Polymer 48 (2007) 3317e3323

www.elsevier.com/locate/polymer

Thermal stability of composite phase change material microcapsules

incorporated with silver nano-particles
Song Qingwen a, Li Yi a,*, Xing Jianwei b, Hu J.Y. a, Marcus Yuen a

a
Institute of Textile and Clothing, Hongkong Polytechnic University, Hung Hom Kowloon, Hong Kong, China
b
Xian Polytechnic University, PO 710048, Xian, China
Received 10 November 2006; received in revised form 31 January 2007; accepted 17 March 2007
Available online 21 March 2007

Abstract

This paper reports a study on the thermal stability of phase change material microcapsules that are incorporated with silver nano-particles
(Ag-NPs). The novel microcapsules were fabricated by the technique of in situ polymerization, with aminoplast as the wall and phase change
material bromo-hexadecane (PCM BrC16) as the core. Thermal gravimetry (TG) analysis was applied to measure the thermal stability of these
microcapsules and surface morphology of the microcapsules was observed by means of scanning electron microscopy (SEM) after an application
of curing treatment at 130  C. Comparing with conventional phase change material microcapsules (PCMMs), nano-composite phase change
material microcapsules (NCPCMMs) have higher thermal stability. This can be attributed to nano-composite structure of the microcapsules,
in which metal Ag-NPs distributed on the surface to increase wall toughness and strength. The possible reinforcement mechanisms of the
nano-composite structure are explored.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Microcapsules; Phase change material; Thermal stability

1. Introduction have good thermal stability and mechanical strength for ensur-
ing intact structure during manufacturing processes. However,
Phase change material microcapsules (PCMMs) are granu- the thermal stability properties and physical strength of these
lar substance with a core and shell structure, where phase PCMMs at present are not capable of making high quality
change materials (PCMs) are the core enwrapped by shell thermal regulated textile products, and studies are needed to
material. The encapsulated PCMs are not easily affected by address such problems [7].
the surrounding environment due to the protection of the shell. Bryant summarized that there are three possible mecha-
PCMMs can absorb and release heat from surroundings in nisms for the damage of microcapsules during the heating pro-
dynamic heat exchange processes, when they take place at cess [8]: (i) increased internal pressure leading to wall rupture,
the melting point (MP) and/or crystallization temperature (ii) diffusion of core materials through the microcapsule shell;
resulting in a temperature regulating function for the PCMMs. and (iii) thermal degradation of wall, followed by a release of
Thus, a relatively comfortable microclimate can be provided the core material.
to wearers if these PCMMs are applied in garments [1,2]. Many studies have been carried out to increase the thermal
In recent years, a range of techniques has been developed to and mechanical stabilities of PCMMs in order to meet the
make temperature regulating textiles and smart garment prod- requirements of thermal stability in manufacturing process.
ucts [3e6]. In these applications, the PCMMs are required to Traditional techniques to improve the thermal and mechanical
stabilities of PCMMs are as follows:

* Corresponding author. Tel.: þ852 2766 6479; fax: þ852 2773 1432. (i) Selecting suitable wall material. It has been found that
E-mail address: [email protected] (Y. Li). amino-aldehyde cross-linking structure copolymer

0032-3861/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymer.2007.03.045
3318 Q. Song et al. / Polymer 48 (2007) 3317e3323

(e.g., melamine-formaldehydes condensate) as shell the new PCM microcapsules with silver nano-particles
materials for PCMMs has a better thermal and mechan- (Ag-NPs). The thermal stability and anti-deformation proper-
ical stability than other shell materials, such as gelatine ties of the NCPCMMs are compared with conventional
Arab gum complex and polyurethane wall materials, PCMMs with same core materials and shell materials. Their
and could provide better protective functions to the performances during the drying and curing processes are
encapsulated PCM core material in dry air as the investigated to see whether the toughness and strength of the
temperature is higher than 120  C [9,10]; wall material can be enhanced by the addition of functional
(ii) Decreasing the ratio of weight percentage of core nano-particles.
material and;
(iii) Encapsulating the core by multi-layers of shell mate- 2. Experimental
rials [11], or;
(iv) Trying to find the optimal molecule ratio of melaminee 2.1. Nano-composite PCM microcapsules
formaldehyde to modify the property of MeF wall
polymer in order to have the best compact texture for In the experiments, silver nano-composite PCM microcap-
wall polymers [12], sules were supplied by the Nano Sports Technologies Ltd.
(v) Increasing microcapsule size [13], and; The PCM microcapsules with core/shell ratio of 5:1 were
(vi) Putting volatile materials into the core, and microen- prepared by an in situ polymerization technique, which was
capsulating them together with PCMs into the micro- described in detail in Refs. [12,23,24]. Bromo-hexadecane
capsule. Then heat them to allow the materials to (PCM BrC16) was used as core PCM material with the melt-
vaporize and obtain a certain reserved volume in the ing point of around 17e18  C and purity of 99% (Sigma-
inner capsule. Thus, the thermal stability of the micro- Aldrich Trading Co. Ltd). The loading rate of Silver
capsules is enhanced [14]. nano-particles (Ag-NPs) as nano-functional additives was 3%
of the mass of core materials. The size of the silver nano-
Although these techniques have certain effects in increasing particles was in the range of 40e60 nm with surface area of
thermal stability, limitations are obvious. For example, in- 30e50 m2/g (BET); most of these silver nano-particles were
creasing the shell ratio and multi-wall encapsulation will in spherical shape, as shown in Fig. 1.
surely decrease the thermal regulating performance of the
PCMMs and thermal regulated textiles.
2.2. Material characterization
Wall properties of PCMMs play an important role in the
thermal stability of PCMMs, and how to strengthen the wall’s
The microcapsules were characterized in terms of surface
toughness is the key to improve the performance of PCMMs.
morphology observation (SEM), surface elemental analysis
Novel techniques using the nano-scale particles have showed
(EDX), thermal gravimetry (TG) and differential scanning
promising potential in changing the characteristics of the
calorimeter (DSC).
wall polymer matrices. It was reported that the rigid nano-
scale particles incorporating with polymer matrices can create
nano-composite structures which demonstrated superior 2.2.1. Surface morphology
properties in mechanic, optics, magnetism, etc. [15e17]. The de-ionized water was added to both of the emulsions
To enhance the wall strength of these PCM microcapsules, of NCPCMMs and PCMMs, rinsed the samples 3 times by
novel nano-composite PCMMs were prepared by using phase centrifugal machine, applied the rinsed samples to clean glass
change materials (bromo-hexadecane with purity 99%) with
the melting point of 16e18  C as core thermal regulating
material and silver nano-particles as functional additives.
This type of composite PCM microcapsules incorporated
with functional nano-materials were fabricated by employing
an in situ polymerization technique [22].
Properties of metal nano-particles are different from those
of bulk materials because of dielectric and quantum confine-
ment effects, which arise due to the reduction in particle
size down to nanometer range [18,19], which can lead to better
thermal stability of the PCM microcapsules. Moreover, the
silver nano-particle may make the microcapsules with other
novel functional properties, such as antibacterial, anti-fugal
and IR radiations [20,21]. Therefore, it can be expected that
silver nano-particles are good potential candidates to be used
to increase wall strength of the microcapsules.
Experiments were conducted to characterize the properties
of NCPCMMs. This paper focuses on the thermal stability of Fig. 1. SEM image of silver nano-particles.
 Q. Song et al. / Polymer 48 (2007) 3317e3323 3319

slides and dried them with hot air. The slides were cured in an
oven with a temperature setting of 130  C for 50 min, and then
these samples, including samples without the curing treatment
were plated with a layer of gold in a vacuum circumstance. For
SEM observation of silver nano-particles, silver powders were
fixed on a clean glass slide by double-side adhesives tape. The
scanning electronic microscope observations were carried out
by JSM6335F (Japan) (see Figs. 1e3).

2.2.2. Surface elemental analysis

Energy dispersive X-ray fluorescence (EDX) is the instru-
ment that performs a qualitative and quantitative analyses of
element composition by measuring re-emitted characteristic
X-ray from atoms of certain elements. The basic principal of
EDX may be defined as a micro-analytical technique that
Fig. 3. Conventional PCMMs.
uses the characteristic spectrum of X-rays emitted by the spec-
imen after excitation by high-energy electrons in order to ob-
tain information about the elemental composition [27]. Sample To further study the thermal stability of the PCMM and
preparations were the same as that of SEM, except that the NCPCMM under the conditions of the industrial manufactur-
gold plating procedure was omitted for the EDX samples. ing processes, 5e6 g of washed and dried microcapsules
The washed and dried samples were tested by a scanning were put into a bottle with known dry bottle weight. The sam-
electron microscope (Leica Stereoscan 440). The energy ples were dried at 80  C until the weight of sample was stable.
dispersive X-ray spectroscopy (EDX) provides information Then, the lid was opened and put the bottle swiftly into an
about elemental compositions of the sample to a depth of oven with a temperature setting of 130  C. Cure the samples
2 mm on the sample surface [25,26]. for the first 10 min. Take the bottle out and cover the bottle
with a lid, weigh it and record as W1 when it cools down.
Put the bottle without lid into the oven again, 10 min later,
2.2.3. Thermal gravimetry (TG) and DSC analyses
take the bottle out and weigh it and record as W2. Repeat
Thermogravimetric analyzer/differential scanning calorim-
this procedure several times until W5 was obtained. The weight
eter (Netzch TGA/DSC, 25  Ce1500  C) was used to test
measured by this process represents the property of high
the NCPCMM and PCMM samples in the temperature range
temperature resistance of the microcapsules under a constant
from room temperature to 450  C in a programmed procedure.
temperature commonly applied in practical textile manufactur-
During the testing process, about 10 mg of clean and dried
ing processes. Three parallel experiments were conducted for
NCPCMM and PCMM powder samples were heated at tem-
one specimen in the experiment. The weight losing percentage
perature raising rate of 10 K/min in argon atmosphere. The
(WLP) was calculated as:
property of thermal stability of the samples was characterized
by measuring the weight (mass) loses with temperature in- Wn  W0
crease. DSC analysis for the tested samples was carried out WLPð%Þ ¼ ð  1Þ  100
W0
simultaneously.
where, Wn (g) is the dry weight of microcapsule powder after
been cured for n time (n  10 min) and W0 (g) is the original
dry weight of microcapsule powder.

3. Results and discussion

3.1. Surface morphology

As shown in the SEM image in Fig. 3, many nano-particles

were distributed on the surface of the capsules. Nano-particles
were dispersed in different locations of capsules: on the shell
and/or wrapped by shell materials. Paraffin (PCM) core mate-
rials were wrapped into the capsules and no broken capsules
were observed. Comparing with the conventional PCM micro-
capsules shown in Fig. 3, NCPCMMs had a rougher surface
due to the nano-composite shell structure. There were no
obvious differences between the NCPCMMs and PCMMs in
Fig. 2. SEM observation of NCPCMMs. the shape and size distributions of microcapsules, indicating
3320 Q. Song et al. / Polymer 48 (2007) 3317e3323

Fig. 4. The surface analysis EDX: (a) NCPCMMs and (b) PCMMs.

that the addition of metal silver nano-particles and the forma- the shell material of NCPCMMs provides a significantly better
tion of nano-composite structure had no adverse effect on the protection for core PCM in the range between 150  C and
formation of PCM microcapsules. 300  C.
The corresponding DSC thermalgram curves are shown in
3.2. Surface elemental analysis Fig. 6. There are two sharp endothermic peaks in the tem-
perature range of 240e300  C for conventional PCM micro-
Comparing the EDX test result shown in Fig. 4, the capsules, while there is only one sharp endothermic peak at
NCPCMMs have more species of surface elements than the temperature of 304  C for the NCPCMMs. The two peaks
the conventional PCMMs. The metal element Ag appears in indicate that large amount of core PCM vaporized and
the spectrum, while conventional PCMMs do not have any
metal elements. Meanwhile, some elements appear in both 100
the specimens, such as nonmetal element of nitrogen, bromine, 90
and oxygen, which represent shell composition of aminoplast 80
and core material of bromo-octadecane, as high-energy elec- 70
Mass (%)

tron beams can penetrate up to 2 mm of depth on the sample 60

surface. Bromine as one part of composition in the core mate- 50
rial was detected. The two peaks for bromine element at dif- 40
30
ferent characteristic energy bands represent the Ka and Kb
20
X-rays, the radiations caused by the outer electron filling the 10
inner vacancy of an element shell [27]. Carbon element, which 0
surely existed in the composition of microcapsules in the shell 150 200 250 300 350 400 450

and core, was not detected by EDX spectrum due to the small Temperature (Celsius Degree)
weight of the carbon atom. NCPCMM PCMM mass (%)
These analysis results show that the two kinds of microcap-
sule were different in shell composition, as metal Ag elements Fig. 5. Thermal gravimetry analysis of NCPCMMs and conventional PCMMs.
appeared on the NCPCMM surface. Combining with the
observation of SEM, silver nano-particles obviously existed
0.6
on the surface of NCPCMMs to form composite structures. 0.4
DSC mW/mg-->endo

0.2
3.3. Thermal stability 0
150 200 250 300 350 400 450
-0.2
Fig. 5 shows the results of thermal stability tests from -0.4
-0.6
Netzch TGA/DSC, which is expressed as sample mass loss
-0.8
(%) and temperature (150e400  C). Both NCPCMM and
-1
PCMM samples loose weight as temperature increases. -1.2
PCMM loss continuously and significantly from 150  C and -1.4
about 80%e90% of their total mass was vaporized when the Temperature (celsius degree)
temperature increased to 300  C. On the other hand, DSC NCPCMM DSC PCMM
NCPCMM was able to keep more than 80% of weight when
temperature increased to 300  C. These results indicate that Fig. 6. DSC thermalgram curves of NCPCMMs and conventional PCMMs.
 Q. Song et al. / Polymer 48 (2007) 3317e3323 3321

0.5 absorbed significant amount of heat at 260  C and 297  C for

0 conventional PCMMs; while the endothermic peak appears
-0.5 150 200 250 300 350 400 450 at temperature of 304  C for NCPCMMs, showing higher
-1 thermal stability and better protection of the composite shell
dm/dT

-1.5 structure than that of conventional PCMM. These results

-2 confirm the observations in Fig. 5.
-2.5 To obtain a more precise analysis of thermal stability, dif-
-3 ferential derivative thermal gravimetry (DTG) was calculated.
-3.5 The weight losing rate (dm/dT ) with temperature was com-
-4 pared between the two samples, as shown in Fig. 7. Both
Temperature (Celcius degree) curves have a large inflexion at the temperature of 307  C
DTG PCMM DTG NCPCMM
and 302  C for NCPCMMs and PCMMs, respectively. The
dm/dT curve for NCPCMMs is significantly deeper and
Fig. 7. Differential derivative thermal gravimetry for NCPCMMs and PCMMs. sharper than that of PCMMs. The weight remains at each tem-
perature inflexion were about 30% and 20%, as shown in
Fig. 5. The weight losing rates for both samples accelerated
at 250  C until they reached their inflexion, accompanied by
Different samples
a dramatically weight drop. The weight losing rate of PCMM’s
conventional MicroPCMs
30.00
nano Ag composite MicroPCMs
was higher than that of NCPCMM’s, indicating that the shell
structure of NCPCMMs provided a better protection and pre-
vented core materials licking from the capsules. The weight
25.00 lose of the samples seems to stop further at the high tempera-
Weight loss (%)

ture of 350e450  C. About only 10e20% of the total mass of

microcapsules remained. The remaining masses would proba-
20.00
bly be some carbonized substances in the capsules, which are
not easily decomposed at this temperature range.
Fig. 8 shows the percentages of weight loss of NCPCMM
and PCMM samples under the condition of temperature of
15.00
130  C for about 10e50 min. This is a simulation of the curing
process in textile manufacturing. The maximal weight loss
percentage for 50 min curing was about 15% for NCPCMMs
10.00
and 32% for PCMMs. Fig. 9 reveals the images of the two
kinds of microcapsules which have been cured under the
10 minutes 30 minutes 50 minutes temperature of 130  C for 50 min. As shown in Fig. 9(a),
20 minutes 40 minutes
NCPCMMs still maintained undamaged structure for each
Curing duration
microcapsule with a total weight loss of about 10e15%,
Fig. 8. Comparison of the weight losing percentage under 130  C at different except a few deformed microcapsules. Meanwhile, most of
time interval for NCPCMMs and PCMMs.

Fig. 9. SEM images of PCM microcapsules after being cured at 130  C for 50 min: (a) NCPCMMs and (b) PCMMs.
3322 Q. Song et al. / Polymer 48 (2007) 3317e3323

the conventional PCMM microcapsules were destroyed and material due to the nano-scale particle size, high activity and
collapsed at 130  C as shown in Fig. 9(b). huge surface areas. The NCPCMMs demonstrated higher
In summary, all the test results of TG, DSC, DTG and SEM thermal stability performance and capable of enduring higher
images have shown that NCPCMMs have significantly better temperature during textile manufacturing processes.
thermal stability in the temperature range of 250  Ce300  C
than PCMMs. These results are consistent with the results
Acknowledgment
from previous studies that the mechanical property of high
polymer materials can be improved by the addition of nano-
The authors would like to thank the Hong Kong Poly-
particles to increase their toughness [17,28,29]. The potential
technic University, Hong Kong research Grant Council and
explanation is that the huge surface areas of nano-silver parti-
Innovation Technology Commission for funding this research
cles enable them to be closely combined with polymer matrix
through projects A188, PolyU5281/03E and ITS-23-03,
to create composite structured wall that has higher strength to
respectively.
resist crack and failure of wall polymer in the curing process.
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