The Particle Stability Investigation of Nano Particle Dispersed Phase Change

Materials over Melting-Solidification Cycles

V. Saydam, X. Duan1
Department of Mechanical Engineering, Memorial University of Newfoundland, St. John’s, NL,
Canada, A1B 3X7

Abstract
Highly conductive nanoparticles were proposed to enhance thermal conductivity of phase

change materials (PCMs) [add a few references]. Many studies have been conducted to

investigate performance of these Nanoparticle Enhanced Phase Change Materials (NePCMs) in

heat transfer and thermal energy storage applications, sometimes with conflicting results [add a

few references]. This study attempts to understand this problem by investigating the stability of

NePCMs under melting-solidification cycles, which was not well explained in previous studies.

We believe that stability of the NePCMs is the basis for any further study on the material since it

is closely related to its thermal properties in the phase change processes. In this study, one of the

most common PCMs, Paraffin wax, was chosen as the base material. Three different types of

nanoparticles were selected as enhancers: multi-walled carbon nanotubes (MWCNTs), graphene

nanoplatelets and aluminum oxide nanoparticles. The nanoparticles were dispersed into paraffin

wax using mechanical dispersion methods (sonication, stirring) with and without different

surfactants at varying mass fractions. Stability of different samples was investigated with visual

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. Different boundary conditions in

heating were also studied for their effects on NePCMs stability during the phase change process.

1
Corresponding author: Tel: + 1 709 864 7108, Email address: xduan@mun.ca

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The “negative” results from this study indicate that stability issue of NePCMs, at least for the

paraffin wax and nanoparticles tested, remains unsolved and requires further research with a

multidisciplinary approach.

Key words: NEPCMs, Paraffin wax, nanoparticles, stability, thermal conductivity,

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 [1,2]. 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 [3,4]. In recent years, there is a growing

interest of dispersing nanoparticles into PCMs for thermal conductivity enhancement [5].

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

compared to metallic oxide nanoparticles [6]. MWCNTs and graphene are the most prominently

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

preferred metallic oxide particles. Although nanoparticles have a great potential in improving

thermal conductivity, there are a few issues including particle stability and suppressed natural

convection due to increased viscosity in liquid phase [7,8].

The term stability for NEPCMs refers to the uniform dispersion of nanoparticles within the base

PCM without any agglomeration or clusters. It is vitally important to maintain high stability of

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the NEPCMs for thermal characterization, and their applications. Marketability of these systems

totally depends on the long term reliable and consistent high performance of NEPCMs.

While there have been numerous efforts studying the thermal property enhancement of

NEPCMs, one of the important aspect of NEPCMs, its stability, has been missed or not fully

examined in these previous studies. Some of the limited studies touched upon the stability of

NEPCMs through visual inspection along with other methods. Kumerasan et. al. [9] observed the

sedimentation behavior of MWCNT dispersed paraffin wax (Tm=19-22°C) to monitor stability.

They claimed visually stable samples for various concentrations (0.15, 0.3, 0.45,0.6 wt.%) after

three months. Weinstein et. al. [10] incorporated graphite with different geometries into paraffin

wax(Tm=56°C) and monitored the heat transfer enhancement by monitoring transient

temperature change at different heat flux. Significant settlement was observed after third thermal

cycle. Therefore, dispersion through sonication was repeated after each test. Another study on

dispersion of MWCNTs in paraffin wax (Tm=52-54°C) was carried out by Wang et. al. [11].

Ball-milling treated MWCNTs were found to be homogeneously dispersed without any

lamination through SEM images after being kept in oven at 70°C for 96 h. Nourani et. al. [12]

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. Fan et. al [13] pointed out that graphene nanoplatelets (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. Similar study by Zeng et al. [14] for CNTs added 1-dodecanol

showed the significant settlement after the third thermal cycle. However, specimens were

claimed to maintain desired stability in liquid phase for several days.

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Another method commonly used by researchers for thermal stability evaluation is Differential

Scanning Calorimeter(DSC) analysis. In this method, thermal stability of nanocomposite is

examined based on the change of phase change temperature and latent heat capacity over

consecutive melting solidification cycles. This has been a very common method for observing

thermal property change for various nanoparticle-wax nanocomposites. Although DSC analysis

is widely used for thermal stability due to simplicity, it does not provide a realistic basis for the

thermal property change due to very small amount of nanocomposite (in milligrams) used in the

analysis. Thus, these analyses do not present the actual condition where NEPCM is in bulk and

therefore more prone to agglomeration. Tang et al. [15] found that octadecylamine treated

MWCNT dispersed wax did not go through any significant change in latent heat of fusion, phase

change temperature and supercooling up to 100 thermal cycles performed using DSC. Wu et al.

[16] also claimed stable Hitenol BC-10 treated Copper nanoparticles dispersed wax

nanocomposites after 100 thermal cycles. Graphene oxide sheets were impregnated into paraffin

wax by Mehrali et al. [17]. Only slight deviations were seen in phase change temperature and

latent heat capacity up to 2500 thermal cycles in DSC analysis.

Monitoring thermal conductivity change over melting solidification cycles is another method

preferred by other researchers. The idea behind this method is that if the enhanced thermal

conductivity is maintained without any significant deviations after thermal cycles, the

nanocomposites can be claimed as stable. Angayarkanni and Philip [18] observed the change in

thermal conductivity of GNPs and MWCNT dispersed paraffin wax having a melting

temperature of 18°C after five thermal cycles. It was found that thermal conductivity

enhancement fluctuates and mainly tends to decrease for solid phase at 10°C as nanocomposites

undergo thermal cycles. Zheng et al. [19] examined the suspension quality of graphite particles

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in hexadecane at low concentration (0.05%). Thermal conductivity remained the same for liquid

phase while a proportional insignificant decrease was seen for solid phase over six

melting/solidification cycles. Overall suspension of graphite flakes was maintained providing the

percolation network both in liquid and solid phase.

Previous studies showed that NEPCM stability is either investigated as a small part of thermal

property enhancement with a shallow approach or neglected. The lack of thorough stability study

in the literature indicates the complicacy of the issue and the need for further research on particle

stability in PCM medium. Thus, NEPCM stability is one of the most challenging aspect of

application of NEPCMs in thermal energy storage systems. This study takes the NEPCM

stability issue in hand to provide a systematic approach. Time dependant thermal conductivity

measurement and visual inspection methods are applied to investigate the effect of sample

preparation (sonication time and surfactant usage) and boundary conditions over melting-

solidification cycles.

2. Material and Methods

2.1. Materials

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

Sigma Aldrich. The paraffin wax has a phase change temperature of 53-57°C. MWCNTs have

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

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

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

were used as surfactants to promote long term stability.

2.2 Sample Preparation

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 NEPCM preparation can be divided into two categories namely mechanical dispersion

and chemical dispersion methods. These methods are mostly adopted from preparation of

nanofluids. 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 [20,21]. 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 [22]. Furthermore, nanoparticles can also be treated through functionalization

(acid treatment) for better dispersion [15].

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 70°C. 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. 1 shows the

sample preparation process.

2.3 Time Dependent 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

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

(Environmental Test Chamber, Tenney Junior). Then, temperature was set to 60°C and

measurements were repeated at that temperature hourly as shown in Fig. 2. 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.

Measurements revealed that thermal conductivity ranges within 0.15 to 0.17 W/m K for paraffin

wax with different concentrations of MWCNTs, Graphene nanoplatelets and Aluminum Oxide

nanoparticles in liquid phase at 60°C. The settlement of majority of nanoparticles took place

when thermal equilibrium was reached after a sufficient time in the chamber. The insignificant

level of thermal conductivity increase was accounted for agglomeration and sedimentation

regardless of nanoparticle content not providing the required particle network within the

measurement region. The thermal conductivity of MWCNT-wax samples was lower than that of

Graphene and Aluminum oxide-wax samples due to complete precipitation. The repeated

measurements showed that there was not any significant change in thermal conductivity within

the first four hours after sample preparation (Fig.2). 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. Thermal conductivity of Aluminum

nanoparticles dispersed wax samples presented a marginal decrease over time as the particle

loading increased. Graphene dispersed wax samples followed the same trend with a milder

decrease.

3. Stability of Paraffin Wax with Nanoparticles

3.1 Effect of Sonication on Stability

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 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 - 80°C.

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

homogeneity of particle dispersion visually. Fig. 3 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. 3. 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. 3-(2-3) that particles formed clusters

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.3). 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 3-(3).

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The degree of settling of MWCNT-paraffin wax nanocomposite in solid phase is shown in Fig.

4.

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. Three different

NEPCM samples including Aluminum Oxide nanoparticles, Graphene nanoplatelets and

MWCNTs were prepared with paraffin wax as base PCM at 0.1% wt. Previous NEPCM

preparation procedure was followed. The 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 25-80°C in the

environmental chamber again to see the effect of surfactant usage on the stability of NEPCM

composites. Images captured after each cycle are shown in Fig. 5 both in solid and liquid phase.

The pictures of samples right after preparation are also included.

As can be seen from Fig. 5, 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

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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

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 . Surfactant to nanoparticle mass ratio was chosen to be 2.5:1 [15].

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.

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 Pictures taken after sample preparation showed a well dispersed stable nanocomposites as

shown in Fig 6. 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

hot plate at 150°C 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

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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.7, the samples 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 and Remarks

NEPCM stability which is often not studied in detail or neglected with the purpose of focusing

thermal property enhancement presents a great hindrance to applicability of NEPCMs in thermal

energy storages. In this study, visual inspection and time-dependent thermal conductivity

measurements were used to evaluate the stability of paraffin wax with MWCNTs, GNPs and

Aluminum Oxide nanoparticles.

Significant precipitation affected the thermal conductivity results. It was seen that particles

started to settle once the dispersion methods (stirring, sonication) are completed proving that

mechanical dispersion methods are not sufficient to achieve long-term stability of NEPCMs.

Therefore, there is only insignificant improvement in thermal conductivity without much

deviation in liquid phase over time.

Usage of surfactants (sodium oleate and octadecylamine) along with stirring and sonication did

not enhance the particle stability over melting-solidification cycles for MWCNTs, GNPs and

Aluminum oxide dispersed paraffin wax.

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Bottom heating during melting-solidification cycles to promote particle stability also did not

result in any improvement in particle stability of MWCNT-paraffin wax composite due to

significant agglomeration

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 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.

We believe that it is the most critical step to prepare and maintain a uniform and stable NePCM

system for any research or application of this type of composite material. One of the objectives

of this study is to show to researchers in this field the importance of stability of NePCM and

difficulties to achieve it. This was done with the “negative” results of most of the experiments

described in this paper. Unfortunately, this study was not able to provide a solution to these

problems, at least not with the paraffin wax and nanoparticles tested.

Acknowlegement

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This study was financially supported by Natural Science and Engineering Council of

Canada(NSERC) and Research and Development Corporation (RDC).

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Figure 1: Sample preparation using mechanical dispersion method

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Figure 2: Thermal conductivity change in liquid phase at 60°C over time right after sample

preparation

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Figure 3: Stability observation of MWCNT-paraffin samples in liquid phase after first (1),

second (2) and third (3) melting/solidification cycles

20
Figure 4: Settling of MWCNTs in paraffin wax in solid phase

21
 Number of

thermal

(Melting- Liquid Phase Solid Phase

Solidification)

cycles

22
 4

Figure 5: Stability observation of various nanoparticles in paraffin wax with sodium oleate

23
 Number of
thermal Liquid Phase Solid Phase
(Melting-
Solidification)
cycles

24
 5

Figure 6: Stability observation of various nanoparticles in paraffin wax with octadecylamine

25
Figure 7: Solidification of 0.02%wt. MWCNT-Paraffin sample after melting on a hot plate at

150°C

26