NIR, DSC, and FTlR as Quantitative Methods for

Compositional Analysis of Blends of Polymers Obtained

From Recycled Mixed Plastic Waste
WALKER CAMACHO and SIGBRITI?KARLSSON*

Department of Polymer Technology

The Royal Institute of Technology (KTH)
S-1 00 44 Stockholm Sweden

Methods for the determination of the composition of two binary blends in mix-
tures of recycled polymeric materials were analyzed and compared. Recycled
polypropylene/polyethylene (PP/HDPE) and recycled poly(acry1-butadiene-styrene)
and polypropylene(AES/PP)were used to develop and validate the methods. Diffuse
reflectance near infrared spectroscopy (NIB) offers high sensitivity and ease of op-
eration and a possibility to perform multivariate data analysis. In comparison, dif-
ferential scanning calorimetry (DSC)and Mid-IR which are commonly used for this
purpose require certain sample preparation and are indeed time consuming. In ad-
dition, the low sensitivity of these two methods to concentrations lower than 1% wt
makes their application in quality control of recycled polymers inappropriate. NIR
can be used for estimating the composition of the recyclate on-line in only a few
seconds, no sample preparation is required, and high precision is achieved. We ob-
tained a root mean square error of prediction (RMSEP)equal to 0.21% wt in the in-
terval from 0- 15%wt of PP in HDPE and a RMSEP equal to 0.91%wt in the interval
0-100%. For blends of PP/MS a RMSEP of 0.74Yo wt in the range 0-100% and
0.32% wt in the range 0-15940wt PP was calculated. Most of the variation in the
spectral data with respect to the polymer blend composition for all the studied
blends were explained by two principal components (PC). The optimal number of
factors (PC) was determined by cross-validationanalysis.

1. INTRODUCTION Acrylonitrile-butadiene-styrene (Al3S) and PP are

the two major components in the automotive indus-
G enerally, household plastic waste from Sweden
contains approximately 33% of HDPE and 24%
of PP. A total separation of these two polymers is dif-
try. During recycling they usually contaminate each
other since a 100% separation is very difficult to
achieve. Many studies on the compatibihtion of re-
ficult because of the great similarity in their physical
cycled ABS and PP demonstrates that good material
properties. Conventional methods of separation, e.g.
properties are achieved (1-4).The quantifkation of the
the sink and float method, cannot be applied, and
different components in the blends remains, however,
manual sorting does not provide ideal separation be-
a very important issue for quality analysis and quality
cause of the human factor and in some cases lack of
control (QA/QC) of the recyclate.
labeling; this method is also cost-ineffective. More so-
Thermal analysis, in general, and differential scan-
phisticated sorting methods such as spectroscopic or
ning calorimetry (DSC), in particular, are widely used
electrostatic separation are still in development and
for characterization of polymer blends. During instru-
do not guarantee 100% purity. Quality assurance of
ment calibration, sample preparation, and analysis of
recycled household plastic is necessary since the
samples, certain criteria should be observed. The sam-
presence of small amounts of PP in HDPE or vice
ple should be in good thermal contact with the base of
versa affects the performance of the material and de-
the sample vessel in order to obtain reliable DSC data:
termines whether the material can be used for high
additionally, the amount of sample to be analyzed is
value applications.
small and would not be representative of the material
as a whole in the case of heterogeneous blends. The
sample must be representative of the material as a
'Corresponding author. whole and the lower limit of the sample mass may be

1626 POLYMER ENGINEERINGAND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9


NIR,DSC, and F77R
determined by the homogeneity of the sample. This is
especially true for composites and polymer blends,
where frequently 10 mg of sample are required before
a representative sample can be prepared. When a large
amount of sample is to be analyzed, the heating rate
should be decreased accordingly to compensate for the
increased temperature gradients in the sample (51,
making the method time-consuming. The thermal his-
tory of a polymer has a strong influence on the charac-
teristic melting and crystallization temperatures and
most of the time has to be erased by cooling the sam-
ple to a temperature below the crystalkation tempera-
ture after having heated it to a temperature above the
melting temperature.
In processing high-grade polymer recyclates there is
an increasing demand for quality determination and
assurance, because polymer recycling processes have
been improved by use of better separation and pro-
cessing techniques. The properties of recycled poly-
mers, especially physical properties, have to be speci-
fied and guaranteed within narrow tolerances by the
manufacturers according to the needs of their cus-
tomers. Without computer-aided data processing and
efficient measuring equipment, quality analysis in
polymer recycling is much more time-consuming.
Therefore it is important to have access to systems
that allow rapid and reliable qualitative and quantita-
tive analysis of multicomponent systems. Many stud-
ies use infrared spectroscopy for quality control and
quality analysis in polymer production. It is particu-
larly used for the determination of the composition of
copolymers and polymer blends and also for determi-
nation of additive and filer contents (6-8).
The near infrared range (12,800-4000 em-') as well
as the mid-infrared range (4004000cm-l)has been
used for spectroscopic detection of physical and
chemical properties of polymer. These techniques
make possible to obtain information about the chemi-
cal composition and structure of polymers. Therefore
this method is widely used for characterization of
polymeric materials (9- 13).
Diffuse-reflectance near infrared spectroscopy (MR)
has,in comparison with other spectroscopic techniques
such as mid-IR and Raman, a high signal-to noise
(S/N)ratio and allows non-destructive sample analysis.
The ease, rapidity and use of fiber optics facilitate the
application of NIR for on-line and in-line measurements
(14,15). For a given molecule many active overtone and
combination bands might be present in the NIR region,
creating as a result a spectrum with a large number of
overlapping bands, which makes spectral interpretation
difficult, but this disadvantage can be overcome by
using multivariate data analysis (16).
FIIR reflectance and transmission spectroscopy is
used for analysis of thin films.As a result of the high
absorbtivities of mid-IR bands, the film thickness
must be limited (up to 100 pm, depenrlmg on the spe-
cific bands chosen) in order to perform an accurate
qualitative analysis. Other IR methods, such as attenu-
(Am
ated total reflectance and photoacoustic methods,
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can provide IR spectra of thick materials, because
they penetrate a very thin layer at the surface of a
sample. The effective path length for the ATR and the
photoacoustic methods depends upon the refractive
index and thermal diffusivity, respectively. Therefore,
the use of this technique for the quantitative analysis
of non-homogeneous materials can be difficult.
The purpose of this work is to compare the effi-
ciency of thermal and spectroscopic methods for de-
termination of PP content in blends of recycled
PP/HDPE and PP/ABS, and highlight the ease and
sensitivity of MR spectroscopy combined with multi-
variate analysis in achieving this goal.
2. EXPERIMENTAL
2.1 Material
Recycled polypropylene and polyethylene were sup-
plied by Lunda Recycljng Plant, Stockholm. The mate-
rial was carefully sorted, washed and dried. Only
transparent and non-colored items were chosen for
these studies.
ABS Magnum 3504 produced by Dow Plastics and
designed for extrusion and injection was purchased
from Ashland AB;dumbbells according to ASTM stan-
dard D 638M were injection molded using a Batten-
feld Plus 250/50 equipped with a single screw (diame-
ter = 2.2 c m and L/D = 16).The barrel temperatures
were 220°C in the first heating zone, 240°C in the sec-
ond and 40°C in the mold. The dumbbells were sub-
jected to thermal aging at 90°C for a month, shred-
ded, extruded and pelletized.
The PP/HDPE blends were prepared in a Brabender
Plasticorder PL2000 twin-screw extruder (diameter =
3.5 cm, L/D = 9) at 220°C in the first and second
heating zone and 230°C in the third. Four strands
were extruded, cooled in a water bath and pelletized.
The PP/ABS was mixed using the same equipment at
T, = 230"C,T2 = 230°C and T3 = 240°C.Two sets
consisting of 17 PP/HDPE and 17 ABS/PP blends, in
which the content of PP and ABS,respectively, varied
in the range 0-100% wt were obtained. Additionally,
three PP/HDPE and three PP/Al3S blends containing
0.5%, 7% and 12% wt of either PP or ABS were manu-
factured for validation of the calibration models.
Pellets were analyzed as obtained by diffuse re-
flectance near infrared (NIR). For the FTIR measure-
ments, pellets were compression molded at 200°C for 2
min at 10 MPa, immediately removed from the press,
and allowed to cool to room temperature. Films with a
thickness of approximately 0.2 mm were obtained in
this way. Samples of suitable shape and size for ther-
mal analysis were cut from pellets using a razor blade.
2.2 Instruments
Thermal analysis was performed on a Mettler Toledo
DSC820 differential scanning calorimeter under a ni-
trogen atmosphere. About 7 mg of sample was heated
to 200"C,subsequently cooled to 25"C,held at that
1627
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Walker Camacho and Sigbritt Karlsson

temperature for 3 min, and heated again to 200°C.
The heating and cooling rate was equal to lO"C/min.
Infi-ared spectra in the Mid-region (FI'IR) were ac-
quired using a Perkin Elmer FI'IR-2000 equipped with
a DTGS detector. Thrty-two scans were averaged at 2
cm-' resolution in the range of 400-4000 cm-'. Sam-
ples were analyzed in duplicate. Curve fitting and
peak area were calculated on a PC using MATLAB ver-
sion 5.
Diffuse-reflectance near infrared (NIR) spectra were
obtained using a FT-NIR &men ME3 series spectropho-
tometer with an InAs detector and quartz-halogen
source was used. Forty scans were averaged at 4
resolution in the range 4000--10,000 cm-', five and
ten replicates of PP/ABS and PP/HDPE, respectively
were analyzed. Unscrambler 4.0 from Cam0 AS, Nor-
way, was used for multivariate data analysis. Princi-
pal component analysis (PCA) was performed on the
spectral data and PLS (Partial linear square) calibra-
tion was carried out on this data, which was previ-
ously treated by multiple scattering correction (MSC)
to compensate for possible physical differences be-
tween the samples, such as pellet size, shape and
light scattering.

9o%M PP

=
n

hl
1

2-+ 0.8
F 0.6
r
z 0.4
Q)
(D
:0.2
z
0
0 20 40 60 80 100
PP content (% wt)
Fig. 1 . a) FlTR-spectraof some PP/HDPE blends. b) Calibration curvefor determination of PP content in PP/HDPE blends.

1628 POLYMER ENGINEERINGAND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9

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NIR,DSC, andFIlR

3.RESULTS AND DISCUSSION
PP/HDPE blends
Qure I ( @ shows infrared spectra of the compres-
sion-molded films of PP/HDPE blends of known com-
position. To prepare the calibration curve, the ratio of
the absorbance (integrated area) of two peaks in the
rocking wagging region, a peak a t 1168 cm-I
characteristic for methyl group wagging in PP and a
peak at 720 cm-l arising from methylene rocking and
typical for HDPE (111, was chosen. A1168/(A1168+A720)
was plotted against the PP content and a quadratic
line was obtained in this way (Fg.I @ ] ) . The non-lii-
earity of the PP/HDPE calibration curve is due to the
difference in intrinsic absortivity of the PE peak at
720 cm-' and PP at 11 6 8 cm-'. The absortivity of the
PE peak is almost twice that of the PP peak. If the ab-
sortivity of both peaks were the same, the relation
would be linear. Reproducibility was checked by scan-
ning three samples of each blend. Using the calibration
curve, the composition of three samples was deter-
mined with a standard deviation equal to 0.84% wt.
Figure Z(a) shows the DSC thermograms of PP,
HDPE and some of the PP/HDPE mixtures. Two dif-

10 %wt PP

50 %wt PP

100 %wt PP PP

I I I I I I I I I I l l l l l l l l l l l 1 1 1 1 I l l I I I I I I I I I I I I I l l l l l l l , , l
100 110 120 130 140 150 160 170 180

I Temperature ("C)

80
70
60
50
tu
2 40
<
30
20
10
0
0 20 40 60 80 100 120
PP content (%wt)
lilg. 2. a)DSC-thermograms of PP, HDPE and some of their blends. b) Calibration curvefor determination of PP content.

POLYMER ENGINEERING AND SCiENCE, SEPTEMBER 2001, Vol. 41, NO. 9 1629
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Walker Cantach0 and Sigbritt Karkson

1
5300 5800 6300 6800 7300 7800 8300 8800
Wavenumber (cm-1)

g 100
*
c 80
a
U

60
00
O-
40
U
a
U

.u
U
20
2!
O - 0
0 20 40 60 80 100
Measured PP content (%wt)

16

-
E
0,
14
12
10
0
0 8
a +Calibration set
&
U 6
Q)
0
1
- 4 RMSEP=0.2 1
U
2 2
Q
n
" I

0 5 10 15
Measured PP content (%wt)
Fg. 3. a)NIR-spectra of PP, HDPE and their blends after MSC-pre-treatment. b) Calibration c m in the range 0-100%w t of PP. c)
Calibration curve in the range 0-15%wt PP in PP/HDPE blends.

1630 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9

NIR, DSC, and FTIR
ferent endothermic peaks one at Tml=130°C (melting
temperature of crystalline HDPE) and the other one at
Tm,= 165°C (melting temperature of crystalline PP)
can be observed even at low concentrations of any of
the components. The presence of two melting peaks
c o n f i i s the inmiscibilty of these polymers, which has
been reported by many other authors (7, 17, 18).
However, concentrations below 1% wt are difficult to
quantify, owing to the sensitivity of the method, which
depends upon the experimental parameters, i.e. heat-
ing ratio. A decrease of the heating ratio from
10"C/min to 5"C/min improves the sensitivity but
doubles the measuring time. An increase in the PP
content depresses the melting temperature of the
HDPE, but this depression is not a defined function of
the blend composition. This type of behavior has been
observed for binary blends and has been attributed to
a possible interplasticizing action caused by some
molecules of one of the components acting as diluent
within the crystalline regions of the other component
(17). Even small contents of HDPE [less than 2.5% wt)
greatly depress the melting enthalpy (4) of PP, the
AHm of pure PP is equal to 82 J / g and samples con-
taining 1% wt HDPE have a A H , equal to 71 J/g. For
this reason, pure PP was not included in the calibra-
tion plot. Figure 2 0 gives the calibration curves as
the normalized area of the melting peaks at Td and
plotted against the PP content. It can be observed that
the percentage of PP and the melting area are linearly
related. The standard deviation was equal to 0.78% wt.
Figure 3(a)presents NIR spectra of the PP/HDPE
blends. PP shows characteristic absorption peaks at
8385 cm-' and 6094 cm-l, which correspond to the
second and first overtone of the C-H methyl stretch-
ing. As the content of HDPE increases, the intensity of
these two peaks decreases, and a new C-H methylene
peak a t 6480 cm-' appears. It can also be observed
that the intensity of a peak at 8216 cm--' and another
at 5774 cm-' increases with the increase of HDPE.
These two peaks are due to the second and f i s t over-
tones of C-H methylene stretching in polyethylene
(19). Because of the high overlapping of the spectral
bands, a n univariate calibration is W c u l t to perform.
Therefore a partial least-square (PLS) calibration has
been used to analyze the spectral data. The biggest
advantage of this procedure is that it allows us to ex-
tract the most information from the acquired data. A
principal component analysis (PCA) was also per-
formed on the data in order to detect possible outliers
and discover trends in the data. The PLS calibration
was preceded by a multiple scattering correction
(MSC) of the data to mathematically separate the mul-
tiplicative effect of light scattering from the additive,
i.e. chemical information.
Figure 3fb) presents the calibration curve; as a first
approach, the calibration was carried out for 0-100%
wt PP content region. Full cross validation (leaving
one out) was used to determine the optimal number of
principal components (PC) and to test the model. Two
PCs fully described the model with a root square
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
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standard error of prediction (RMSEP) equal to 0.91%
wt. Since the method is intended to be used for deter-
mination of very small amounts of PP in recycled
HDPE, which has been carefully separated from PP
and other household plastics, a PLS in a narrower in-
terval, 0-15% wt PP, was designed. Even in this case,
two PCs fully described the model. The model was val-
idated by either cross validation or a test set consist-
ing of three samples with 0.5, 7.0 and 12.0Yo wt PP
content. The FNSEP was equal to 0.21% wt obtained
from the calibration curves shown in R g 3(c).
PP/ABS blends
Figure 4(a) shows the infrared spectra of some
PP/ABS blends with different compositions. Several
peaks attributed to either AI3S or PP were observed,
and their suitability for calibration purposes was
studied. For instance, it can be seen that the intensity
of the peak at 757 an-', which is characteristic for the
aromatic C-H wagging, increases with increasing con-
tent of ABS in the polymer blends. The band at 700
cm-' has been used by Cole et aL (20) for quantifica-
tion of PS in PPE/PS blends. An attempt to use this
band for the determination of ABS content was made,
but because of the strong absorbance of this band, it
was not possible to measure the peak intensity for
blends with a PP content of 35% wt or less. A peak at
2150 cm-', which corresponds to the C=N stretching
band, which has been used for monitoring the ABS
content in PC/ABS blends (21). also increases with
the rise in AI3S content. However, the band at 757
cm-' appeared to be the most proper for monitoring
the AI3S content in the polyblends because of its high
resolution and moderate intensity. The intensity of a
band at 1 168 cm-' ascribed to methyl group wagging
in PP decreases as the ABS percentage increases.
Therefore, this peak was chosen to monitor the PP
content. A,,,,/(A,,,, + AT5J was plotted against the
PP content in the blends. Figure 41b)depicts the cali-
bration curve obtained.
ABS is an amorphous polymer; therefore, no melt-
ing peak can be detected in DSC experiments. Figure
5(4 displays the thermograms of several AI3S/PP mix-
tures. A Tg = 108°Cattributed to styrene-acrylonitrile
was observed; this value is in good agreement with
the value reported in the literature (5, 21, 22). The Tg
remains constant for all blends analyzed, though is
less noticeable for blends with high PP content. The
melting temperature of PP decreases with the increase
of ABS, but a functional relationship between the ABS
content and the melting temperature was not found.
Figure 51b) shows the calibration curve obtained by
plotting the integral of the peak at Tm = 165"C, i.e.,
the melting temperature of PP against the composition
of the PP/ABS blends. A linear relation with a
standard deviation equal to 0.32% wt was obtained.
mure S(a) shows the NIR spectra of the PP/ABS
blends after MSC correction. Several peaks corre-
sponding to the methyl group in PP and to the C-H
1631
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Walker Carnacho and Sigbritt Karkson

bonds in the aromatic ring of ABS have been identi-
fied. ABS shows a strong peak at 8741 cm-' and a
weaker one near 5934 cm-' related to the aromatic
C-H stretching second overtone and aromatic C-H
stretching first overtone, respectively. As the Al3S
is replaced by PP, the intensity of these b a n d s
decreases, and two peaks, one at 8385 cm-1and the
other 5890 em-', arise. These peaks are characteristic
for C-H methyl stretching second overtone and C-H
methyl stretching first overtone, respectively (19).The
growth of a band at 7353 cm-' (a C-H methyl combi-
nation band) can readily be observed as the AI3S con-
tent decreases. However, curve fitting and integration
of these bands would be very difficult and not precise.
The use of multivariate calibration methods in general
and PLS in particular allows the extraction of the
maximum of information from not very selective data
(16). For this blend system, a PLS calibration was

UiLm 75 % wt PP

U L PP - L J L W b
50 % wt

1200 1150 1100 1050 1000 950 900 850 800 750
Wavelength (cm-')

y =2E-05~ + ~0.0074~
F
R2 = 0.9973
Y

a 0 I I I

0 20 40 60 80 100
PP content (%wt)
Q. 4. a)FTLR-spectraof some PP/ABS blends. b) Calibration curvefor determinationof PP content in PP/ABS blends.

1632 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER2001, Vol. 41, No. 9

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NIR,DSC,

performed on the MSC pretreated data in the interval
6545 cm-' to 9090 cm-l for the 0-100% wt PP/ABS
calibration set blends. It was found that two PCs ex-
plained the whole variation in the spectral data. The
optimal number of PCs and the validation of the
model were achieved by cross validation. Figure S(b)
shows the calibration curve obtained: the MRSEP was
equal to 0.74% wt. A second PIS calibration was per-
formed on the same spectral region and data, but in a
narrower range, 0-15Yowt PP in ABS,since the appli-
cation of this method is intended for detection and
quantification of small amounts of PP in recycled ABS.
Also in this case, two factors fully explained the
model, which was validated by the test set and full
cross validation. The calibration curve with RMSEP
= 0.32% wt is displayed in Rg. 6(c). Better RMSEP
values are obtained for PP/ABS blends since PP and
ABS greatly differ in chemical structure, whereas PP

B
+s-
4Z.P
Z2E 100 % w t PP

90 % r v t PP
7 5 % w t PP

50 %wt PP 1

25 4 w t PP
-
10 % w t FP

0 %wt PP
-. --

I I I I I I I I I I I I

80 100 120 140 160 180

Temperature ("C)

(b)
90
80
,
70
60
50
5 40
30
20
10
0
0 20 40 60 80 100
PP content (%wt)
Fig. 5. DSC-thennograms of PP,ABS and some of their blends. b) Calibration cuniefor determination of PP content.

POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9 1633
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Walker Carnacho and Sigbritt Karlsson

6500 7000 7500 8000 8500 9000

Wavenumber (cm-1)

100

80

60

40

20

0
0 20 40 60 80 100
Measured PP content (wt)

0
0 5 10 15
Measured PP content (Ymt)
FQ. 6. al NlR-spectra of PP, ABS and their blends afler MSC-pre-treatment. b) Calibration curve in the range 0-100%wt of PP. c) Cali-
bration curue in the range 0-15%w t PP in PP/ABS blends.

1634 POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9

NIR, DSC, andFTIR
and HDPE contain methyl groups, which overlap and
d e c t the spectra of the blends.
The presence of low-molecular-weightcontaminants
in recycled household packaging, which been studied
in a previous work (23)does not affect the measure-
ments of blend composition, since the analytical
methods used cannot detect such low concentrations.
4. CONCLUSIONS
The present paper shows that NIR is a good candi-
date for online measurements of compositions of
mixed polymer fractions from recycled plastic waste.
Diffuse-reflectance NIR allows a rapid and reliable
measurement of pellets and requires no previous
sample preparation. NIR has also a hgh signal/noise
ratio in comparison with the other methods. The NIR
spectra show broad and highly overlapped peaks but
they are readily interpreted by the use of multivariate
analysis. The use of PC analysis and PLS-calibration
make it possible to extract the most information from
the acquired spectral data and detect small changes
in it, which are related to small changes in the com-
position of the blends. The composition of the blends
can be determined with high precision. The PP con-
tent in the PP/HDPE blends was predicted with a
RMSEP equal to 0.46% wt in the &15% wt region,
and the RMSEP for PP in the PP/ABS blends was
0.3% wt.
DSC works well for determination of concentration
above 1% wt, but lower concentrations are difficult to
detect at a heating rate equal to 10°C/min and mea-
surements take too long time. Since small amounts
(7.0-10.0 mg) are analyzed, the sampling procedure is
important to obtain representative samples. The sen-
sitivity of the DSC method can be improved by de-
creasing the scanning rate. However, this procedure
increases the analysis time, which makes the applica-
tion of this method inappropriate for on-line monitor-
ing of polymer blends. Generally, the FTIR method re-
quires tedious sample preparation, since the
fabrication of thin films can be in some cases trouble-
some and time-consuming. The use of the ratio of cer-
tain spectral bands (peak area/height) compensates
for the difference in thickness between the samples.
POLYMER ENGINEERING AND SCIENCE, SEPTEMBER 2001, Vol. 41, No. 9
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For PP and HDPE concentrations below 1% wt in PP/
HDPE blends, the intensity of the chosen characteris-
tic bands is low, which makes their integration inac-
curate and difficult.
ACKNOWLEDGMENTS
Financial support given by the European Commis-
sion, "Electrostatic Recovery of Paper and Plastic
Packaging Wastes" (ELREC), BRPR-CT96-0247, is
gratefully acknowledged.
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