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Polyethylene characterization by FTIR

Article in Polymer Testing · August 2002

DOI: 10.1016/S0142-9418(01)00124-6

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 Polymer Testing 21 (2002) 557–563
www.elsevier.com/locate/polytest
Test method
Polyethylene characterization by FTIR
J.V. Gulmine a, P.R. Janissek b, H.M. Heise c, L. Akcelrud d,*

a
Instituto de Tecnologia para o Desenvolvimento LACTEC, Caixa Postal 19067, CEP 81531-990 Curitiba, PR, Brazil
b
Centro Universitário Positivo, Campus II, CEP 81280-330 Curitiba, PR, Brazil
c
Institute of Spectrochemistry and Applied Spectroscopy, 44139 Dortmund, Germany
d
Departamento de Quı́mica, Centro Politécnico da UFPR, Universidade Federal do Paraná, CP 19081, 81531-990 Curitiba, PR,
Brazil

Received 5 September 2001; accepted 16 October 2001

Abstract

Important experimental parameters for FTIR spectra acquisition were studied: apodization, beam aperture, number
of scans and spectral resolution, using polyethylene samples. The optimum conditions for the analyses were established
and permitted unequivocally to identify the three most important commercially available grades: low density, high
density and linear low density products (LDPE, HDPE and LLDPE respectively).  2002 Elsevier Science Ltd. All
rights reserved.

Keywords: FTIR; Attenuated total reflectance; Polyethylene

1. Introduction and the possibility of working under vacuum, which

The physical properties of polymeric systems depend,
in the first instance, upon the chemical constituents and
the configuration of the macromolecules and also on the
relationships among the chains (morphology) the para-
meters defining such as crystallinity and phase segre-
gation. Many spectroscopic techniques are available
nowadays to access these features, and FTIR-spec-
troscopy is perhaps the most widely used due to its ver-
satility in determining composition, taticity, confor-
mation, crystallinity, among others [1–14]. Nevertheless,
to fully explore the potential of this method, some skill
is needed in developing a methodology that will permit
optimization of the analysis. In this contribution we
present an experimental approach for spectra acquisition,
exploring the capabilities of the high resolution BOMEM
DA8 equipment, including a set of different detectors
* Corresponding author.
E-mail addresses: joseane@lactec.org.br (J.V. Gulmine),
janissek@zaz.com.br (P.R. Janissek), akcel@onda.com.br
(L. Akcelrud).
improves the spectra quality, minimizing interferences
and spectral noise due to absorption from carbon dioxide
and moisture from the atmosphere. Samples of poly-
ethylene representing the three commercially available
grades were used: high density (HDPE), low density
(LDPE) and linear low density (LLDPE). We show that
with appropriate choice of conditions it is possible to
distinguish between each one, which is not found in the
literature by comparing the library of standard spectra.
2. Experimental
2.1. FTIR analysis
The equipment used, a BOMEM DA8 spectrometer,
is a FTIR spectrometer specially designed for research,
where the basic configuration, such as light sources,
beam splitters and detectors can be altered by the user.
In order to obtain the best signal to noise ratio in the
spectral regions of interest, the parameters defining apod-
ization, beam aperture (radiation source) and number of
scans. The criterion used was the ratio obtained by com-

0142-9418/02/$ - see front matter  2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 1 4 2 - 9 4 1 8 ( 0 1 ) 0 0 1 2 4 - 6
558 J.V. Gulmine et al. / Polymer Testing 21 (2002) 557–563

Fig. 1. (A) reference acquisition under atmospheric conditions. (B) reference acquisition under reduced pressure (⬍4 hPa). (C)
sample acquisition under reduced pressure (⬍4 hPa).

Fig. 2. Doublet in the region 1473–1463 cm⫺1 for LDPE showing the effect of resolution.

paring the height of the sample absorbance peaks with

the base line noise (blank). The bands chosen for poly-
ethylene analysis were in the regions 3000–2800, 1550–
1400 and 750–650 cm⫺1.
For the spectral resolution study, the interferograms
were acquired with 0.5 cm⫺1 and the spectra was recal-
culated for 0.5 1, 2, 4 and 8 cm⫺1 resolution using the
following mathematical treatments: Bartlet (triangular),
Hamming, Medium with apodization and Boxcar, with-
out apodization.
We have found out that the Attenuated Total Reflec-
tance (ATR) accessory used represents the most critical Fig. 3. Influence of resolution on band intensity, for Bartlet
condition for spectra acquisition, due to difficulties in apodization (triangular) for de doublet 1473–1463 cm⫺1.
obtaining good sample/crystal contact. The effectiveness
of the sample contact will dramatically affect the quality
of the final result. The detector used was an alanine
doped with deuterated triglycine in CsI windows avoid interference from the atmosphere the measure-
(DTGS), which is more suitable than the mercury cad- ments were performed under reduced pressure below
mium teluride (MCT) for quantitative analysis [15]. To 4hPa.
 J.V. Gulmine et al. / Polymer Testing 21 (2002) 557–563 559

Fig. 4. Base line spectrum used for the analysis of signal to noise ratio. Range correspondent to LDPE bands at 1473–1463 cm⫺1.

Fig. 5. Noise amplitude in the 1473–1463 cm⫺1 range, for the different apodizations.

2.2. Sample preparation 3. Results and discussion

HDPE, LDPE and LLDPE commercial samples, 3.1. Analysis optimization

received as pellets, were analyzed in film, KBr disks and
sheet form. The film and disk measurements were perfor-
med in the transmission mode and the sheets using the
ATR (attenuated total reflectance) technique. In order to
compare the results from both methods. The films were
prepared using a film-maker device, which is a special
accessory to prepare samples of controlled thickness.
The assembly was submitted to a load pressure of
2.77×107 kgf/m2 at 130°C in a GRASEBY SPECAC
press, model P/N 15620. By using different spacers,
films with 3 cm diameter and about 20, 30 and 50 µm
thick were obtained. The KBr disks were prepared with
a 5.67×108 Pa load, with no heating, in a stainless steel
mold. The sheets (10 cm × 10 cm × 0.1 cm) were pre-
pared by pressing the material at 130°C for 5 mins, with-
out any load pressure, using a 1.62×108 Pa load for
further 5 min., and with application of a 3.25×108 Pa
load for 2 min.
The importance of using vacuum within the spec-
trometer for the analyses is illustrated in Fig. 1. Under
normal atmospheric conditions, (without vacuum),
(spectrum A) a high interference due to moisture and
carbon dioxide is observed in the spectra. This problem
was eliminated with the acquisition of reference (B) and
sample spectrum (C) under vacuum. Several minutes are
required to establish vacuum equilibrium for each run,
resulting in a more time consuming measurement than
the standard procedure.
Interferograms with different maximum optical phase
differences were collected to verify the influence of the
spectral resolution on absorption band shape. This is
characterized by the distance in cm⫺1 between two bands
that the instrument can recognize [15]. In Fig. 2 the
results of changing the spectral resolution from 8.0 to
2.0cm⫺1 can be observed. When lower resolutions are
560 J.V. Gulmine et al. / Polymer Testing 21 (2002) 557–563

Table 2
Main absorptions of polyethylene in the IR region and their
assignment

Band (cm⫺1) Assignment Intensity

2919 CH2 asymmetric Strong

stretching
2851 CH2 symmetric Strong
stretching
1473 and 1463 Bending Strong
deformation
1377 CH3 symmetric Weak
deformation
1366 and 1351 Wagging Medium
deformation
1306 Twisting Weak
deformation
1176 Wagging Very weak
deformation
731–720 Rocking Medium
deformation

upon the absorption bands within the measured spectra.

Fig. 6. Schematic representation of the infrared radiation path
and contact type for the different techniques.
used and the distance between two adjacent bands is near
or less than this resolution, the effect can be quite dra-
matic, as can be seen for resolution 8.0 cm⫺1 in Fig. 2.
The influence of resolution on band intensity is illus-
trated in Fig. 3 for the 1473–1463 cm⫺1 doublet. The
data were obtained from the LDPE sample with Bartlet
apodization. A decrease in the intensity signal is
observed for lower resolutions.
Each type of apodization exerts a specific influence
In order to measure the influence of the available apodiz-
ation types in the software, the noise amplitudes were
estimated, taking the most intense minimum and
maximum points of the baseline (without sample), in the
regions where the PE bands are located and taking the
difference between them, as shown in Fig. 4. In Fig. 5
the results from calculations made for each of the four
apodization types are shown. It was noted that Bartlet
apodization (triangular) afforded the lowest noise level,
and was thus adopted in all the analyses.
Taking into account the results concerning noise, sig-
nal intensity and time required for spectra acquisitions
altogether, the following conditions were established:
2.0 cm⫺1 for resolution, Bartlet apodization, 128
accumulations (scans) and pressure below 3.0 Torr.

Table 1
Characteristics of the diverse techniques for polyethylene analysis by FTIR

Technique Use Sample preparation Remarks

Heating could alter the

Polymer identification material in some way.
Transmittance Film Heating and pressing
general purpose Very thin films show
fringes in the spectra
Pressing of the pure
Very seldom used in A fine powder is often
Disk material on blended with
thermoplastics difficult to obtain
KBr
The spectra from those
None.
Soft polymers surface obtained by transmittance.
Reflectance ATR Different accessories may
analysis A good constant
be needed
crystal/sample is needed
 J.V. Gulmine et al. / Polymer Testing 21 (2002) 557–563 561

Fig. 7. LDPE spectra acquired by different FTIR techniques: (A) transmission — film; (B) transmission — KBr disk and (C) ATR
obtained with ZnSe and 45° incidence beam.

Fig. 8. LDPE spectra acquired by transmission (film) (A) and by ATR (sheet) (B), showing antioxidant absorptions (circled regions).

The transmission and reflectance techniques are sche-
matically represented in Fig. 6.
3.2. Polyethylene analysis
The characteristics of the different methods for poly-
ethylene analysis are depicted in Table 1. These methods
were employed in order to verify their possible influence
in sample alteration and spectra quality.
3.2.1. Comparison between different methods for
sample preparation, analysis and band assignment
The spectra obtained in transmittance and ATR using
the three different techniques of sample preparation is
shown in Fig. 7.The KBr (B) disks resulted in non-homo-
geneous materials due to the PE softness and mismatch
of polarity between the two components. In addition, the
KBr acts as a diluent, decreasing the strong absorptions
in the 3000 cm⫺1 region. For films (A) these bands were
always very intense causing opaque spectral intervals,
even for very thin films. The ATR technique (C)
afforded well-resolved and less intense bands, much like
the ones seen with the KBr disks. The advantage of ATR
is the possibility of obtaining the spectra directly from
the sheet, without any further sample preparation. Essen-
tially the same fundamental vibrations are detected with
variations in intensity.
The comparison between ATR and transmission data
is not straightforward as a correction is needed. In trans-
mission, the optical path is the material thickness,
whereas in ATR the depth of the penetration (dp) (which
is the counterpart of the optical path) is directly pro-
portional to the wavelength (l), as described in Eq. (1).
The consequence of this fact is that in ATR spectra,
when the wave number decreases (and l increases), the
band intensity is also increased accordingly, due to a
562 J.V. Gulmine et al. / Polymer Testing 21 (2002) 557–563

Fig. 9. Polyethylene spectra (film form). (a) Full range; (b) magnification of the 1300–1400 cm⫺1 range.

deeper penetration (dp) of the radiation into the sample..
This effect can be visualized in spectrum (Fig. 7(C)),
without correction.
l 3.2.2. Identification of the different polyethylene types
dp ⫽
2pn1(sin2 qef−n221)1/2
where dp is the penetration depth of the radiation, l the
wavelength in µm, n1 the refraction index of the ATR
crystal, n21 the ratio between the refraction indexes of
the sample and of the crystal and qef the effective inci-
dent angle in degrees
In Table 2 the qualitative analyses of the PE samples
are shown, with band assignments [16,17].
ATR is a very sensitive technique and is specially suit-
able for surface analysis. The utmost care should be
taken in sample manipulation to avoid contamination. To
illustrate the technique’s sensitivity we show in Fig. 8
the spectra taken by transmittance (A) and by ATR (B)
of the same sample. In Fig. 8(B) it was possible to dis-
tinguish the characteristic vibrations of amines at 3200–
3400 and at 1600 cm⫺1 originated by the UV stabilizers
of the type HAS (hindered amine stabilizers, as TINU-
VIN, CHIMASORB or CYASORB UV) [18,19],
whereas in Fig. 8(A) the presence of the additive could
not be detected.
(1) by FTIR-spectroscopy
The spectra of the three types of polyethylene acquired
in film form are shown in Fig. 9. In Fig. 9(a) it is noted
that all present the same absorptions, varying only in
terms of intensity, which can be attributed to differences
in film thickness. In Fig. 9(b) the region 1300–
1400 cm⫺1 is displayed using an enlarged scale, and one
can clearly see differences in the absorption pattern of
the samples. Three bands assignable to CH2 and CH3
groups are present: band I at 1377 cm⫺1, band II at
1366 cm⫺1 and band III at 1351 cm⫺1. The major differ-
ence between the polyethylenes is their degree of branch-
ing, that is, number and size of ramifications. A literature
survey in the electronic libraries lead to the assignment
of the polymer in which band I is absent to DPE and the
polymer in which band I is stronger than band II to DPE.
Consequently, the polymer in which band I is weaker
than band II is LLDPE, a result not reported so far. Band
III is constant for the three samples of polyethylene.
 J.V. Gulmine et al. / Polymer Testing 21 (2002) 557–563
Therefore, in this work we demonstrate for the first time
that it is possible to distinguish HDPE, LDPE and
LLDPE by FTIR, when the appropriate analysis con-
ditions are met.
4. Conclusions
The influence of optimization of FTIR analysis was
demonstrated through data treatment, taking into account
resolution, apodization, accumulation number (number
of scans) and vacuum conditions.
It was also demonstrated that under optimized con-
ditions it is possible to identify the three most important
types of commercial polyethylenes: high density, low
density and linear low density.
Acknowledgements
We wish to thank COPEL (Companhia Paranaense de
Energia) for financial support. J.V.G. thanks LACTEC
for a doctoral scholarship, L.A. thanks CNPq for a
research grant and H.M.H. acknowledges the support
given by a CNPq travel grant.
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