no second peak
was observed for the coating materials.
4.6 Thermal Cycling Test
One of the most severe tests that phase change heat storage materials must undergo is
thermal cycling involving repeated melting/solidifying. To determine the effect of a large
number of accelerated thermal cycles on thermodynamic properties of microencapsulated
paraffin wax, six samples, three coacervated samples of three different core to coating
ratios and three spray dried samples of three different core to coating ratios, were used.
The energy storage and release capacities were estimated from the area of endothermic
and exothermic curves, respectively, under the peak by numerical integration. The phase
transition temperature of the samples was taken as the onset obtained by line fitting of the
rising part of the peak. The specific heat capacities of the sample were measured by using
isothermal-ramp-isothermal with sapphire software.
The energy storage and release capacities of both coacervated and spray-dried samples
were measured after 0, 500, 1000, 1500 and 2000 accelerated test cycles. The measured
75
energy storage/release capacities for all the samples are given in Tables 4.9-4.14. Typical
DSC curves for coacervated and spray-dried samples are shown in Figures 4.17 to 4.20.
It was evident that no significant variations for energy storage/release capacities of both
coacervated and spray-dried samples occurred for three different core to coating ratios
after 500, 1000, 1500 and 2000 cycles. Energy storage/release capacities of both
coacervated and spray dried samples (2:1, 1:1 and 1:2) were found to remain constant
level after 500, 1000, 1500 and 2000 cycles. This might be attributed to the fact that there
was no degradation or variation of chemical structure of the paraffin wax with increasing
number of cycling. Therefore, the heat storage material could form the first crystal
structure (in a fresh state of PCM) during the solidification period of the repeated thermal
cycling. Over a large number of transition processes, no new compounds were formed and
only fresh paraffin wax was obtained so it was naturally seen that the samples had nearly
the same energy storage/release capacity in comparison with the fresh state. In addition,
having low impurity or without impurity during thermal cycling might favor no
degradation of PCMs.
Results pertaining to the effect of thermal cycling on the melting point and the specific
heat capacity of three types of coacervated samples (2:1, 1:1 and 1:2) are summarized in
Tables 4.15-4.20. Typical DSC curves showing the melting temperatures for coacervated
and spray-dried samples are shown in Figures 4.21-4.24. Results showed that melting
range was almost constant between 49-65°C and solidification range was nearly constant
between 49-60°C for all samples.
76
Table 4.9 Energy storage and release capacities of microencapsulated paraffin wax (2:1
coacervated sample)
No. of test cycles Energy storage capacity Energy release capacity

(J/g) (J/g)
0 239.4 239.6
500 239.0 233.8
1000 238.3 233.6
1500 237.94 233.0
2000 237.2 229.9
coacervated sample)

(J/g) (J/g)
0 167.3 165.2
500 167 165
1000 166.7 163.8
1500 165.8 163.4
2000 165.3 161.9
coacervated sample)

(J/g) (J/g)
0 106.6 104.4
500 105.96 103.2
1000 105.2 103.2
1500 105 101.2
2000 104.8 98.1
77
spray dried sample)

(J/g) (J/g)
0 216.3 216.2
500 215.7 211.98
1000 215.2 213.2
1500 214.7 213.8
2000 214.6 213.2
spray dried sample)

(J/g) (J/g)
0 156.4 156
500 155.5 154
1000 155.3 152.3
1500 154.1 152.1
2000 153.7 151.1
spray dried sample)

(J/g) (J/g)
0 93.25 91.51
500 92.04 92.1
1000 91.77 91.1
1500 91.2 91.1
2000 90.7 90.3
78
Figure 4.17 DSC output curve for 1:1 coacervated sample after 500 cycles
Figure 4.18 DSC output curve for 1:1 coacervated sample after 2000 cycles
79
Figure 4.19 DSC output curve for 2:1 spray-dried sample at 0 cycle
Figure 4.20 DSC output curve for 2:1 spray dried sample after 1500 cycles
80
No noticeable variation was detected for the phase transition range with increasing the
number of cycles. The melting temperature for both coacervated and spary-dried samples
was found to be 53°C after various thermal cycling. Therefore, this constant phase change
behaviour exhibited that congruent melting was observed, no supercooling was observed,
no significant change in volume took place, and no material degradation was seen.
Figures 4.25-4.28 show typical specific heat capacity measurement results for spray-dried
and coacervated samples collected at different thermal cyclic conditions. Specific heat
capacities depend upon the temperature. For comparison, values at 40°C were considered.
Specific heat capacity values for all samples tested for different thermal cyclic conditions
are presented in Tables 4.15-4.20. Measured heat capacities varied with core to coating
ratio. This is expected with varying ratio of paraffin wax and coating materials. Results
showed that for same samples, the heat capacity did not change significantly even after
2000 cycles.
Therefore, during the “lifespan testing” of microencapsulated paraffin wax, it was seen
that both coacervated and spary-dried samples could run immense number of thermal
charging and discharging cycles. Neither heat storage/release capacities nor
thermodynamic properties (melting temperature, melting range, solidification range and
specific heat capacity) changed over the number of thermal cycling. Hawlader et al. (2002)
also reported similar results for coacervated paraffin wax capsules up to 1000 cycles.
81
Table 4.15 Thermophysical properties of microencapsulated paraffin wax (coacervated

2:1) with test cycles
No. of test cycles Melting temperature (Tm) Specific heat capacity (cp) at
(°C) 40°C
(J g-1 K-1)
0 53 1.820
500 53 1.823
1000 53 1.825
1500 53 1.822
2000 53 1.827

(°C) 40°C
(J g-1 K-1)
0 53 1.733
500 53 1.734
1000 53 1.735
1500 53 1.730
2000 53 1.730

(°C) 40°C
(J g-1 K-1)
0 53 1.649
500 53 1.653
1000 53 1.653
1500 53 1.652
2000 53 1.651
82
Table 4.18 Thermophysical properties of microencapsulated paraffin wax (spray-dried 2:1)

with test cycles
(°C) 40°C
(J g-1 K-1)
0 53 1.795
500 53 1.793
1000 53 1.795
1500 53 1.793
2000 53 1.795

with test cycles
(°C) 40°C
(J g-1 K-1)
0 53 1.708
500 53 1.709
1000 53 1.709
1500 53 1.711
2000 53 1.711

with test cycles
(°C) 40°C
(J g-1 K-1)
0 53 1.637
500 53 1.639
1000 53 1.640
1500 53 1.641
2000 53 1.641
83
53°C (onset temperature)
Base line
60°C
Figure 4.21 DSC measurement of melting temperature of microencapsulated paraffin

wax (spray-dried1:1) after 500 cycles
Base line
60°C

wax (spray-dried 1:1) after 2000 cycles
84
Base line
60°C

wax (coacervated 2:1) at 0 cycle
Base line
60°C

wax (coacervated 2:1) after 2000 cycles
85
Figure 4.25 DSC measurement of specific heat capacity of microencapsulated paraffin

wax (spray-dried 1:2) at 0 cycle

wax (spray dried 1:2) after 1000 cycles
86


87
Unlike many other latent heat storage materials, microencapsulated paraffin wax prepared
by both methods were long-lasting and stable throughout phase change cycles. This might
be the fact that there was no chemical reaction during thermal energy storage and release
process, not within material itself, not with heat transport medium, air, not with coating
materials, gelatin and acacia, not with holding container materials used in the thermal
cycling. Melting and solidification are purely physical processes, which is the reason why
thermal energy storage/release capacities, melting temperature and specific heat capacities,
in the case of both coacervated and spray dried samples, remains at a nearly constant level,
throughout the unit’s working life. Both samples exhibited their reproducibility in thermal
performance and melting and solidifying behavior and they also showed thermal
reliability with heat transfer fluid, air so that they assured long-term performance of heat
store.
4.7 Structural Stability
Investigations of chemical structure and degradability can be studied by optical analyses.
Chemical stability, after various thermal cycling: 0, 500, 1000, 1500 and 2000 cycles, was
evaluated by using FTIR spectrophotometer. FTIR spectra were obtained on
spectrophotometer with 53 scans at a resolution of 4 cm-1. Figures 4.29 and 4.30 represent
FTIR output spectra of coacervated and spray-dried samples, respectively, after thermal
cycling test. The energy at which the peaks for 0, 500, 1000, 1500 and 2000 cycles
occured in an absorption or transmission spectrum corresponded to the vibration of
molecules. Similar bands of transmittance were found for 0, 500, 1000, 1500 and 2000
cycles in both samples providing information on the stability of functional groups in the
88
molecule. Results showed that no destruction of chains by breaking, splitting of fragments
for the main chain or side constituent of the core and coating materials. Therefore, it was
found that in both microencapsulated paraffin waxes, core materials were compatible with
coating materials and both samples had desirable lifetime. In addition, no degradation has
occurred in repeated heating/cooling conditions. In view of significant chain stability,
both coacervated and spray-dried samples led to using for long-term heat storage material.
89
70
60
transmittance (%)
50 0 cycle
500 cycles
40
1000 cycles
30
1500 cycles
20 2000 cycles
10
0
0 1000 2000 3000 4000
wave number (cm-1)
Figure 4.29 FTIR output curve for spray-dried samples with 1:1 core to coating ratio
70
60
transmittance (%)
50 0 cycle
500 cycles
40
1000 cycles
30
1500 cycles
20 2000 cycles
10
0
0 1000 2000 3000 4000
Wave number (cm-1)
Figure 4.30 FTIR output curve for coacervated sample with 1:1 core to coating ratio
90
4.8 Thermal performance of microencapsulated PCM in fluidized bed heat
exchanger
Experiments have been carried out to study the thermal performance of spray-dried
encapsulated paraffin wax (1:1 core to coating ratio) in a fluidized bed air heating and
cooling process. Experimental conditions were: size of PCM capsules ~ 300 µm;
density of samples = 997.8 kg/m3;
amount of samples = 40 g;
flow rate of heat transfer fluid = 10 L/min;
superficial velocity = 0.32 m/s;
inlet air temperature ~ 60°C (heating);
outlet air temperature ~ 20°C (cooling).
4.8.1 Temperature profiles
During the heating and cooling process, the air temperatures were recorded at the inlet,
outlet and three axial positions inside the fluidized bed. The measured temperature
profiles are shown in Figures 4.31 and 4.32. During the heating cycles (figure 4.31) the
inlet air temperature remained fairly constant at about 63°C. Not much axial variation of
temperature in the bed was observed. Both the outlet and bed temperatures did not
increase significantly during the initial 200 seconds. It was believed that the major portion
of heat transfer to the PCM took place during this period. Then there was a gradual
temperature rise followed by a sharp increase at about 250 seconds. The sudden increase
in temperature indicated the completion of phase transition of PCM. After about 300
seconds, there was gradual increase of temperature to a steady value of about 55°C. This
91
part reflected the heat transfer as sensible heat to the PCM. The whole heating cycle took
about 700 seconds.
The temperature profiles during heat release from the PCM as it solidified followed
similar pattern during melting. Large amount of heat was released in the initial 200
seconds when the high bed and outlet temperatures were recorded. After 200 seconds,
there was a sharp decrease in temperature indicating end of PCM solidification process.
After this, gradual decrease in temperature referred to PCM sensible heat loss. Total heat
release cycle was about 600 seconds. During heating and cooling processes, the axial
temperature profiles were found to be very close which indicated good mixing of PCM
and heat transfer fluid.
The present study on heat transfer in a air fluidized bed using encapsulated PCM showed
a fairly rapid heating and cooling cycles of about 10/12 minutes. Banazek et al. (1999)
studied indirect heat transfer in spiral heat exchanger using conventional PCM. With heat
transfer fluid (air) temperature of 90°C, it took more than 100 minutes to complete the
heat storage. In comparison to the results of Banezek et al., a fluidized bed heat
exchangerusing encapsulated PCM could be ten times faster in energy charging or
discharging. This was one of the advantages of using encapsulated PCM with high heat
transfer area per unit mass.
92
70
60
T in
temperature (癈)
50
T bed 1
40
T bed 2
30
T bed 3
20 T out
10
0
0 200 400 600 800
time (seconds)
Figure 4.31 Temperature profiles during heat storage stage
60
50
T in
temperature (癈)
40
T bed1
30 T bed2
T bed3
20
T out
10
0
0 200 400 600 800
time (seconds)
Figure 4.32 Temperature profiles during heat release stage
93
4.8.2 Total heat storage and release
The time-temperature profiles of the inlet and outlet air in the fluidized bed heat
exchanger as shown in Figures 4.31 and 4.32 and they were used to estimate the amount
of heat transferred during heating and cooling processes as function of time. A different
time of 25 seconds were considered for the calculations. Knowing the air flow rate,
average inlet and outlet temperatures during the time interval and the specific heat
capacity of air, the amount of heat was calculated as sensible heat. A sample calculation is
shown in Appendix I.
Upon summation, the total heat transferred at certain time was obtained. Figures 4.33 and
4.34 show the calculated heat transferred for heating and cooling processes. Results
showed that per gram of encapsulated PCM, the maximum amount of energy stored and
released are 74 and 61 J respectively. This is much lower than the experimental energy
storage/release capacity of the capsules (~165 J/g). The encapsulated PCM used in this
study were obtained by spray-drying method, where unused coating materials were not
removed by solvent washing. The materials used in the fluidized bed might contain
significant quantity of coating materials without any PCM. This led to lower overall heat
storage. Another possible reason for lower heat storage was inefficient fluidization of the
bed where a significant amount of particles near the wall were not fluidized and as a result
sufficient heat was not transferred.
94
80
70
Qs, Energy storage (J/g)
60
50
40
30
20
10
0
0 100 200 300 400 500 600 700 800
time (seconds)
Figure 4.33 Heat storage with time during heat storage stage
70
QR, Energy release (J/g)
60
50
40
30
20
10
0
0 200 400 600 800
time (seconds)
Figure 4.34 Heat release with time during heat release stage
95
Chapter 5 Conclusions andRecommendations
CHAPTER 5
CONCLUSIONS AND RECOMMENDATIONS
5.1 Conclusions
The present work has been carried out on the preparation and evaluation of characteristics
and performances of microencapsulated paraffin wax prepared by different methods.
Thermal performance of spray-dried microencapsulated paraffin wax is also studied in
fluidized bed heat exchanger.
From the results of this study, the following conclusions can be drawn.
Both complex coacervation and spray drying methods could be used to produce
microencapsulated paraffin wax.
In complex coacervation method, the encapsulation efficiency was dependent on
homogenizing time and the amount of cross-linking agent for different core to
coating ratios. The maximum encapsulation efficiency was found at 10 minute
homogenizing time with 6~8 ml cross-linking agent for 200 ml suspension.
Microencapsulation efficiency decreased with increase of core to coating ratio.
The influence of variables on encapsulation efficiency was presented by non-linear
regression equations.
96
In spray-drying method, the encapsulation efficiency depended on core to coating
ratio and it increased with decrease in core to coating ratio.
Core to coating ratio (measured) depended on relative proportion of core and
coating materials used in preparation. Higher concentration of core material led to
higher core and coating ratio.
DSC results showed that the microcapsules prepared by both methods had high-
energy storage/release capacities (91-239J/g) and it depended on core to coating
ratio.
SEM analysis showed that the microcapsules prepared by both methods were
globular in shape and more spherical for spray-dried capsules compared to
coacervated samples. Size of coacervated samples ranged from 3.3 and10.5 µm
whereas size of spray-dried samples was between 1.3 and 10.1 µm.
Inner structures of the microcapsules, as found by SEM analysis, showed that the
coating material formed the wall and inside matrix type network for both
coacervated and spray-dried capsules. PCM was embedded as small particles of
discrete phase within the matrix network of the coating material.
97
Thermogravimetric analysis showed high thermal stability for core and coating
materials for both coacervated and spray-dried samples. The peak decomposition
temperatures for coating materials (350°C for coacervated sample and 340°C for
spray-dried sample) were higher than that of core material (260°C for both
coacervated and spray-dried samples). This showed that the coating materials were
suitable for encapsulation of PCM in thermal energy storage at high temperature.
Both cocervated and spray dried samples showed no regular degradation in their
thermal properties as a function of latent heat, melting temperature, phase
transition range and specific heat capacity after 2000 melt/freeze cycles.
The analysis of FTIR spectra of both coacervated and spray dried samples
indicated good stability of chemical structure of the core and coating materials
during thermal cycling up to 2000 cycles. No apparent oxidation and thermal
degradation were observed by thermal cycling. Furthermore, the core material
paraffin wax was compatible with coating materials.
A fluidized bed heat exchanger using spray-dried encapsulated PCM and air as
heat transfer fluid was found to be an efficient heat exchanging system. It might
achieve about ten times faster energy storage and release cycles compared to a
conventional PCM heat exchanger system.
98
5.2 Recommendations
On the basis of the present experiments carried out and results obtained the following
recommendations are suggested for future studies:
Spray-dried microcapsules showed quite good thermal performance and
stability to thermal cycling up to 2000 cycles. Spray drying process need to be
developed into cost effective and efficient technique for commercial utilization
of energy storage material. The present study is focused on the effect of core to
coating ratio in encapsulation efficiency, thermal performance and long term
storage stability. For encapsulation process by spray-drying, the effects of
other process parameters, such as feed flow rate, feed pump rate, airflow rate,
aspirator condition, and inlet and outlet air temperature are not examined in
details. It is recommended that further investigations should be carried out to
determine these effects and their optimal operation conditions.
This study focused on two methods, complex coacervation and spray-drying
for microencapsulation of paraffin wax. Hence, further studies on other
encapsulation methods such as interfacial polymerization and dip coating and
evaluation of performance are considered valuable.
More investigation is needed for fluidized bed heat exchanger using

encapsulated PCM. Future work should focus on improving fluidization in the
bed, insulating the column and operating over wider range of process
conditions.
99
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Appendix A Encapsulation efficiency
Table A1. Encapsulation efficiency of coacervated samples for different homogenizing

time and core to coating ratios [x = homogenizing time (minutes), z = encapsulation
efficiency (%) and RSD = relative standard deviation (%)]

1:2 1:1 2:1
x z RSD x z RSD x z RSD
5 73.12 6.10 5 71.56 12.26 5 67.89 13.43
72.14 5.40 71.03 5.95 67.05 3.92
72.54 0.70 69.00 18.22 65.25 18.12
7 77.51 3.98 7 74.19 4.98 7 70.96 12.44
76.58 6.60 74.78 1.85 71.23 15.67
77.39 2.62 74.89 3.13 67.57 28.10
10 87.16 6.23 10 85.65 1.30 10 81.98 18.37
86.79 2.26 85.68 1.62 83.96 3.28
85.79 8.49 85.26 2.92 85.04 15.09

time and the amount of cross-link agent at different core to coating ratios [x =
homogenizing time (minutes), y = the amount of 30% formaldehyde (ml), z =
encapsulation efficiency (%) and RSD = relative standard deviation (%)]

1:2 1:1 2:1
x y z RSD x y z RSD x y z RSD
10 3 91.71 9.97 10 3 91.29 1.57 10 3 89.48 5.90
92.31 3.73 91.21 0.73 90.38 3.58
93.99 13.71 90.92 2.30 90.26 2.32
6 94.91 0.21 6 94.12 1.44 6 92.08 2.50
95.24 3.59 93.96 0.21 91.53 3.23
94.52 3.80 93.86 1.24 91.91 10.44
9 91.80 4.18 9 90.51 1.89 9 89.53 4.02
90.77 6.59 90.28 0.53 89.10 0.53
91.63 2.41 90.20 1.37 88.82 3.50
20 0 84.52 1.74 20 0 83.91 2.73 20 0 81.97 7.65
84.31 0.54 83.47 2.08 81.41 1.44
84.25 1.20 83.60 0.66 80.46 9.10
3 89.52 4.34 3 88.07 0.64 3 86.48 4.08
89.16 0.53 88.01 0.0 86.99 1.39
88.65 4.87 87.95 0.64 87.11 2.68
6 93.22 0.41 6 92.14 1.04 6 89.98 1.69
93.25 0.73 91.95 1.04 89.85 0.32
93.07 1.14 92.03 0.10 89.63 2.00
113
Table A2 (Continued)
9 89.21 2.01 9 87.99 0.75 9 87.18 1.72

89.01 0.11 87.87 0.53 87.10 0.86
88.84 1.91 87.90 0.21 86.78 2.57
30 0 82.38 0.66 30 0 82.09 7.43 30 0 80.99 10.17
81.98 3.75 82.01 6.54 80.90 9.16
82.60 3.09 81.93 5.65 78.35 19.33
3 88.79 2.55 3 87.99 5.77 3 86.67 3.23
88.39 1.70 87.56 1.18 86.60 2.47
88.47 0.85 86.80 6.95 85.84 5.70
6 89.86 0.84 6 88.78 0.32 6 87.66 0.11
89.79 0.11 88.83 0.21 87.59 0.64
89.69 0.95 88.82 0.11 87.70 0.53
9 87.19 1.93 9 86.52 5.82 9 83.42 2.41
87.09 0.86 86.41 4.64 83.25 0.55
86.75 2.79 85.01 10.46 82.93 2.96

time and the amount of cross-link agent at different core to coating ratios [x =
homogenizing time (minutes), y = the amount of 50% gluteraldehyde (ml), z =
encapsulation efficiency (%) and RSD = relative standard deviation (%)]

1:2 1:1 2:1
x y z RSD x y z RSD x y z RSD
10 3 92.31 0.21 10 3 92.12 1.15 10 3 90.21 0.74
92.28 0.52 92.04 0.31 90.18 1.05
92.40 0.73 91.87 1.46 90.45 1.79
6 95.57 1.12 6 94.09 0.10 6 92.47 5.11
95.44 2.45 93.81 2.78 91.87 1.15
96.03 3.58 94.34 2.68 91.60 3.96
9 90.56 0.84 9 89.46 4.66 9 87.31 1.18
90.88 4.21 88.79 2.44 87.51 0.96
90.00 5.05 88.81 2.23 87.44 0.21
20 3 89.65 0.32 20 3 88.09 0.53 20 3 87.81 0.53
89.51 1.16 88.21 0.75 87.71 0.53
89.70 0.85 88.12 0.21 87.76 0.00
6 93.34 1.35 6 92.51 1.35 6 89.78 0.53
93.18 0.31 92.40 0.21 89.24 6.22
93.11 1.04 92.23 1.56 90.47 6.75
9 89.71 0.95 9 88.01 3.94 9 85.99 0.65
89.51 1.16 88.36 0.21 86.05 0.00
114
Table A3 (Continued)
89.64 0.21 88.77 4.15 86.11 0.65

30 3 88.49 1.38 30 3 88.14 4.38 30 3 86.50 0.54
88.76 1.49 87.64 0.96 86.22 3.55
88.61 0.11 87.41 3.42 86.93 4.08
6 90.00 0.21 6 88.89 0.74 6 87.11 1.93
89.91 0.74 88.79 0.32 87.20 0.96
90.03 0.53 88.78 0.42 87.56 2.89
9 86.29 0.11 9 85.37 0.76 9 80.84 15.11
86.36 0.22 85.42 0.22 82.29 0.88
86.49 1.18 85.53 0.97 83.50 14.23
Table A4. Encapsulation efficiency of spray-dried samples
Core to coating ratio Encapsulation efficiency Relative standard deviation,

(%) RSD (%)
1:2 82.99 0.77
82.87 0.55
82.90 0.22
1:1 75.54 0.35
75.69 1.04
75.57 0.35
2:1 70.97 0.36
71.09 1.07
70.94 0.71
Appendix B Core to coating ratio
Table B1. Estimation of core to coating ratios
Coacervated sample Spray-dried sample

Expected Measured Relative Expected Measured Relative
core to core to standard core to core to standard
coating ratio coating ratio deviation, coating ratio coating ratio deviation,
RSD (%) RSD (%)
0.5 (1:2) 0.431 1.39 0.5 (1:2) 0.364 1.80
0.415 1.08 0.381 0.98
0.420 0.31 0.380 0.82
1.0 (1:1) 0.794 1.23 1.0 (1:1) 0.718 0.59
0.811 0.67 0.707 0.71
0.810 0.56 0.714 0.12
2.0 (2:1) 1.854 1.32 2.0 (2:1) 1.427 0.75
115
Table B1 (Continued)
1.886 1.02 1.444 0.67

1.876 0.29 1.437 0.08
Appendix C DSC output curves after thermal cycling
Figure C1. DSC output curve for 1:1 coacervated sample at 0-cylce
Figure C2. DSC output curve for 1:1 coacervated samples after 1000 cycles
116
Figure C3. DSC output curve for 1:1 coacervated samples after 1500 cycles
Figure C4. DSC output curve for 2:1 spray-dried samples after 500 cycles
117
Figure C5. DSC output curve for 2:1 spray dried sample after 1000 cycles
Figure C6. DSC output curve for 2:1 spray-dried samples after 2000 cycles
118
Base line
60°C
Figure C7. DSC measurement of melting temperature of microencapsulated

paraffin wax (spray-dried1:1) at 0 cycle
Base line
60°C
Figure C8. DSC measurement of melting temperature of microencapsulated paraffin

wax (spray-dried 1:1) after1000 cycles
119
Base line
60°C
Figure C9. DSC measurement of melting temperature of microencapsulated paraffin

wax (spray-dried 1:1) after1500 cycles
60°C
Base line

120
Base line
60°C

Base line
60°C

121
Figure C13. DSC measurement of specific heat capacity of microencapsulated
paraffin wax (spray dried 1:2) after 500 cycles

paraffin wax (spray-dried 1:2) at 1500 cycles
122
Figure C16. DSC measurement of specific heat capacity of microencapsulated paraffin

wax (coacervated 1:2) at 0 cycle
123

124
Appendix D FTIR output curves
90
80
70
Transmittance (%)
0 cycle
60
500 cycles
50
1000 cycles
40
1500 cycles
30
20 2000 cycles
10
0
0 1000 2000 3000 4000
-1
Wave number (cm )
Figure D1. FTIR output curve for 1:2 coacervated sample
60
50
Transmittance (%)
0 cyle
40
500 cycles
30 1000 cycles
1500 cycles
20
2000 cycles
10
0
0 1000 2000 3000 4000
Wave number (cm-1)
Figure D2. FTIR output curve for 2:1 coacervated sample
125
100
90
80
Transmittance (%) 70 0 cycle
60 500 cycles
50 1000 cycles
40 1500 cycles
30 2000 cycles
20
10
0
0 1000 2000 3000 4000
Wave number (cm-1)
Figure D3. FTIR output curve for 1:2 spray-dried sample
60
50
Transmittance (%)
0 cycle
40
500 cycles
30 1000 cycles
1500 cycles
20
2000 cycles
10
0
0 1000 2000 3000 4000
Wave number (cm-1)
Figure D4. FTIR output curve for 2:1 spray-dried sample
126
Appendix E Size distributions measured by particle analyzer
Figure E1. Size distribution for spray-dried samples
Figure E2. Size distribution for coacervated samples
127
Appendix F Minimum fluidization velocity
uf = (dp2/150) [(ρs - ρf)/µ] [g*ε/ (1- ε)]
uf = minimum fluidization velocity
ρs = density of particle = 997.8 kg/m3
ρf = density of fluid = 1.2889 kg/m3
dp = diameter of particle = 3 x 10-4 m
ε = void fraction = 0.4 (assuming)
Hence, uf = 0.064 m/s
Appendix J Sample calculation for heat storage/release base on inlet air

and outlet air temperature
Equation used : Qs = m cp ∆T, QR = m cp ∆T
Qs = heat storage during 25 seconds, QR = heat release during 25 seconds.
m = mass of air passed through the fluidized bed
cp = specific heat capacity of air
∆T = (T1-T2), where T1 = average inlet air temperature during 25 seconds and T2 =
average outlet air temperature during 25 seconds.
Average inlet temperature = 61.8988°C
Mass of air at average temperature 44.948 °C during 25 seconds = 5.0556 grams
Cp of air = 1.008 kJ/kg K
Average outlet temperature = 27.9972°C
Hence, heat storage during 25 seconds = 172.7634 J
Specific heat storage = 4.3191 J/g
128
Appendix K List of publications
Hawlader M.N.A, M.S. Uddin and Mya Mya Khin. Microencapsulated PCM thermal-
energy storage system. The 9th International Energy Conference, 19th – 24th June,
Cracow, Poland. 2002.
M. N. A. Hawlader, M. S. Uddin and Mya Mya Khin. Microencapsulated PCM

thermal-energy storage system, Applied Energy, Vol. 74, Issue 1-2 ,pp 195-202, 2003.
Mya Mya Khin, M. N. A. Hawlader and M. S. Uddin. Microencapsulation of phase

change Materials, Paraffin Wax. 9th APPChE Congress and CHEMECA,
29thSeptember-3rd October, Christ Chruch, New Zealand. 2002.
129

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ENCAPSULATION OF PHASE CHANGE MATERIALS (PCMS)

FOR HEAT STORAGE

MYA MYA KHIN

(B.E., Yangon Technological University)

FOR THE DEGREE OF MASTER OF ENGINEERING

DEPARTMENT OF CHEMICAL & ENVIRONMENTAL ENGINEERING

NATIONAL UNIVERSITY OF SINGAPORE

 To the National University of Singapore, for the postgraduate research

scholarship, without which I would not be able to continue my higher degree

 To my supervisors, Associate Professor M.S Uddin and Associate Professor

Engineering Department for their patience and help.

on different occasions, discussion and for their encouragement during my tenure at

their continuous love and encouragement throughout the study.

make this thesis possible.

LIST OF FIGURES viii

1.1 General background 1

1.2 Objective and scope of thesis 4

CHAPTER 2 LITERATURE REVIEW 6

2.1 Thermal energy storage 6

2.2 Thermal energy storage techniques 7

2.3 Candidate heat storage materials 15

2.4 Factors affecting the energy storage capacity of PCM 20

2.5 Encapsulation of phase change materials 20

2.6 Methods of microencapsulation 25

2.7 Thermal cycling test for encapsulated PCM 30

2.8 Heat transfer of PCMs 31

2.9 Scope of the present work 34

CHAPTER 3 MATERIALS AND EXPERIMENTAL 34

3.3.1 Complex coacervation 40

3.3.2 Spray drying 42

3.4 Characteristics and performance of microcapsules 44

3.4.1 Energy storage and release capacities 44

3.4.2 Thermogravimetric analysis 45

3.4.3 Surface morphology and characterization of inner 46

3.4.4 Microencapsulation efficiency 47

3.4.5 Estimation of core to coating ratio 47

3.4.6 Chemical structure stability evaluation 48

3.5 Accelerated test process 48

3.6 Fluidized bed heat exchanger for microencapsulated PCM 51

CHAPTER 4 RESULTS AND DISCUSSION 54

4.1 Encapsulation efficiency 54

4.2 Estimation of core to coating ratio 63

4.3 Thermal performance 64

4.4 Surface morphology and inner structure characterization 68

4.4.1 Surface morphology 68

4.4.2 Inner structure 69

4.5 Thermogravimetric analysis 70

4.6 Thermal cyclic test 75

4.8 Thermal performance of microencapsulated PCM in 91

fluidized bed heat exchanger

4.8.1 Temperature profiles 91

4.8.2 Total heat storage and release 94

CHAPTER 5 CONCLUSIONS AND RECOMMENDATIONS 96

microencapsulating paraffin wax by polymeric materials (gelatin and acacia) in an

aqueous system. Experiments on operational variables to select suitable conditions were

efficiency and the parameters studied. In spray-drying method, decrease in encapsulation

coating ratio was found to be 1:2.

In the studies on thermal performance analysis by Differential Scanning Calorimetery

storage/release capacities. The energy storage/release capacities of the coacervated

prepared under different conditions.

both coacervated and spray-dried samples consisted of a polymeric matrix surrounding

Thermogravimetry (TG) analysis. Thermal decomposition temperatures of core and

To the National University of Singapore, for the postgraduate research

To my supervisors, Associate Professor M.S Uddin and Associate Professor