Stability and Thermal Properties of Paraffin Wax with Various Nanoparticles

V. Saydam 1, X. Duan 1

1
Department of Mechanical Engineering, Memorial University of Newfoundland, St. Johns, NL,
Canada, A1B 3X7

Abstract
In this study, stability of nanoparticles and thermal properties of NEPCMs were

investigated. Paraffin wax with a phase change temperature of 53-57 C was chosen as a PCM.

Multi-walled carbon nanotubes(MWCNTs), graphene nanoplatelets and Aluminum oxide

nanoparticles were selected as enhancers. Nanoparticles were dispersed into paraffin wax using

mechanical dispersion methods (sonication, stirring) with and without surfactants at varying mass

fractions (0.1,0.5,1,2 wt.%). Thermal conductivity of samples was measured using KD2 Pro

(Decagon Devices) based on Transient-Hot-Wire(THW) method. Results showed that the increase

of nanoparticle content did not improve thermal conductivity significantly with the highest

enhancement of 13% for 2 wt. MWCNT added wax at 35C. Stability of nanoparticles were

investigated extensively. Visualization method was adopted for stability observation after

consecutive melting-solidification cycles performed in an environmental chamber. Significant

deposition and coagulation were seen over thermal cycles regardless of the nanoparticle type,

nanoparticle content and dispersion methods. DSC study revealed that unlike the common belief,

supercooling effect became worse with the addition of nanoparticles except for 0.5 and 1 wt.%

MWCNT-wax sample.

Keywords: NEPCMs,Paraffin wax, nanoparticles, stability, thermal conductivity, DSC

1
 1.Introduction

Growth of energy demand throughout the world requires efficient use of renewable energy

sources. The intermittency and inconsistency of renewable energy sources such as wind and solar

necessitates the usage of energy storage. Application of latent heat energy storage systems has a

great potential. Thermal energy storages that take advantage of the high latent heat of phase change

materials (PCMs) have been used extensively [1]. Many PCMs have low thermal conductivities

and several methods have been tried to improve that, for example by inserting metallic fins and

matrix structures into PCM containers [2]. In recent years, there is a growing interest of dispersing

nanoparticles into PCMs for thermal conductivity enhancement [3].

Carbon-based nanoparticles are promising nanofillers due to their high thermal

conductivity compared to metallic oxide nanoparticles [4]. MWCNTs and graphene are the most

prominently used carbon based nanoparticles while Aluminum oxide and Copper oxide are also

commonly preferred metallic oxide particles. There have been numerous studies with various

nanoparticles. Fan et al. [5] compared the effects of various nanoparticles on paraffin wax and

found that increasing temperature resulted in lower thermal conductivity. However, the increasing

content of nanoparticles gave rise to dramatic improvement for GNPs from 0.264 W/m K to 0.7

W/m K for 5 wt.% concentration. The outstanding performance of GNPs was attributed to the planar

structure and reduced interfacial thermal resistance. They also found that long and short-walled CNTs

did not provide notable enhancement in thermal properties. Angayarkani and Philip [6] observed

considerable thermal conductivity increase for hexadecane with MWCNT and GNPs dispersed at

0.5 wt% up to %195 and %180, respectively. They reported that enhancement only took place up

to a certain nanoparticle concentration. Higher concentrations could lead to decrease in thermal

conductivity due to agglomeration of nanoparticles. Warzoha and Fleischer [7] examined the effect

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of various nanoparticles including graphene, MWCNTs, on the thermal properties of

paraffin(Tm=56C) at high concentration (20 vol.%). The thermal conductivity of graphene and

MWCNTs added samples was improved enormously by 2800% and 832% respectively.

Wang et al. [8] studied paraffin wax with a melting temperature range of 52 to 54 C

incorporated with MWCNT of 0.2 to 2 wt. % and reported thermal conductivity enhancement of

40% at 60 and 35% at 35 . Another study done by Kumaresan et al. [9] showed that increasing

volume concentration of MWCNT from 0.15% to 0.6% in paraffin not only improved thermal

conductivity of the PCM but also mitigated the super cooling issue. Tang et. al [10] observed

thermal conductivity enhancements with increasing amounts of functionalized-MWCNTs in

paraffin wax. This improvement was further confirmed by reduction in heating and cooling time

of the samples with 1, 5 and 10 wt.% f-MWCNTs content. A research by Yu et al. [11] found

insignificant improvement in thermal conductivity in liquid phase paraffin wax (with 1 to 4 wt. %

MWCNT) and highly clustered emulsions. Wu et al. [12] also reached the same conclusion after

dispersing MWCNT to paraffin. Fan et al. [13] dispersed graphene nanoplatelets into 1-

tetradecanol at varying concentrations (0.5, 1, 3 wt.%). The presence of graphene doubled the

thermal conductivity at 45C for 3 wt.% nanoparticle content. Wang et al. [14] analysed the impact

of -Al2O3 nanoparticles on the thermal properties of paraffin wax having a melting temperature

range of 52-54C. Higher enhancement was achieved for solid phase at various levels than liquid

phase reaching up to %25 with increasing loadings of nanoparticle. However, the increase in

temperature lowered the thermal conductivity both in liquid and solid phases. Ho and Gao [15]

prepared alumina(Al2O3) nanoparticles (5 and 10 wt.%) doped n-octadecane to examine changes

in thermal properties. Non-linear thermal conductivity improvement with increasing nanoparticle

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loading was seen. Increased temperature, particularly at 60C, led to higher enhancement in

thermal conductivity.

Another important part of dispersion of nanoparticles into PCMs is stability. Stability term

for NEPCMs is referred to the uniform dispersion of nanoparticles within the base PCM without

any agglomeration or clusters. It is vitally important for the future of thermal energy storage units

with NEPCMs. Marketability of these systems totally depends on the long-term reliability and

consistent high performance of NEPCMs. NEPCMs should perform with their enhanced properties

invariably over a long time. Therefore, NEPCMs must be tested with the conditions that are like

real applications to ensure their performance in the long term.

Some studies considered stability of nano-enhanced PCMs through observing the thermal

properties over thermal cycles. Kumerasan et. al. [9] did a visual inspection of MWCNT dispersed

paraffin (Tm=19-22C) to monitor stability. They claimed visually stable samples for various

concentrations (0.15, 0.3, 0.45,0.6 wt.%) after three months. Tang et. al. [10] found that stability

of functionalized MWCNTs through acidic treatment with octadecylamine was much better

without any visible settlement than crude MWCNTs in toluene. Cyclic stability was also

maintained after 100 thermal cycles without any significant change in latent heat of fusion, phase

change temperature and supercooling. Another study on dispersion of MWCNTs in paraffin

wax(Tm=52-54C) was carried out by Wang et. al. [8]. Ball-milling treated MWCNTs were found

to be homogeneously dispersed without any lamination through SEM images after being kept in

oven at 70C for 96 h. Angayarkanni and Philip [6] observed the change in thermal conductivity

of GNPs and MWCNT dispersed paraffin having a melting temperature of 18C after five thermal

cycles. It was found that thermal conductivity enhancement fluctuates and mainly tends to decrease

for solid phase at 10C as nanocomposites undergo thermal cycles. Weinstein et. al. [16]

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incorporated graphite with different geometries into paraffin wax(Tm=56C) and monitored the

heat transfer enhancement by monitoring transient temperature change at different heat flux.

Significant settlement was observed after third thermal cycle. Therefore, sonication application

was repeated after each test. Wu et. al. [17] dispersed Cu, Al, and C/Cu nanoparticles into

paraffin(Tm=58-60C) with different surfactants to see the effects on thermal properties and

stability. Samples with Hitenol BC-10 surfactant were found to be most stable after 12 h by visual

inspection. Nanocomposites were observed to be stable in terms of phase change temperature and

latent heat of fusion after 100 thermal cycles. Fan et. al [13] pointed out that GNPs dispersion in

1-tetradecanol substantially improved its stability up to 5 melting/solidification thermal cycles due

to the presence of commercial dispersant. However, further thermal cycles caused significant

precipitation. Cyclic stability of CNTs added 1-dodecanol (Tm=22C) was examined visually by

Zeng et. al [18]. Specimens were found to be settlement-free after two melting/solidification

cycles. With the third cycles, sedimentation took place. However, specimens were observed to

maintain desired stability in liquid phase for several days.

Surfactant treated stearic acid with MWCNT, graphene and graphite NEPCM was studied by Choi

et al [19]. It was noted that samples with PVP surfactants did not experience settlement after 10

days whereas samples without surfactants were found to be immensely agglomerated and settled.

Wang et al. [20] compared the stability of palmitic acid with pristine and oleylamine-octanol

treated CNTs. Thermal cycles performed in an oven showed that grafted CNTs maintained their

homogeneity after 80 melting/solidification samples while delamination was prevalent for pristine

CNTs- palmitic acid sample even after first cycle. Zhang et al. [21] investigated the suspension

time of untreated and surface treated MWCNTs with various surfactants in n-hexadecane. Surface

treated MWCNT with 1-decanol provided the longest suspension time (290 min) compared to

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other combinations. Zheng et al.[22] examined the suspension quality of graphite particles in

hexadecane at low concentration (0.05%). Overall suspension of graphite flakes was maintained

providing the percolation network both in liquid and solid phase. Mehrali et. al. [23] impregnated

paraffin wax (Tm= 50-60C) into graphene oxide(GO) sheets to create stabilized nano composites

for thermal energy storage systems. DSC measurements revealed that the nanocomposites

maintained their properties, particularly; latent heat and phase change temperature with only slight

deviations up to 2500 thermal cycles. Nourani et. al. [24] conducted a stability study of Al2O3

dispersed paraffin wax using image analysis. They found that sedimentation rate increased

proportionally as the samples underwent up to 25 melting/solidification cycles.

Previous studies mostly focused on the thermal stability of NEPCMs based on DSC results.

Moreover, thermal conductivity enhancement results were usually obtained when the samples are

at the most stable state. As per the authors knowledge, nothing systematically was done pertaining

to the stability issue of NEPCMs after melting/solidification cycles and monitor the thermal

conductivity of NEPCMs over time. Given this fact, comprehensive stability study was conducted

to address stability issue along with thermal conductivity enhancement.

2. Material and Methods

2.1. Materials

All the materials including nanoparticles, base PCM and surfactants were purchased from

Sigma Aldrich. Paraffin wax has a phase change temperature of 53-57C. MWCNTs have the

following parameters:6-9 nm in diameter and 5 m in length. Aluminum oxide(Al2O3)

nanoparticles have less than 50 nm particle size and graphene nanoplatelets have lateral

dimensions of about 2-3 as specified by the manufacturer. Sodium oleate and octadecylamine

were used as surfactants to promote long term stability. Fig.1 shows the materials.

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2.2 Sample Preparation

NEPCM preparation can be divided into two categories namely mechanical dispersion and

chemical dispersion methods. These methods are mostly adopted from nanofluid science.

Mechanical dispersion method consists of stirring and sonication where mechanical energy is used

to agitate nanoparticles. Stirring helps nanoparticles disperse at macro scale by spinning a stirring

bar in the liquid medium whereas sonication basically creates cavitation during application

resulting in micro bubble formation. The collapse of these micro bubbles leads to the

disentanglement of clustered and agglomerated nanoparticles and therefore provides good

dispersion [25]. In chemical dispersion methods, surfactants are used to make nanoparticles more

miscible by lowering the surface energy levels at the interface of base PCM and nanoparticles [26].

Furthermore, nanoparticles can also be treated through functionalization (acid treatment) for better

dispersion [10].

The first batch of samples were prepared with only mechanical dispersion method. A desired

amount of each nanoparticles corresponding to 0.5, 1 and 2 % by mass and paraffin wax were first

weighed on the electronic scales (Denver Instrument-Model P-214, Ohaus Corporation-

Adventurer Pro AV8101C, respectively). Then, paraffin was melted in a beaker on a hot plate

stirrer (SP131320-33Q, Cimarec - Thermo Scientific). Temperature of the hot plate stirred was

kept above melting temperature at 70C. Magnetic stirring was applied for 1 h at average speed

after adding the specified amount of nanoparticles. Stirring was followed by sonicating the samples

for an hour at 30% amplitude (50W, Sonifier Cell Disrupter, Branson). Fig. 2 shows the sample

preparation process.

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2.3 Thermal Conductivity Measurements

Thermal conductivity measurements were taken using a KD2 Thermal Conductivity

Analyzer (Decagon Devices, USA). The measurement technique is based on the transient hot

wire(THW) principle. After sonication, samples were taken to environmental chamber and thermal

conductivity measurements were first conducted in liquid phase at 70C within the first hour after

sample preparation. Then, temperature was set to 60C and measurements were repeated at that

temperature hourly as shown in fig 3. Four measurements were taken at each point, at least. The

main purpose was to observe if there is any change in thermal conductivity due to sedimentation

and particle instability over time.

After the measurements were done in liquid phase, the samples were poured into a mold

designed for solid phase measurements. The mold was printed on a 3-D printer to create a pilot

hole in the sample during solidification (fig.4). Once samples were fully solidified at ambient

temperature, measurements were conducted in the thermal chamber at 25, 35 and 45C. The

pictures of solid samples can be seen in fig 5. At least 3 measurements were taken for each point.

Measurements revealed that thermal conductivity ranges within 0.15 to 0.16 W/m K for

paraffin wax with different concentrations of MWCNT in liquid phase at 60C. There was not any

significant change in thermal conductivity within the first four hours after sample preparation

(Fig.3). However, there was an anomaly for 1 wt.% MWCNT at 60C after 1 h. It was seen that

samples were highly viscous with mud-like texture as the MWCNT content increased from 0.5 to

2 wt.%. This could deteriorate the natural convection induced melting. After the consecutive

measurements, the samples were put into a mold and left to solidify at room temperature. Solid

phase measurements exhibited temperature-dependent trend where thermal conductivity peaked at

35C for all the concentrations possibly due to solid-solid transition. The highest enhancement was

8
achieved for 2 wt.% MWCNT-paraffin wax by 13% at 35C (Fig.6). Overall, no significant

improvement in thermal conductivity was observed with the addition of MWCNT. In some cases,

presence of MWCNTs deteriorated thermal conductivity.

Graphene was expected to increase paraffins thermal conductivity significantly. Hence,

initial measurements right after sample preparation within the first hour showed that thermal

conductivity increases sharply for all the concentrations from 0.15 to 0.21 W/mK at 70C(Fig.6).

This increase caused by the natural convection induced by particle motion. However, after the first

hour, the measurements at 60C indicated only a marginal increase. This can be accounted for the

sedimentation of majority of graphene particles when thermal equilibrium was reached after a

sufficient time. Thermal conductivity measurements changed slightly for the consecutive

measurements made at 60C. After liquid phase measurements, samples were poured into the

mold. It was seen that majority of particles were stuck on the bottom surface proving the settlement

of particles. Therefore, it could be said that measurements for graphene doped paraffin do not

really represent the actual nanoparticle content of the samples. Only small fraction of particles that

were dispersed in to paraffin were uniformly scattered improving the thermal conductivity slightly.

Thus, the accuracy of measurements are questionable due to instability for graphene added paraffin

wax samples. Addition of graphene nanoplatelets increased the thermal conductivity only

marginally ranging from 0.16-0.17 W/m K at 60C (Fig.8). Increasing nanoparticles linearly did

not lead to proportional enhancement in thermal conductivity. The particle settlement played an

important role in not providing the desired enhancement. This is more evident in solid phase where

measurements were made at 25, 35 and 45 C. It was seen that increasing graphene nanoplatelet

content led to a minor increase. This is also attributed to reduced graphene content due to not being

9
able to transfer particularly the particles that got stuck on the bottom surface into a mold.

Consequently, graphene did not provide the desired thermal conductivity enhancement.

Presence of Aluminum oxide(Al2O3) nanoparticles also enhanced the thermal conductivity

slightly. This enhancement, however, was not proportional with the nanoparticle increase. Lower

loadings of Al2O3 resulted in higher enhancement in liquid phase even with an outlier at 70C for

0.5 wt.% Al2O3 due to natural convection possibly induced by Brownian motion (Fig. 6).

Precipitation issue again affected the measurements. It was seen that particles started to settle

immediately once sonication is completed. Therefore, it is not possible to evaluate the potential of

nanoparticles based on the obtained data. Solid phase measurements also revealed biased results

mainly fluctuating within the vicinity of pure paraffin waxs thermal conductivity without any

clear trend. It was also seen that there is just a little change in thermal conductivity with a mild

decrease for the measurements that were done an hour later after sample preparation (Fig. 3). This

is possibly due to already deposited particles within the first hour.

2.4 Differential Scanning Calorimetry Measurements

DSC study was carried out to determine melting/solidification temperatures and latent heat

capacity of paraffin wax nanocomposites (Mettler -Toledo DSC1, Differential Scanning

Calorimeter). Fig. 7 shows the heating and cooling curves of the samples with a heating/cooling

rate of 5C/min. Two distinct peaks can be seen on both heating and cooling curves where smaller

peak corresponds to solid-solid transition at around 35C and larger peak exhibits the solid-liquid

transition around 50-55C.

The peak temperatures of pure paraffin wax for melting and freezing were found to be 54.86 and

53.02 C respectively. This demonstrates the insignificant supercooling with 1.84C. The presence

10
of nanoparticles seemed to increase the melting peak temperatures by1-2C except for MWCNT-

wax samples while the freezing peak temperature were reduced with the same effect except for 0.5

wt.% Al2O3 -wax sample. Supercooling issue became worse with the addition of nanoparticles

reaching up to 4.25C except for 0.5 and 1 wt.% MWCNT-wax samples. This unusual behavior

contradicts the common belief that nanoparticles lessen the supercooling issue by acting as a

nucleating agent [9, 10]. Phase change enthalpies were also found to be 124.61 and 126.84 J/g for

pure paraffin during melting and freezing curves, respectively. Nanoparticle addition had different

effects on the phase change enthalpies. A varying degree of decrease in enthalpies was seen for all

the nanoparticle-wax samples at the highest concentration(2wt.%).However, the trend for other

concentrations was somewhat unclear with random increase and decrease.

3. Stability of Paraffin Wax with Nanoparticles

3.1 Effect of Sonication on Stability

One of the main objectives of this study was to investigate the effect of mechanical

dispersion (particularly sonication time) on the stability of samples. To do that, melting-

solidification thermal cycles were performed in an environmental chamber between 25 - 80C.

Pictures of samples were taken after each cycle in liquid phase to assess the uniformity and

homogeneity of particle dispersion visually. Fig. 8 shows the samples with varying sonication time

at different MWCNT loadings after three thermal cycles.

Reasonably stable condition with insignificant settlement was attained for all the samples

after the first thermal cycle as shown in Fig. 8. However, considerable particle settlement took

place with the second thermal cycle. After the third thermal cycle, significant precipitation and

agglomeration were observed. It can be clearly seen in Fig. 8(2-3) that particles formed clusters

11
on the lower portion of the container whereas the upper part is mainly composed of paraffin. It is

evident after the third thermal cycle that up to a certain height, samples have dark color potentially

indicating highly agglomerated regions(Fig.8). However, the region close to surface seems

transparent showing that there is no particle network. This could be attributed to the fact that the

density of the nanoparticle is higher than that of paraffin resulting in particles settled on the lower

part.

It was noticed that different sonication durations do not seem to have any effect on the

improvement of stability at the investigated nanoparticle loadings. Significant agglomeration and

settlement are unavoidable over these thermal cycles. It was also found that stability becomes

worse dramatically for all the samples regardless of MWCNT content. It should be noted that

temporary stable NEPCM was observed for sample D and E after the second thermal cycle. That

was due to beaker replacement. However, sample D and E follow the same trend as sample A, B

and C in terms of particle settlement as it is obvious after the third thermal cycle in Fig 8.(3).

3.2 Effect of using surfactants on Stability

3.2.1. Various Nanoparticles in Paraffin Wax with Sodium Oleate

After the first stage of the stability study, it was acknowledged that mechanical dispersion

methods namely stirring and sonication are not sufficient to achieve long term stability.

Consequently, it was decided that surfactant should be used to stabilize nanoparticles. For this

purpose, sodium oleate (anionic) was used during the preparation of samples (Fig.1-E). Three

different NEPCM samples including Aluminum oxide (<50 nm particle size, spherical), Graphene

nanoplatelets (lateral dimensions of about 2-3 , planary) and MWCNTs were prepared with

paraffin wax as base PCM at 0.1% wt. Previous NEPCM preparation procedure was followed. The

12
only difference was that sodium oleate with the mass ratio of 1:10 to nanoparticle amount was

added to molten paraffin wax-nanoparticle solution during stirring. Then, sonication was done for

1h at %30 amplitude. After all the samples were prepared, melting-solidification thermal cycles

were performed between 25-80C in the environmental chamber again to see the effect of

surfactant usage on the stability of NEPCM composites. Pictures taken after each cycle are shown

in Fig. 10 both in solid and liquid phase. The pictures of samples right after preparation are also

included.

As can be seen from Fig 10., the stability evaluation for MWCNT-paraffin wax composite

is much more distinct than the other two samples. It can be said that MWCNTs within paraffin

seems uniformly dispersed and relatively stable after sample preparation in liquid phase (pictures

labeled as 0). However, the thin particle free regions appeared with the second thermal cycle. As

the MWCNT-paraffin wax sample went through thermal cycles, those regions started growing and

finally forming a particle-free layer on top while the MWCNTs settled on the bottom of the

container. The deterioration of uniform dispersion is apparent in both liquid and solid phase for

MWCNT-paraffin sample.

It is hard to assess the stability of Aluminum particles in solid phase due to color turning

white during solidification. However, it was noticed that majority of white aluminum particles

precipitated at the bottom of the container even after the first thermal cycle in liquid phase. Only

small number of particles were floating within the paraffin matrix. Closer look to the sample

revealed that the portion of particles suspended in paraffin wax decreased as the Aluminum oxide-

paraffin sample experienced thermal cycles.

Even though evaluating graphene nanoplatelets dispersion in paraffin wax is not as easy

as MWCNTs, it can be said that graphene nanoplatelets dispersion was better compared to

13
Aluminum oxide and MWCNTs. In liquid phase, graphene nanoparticles seemed to maintain its

uniform dispersion over thermal cycles. However, when the samples were solidified after each

cycle, graphene nanoplatelets were seen to be deposited on the bottom.

3.2.2. Various Nanoparticles in Paraffin Wax with Octadeylamine

The same sample preparation procedure which was used for previous (sodium oleate-

treated) samples was applied. First, paraffin was melted on a hot plate. Octadecylamine was added

to liquid paraffin wax (Fig.1-F). Surfactant to nanoparticle mass ratio was chosen to be 2.5:1 [10].

Upon magnetic stirring for half an hour, MWCNTs at 0.1 wt.% was dispersed into paraffin wax-

surfactant emulsion. Magnetic stirring kept going on for another half an hour. Then, obtained

suspension was sonicated for 1h at % 30 amplitude.

Pictures taken after sample preparation showed a well dispersed stable nanocompositions

as shown in Fig 10. The precipitation did not take place upon solidification of the samples at room

temperature after sample preparation. However, octadecylamine treated-MWCNTs dispersion

stability worsened over thermal cycles as the sodium oleate treated-MWCNTs samples in previous

study. The same pattern applies to octadecylamine treated aluminum oxide and graphene

nanoparticles. Regardless of nanoparticle type and shape, nanoparticles tend to deposit on the

bottom of the containers.

3.3 Effect of Boundary conditions on Stability

Previous study involving melting-solidification cycles in an environmental chamber

proved that MWCNT-paraffin samples could not maintain the dispersion quality over cycles.

Boundary conditions could affect the dispersion quality of nanoparticles within NEPCMs during

heating and cooling. With this idea in mind, thermal cycles were run by placing the sample on a

14
hot plate at 150C for melting and leaving the sample at ambient room temperature for

solidification. Prior to conducting melting-solidification cycles, new sample was prepared using

the same concentration MWCNT (0.1wt.%) with octadecylamine (1:10 ratio to nanoparticle).

After adding specified amount of MWCNT and octadecylamine, magnetic stirring was done for

1h and it was followed by sonication for 1h at %30 amplitude . After that, the sample was left to

solidify at room temperature.

Visual observation revealed that heating the sample from the bottom resulted in natural

currents preventing MWCNTs from settling due to constant motion of particles. Highly dense

region of MWCNTs at the bottom expands and becomes less dense due to heating. Therefore, it

rises above the colder region of MWCNT-paraffin wax. As the hotter solution gets further away

from the heat source, it starts to cool down and become denser. Then, it starts to sink again. The

whole process of rising and falling keeps the MWCNTs in motion. The dispersion quality is much

better than the previous study where there is a clear separation of MWCNTs settling at the bottom

and paraffin wax layer on top.

As can be seen from Fig.12, the sample seemed to be stable after melting on the hot plate

for 2h. No separation was observed between MWCNT and paraffin region in liquid phase due to

promoted natural convection after each cycle. However, agglomerated regions started to form with

the onset of solidification. Observing clustered regions became difficult due to darkening color as

the samples solidified completely over time.

4.Conclusions

The effect of temperature, nanoparticle content on the thermal conductivity was investigated.

Several measurements both in solid and liquid phases were made. Thermal conductivity of

15
NEPCMs were found to be temperature dependent. Increasing nanoparticle content resulted in

insignificant improvement. This is basically attributed to particle deposition and instability

associated with the lack of dispersion quality. Therefore, the measurements did not really represent

the concentrations stated. The main reason is that particle concentration in the measurement region

was much less than the actual nanoparticle concentration.

The first part of the stability study revealed the inadequacy of mechanical dispersion methods,

particularly sonication, for providing long term stable samples. Stability of MWCNT-paraffin wax

samples became worse regardless of nanoparticle content and sonication time over melting-

solidification cycles performed in environmental chamber. It was concluded that mechanical

dispersion methods namely stirring and sonication are not sufficient to achieve long term stability

of MWCNT-paraffin NEPCMs.

Having found out the ineffectiveness of sonication, a new approach in sample preparation was

taken. Sodium oleate surfactant(anionic) and octadecylamine were used along with stirring and

sonication. Different nanoparticles such as graphene nanoplatelets, aluminum oxide nanoparticles

along with MWCNTs having planar, spherical and tubular structure respectively were analyzed in

terms of precipitation and stability. Melting -solidification cycles presented the deterioration in

stability due to great agglomeration for MWCNTs and Aluminum oxide. However, the dispersion

of graphene platelets was better than the other two nanoparticles. This could be attributed to the

planary 2-D structure of graphene particles. Nevertheless, the significant deposition of graphene

particles was detected in solid phase.

The effect of boundary conditions during melting and solidification is another significant factor

on the dispersion and movement of nanoparticles. It has been shown that uniform heating in

thermal chamber followed by solidification in ambient environment resulted in considerable

16
agglomeration. So, changing boundary conditions during heating and cooling was thought to

change the way the nanoparticles move and settle. For instance, heating the MWWCNT-paraffin

wax sample from the bottom contributed to the initiation of convection currents carrying

nanoparticles from bottom to the top helping achieve uniform dispersion. It was shown that heating

the sample from the bottom certainly helped obtain more stable suspension after fully melting.

However, changing the way the sample heated did not prevent MWCNT particles from

agglomerating after it became fully solid.

Stability issue raises the question of reliability of thermal property measurements. For instance,

the thermal conductivity measurements made right after sample preparation when the samples are

at most stable state with perfect dispersion do not provide a realistic performance enhancement.

The reason for this notion is that the nanoparticle deposition and agglomeration are usually not

considered even though some researchers claim that agglomeration also contributes to thermal

conductivity enhancement[27]. The thermal conductivity improvement that was obtained should

be compared with the measurements after melting-solidification cycles. Another debatable point

is that the DSC (Differential Scanning Calorimeter) analysis is usually done by researchers to

indicate whether any change in phase change temperature and latent heat of fusion takes place

after cooling and heating cycles. The reliability and consistency of NEPCMs are based on this

study. However, tiny amount of samples used in DSC analysis do not present the real situation

where NEPCM is in bulk. The whole system should be considered.

It can be concluded that stability of NEPCMs remains to be an unresolved issue. There are many

parameters involved in the particle stability for colloidal. Finding out the effect of each parameters

and the optimum conditions seems to be the key to achieve stable NEPCMs. Researchers should

focus more on achieving reliable, stable NEPCM that could perform steadily for many cycles in

17
latent heat storage systems rather than the abnormal thermal property improvements, particularly

thermal conductivity, without any solid reasoning. It is undebatable that collaboration is a must if

any significant progress is to be made. Usage of chemicals, the compatibility of nanoparticles and

the base fluid and how they interact with each other in terms of heat transfer and particle dispersion

are some of the multi-disciplinary aspects of the NEPCM study. Researchers from material

science, engineering, chemistry and physics should contribute all together to obtain the best

NEPCMs with optimum properties.

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List of figures

Figure.1: A: Paraffin wax, B: MWCNTs, C: Aluminum oxide particles, D: Graphene nanoplatelets.

E: Sodium oleate, F: Octadecylamine,

Figure 2: Sample preparation using mechanical dispersion method

Figure 3: Thermal conductivity change in liquid phase over time right after sample preparation

Figure 4: 3-D printed mold for thermal conductivity measurements in solid phase

Figure.5: Picture of each sample after being extracted from the mold

Figure 6: Thermal conductivity change with temperature right after sample preparation

Figure 7: DSC heating and cooling curves of paraffin wax with MWCNT, graphene

nanoplatelets and Aluminum oxide nanoparticles at different concentrations.

Figure 8: Stability observation of MWCNT-paraffin samples in liquid phase

Figure.9: Settling of MWCNTs in paraffin wax in solid phase

Figure 10: Stability observation of various nanoparticles in paraffin wax with sodium oleate

Figure 11: Stability observation of various nanoparticles in paraffin wax with octadecylamine

Figure 12: Solidification of 0.02%wt. MWCNT-Paraffin sample after melting on a hot plate at

150C

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Table 1: DSC results of nanoparticle dispersed paraffin wax samples (Tm,peak:peak melting

temperature, Tf,peak:peak freezing temperature, Hm: enthalpy of solid-liquid transition during

melting, Hf: enthalpy of solid-liquid transition during freezing )

Samples Tm,peak(C) Tf,peak(C) T(C) Hm(J/g) Hf(J/g)

Paraffin wax 54.86 53.02 1.84 124.6085 126.8456
0.5 wt. % MWCNT-wax 54.09 52.95 1.14 127.5281 124.7191
1 wt. % MWCNT-wax 52.72 53.1 -0.38 130 127.1875
2 wt. % MWCNT-wax 54.77 52.15 2.62 120.3365 120.8109

0.5 wt. % Graphene-wax 56.18 52.17 4.01 114.7383 112.2494

1 wt. % Graphene-wax 56.18 52.17 4.01 133.8488 134.1877
2 wt. % Graphene-wax 55.88 52.44 3.44 115.3103 114.5671
0.5 wt. % Aluminum oxide-wax 56.19 53.76 2.43 138.1738 136.1664
1 wt. % Aluminum oxide-wax 56.19 51.94 4.25 94.29853 93.62517
2 wt. % Aluminum oxide-wax 55.33 52.4 2.93 117.2595 116.3339

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 A B C D E F

Figure.1. A: Paraffin wax, B: MWCNTs, C: Aluminum oxide particles, D: Graphene nanoplatelets.

E: Sodium oleate, F: Octadecylamine,

Figure 2: Sample preparation using mechanical dispersion method

24
 Figure 3: Thermal conductivity change in liquid phase over time right after sample preparation

Figure 4: 3-D printed mold for thermal conductivity measurements in solid phase

25
 Figure.5: Picture of each sample after being extracted from the mold

Figure 6: Thermal conductivity change with temperature right after sample preparation

26
 Figure 7: DSC heating and cooling curves of paraffin wax with MWCNT, graphene

nanoplatelets and Aluminum oxide nanoparticles at different concentrations.

Figure 8: Stability observation of MWCNT-paraffin samples in liquid phase

27
 Figure.9: Settling of MWCNTs in paraffin wax in solid phase

Figure 10: Stability observation of various nanoparticles in paraffin wax with sodium oleate

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Figure 11: Stability observation of various nanoparticles in paraffin wax with octadecylamine

29
Figure 12: Solidification of 0.02%wt. MWCNT-Paraffin sample after melting on a hot plate at

150C

30