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Identification and quantification of polymers in waste plastics using

differential scanning calorimetry

Article · January 1997

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A. Manivannan Mohindar Seehra

Krishnasamy college of engineering and technology West Virginia University
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 IDENTIFICATION AND QUANTIFICATION OF POLYMERS IN WASTE
PLASTICS USING DIFFERENTIAL SCANNING CALORIMETRY
A. Manivannan and M. S. Seehra
Physics Department, West Virginia University
Morgantown, WV 26506-6315, USA

KEYWORDS: Waste plastics, characterization, differential scanning calorimetry

ABSTRACT
Experimental results on the use of differential scanning calorimetry (DSC) for the identification
and quantification of various polymers in post-consumer waste plastics are presented.
Experimental studies are presented for the model polymers such as different grade of
polyethylene (PE), polypropylene (PP). polyethylene terephthalate (PET), polystyrene (PS) and
polyvinyl chloride (PVC). It is argued that the glass transition Tgand the melting temperature
T, of the polymers can be used for their identification whereas the enthalpy of fusion AH
determined from the heat flux versus temperature curves of DSC is useful for quantification.
For the standard mixtures of PE and PP, a linear curve of AH versus concentration is obtained
showing the applicability of this technique. This methodology is then applied to analyze two
samples of waste plastics. A sample of commingled plastics obtained from the American
Plastics Council is found to contain high density PE (-82%). PP (-7%) and PET (-10%)
whereas a German plastics sample is found to contain HDPE, MDPE, PP and PVC.
Complementary information is obtained from thermogravimetric analysis for the PVC case.

INTRODUCTION
As an alternative to the serious environmental problem of the disposal of post-consumer waste
plastics, some initial experiments into the liquefaction of waste plastics and their coliquefaction
with coal have been reported recently [I-51. The liquefaction approach is logical because the
atomic hydrogen to carbon ratio in waste plastics vis-a-vis coal is closer to that in petroleum.
The recently reported studies include the thermal and catalytic liquefaction of model polymers
such as high density polyethylene (HDPE), polypropylene (PP), polystyrene (PS) polyethylene
terephthalate (PET) and their mixtures [ 1-51, Catalysts tested in these experiments included
HZSM-5 zeolite, nanoscale FeOOH, Si02-Al203, WSi02-AI203, m i 0 2 (M = Pt, Ni, Pd, Fe),
and NiMo/Al;?O3. Also, two independent studies [6,7] have recently reported that elemental
sulfur promotes depolymerization of PE and PP and improves the quality of liquefaction
products.
A typical sample of post-consumer waste plastics may contain the above listed polymers, along
with PVC (polyvinyl chloride) and other impurities. Determining the concentrations of each
polymer in a sample thus becomes an important issue since each polymer may behave quite
differently under the high temperaturehigh pressure conditions of liquefaction. In this paper,
we report the results of our investigations on the detection and quantification of these polymers
using DSC (Differential Scanning Calorimetry). After presenting the DSC results, we apply the
technique to determine the polymer concentrations in two commercial samples. Both the success
and limitations of the DSC technique for this purpose are outlined.
EXPERIMENTAL DETAILS
The samples of model polymers used in these experiments were obtained from commercial
sources. The two samples of waste plastics investigated here include a sample from the
American Plastic Council (APC), elemental analysis of which has been given in a recent paper
[7]. X-ray diffraction analysis of this sample indicated it to contain primarily high density
polyethylene (HDPE) with smaller amounts of PP and PET [7]. The second sample of waste
plastics is of German origin (DSD waste plastics). The DSC measurements were carried out
with the Mettler TA3000 system using the DSC 30 system.
As polymers are heated, they may undergo a number of phase changes such as the glass
transition (Tg),crystallization transition (Tc) and melting (T,). Locations of these transitions are
used to identify the polymers whereas the heat of fusion AH determined from the heat flux
versus temperature curves in DSC are used to quantify the polymers [SI. For HDPE and PP, we
have used standard samples of known compositions to establish the linearity of AH with the
concentration of a polymer.
RESULTS AND DISCUSSION
The typical heat flux versus temperature DSC curves for three grades of polyethylene (HDPE,
MDPE and LDPE) are shown in Fig. I. The sharp peaks are due to polymer melting to yield
completely amorphous polymers above T, whereas the smaller anomalies at the lower
temperature are mostly likely due to the glass transition [ 9 ] . The areas under the peaks give the
heats of fusion (AH). It is noted that in the above DSC curves, the melting point Tm 131°C
for HDPE is in complete agreement with the in-situ x-ray diffraction measurements where
disappearance of the crystalline Bragg peaks was observed between 130°C and 135°C [IO].

1028
Normally, the melting transition are supposed to be first order; however, it is certainly not so in
case of polymers since the transitions are spread over a large temperature range. For first order
transition, the Gibbs free energy for the two phases equal at T,, leading to the result [8l
T, = AH/& -.
. - - - - - - - -.- - - - - - - - (1)

showing T, depends on the enthalpy of fusion AH and entropy of fusion AS. In Fig. 2, we
have plotted T, against AH, both evaluated from Fig. 1. It should be kept in mind that
differences in AH and AS between the melt and crystalline phase determine T,, assuming first
order transition.
In order to use AH for quantification, we prepared several standard mixtures of HDPE and PP
and DSC plots of these mixtures are shown in Fig. 3. The higher Tm = 166°C of PP allows an
easy identification of PP in the presence of PE in Fig. 3. The enthalpy of fusion for PE and PP
were determined from the areas under the peak following the procedures shown in Fig. 1 and
T, is represented by the peak temperature. In Fig. 4 we show plots of AH versus % PE
whereas similar plots for % PP are shown in Fig. 5 . The fact that T, does not change with %
PE and % PP shows that there is no measurable interaction between PE and PP. On the other
hand, AH varies linearly with YO PE and % PP demonstrating that AH provides an excellent
techniaue for auantifvine the crvstalline oercentages of PE and PP in a mixture. This forms the
basis for quantification of these polymers in a mixture.
Next we consider the DSC curves for other model polymers (viz. PET, PS and PVC) likely to
be found in post-consumer plastics. In Fig. 6, we present a comparative view of the DSC
curves for HDPE, PP, PET, PS and PVC. For PET. we show two figures. During the first
heating, one observes Tg. an exothermic peak near T, = 1 2 5 T due to crystallization [9] and
polymer melting near T, = 26OOC. On subsequent cooling and then reheating, only the melting
peak is observed. For PS, the glass transition T, = 100°C is observed; however no melting
peak is observed in this case. For isotactic polystyrene, a T, = 240°C is known [8]. Our
failure to observe a peak in the DSC curve is most likely to the nature of our sample. For PVC.
a glass transition near Tg = 80°C is clearly observed and this agrees with the literature values.
Also, syndiotactic PVC is known to have T, = 280°C [8]. However our experiments (Fig. 6)
show an exothermic peak around this temperature presumably because of the decomposition of
our sample since the sample is severally charred. Further evidence for this comes from
thermogravimetric experiments (Fig. 7) where large decreases in mass occur beginning around
280'C. This clearly is due to the decomposition of PVC.
Now we apply the above methodology to the identification and qb Afication of polymers in two
post-consumer waste plastics. In Fig. 8, we show the DSC curve for the APC commingled
plastic sample which has been the focus of studies in a number of recent papers [5,7,10]. The
DSC curve clearly shows three peaks which are easily identified with HDPE, PP and PET from
the known T, values, with the largest peak being from HDPE. This is consistent with the
earlier estimates from x-ray diffraction [7,10] although PET was difficult to detect in x-ray
diffraction because of overlapping Bragg lines. In contrast, in DSC, the peaks from PE, PP and
PET are well resolved (Fig. 8).
To determine the concentrations of PE, PP and PET in the APC sample, the calibrations of Fig.
4 and Fig. 5, along with assuming a similar linear curve for PET, are used. From this analysis,
we find the following concentrations in the APC sample: HDPE = 82 f 3%. PP = 7 k 3%, PET
= IO f 3%. These concentrations are consistent with those determined from x-ray diffraction,
although the actual numbers for HDPE and PET are somewhat different. As indicated earlier,
PET is difficult to identify by x-ray diffraction because of interferences of its Bragg lines by
those from PE.
For the German sample of DSD waste plastics, the DSC curve is shown in Fig. 9. The peaks
due to MDPE, HDPE and PP are easily identified and their concentrations from linear
calibrations are as follows: PE = 38% PP = 7%. The other major feature of the data in Fig. 9 is
the exothermic peak near 230°C. Thermogravimetric measurements in the German plastics
sample (Fig. IO) show mass loss beginning near 3OO0C, with the massive loss occurring
between 450 and 500°C. These observations are very similar to the thermogravimetric and DSC
data for PVC. Thus it is likely that this sample contains a significant amount of PVC. Since x-
ray diffraction of PVC does not contain any sharp Bragg lines, additional confirmatory evidence
for PVC from x-ray diffraction could not be obtained.

CONCLUSIONS
Results presented here have shown that DSC is a promising technique for the identification and
quantification of polymers in post-consumer plastics. However, supporting evidence from
thermogravimetry and x-ray diffraction is occasionally required. Additional experience with
other polymers likely to be found in post-consumer plastics is needed to provide additional
confidence in the use of DSC for quantitative purposes. Further studies are in progress to
establish the methodology for quantifying PVC by this technique.

1029
ACKNOWLEDGEMENTS
This work was supported in part by the U S . Department of Energy through the Consortium for
Fossil Fuel Liquefaction Science, Contract No. DE-FC22-93PC93053. We thank Eric Hopkins
for assistance with some of the experimental work.
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4. Joo, H. K.; Curtis, C. W., Energy Fuels 1996, l.Q,603-61 1.
5. Ding, W. B.; Tuntawiroon, W.; Liang, J. and Anderson, L. L., Fuel Process. Technol.
1996, e, 49-63.
6. Sivakumar, P.; Jung, H.; Tierney, J. W.; Wender, I., Fuel Process. Technol. 1996, e,
2 19-232.
7. Ibrahim, M. M.; Seehra, M. S., Energy Fuels 1997, July issue (in press).
8. See e.g. Polvmer Chemistrv. an Introducation by G. Challa (Ellis Horwood, 1993), page
147.
9. Introduction to Phvsical Polvmer Science by L. H. Sperling (John Wiley & Sons, second
edition 1992) page 322.
IO. Ibrahim, M. M.; Hopkins, E.; Seehra, M. S., Fuel Process. Technol. 1996, Q, 65-73.
140
h

& 120

90
80 100 120 140 160 180
Enthalpy of Fusion (AH, J/g)

60 80 100 I20 140 140

Temperature CC)
(left) Figure 1. DSC curves for high, medium and low density
polyethylene. (right) Figure 2. Enthalpy of Fusion(A H) vs.
melting point (Tm) for low, medium and high density polyethylene

=
Figure. 3 DSC curves for PE/PP blends
of various compositions.

PE 10% + PP 80%

) Temperature
80 100 120 140(‘C)
1 6 0 1 8 0 200

1030
 150.

h .
h 60
. . M
5 50

96 PE 96 PP

(left) Figure 4. Plot f o r d H vs.% PE and (right) Figure 5. Plot for

O H vs. Yo PP measured from various compositions of PE+PP.

? B
\

60 80 100 120 140 160 60 90 120 150 180

Temperature ("C) Temperature ("C)
\
\

\
50 100 150 200 250 300 50 100 150 200 250 3 0
Temperature ("C) Temperature ("C)

I . . . . I . . . . I , , . , , , .

60 90 120 150 180 50 100 150 200 250 300 350

Temperature ("C) Temperature ("C)

Figure. 6 DSC curves for A) PE, B) PP, C) PET (1st run), D) PET (2nd run),
E) PS, and F) PVC.

1031
 25
Figure 7. TGA of PVC indicating weight
loss beginning around 280 'C.

0 100 200 300 400 500 600

Temperature ("C)

,
Figure 8. DSC of APC commingled plastics.
The endotherms for HDPE, PP, PET are
identified.
I

U
PP -7%
-
HDPE 82%
PET -10% r
;

100 150 200 250 300

Temperature ('C) ,I

Figure 9. DSC of DSD waste plastics. I

Endotherms for HDPE, MDPE and PP
are noted. Large exothermal peak
0 around 230 'C is due to PVC.
,

,
V

50 100 150 200 250 300

Temperature ("C)

Figure. 10 TGA of DSD waste plastics

showing the weight loss occuring
from 300 - 500 'C.

- 0
100 200 300 400 500 600
Temperature ("C)

1032

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