Heat TransferAsian Research, 36 (7), 2007

Measurement of the Specific Heat Capacity of Plastic Waste/Fly

Ash Recycled Composite Using a Differential Scanning
Calorimeter

Junichi Fujino and Tomohiro Honda

Department of Mechanical Engineering, Fukuoka University, Japan

This paper deals with measurements of the specific heat capacity of plastic
waste/fly ash recycled composite and its components using both a differential scanning
calorimeter and sapphire disks as standard reference material. The measurement is
carried out at temperatures below the melting point of the plastic component. The
constant heating rates are set at 2, 5, and 10 Kmin1.
The specific heat capacity of the recycled composite increases from 1.3 to 1.6
kJkg1K1 with increasing the temperature from 305 to 360 K, when the heating rates
are set at 2 and 5 Kmin1. In addition, the deviation in the data is within 3%.
However, the data for 10 Kmin1 are about 2% lower than those for 2 Kmin1. The
specific heat capacity is independent of the shape and mass of the recycled composite
sample. The uncertainty for the specific heat capacity data of the recycled composite
is estimated to be within 4%. The specific heat capacity of the fire retardant is as
large as that of the fly ash. In addition, the specific heat capacity of the recycled
composite depends largely on the content of the plastic waste. 2007 Wiley Peri-
odicals, Inc. Heat Trans Asian Res, 36(7): 435448, 2007; Published online in Wiley
InterScience (www.interscience.wiley.com). DOI 10.1002/htj.20164

Key words: composite, differential scanning calorimeter, fly ash, plastic

waste, recycle, specific heat, thermophysical properties

1. Introduction

Plastic waste/fly ash composite (which the authors call PWFA for short) is a recycled item,
which is made mostly from plastic waste and fly ash. The composite is one of the materials developed
for the purpose of recycling. Plastic wastes, which are irregular in shape and size, different types and
unsuitable for recycling with an existing technology, can be mixed with the ingredients of the PWFA.
The plastic waste and fly ash components account for over 80% of the total mass, as shown in Table
1. A small amount of glass fiber as reinforcement and a fire retardant is added to the PWFA. The
recovered plastic waste mainly consists of polypropylene and polyethylene resins used for home
wrapping materials. Both resins are thermoplastics. Fly ash was generated at a domestic coal-fired
power plant.
2007 Wiley Periodicals, Inc.
435
 The compressive strength and density of the PWFA depend upon the content of the fly ash.
Although the density of the PWFA is about one fifth that of concrete, it has a comparable compressive
strength. Therefore, PWFA can be used as a substitute for concrete, which will reduce the transport
cost and improve the safety and efficiency of work at the construction site. Currently, PWFA is used
for cable troughs shielding underground lines. The thermal conductivity and specific heat of the
PWFA must be determined in order to estimate the heat transmitted through the cable trough and the
temperature rise in the cable and cable trough, because the excessive temperature rise of the cable
causes serious problems. However, there is little information concerning the thermophysical proper-
ties of the PWFA.

The specific heat of the PWFA can be estimated using the additivity rule just like conventional
composite materials [1], and can be expressed by Eq. (1).

c = (ci i) = c1 1 + c2 2 + . . . + cn n (1)
i=1

where c and are the specific heat and mass ratio of components, respectively. And subscript n means
the nth term of components. However, the name, chemical formula, composition, and some details
concerning the fire retardant are not disclosed by the manufacturer of the material, because it is an
industrial secret. Consequently, the specific heat of the fire retardant cannot be determined from
databases of thermophysical properties. On the other hand, the plastic wastes are heated over their
melting points and kneaded during the rebirth process of the PWFA. Neither the effect of the heating
on the properties of the plastic nor the properties of the plastic composite material combined during
the melting of different plastics are clear. Therefore, the specific heat of the components of the PWFA
also need to be discussed in terms of the heat transfer in the PWFA, in order to create the different
proportion of the composite material and for estimating by Eq. (1).

This paper discusses the specific heat capacity of the PWFA, PP/PE composite, and fly ash
measured using a differential scanning calorimeter (DSC) and the estimation of the specific heat
capacity of the fire retardant. The measurements were repeatedly carried out at temperatures not
exceeding 365 K to prevent the melting of the plastic components. The constant heating rates were
set at 2, 5, and 10 Kmin1.

Table 1. Composition of PWFA

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 Nomenclature

c: specific heat, kJkg1K1

M: mass, mg
T: temperature, K
Yec: DSC output of empty capsule, mW
Yr: DSC output of standard reference material with capsule, mW
Ys: DSC output of sample with capsule, mW
: content per unit mass, kgkg1

Subscripts

fa: fly ash

fr: fire retardant
g: glass fiber
p: waste polypropylene (PP)/waste polyethylene (PE) composite
pe: polyethylene (PE)
pm: polypropylene/polyethylene mixture
pp: polypropylene (PP)
pw: plastic waste/fly ash recycled composite
r: standard reference material
s: sample

2. Experimental Apparatus and Measuring Procedures

The specific heat capacity was measured using a heat-flux differential scanning calorimeter
[2] and synthetic sapphire disks, 19.6 and 29.6 mg in mass [2], as a standard reference material. The
measurement sensitivity of the differential heat of the calorimeter is within 1.6 W at temperatures
from 150 to 725 C. The synthetic sapphire disks have a diameter of 3.5 mm and a purity of 99.99%.
The data used for specific heat of synthetic sapphire [3] are shown in Table 2.

Specimens, standard reference material and sample (test substance), were placed into a
separate aluminum capsule [2] with a capacity of 15 microliters. The aluminum capsules ranged from
206.75 to 206.85 mg in mass. The capsule was sealed with a sealer. The mass of the specimen and

Table 2. Specific Heat Data of Sapphire and Water

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the capsule was measured using an electronic balance [4] with the maximum capacity of scale of 32
g and the sensitivity of 0.01 mg.

In order to determine the specific heat capacity of the sample, it is necessary to obtain the DSC
outputs of the empty capsule and capsules containing the specimen using the DSC. The DSC outputs
were obtained using the following steps. Figure 1 shows a schematic diagram of the heat detecting
element of the calorimeter [2, 5, 6].

Step 1: Both aluminum receivers and aluminum lids were prepared. The aluminum receivers
ranged from 134.00 to 134.10 mg in mass. The aluminum lids ranged from 72.70 to 72.80 mg in mass.
Four clean empty capsules, composed of an aluminum receiver and aluminum lid, were selected. The
empty capsules ranged from 206.75 to 206.85 mg in mass. One of the capsules received one sapphire
disk as a standard reference material. Another capsule received the sample. The remaining capsules
were empty. All capsules were sealed with the sealer.

Step 2: The heating rate and the temperature range were both entered into a computer; i.e.,
the control program of temperature or the heating curve was fixed.

Step 3: An empty capsule was placed on the R-side capsule holder, as shown in Fig. 1. In
addition, another empty capsule was placed on the other capsule holder (S-side capsule holder). The
relationship between the DSC output of the empty capsule and the temperature, i.e., the DSC curve
of the empty capsule, was measured with the calorimeter.

Step 4: The empty capsule on the S-side capsule holder was replaced with the capsule
containing the standard reference material (which is called the reference material capsule for short).
As in the case of the empty capsule, the DSC curve of the reference material capsule was measured.

Step 5: The reference material capsule was replaced with the capsule containing the sample
(which is called the sample capsule for short). As in the case of the empty capsule, the DSC curve
of the sample capsule was measured.

During the series of measurements, the authors never touched the empty capsule on the R-side
capsule holder and never removed the empty capsule. After the end of the measurements, the capsules
remained in the apparatus and then were cooled by natural cooling. The capsules were not removed

Fig. 1. Schematic diagram of the heat detecting element of the calorimeter [2, 5, 6].

438
until the temperature of the capsule cooled to nearly an ambient temperature. The mass of each empty
capsule was measured before the specimen was encapsulated. In addition, the mass of the sample and
reference material capsules were measured after every measurement. The mass of the sample was
obtained from the mass difference between the sample capsule and empty capsule. As in the case of
the sample, the mass of the standard reference material was obtained after every measurement. By
the measuring steps 3, 4, and 5, three DSC curves were obtained.

Figure 2 shows the experimental results of the DSC curves of the PWFA when the heating
rate was set at 5 Kmin1. Symbol T is the temperature. And symbols Yec, Yr, and Ys represent the DSC
outputs of the empty, reference material and sample capsules, respectively. The DSC outputs changed
transiently at the beginning and end of the rise of temperature. Furthermore, the DSC output varied
linearly with time or temperature, except during the two periods of transient behavior. The DSC data
excluded the effect of the transient behavior, and was used for the calculation of the specific heat
capacity. The specific heat capacity of the sample cs is given by

Mr (Ys Yec)
cs = cr (2)
Ms (Yr Yec)

where cr is the specific heat capacity of the standard reference material, and Mr and Ms are the mass
of the standard reference material and the sample, respectively.

The experimental results of the DSC outputs for the empty capsule Yec and the reference
material capsule Yr containing a sapphire disk of 19.6 mg are listed in Table 3. The table is used to
show the mean value and variation range of DSC output at the temperatures from 303 to 387 K when
the heating rate was set at 5 Kmin1. The variation in the DSC output of reference material capsule
Yr increased with temperature, and it was within 21 W at the highest temperature of 387 K. The
uncertainty of the specific heat capacity caused by the measurements of the DSC output for Yr was

Fig. 2. Experimental results of the DSC curves of the PWFA.

439
 Table 3. DSC Outputs Yr and Yec for Heating Rate of 5 Kmin1

largest at the highest temperature of 387 K and it was estimated to be within 1.2%. On the other
hand, the variation in the DSC output of the empty capsule Yec was within 29 W. In the present
study, experiments were carried out on the condition that the ratio of (cs Ms) to (cr Mr) or the ratio
of (Ys Yec) to (Yr Yec) be around unity. Therefore, the uncertainty of specific heat capacity caused
by the measurements of the DSC output for Yec was estimated to be within about 1%. As previously
reported [7], the authors measured the specific heat capacity of commercial purified water using the
same apparatus at the temperatures from 300 to 333 K, when the heating rates were set at 2 and 5
Kmin1. The published data were independent of the heating rate and it agreed with the reference
data for pure water [1] listed in Table 2 within 3.5%. In addition, the effect of water leakage in the
sample capsule on measurement was negligibly small, because the mass of water contained in the
sample capsule had no change before and after experiments. Consequently, the uncertainty for the
specific heat capacity of purified water measured using the present apparatus was estimated to be
within 4.5%.

3. Specimen

Figure 3 shows the observation of the particles of fly ash using a scanning electron microscope
(SEM). Fly ash particles were globular in shape and under 60 m in diameter.

Specimens of the PWFA, which had a bulk density of 1330 kgm3 [8], were cut out from a
cable trough. The cable trough is the first recycled product made from recovered plastic waste
materials. Figure 4 shows the observation of the polished surface of the PWFA using a metalloscope.
The sample surface for observation was polished with three sandpapers which have an abrasive
particle size of 30, 12, and 9 m, respectively. In addition, the surface was buffed with a polishing
solution containing alumina particles 0.1 m in size. After the polished sample was cleansed with
ion-exchange water inside an ultrasound bath, it was dried in a thermostatic chamber set at a constant
temperature of 323 K.

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 Fig. 3. Fly ash particles (300: with SEM).

The round particles of fly ash disperse at irregular intervals in the matrix. Each particle of fly
ash is surrounded by the matrix composed of the plastic waste and the fire retardant. The shape of the
matrix is a continuous phase. Fly ash was heated up to the melting temperature of the plastic waste
and mixed with the plastic waste. But the broken and deformed particles of fly ash could not be found.
Fly ash was not fused with other components. As with fly ash particles, glass fibers dispersed at
irregular intervals in the matrix [8]. The glass fibers had a size of several tens of micrometers and a
length of 200 m. Glass fibers were also not fused with other components. In contrast, the distribution
of plastic and fire retardant components and some details concerning the matrix are unclear.

In order to measure the specific heat capacity of the PWFA, the authors prepared the granular
and plate samples of the PWFA. The granular sample, which was grated, had a grain size of not more
than about 0.5 mm. In the case of plate samples, the surfaces of sample were polished and cleansed
in the same way as the sample for observation. The plate sample had a size of about 2.5 2.5 mm2
and a thickness of about 1 mm or less. The PWFA samples ranged from about 10 to 19 mg in mass.

Fig. 4. Observation of the polished surface of the PWFA using a metalloscope (1000).

441
 The polypropylene/polyethylene (PP/PE) composite, which is specifically prepared for this
work by the manufacture of the material, is made from plastic waste material used as an ingredient
of the PWFA. The PP/PE composite has a PP-to-PE ratio of 63:37, which almost equals the PP-to-PE
ratio for the PWFA. The PP/PE composite was molded by a simplified die with the same temperature
for the PWFA manufacturing process. The plastic molding had a size of 10 10 mm2 and a length of
100 mm. In this study, the granular sample, which had a grain size of not more than about 0.5 mm,
was prepared in the same way as the PWFA sample.

4. Results and Discussion

Figure 5(a) shows the experimental results of the specific heat capacity of the PWFA cpw when
the heating rate was set at 5 Kmin1. Equation (3) on the figure was obtained from these results using
the least-square method. The result calculated by Eq. (3) is plotted by a solid line.

The specific heat capacity cpw increased from 1.3 to 1.6 kJkg1K1 with increasing the
temperature from 305 to 360 K. The variation in the data for cpw was within 1%, when the DSC
output for Ys was repeatedly measured while the sample capsule was set in the apparatus. On the other
hand, the variation in the data for cpw was within 3%, when the DSC output for Ys was measured
every time the sample capsule was set in the apparatus. As a result, the situation of the capsule in the
apparatus is considered to be a source of measurement errors. For the granular sample ranging from
10 to 19 mg in mass or the plate sample ranging from 11 to 17 mg in mass, the results demonstrated
that the effect of the mass and the shape of sample on the measured data were within 3%.

Figure 5(b) shows the experimental results for the heating rate of 2, 5, and 10 Kmin1. In the
case of the data obtained for 2 and 10 Kmin1, the variation range in the measured value is indicated
in the figure. The data for 2 Kmin1 agreed with those for 5 Kmin1 within 0.2%. However, the data
for 10 Kmin1 were about 2% lower than those for 5 Kmin1. The variation in the data for 2 and 10
Kmin1 was within about 3%, respectively.

Figure 6 shows the experimental results for the PP/PE composite cp. The results for 2 and 10
Kmin1, which are respectively indicated by a short dashed line and a dotted and dashed line, is
approximated from the measured data by the least-square method. Symbols cpe, cpp, and cpm represent
the specific heat data of polyethylene, polypropylene, and polypropylene/polyethylene mixture,
respectively. The data cpe and cpp are listed in Table 4 [1, 9, 10]. In addition, the data cpm for the
PP-to-PE ratio of 63:37 is calculated by the following equation:

cpm = cpp 0.63 + cpe 0.37 (4)

The specific heat capacity cp increased from 1.9 to 2.5 kJkg1K1 with increasing the
temperature from 305 to 360 K. The result for 2 Kmin1 agreed with that for 5 Kmin1 within 1%,
but the result for 10 Kmin1 was about 2% lower than that for 5 Kmin1. The variation in the data
for 5 Kmin1 was within 3.5%. In addition, the variations of the data for 2 and 10 Kmin1 were
within 3%. The value for the PP/PE composite cp was between cpe and cpp, and it was higher than
the estimated value for cpm. The difference of between cp and cpm increased with increasing
temperature.

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 Fig. 5. Results for the PWFA cpw.

Figure 7 shows the experimental results of the specific heat capacity of the fly ash particles
cfa when the heating rate was set at 5 Kmin1. Specific heat data of SiO2, Al2O3, Fe2O3, CaO, and
MgO, which are the constituents of fly ash [11], is plotted as shown in the figure. The specific heat
data of those metal oxides [1, 3] are listed in Table 5. The specific heat value for CaO and MgO was
calculated by the method of linear interpolation between the values at 300 and 500 K. The data for
Al2O3 is the specific heat value of synthetic sapphire in Table 2.

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 Fig. 6. Results for the PP/PE composite cp.

The specific heat capacity cfa increased from 0.75 to 0.88 kJkg1K1 with increasing the
temperature from 310 to 385 K. The variation in the data for cfa was within 7% and it was larger
than those for cpw and cp. As shown in Fig. 7, the specific heat of the metal oxides ranges from 0.6 to
1 kJkg1K1. In addition, the specific heat capacity of the fly ash is as great as those for SiO2, Al2O3,
and CaO. According to Ref. 11, SiO2 and Al2O3 contents account for 70 to 80% of the total constituent
of fly ash. Although the components ratio of the fly ash used for the present study is unclear, the

Table 4. Specific Heat Data of Polymer

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 Fig. 7. Results for the fly ash particles cfa.

Table 5. Specific Heat Data of Metal Oxide

445
authors consider that the fly ash used for the present study is made mostly from SiO2 and Al2O3,
because the results cfa agreed well with the specific heat values for SiO2 and Al2O3.

The additivity rule is applied to the estimation of the specific heat of the PWFA cpw, then Eq.
(5) can be derived from Eq. (1).

cpw = cp p + cfa fa + cfr fr + cg g (5)

where the subscripts fa, fr, g, and p mean fly ash, fire retardant, glass fiber, and PP/PE composite,
respectively.

The PWFA has a much lower content of the glass fiber than the other components, illustrated
in Table 1. The term (cg g) in Eq. (5) is ignored, then the specific heat capacity of the fire retardant
cfr can be estimated using Eq. (6).

cpw (cp p + cfa fa) (6)

cfr =
fr

Figure 8 shows the specific heat capacities of the PWFA and its components. The specific
heat capacity of the fire retardant cfr was calculated by Eq. (6), when the content of glass fiber fr
equals 0.17. As listed in Table 1, the values for p and fa equal 0.45 and 0.38, respectively. In addition,
the data substituted for cpw, cp, and cfa are the approximated values obtained from the measured data
for 5 Kmin1 using the least-square method. The approximated results for cpw, cp, and cfa are plotted
in the figure.

The data for the PP/PE composite cp are the highest and that for the fly ash cfa are the lowest.
The value for cp is at least 2.5 times higher than that for cfa. However, the value for cfr is as large as
that for cfa. Therefore, the specific heat capacity of the PWFA cpw depends largely on the content of
the plastic waste p. The authors have not yet obtained the information concerning the specified
distribution of plastic waste in the matrix. However, it was speculated that the plastic waste contents
for the granular sample agreed with those for the plate sample within about 3%, because the variation

Fig. 8. Specific heat capacities of the PWFA and its components.

446
in the specific heat capacity data for the PWFA samples with different mass and shape was within
3%.

The uncertainty caused by the mass measurement was estimated to be within 0.5%, because
both the sample and the standard reference material weighed more than 10 mg. Taking into account
the uncertainty of the mass measurement, the uncertainty for the measurement of the DSC output of
the reference material, sample and empty capsules, and the variation and reproducibility of the specific
heat capacity data, the uncertainty for the specific heat capacity of the PWFA was estimated to be
within about 4% [12]. In addition, the uncertainty for the PP/PE composite and the fly ash were
estimated to be within about 5% and 8%, respectively.

5. Conclusion

In order to determine the specific heat capacity of a recycled composite made mostly from
plastic waste and fly ash, the authors measured the specific heat capacity of the recycled composite,
polypropylene/polyethylene (PP/PE) composite, and fly ash using a differential scanning calorimeter
and sapphire disks as standard reference material. The PP/PE composite, which is specifically
prepared for this work, is made from plastic waste material. In addition, the PP-to-PE ratio of the
PP/PE composite is the same as that of the recycled composite. In the present study, the granular and
plate samples for the recycled composite and the granular sample for the PP/PE composite were used.
The granular sample, which was grated, had a grain size of not more than about 0.5 mm. On the other
hand, the surfaces of the plate sample were polished. The measurements were repeatedly carried out
at a temperature not exceeding 365 K to prevent the melting of the plastic components. The constant
heating rates were set at 2, 5, and 10 Kmin1. The specific heat capacity of fire retardant was estimated
based on the measured results for the recycled composite, PP/PE composite, and fly ash. The following
conclusions were obtained.

1. The specific heat capacity of the recycled composite increases from 1.3 to 1.6 kJkg1K1
with increasing the temperature from 305 to 360 K. In addition, the specific heat capacity data are
independent of the shape and mass of the recycled composite samples.

2. The uncertainty for the specific heat capacity data of the recycled composite is estimated
to be within 4%. In addition, the uncertainty for the PP/PE composite and the fly ash are within 5%
and 8%, respectively.

3. We can consider that the recycled composite is made from plastic waste, fly ash, and fire
retardant, because the recycled composite has a much lower content of the glass fiber than the other
components. The specific heat capacity of the fire retardant is as large as that of the fly ash. In addition,
the specific heat capacity of the recycled composite depends largely on the content of the plastic waste.

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"F F F"

Originally published in Netsu Bussei 20, 2006, 166172.

Translated by Junichi Fujino, Department of Mechanical Engineering, Fukuoka University, 8-19-1,
Nanakuma, Fukuoka, 814-0180 Japan.

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