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Automatic identification and sorting of
plastics from different waste streams
Infrared Spectroscopy (IR) - a status report
Background

Infrared spectroscopy is one of the most
widely used analytical techniques for
identifying different types of polymers and,
in some cases, different grades and/or
additives within the same polymer family. It
is considered to be highly accurate and
precise, but it has been traditionally used
mostly in laboratory settings by highly
trained technicians or scientists.

Groups of atoms in molecules vibrate with
sharply defined frequencies that are
predictable and unique. When a sample is
exposed to a beam of infrared radiation it
absorbs energy at frequencies characteristic
of specific atomic arrangements and bonds.
When the radiation that is transmitted
through or reflected from a given plastic
sample is examined, it will be changed based
on those frequencies which were most highly
absorbed by the material. The resulting
spectrum is a pattern of peaks and valleys
corresponding to
frequencies of the
radiation that were
highly absorbed.
Infrared spectra are
considered so
characteristic of
molecular
arrangements that parts of it are referred to as
the polymer fingerprint region.

Instruments specifically developed for
plastics identification operate in the short
wave near infrared range (SWNIR) from
700-1 100 nm wave length, in the near
infrared (NIR) range from 700-2500 nm or in
the mid infrared range (MIR) from 2500-
15000 nm.

While MIR is the most surface-sensitive of
the three, none can see through typical paints,
metallic coatings, labels or most other
common surface coverings on plastic items.
Coatings must therefore be removed, or an
area free of coatings must be examined for
these techniques to be useful.

Short wave near infrared
spectroscopy (SWNIR)

This technology measures overtones and
combinations of the fundamental molecular
vibrations that occur for plastics in the mid
infrared region. The SWNIR range is less
rich in spectral information than either NIR
or MIR, and the range of polymer types that
such a system can identify is therefore
limited. However, fibre optic probes, fixed
ratings and charge coupled device
detector arrays can be used in this range
of infrared frequencies. This can make
such instruments very compact, robust,
easy to use and of relatively low in cost.
Although the existing technology has
been designed to differentiate between
ABS and HIPS, it may be able to identify
more plastic types by means of
improvements of the software and the
reference library.

Black and darkly pigmented plastics can not
be identified using SWNIR because too little
Authors: Bruno Krummenacher, Patrick Peuch, APME, Michael Fisher, APC,
Michael Biddle, MBA Polymers, Inc.
IR spectroscopy has been
traditionally used mostly in
laboratory settings by
highly trained technicians
or scientists
Copyright 2002 Plastics in End-of-Life Vehicles www.plastics-in-elv.org Page 2 of 3
radiation is reflected back to the sensors at
this frequency range. Furthermore, SWNIR
will probably never be able to differentiate
between more than a few polymers at a
time because of the limited information it
extracts.

Near infrared spectroscopy
(NIR)

Near infrared spectroscopy is the most
commercially available technology that
offers effective polymer identification in
less than one second (and less than 100
milliseconds in some cases). It operates
in the spectral range of 700-2500 nm,
which, like SWNIR, is dominated by
overtone and combination vibrations.
NIR, however, captures more unique
spectral characteristics, and some
systems have demonstrated a
remarkable ability to identify a wide
range of plastics quickly and accurately.

A wide range of photo-detectors with short
response times and high selectivity are
available in the NIR range. Quartz optical
fibres with low attenuation enable remote
sensing. Identification from a distance of
more than 10 cm is also possible with some
systems. Acousto-optical tuneable filters
(AOTF), where the optical diffraction of a
crystal is changed by acoustic frequencies
generated by piezo-electric transducers,
have been developed. Instruments
employing AOTF technology can be made
containing no rotating gratings or other
moving parts, allowing them to be compact
and rugged. The primary drawback of such
systems is their difficulty in identifying
black pigmented materials, because carbon
black both absorbs and scatters highly at
NIR frequencies. Their use in an integrated
system with other methods could therefore
be beneficial. Prices of NIR instruments
are in the range of 20,000 - 70,000.

A portable plastics identification
instrument was recently developed using
an AOTF crystal. This instrument,
controlled from a laptop PC, has a weight
of only 1.8 kg and is able to identify many
types of standard polymers with nearly
100% accuracy and within a measuring
time of 50-500 milliseconds (except for
black and dark plastics, of course). The
price of the instrument is expected to
eventually fall to around 10,000.

Numerous automated identification and
sorting systems
have been
developed for
plastic bottles,
and many of
these use NIR
spectroscopy for
at least part of
the
identification step. NIR works well in this
application because it can obtain spectra of
the plastics without touching the parts, it is
fast (tens of milliseconds), it only needs to
identify about five different plastics at the
most, and black plastics are not common in
bottles. Recently a German company
developed an automated NIR system for
durable goods, specifically computer and
business equipment parts. While the parts
are quite different from bottles from a size
and shape standpoint, they are mostly
lightly coloured and are typically made
from only six or seven different types of
plastic.

Fourier transform mid
infrared spectroscopy
(FTMIR)

Fourier transform mid infrared (FTMIR)
instruments generate spectra in the
Automatic identification and sorting of plastics from different waste streams
Infrared Spectroscopy (IR) - a status report (Cont.)
Near infrared spectroscopy
is the most commercially
available technology that
offers effective polymer
identification in less than
one second...
Copyright 2002 Plastics in End-of-Life Vehicles www.plastics-in-elv.org Page 3 of 3
"fingerprint" region, which contains the
fundamental vibrational frequencies of the
functional groups within molecules. Some
instruments operate in diffuse reflectance
(DR) mode, where the light is reflected
from the
material in a
scattered
manner.

This
approach
usually
requires that a powder sample be placed in
the spectrometer. (Powder samples from
plastic items are usually obtained by
scraping with an abrasive pad.) While this
technique is faster and simpler than many
that preceded it (for example making salt
crystals from powders or casting films
from polymer solutions), it is still rather
time consuming compared with other
reflectance techniques.

Most new spectrometers that have been
developed for the rapid identification of
plastic samples use a specular reflectance
(SR) technique. In this mode, the infrared
light is reflected back from the material
surface like visible light from a mirror.
Although only a small portion of the light
is reflected back, this results in high
spectral contrast. A relatively smooth
surface is therefore required for good
measurements, which is the primary
drawback of this approach. The main
advantage of SR is that it usually requires
little or no sample preparation. The part is
simply brought into contact with a conical
probe affixed to the instrument, a switch is
activated (often with a foot), and the
identification displayed on a computer
screen within a few seconds. As with most
techniques, there is a balance between
speed and sampling ease on the one hand
and accuracy and precision on the other.

In most cases fibre optics are generally not
used because the only instruments
available in the MIR range are expensive,
somewhat delicate, and do not cover some
of the important frequency ranges. In most
of the cases using MIR, the sensor must
be in close proximity to the plastic
item (within a few centimetres) and it
must be essentially motionless for at
least one second. Within
approximately two further seconds a
clear identification is usually made by
comparing the spectra with a reference
library, or by using some type of software
manipulation and analysis of the spectra.

J apanese automotive researchers (the same
group that developed the hand-held
dielectric clamp) have developed a
pyrolysis FTIP approach to facilitate the
identification of painted plastics. They use
a high-intensity infrared light to pyrolyse
the surface of a polymeric sample, sweep
the resulting vapours to a gas cell situated
inside a normal FTIK spectrometer, and
perform a vapour-phase analysis. The
researchers chose an infrared source
instead of a laser to perform the pyrolysis
for safety and cost reasons. The instrument
is capable of identifying first the paint,
then with subsequent scans identifying the
underlying plastic substrate. The probing
and analysis time is similar to that with SR
systems; a few seconds.

The main overall advantage of MIR
systems is their precision and accuracy,
especially their ability to identify blends,
dark and black pigmented polymers, a
range of fillers and even some additives.
Most FTMIR instruments use fairly
delicate interferometers, which makes the
somewhat expensive and less robust than
systems Without moving parts.
Nevertheless, prices have now reached as
low as around 30,000 for commercial
units.
Automatic identification and sorting of plastics from different waste streams
Infrared Spectroscopy (IR) - a status report (Cont.)
Japanese automotive
researchers have developed a
pyrolysis FTIP approach to
facilitate the identification of
painted plastics.