INFRARED SPECTROSCOPY IN ANALYSIS OF PLASTICS RECYCLING 1

Infrared Spectroscopy in and additives, e.g. flame retardants, which also have to be
identified to allow economic recycling.
Analysis of Plastics Recycling Solid samples absorb IR radiation strongly, and the
fundamental vibrations of the molecules are especially
intense. The near-infrared (NIR) spectral range with
Norbert Eisenreich and Thomas Rohe the overtone and combination bands is appropriate for
Fraunhofer Institut für Chemische Technologie analyzing bulky materials in reflection and transmission
(ICT), Pfinztal, Germany modes. The plastics from domestic wastes can be reliably
identified by the first overtone of the C H bands between
1600 and 1800 nm. Extending this wavelength range to
1 Introduction 1 1000 nm, technical non-black plastics can also be treated. In
1.1 Government Regulations 2 the case of black plastics, which are often used in audio and
1.2 Plastics Consumption and Waste 3 video appliances, the mid-infrared (MIR) spectral range
1.3 Economic and Technical Demands 3 has to be applied, owing to the reduced penetration depth
of radiation into these materials. Also, larger amounts of
2 Materials 4
additives such as plasticizers and flame retardants can be
2.1 Waste Streams 4
analyzed.
2.2 Methods of Analysis 5
The identification of plastics from household waste
3 Infrared Bands of Plastic Materials 6 requires fast scanning techniques in the millisecond range,
3.1 Principles of Vibrational especially if many samples are to be taken for one
Spectroscopy 6 identification on movement. Mainly acousto-optic tunable
3.2 Spectra of Plastics in the Infrared filter (AOTF) spectrometers or grating spectrometers
and Near-infrared Wavelength with diode arrays can be applied. Germanium (Ge)
Range 7 and indium gallium arsenide (InGaAs) detectors with
3.3 The Spectra of Industrial Plastic extended wavelength sensitivity cover the spectral range
Samples 9 of interest. The movement excludes Fourier transform
3.4 Near-infrared Spectra 9 infrared (FTIR) spectrometers with e.g. indium antimonide
3.5 Mid-infrared Spectra 11 (InSb) and mercury cadmium telluride (HgCdTe) diodes,
3.6 Gas-phase Spectra 12 but its application to technical plastics is possible because
4 Identification Measurement Systems 13 these pieces are heavier and can be identified in a fixed
5 Identification and Performance 15 position.
5.1 Identification Algorithms 15 Identification for recycling means a qualitative analysis.
5.2 Applications 17 Simple algorithms such as those forming the differences of
normalized spectra are sufficient for comparing measured
6 Conclusions 18
with stored spectra. The performance of microprocessors
List of Symbols 18 also allows the application of more complex algorithms
Abbreviations and Acronyms 18 such as multivariate analysis or even neural networks. The
Related Articles 19 use of NIR spectroscopy in industrial recycling started with
References 19 application to sorting systems for plastics from household
wastes or hand-held sensors for cable recycling. The MIR
technique still suffers from its sensitivity to harsh industrial
environments and has been used only rarely and needs
Plastics recycling recovers valuable materials to save further development.
natural resources which are limited in the long term.
Reprocessing of the materials requires the identification
of the various types of polymers. Difficulties in applying
physical separation techniques led to the modification of 1 INTRODUCTION
methods of chemical analysis which have to be operated
fast and reliably under harsh industrial environments Plastics are of great importance in our modern industrial
favoring infrared (IR) methods. world. They are used in nearly every industrial branch and
In general, the plastic products to be handled can be can be made from cheap raw materials. A broad variety
separated into two main fractions. Domestic wastes contain of types and blends modified by plasticizers, fillers, and
only five relevant polymers in large quantities. Technical pigments account for various properties required by the
products use a broad variety of polymers containing fillers applications. Moreover, they have a low density (about

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DOI: 10.1002/9780470027318.a2011
2 POLYMERS AND RUBBERS
0.8 – 1.5 g cm 3 ), can be easily processed, formed, and
colored at low temperatures and can be adapted to fulfill
low- and high-grade specifications of packaging materials
and engineering plastics. Owing to their currently high
and still strongly growing production, plastics cause
environmental problems when the materials used have
to be taken care of after the end of life of the product.
Even after decades they do not degrade substantially in
landfill sites. Therefore, plastics recycling has become a
mandatory task today and will remain challenging in the
future.
Recycling of plastics is carried out in different ways,
as shown in Figure 1. Material recycling means that the
material itself is directly reused for the manufacture of
new products. Application with a high technical standard
demands, of course, appropriate identification and sorting
of the various types including important additives,
because mixed plastics can only be processed to low-grade
materials with limited use. This step is also necessary for
the alternatives: raw-material recycling (feedstock), i.e.
the polymer is cracked into its monomers, which are
used for the production of virgin polymer granulates, and
energy utilization, i.e. use of the heat of combustion. In
both cases the used plastic parts have to be characterized
to avoid process instabilities or ineffective processes. In
the case of halogenated materials such as poly(vinyl
chloride) (PVC) or brominated flame retardants, even
the various thermal treatments are suspected to produce
harmful constituents or to corrode the facility.
In conclusion, this means that recycling requires an
effective and reliable separation system. IR spectroscopic
methods have proved to be the most powerful iden-
tification techniques. They fulfill the specifications for
plastics recycling within the framework consisting of
New parts
Processing
Plastics
Production
waste
Recycled
Polymerization types
Value
Monomer Modification
Recovery of
Energy monomer
Incineration
Landfill
Material Raw material Energy
recycling utilization
recycling
Figure 1 Recycling concepts.
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government regulations, amounts and various streams
of plastic waste, economic demands, and technical and
industrial conditions.
1.1 Government Regulations
In the last two to three decades, the awareness of our
environment has grown tremendously. Most countries
are aware of the growing problem of pollution and the
decrease in natural resources. The consequences force
us to economize on these natural resources and to re-
use post-consumer products. Meanwhile, the legislative
authorities in different countries, especially in Europe,
have become aware of these consequences and have
taken action.
One of the most progressive countries in this context
is Germany, where the Packaging Ordinance was intro-
duced in 1991 with the goal of avoiding packaging waste.
This ordinance is based on the take-back duty of packag-
ing materials by trading companies. These companies are
not in a position to take care of professional recycling, so
an organization was founded which is responsible for this
duty, the Duales System Deutschland (DSD). The DSD
marks packaging materials with the so-called Green Dot,
which demonstrates to the consumer that this material
will be recycled and that the manufacturer or trader of
this product has a contract with the DSD.
However, not only the packaging waste from house-
holds is covered by national legislation. In 1991, the first
draft of an Electronic Scrap Ordinance was published in
Germany. Since then there have been years of discus-
sion between all stakeholders involved. The first Member
States of the European Union (EU) have already issued
producer responsibility legislation, and others are prepar-
ing corresponding regulations or seem to be waiting for
general guidelines given by the EU. The current status of
the EU Member States’ legislation on take-back of waste
of electrical and electronic equipment is as follows:
Use
ž (draft) legislation already developed or adopted:
Austria, Denmark, Germany, The Netherlands, Swe-
den, Switzerland;
Post-consumer ž draft legislation under development: Belgium, Fin-
products
land, France, Italy, Norway, United Kingdom;
Collecting
sorting ž no significant official steps taken: Greece, Ireland,
dismantling Portugal, Spain.
separating
Harmonization within the EU is very likely to take
place at the beginning of the next millennium, as it is
already standard in other sectors of waste management
legislation..1/ Product return legislation has also been
Landfill established in Japan, and is under construction in the
USA..2 – 6/ The reason for this legislation all over the
world is simple: consumers want to return used plastic
INFRARED SPECTROSCOPY IN ANALYSIS OF PLASTICS RECYCLING
material and to be assured that it will be recycled in the
most ecological and nonpolluting way.
1.2 Plastics Consumption and Waste
All over the world, plastics production, and hence
consumption, have grown tremendously since World
War II. World production of plastics in 1997 was about
150 million tons..7/ If all these plastics were to be made
as one thread and passed around the earth, it would
have a diameter of about 1.8 m, and if this thread
were to be tied between the Earth and the Moon, it
would have a diameter of about 0.5 m! This demonstrates
the huge amount which is produced year by year. The
world distribution can be seen in Figure 2; 28% came
from North America and 32.5% from Europe. Of the
41 million tons of plastics produced in Western Europe,
the largest part of about 26 million tons was the so-called
standard plastics, which are polyethylene (PE), PVC,
polypropylene (PP), polystyrene (PS), and poly(ethylene
terephthalate) (PET) (see Figure 3). These standard
plastics are mainly used in packaging, which is the
largest application field of plastics today (see Figure 4).
However, other branches of industry are now using more
Rest of world 11.5%
USA 28%
Rest of Europe 17.5%
Italy 3%
France 4% Japan 10.5%
Germany 8%
Rest of south-east Asia 17.5%
Figure 2 World production of plastics.
7 PP
PVC
6
Production (106 t)
5 PE-LD
PE-HD
4 very impressive, but it has to be kept in mind that most
3 of these products are of only low technical value, e.g.
PS
2 PE-LLD
PET
1
0
Figure 3 Distribution of plastic production by plastic types.
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3
Others
21%
Packaging
Agriculture 41%
2%
Automotive
7%
Electronic/electrical
9%
Building
20%
Figure 4 Distribution of plastics according to different
industries.
and more plastics for manufacturing. Some examples of
the variety of applications for plastics are foils, bottles,
cups, window frames, isolation mats, fenders (bumpers),
synthetic fibers, housings for monitors, television (TV)
sets, inline skates, biker helmets, and tools.
In summary, a huge amount of plastics is produced
each year and it is expected that the production and
consumption of plastics will have an annual growth of
4 – 5% per year. This gives rise to the question of what to
do with this material after the end of life of the products
made out of plastics.
There are many recycling operations all over the world
and here the statistics of recycling operations in Germany
will be examined..8/ In 1995, about 1 million tons of
plastics were taken for this purpose; 54% came from
post-consumer products and 46% were production or
processing waste. This material was recycled in different
ways; 38% were reused for new self-manufactured
products. This means, for example, that production waste
remaining from injection-molded products, which can
be ground and regranulated, is reprocessed directly,
because the material is well known and has properties
close to those of the virgin material. Some 58% of the
collected plastics was delivered to recycling companies
and 4% went to waste incineration or landfill. The
percentage of old plastics which was recycled to real
marketable products was about 70%. This percentage is
benches or sound-protection walls. The reasons for this
low-level reuse will be given in the next section.
1.3 Economic and Technical Demands
Landfill or incineration is in nearly every case cheaper
than recycling of mixed plastics. However, there is a
4 POLYMERS AND RUBBERS
solution for an economic recycling operation which is
based on the reuse of high-quality polymers for high-
end applications to recover the real value of the plastic
material. If the plastics have to be used at a similar
grade to the end-of-life product, the various types of
polymers need specifying and important additives and
fillers have to be identified and sorted out of the waste
stream of mixed materials. Only then is rigorous repro-
cessing to high-tech applications possible, because even
small quantities of impurities could spoil the quality of
the final product. Only sophisticated diagnostic tools can
fulfill the separation requirements. They have to mea-
sure directly the chemical composition or the structure of
the polymer and the other constituents. Other physical
methods, e.g. based on the density, thermal conductiv-
ity, or dielectric properties, failed in the separation of
polymers, especially polymers from technical applica-
tions, with sufficient purity. Therefore, various standard
methods of chemical analysis have been discussed in
the past whereas qualitative or semiquantitative results
are sufficient. Extensive investigations were performed
using X-ray fluorescence, X-ray diffraction, pyrolysis mass
spectrometry, laser breakdown spectroscopy (LBDS), IR
spectroscopy, etc.
The identification methods have to guarantee a high
throughput to provide economic operation. The instru-
ments have to work on-line, fast, and reliably in harsh
industrial environments. They are often operated auto-
matically or by unskilled staff and should not need
much servicing. On the other hand, the instruments have
to identify samples which may be lacquered, partially
covered and polluted, deformed, and not precisely posi-
tioned. The recorded signals are of a quality far removed
from laboratory standards. Also considering these con-
straints, the results obtained favor IR techniques, which
are described in more detail later. However, the objects
of interest, i.e. the plastic pieces to be recycled, must
be examined in more detail, because the different waste
streams require different IR techniques.
2 MATERIALS
The different waste streams of plastic materials have
to be characterized with respect to volume, type, and
identification requirements, because there are consider-
able differences between, e.g. packaging materials from
household waste and technical plastics in audio and video
appliances (e.g. portable stereos, video recorders, hous-
ings of TV sets), automotive parts [fenders (bumpers)],
telecommunication equipment (e.g. telephones, mobile
phones, fax machines) and data processing facilities (e.g.
copying machines, computers).
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2.1 Waste Streams
In general, the plastic products to be handled can be
divided into two main fractions:
ž the packaging materials mainly in domestic (house-
hold) waste;
ž the plastics used in technical equipment.
Domestic waste contains about 5 – 10% plastics,.9/
consisting of bottles, beakers, foil, etc. These consist
predominantly of five relevant polymers, PE [high-density
polyethylene (PE-HD); low-density polyethylene (PE-
LD); linear low-density polyethylene (PE-LLD)], PP,
PS, PET, and PVC,.9/ which have only to be identified
and sorted. In Germany, for example, about 535 000 t
of packaging materials from household wastes were
collected in 1996 and sorted by the DSD..10/ Up to now
these plastics parts have been mainly sorted from the
waste manually and therefore no differentiation between
the different polymers is implemented. However, these
plastics, apart from some special-purpose formulations,
contain relatively small amounts of additives and hardly
any fillers. The pieces are dyed in a broad variety of
colors and can contain print and labels on the surface.
Screw caps are often made of a different material from
the accompanying bottle. Nevertheless, a well-processed,
thoroughly graded pure recyclate can closely approach
the quality of virgin materials. Owing to the low weight of
the materials (60% have a weight of less than 10 g),.10/ the
identification has to be very fast to guarantee a relevant
and economic throughput. In medium-sized recycling
enterprises, the total waste throughput is in the range
of about 500 kg h 1 , which corresponds to a throughput
of about 42 000 pieces h 1 assuming a medium weight of
12 g. This would demand an identification rate of at least
12 parts s 1 . Taking into account the higher price to be
obtained for sorted pure plastics, an identification rate of
a few parts less per second is actually still acceptable for
recyclers. However, this high identification rate means
that the plastic pieces have to be identified while moving,
e.g. on a conveyor belt.
Compared with the above-mentioned standard poly-
mers, technical products use a much broader vari-
ety of plastics, e.g. acrylonitrile – butadiene – styrene
(ABS), polycarbonate (PC), poly(oxymethylene) (POM),
styrene – acrylonitrile copolymers (SAN), polyamide
(PA), polybutadiene (PB), poly(butylene terephtha-
late) (PBT), polyurethane (PU), poly(methyl methacry-
late) (PMMA), poly(phenylene ether) (PPE), and
styrene – butadiene (SB). In the case of PA there has also
to be a differentiation between the various modifications,
the most important being PA6, PA66, PA11, and PA6/12
(the numbers indicate the number of different conden-
sation units). These polymers differ in the configuration
INFRARED SPECTROSCOPY IN ANALYSIS OF PLASTICS RECYCLING
of the two monomers involved. In addition to the pure
polymers, there are also many polymer blends such as
ABS/PC and SB/PPE. These blends are intended to com-
bine the different properties of the pure polymers to give
a new material with advanced properties. For these poly-
mer blends also different amounts of ingredients have to
be taken into account.
To the basic polymers there are added numerous
additives and fillers. Fillers include reinforcing materials
such as glass or carbon fibers to increase the stiffness of
polymers. However, other fillers such as talcum, chalk,
titanium dioxide (TiO2 ), and calcium carbonate (CaCO3 ),
are also used to increase the volume with materials
cheaper than the polymer itself. Other additives include
dyes (especially carbon black in the automotive and
consumer electronics industries), plasticizers, pigments,
stabilizers, flame retardants (mostly based on halogens),
and other additives necessary for processing or modifying
material properties. The surfaces of the materials are
often lacquered or treated by special techniques to create,
e.g. specular effects or roughness. However, heavy metals
such as lead (Pb), cadmium (Cd), chromium (Cr), and
mercury (Hg) are also often found in post-consumer
products.
An example of the combination of many of these
components is a printed circuit board. It consists normally
of glass fibers, unsaturated polyester, or phenol resins and
contains polybrominated aromatic carbon hydrates as
flame retardants and often heavy metals such as cadmium
and antimony trioxide as synergists. In many cases the
surface is lacquered and partially coated by metals. All the
main constituents have to be identified to allow economic
recycling.
Owing to the higher weight of technical plastics
compared with packaging materials from domestic waste,
the identification rate can be lower. A normal TV set
has a weight of about 27 kg. The pure plastic material
(without printed circuit boards) constitutes about 3 kg..11/
Assuming an average weight of only 500 g for a plastic
piece, an identification rate of only 1 part s 1 would
result in an overall throughput of 1.8 t h 1 . However,
all important components have to be identified.
2.2 Methods of Analysis
Summarizing, the information which is necessary for
recycling of plastic waste comprises:
ž the main polymer and composition in the case of
blends;
ž main additives such as plasticizers, flame retardants,
etc.;
ž fillers and reinforcing fibers;
ž heavy metals such as cadmium (Cd) or tin (Sn).
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The most promising methods to obtain this information
are spectroscopic ones because they measure directly the
chemical composition or the structure of the polymer and
the other constituents. From the current point of view,
the most successful analytical methods are:
ž NIR spectroscopy;
ž MIR spectroscopy;
ž laser-induced pyrolysis spectroscopy (LIPS) or
LBDS;
ž sliding spark spectroscopy;
ž pyrolysis/mass spectrometry;
ž pyrolysis/IR spectroscopy;
ž X-ray fluorescence spectroscopy;
ž X-ray diffraction.
NIR, MIR and pyrolysis/IR spectroscopy will be
described in detail later.
Using LIPS, a high-power laser is focused onto the
plastic surface under investigation and generates a
plasma plume, which is observed by an ultraviolet/visible
(UV/VIS) spectrometer delivering information about the
vaporized and ionized atoms. Therefore, this method
enables one to identify atoms, predominantly metals
(especially heavy metals), chlorine and bromine as
indicators for halogenated flame retardants, and silicon
pointing to glass fibers as reinforcing material.
Pyrolysis/mass spectrometry uses a mass spectrometer
to detect vaporized and ionized molecules and atoms
which are produced by a heat source. The main disad-
vantage is that the material has to be transferred to a
vacuum by capillary tube, which tends to become plugged
by impurities.
X-ray fluorescence is mainly used for the identification
of PVC plastics, because it is sensitive to heavy atoms
such as chlorine and insensitive to light atoms such as
carbon and hydrogen, which are the main components of
polymers.
X-ray diffraction analyzes the crystal structure of
materials so it is limited to polymers which crystallize
in sufficient amounts.
Particularly important characteristics of the methods
include:
ž selectivity with respect to polymers and plastics
additives;
ž response rate, repeating rate of the measurement;
ž penetration depth into the material to be detected;
ž sensitivity to disturbances and contamination;
ž user friendliness, ease of automation, and costs.
Only the IR techniques and X-ray diffraction deliver
direct information on the polymer and are favored for
identification. Some of the requirements of recycling can-
not be fully met by these methods, e.g. the identification
6 POLYMERS AND RUBBERS
of metals, heavy metals, and their compounds. Especially
in the case of plastics from technical products the iden-
tification will possibly require a combination of methods
of analysis. The combination of, for example, an IR tech-
nique with LIPS or LBDS could be a solution for technical
plastics.
3 INFRARED BANDS OF PLASTIC
MATERIALS
The main polymers, important additives such as plas-
ticizers and flame retardants, and gaseous pyrolysis
products in the gas phase are mainly composed of carbon,
hydrogen, oxygen, and nitrogen. The polymers comprise
aliphatic (e.g. PE) and aromatic structures and various
combinations (e.g. PS). Therefore, predominant bands
arise from the fundamental vibrations of the related sub-
molecular groups and their overtones and combination
bands.
3.1 Principles of Vibrational Spectroscopy
The interpretation of vibrational spectra assumes the
molecules to be oscillators which are excited by absorbing
IR radiation. In a classical description (Equation 1) the
frequencies n of an oscillator which consists of two atoms
of masses m1 and m2 are derived from a force constant f
and the reduced mass µ:
s molecular nitrogen (N2 ), molecular oxygen (O2 ), sodium
1 f m1 m2
nD µD .1/
2p µ m1 C m2
Following a quantum mechanical description, the energy
levels of the oscillator (Equation 2) are characterized by
the quantum number n:

where Equation (4) holds:
Evib D hn n C 12 n D 0, 1, 2 .2/
In the case of small molecules with the possibility of
rotation (e.g. in the gas phase), each vibrational energy
level is split up by the energy levels Erot of the quantum
mechanical rotator assigned to the molecule. The masses
m1 and m2 are given by the related atoms and the force
constant f by the chemical bondage between them. The
simple relationships (Equations 1 and 2) explain that the
combination of atoms lead to distinguishable absorption
spectra of different molecules.
However, the absorption and emission of real
molecules are more complicated. The complex molecules
especially of long polymeric chains are assumed to build
a system of coupled oscillators: The rigorous deriva-
tion of the absorption bands requires a sophisticated
mathematical treatment. Various effects must be taken
into account, e.g.
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ž the oscillators of real molecules are inharmonic,
the energy levels are modified with respect to
Equation (2) and allow transitions between various
vibration modes;
ž strongly and weakly coupled molecular groups of
atoms;
ž the true motion of the atoms is composed of normal
modes of vibration of these groups;
ž group theory determines the modes to be observed,
depending on the symmetry of the groups.
The molecules absorb photons of energy Evib (Equa-
tion 3) from the electromagnetic field of radiation corre-
sponding to the energy levels of the normal modes and
the combinations of them, thus forming IR spectra:
Evib D hnphoton D hni hnj .3/
The electromagnetic fields interact directly only with
polarized molecules, so causing the strong IR bands and
the intensities to be proportional to the square of the
derivative dipole moment with respect to the coordinate
of the normal vibration mode. An effect of second order,
the Raman effect (which is not discussed further here),
is encountered if the radiation field interacts with the
dipole moment which was transiently induced by the
electromagnetic field itself. Molecules which reveal a
fully symmetric distribution of the electrons such as
chloride (NaCl) or potassium bromide (KBr) show no
permanent dipole moment, and are inactive with respect
to IR radiation.
To describe the spectra of molecules in the IR
region, the vibration frequencies n (s 1 ) are expressed
by wavenumbers nN (cm 1 ) and/or wavelengths l (µm)
n 1
nN D D .4/
c l
The wavelength of IR radiation ranges from 700 nm
to 50 µm, corresponding to wavenumbers from 14 000 to
200 cm 1 . Wavelengths up to 2.5 µm are assigned to the
NIR and wavelengths from 2.5 to 20 µm to the MIR
region.
The IR radiation of intensity I penetrating a material
of thickness x is diminished by I by the vibrations
with absorptivity a of component concentration cŁ fol-
lowing the simple Beer – Lambert – Bouguer relationship
(Equations 5 and 6):
I D acŁ Ix .5/
I acŁ d
TD De .6/
I0
INFRARED SPECTROSCOPY IN ANALYSIS OF PLASTICS RECYCLING
The transmittance T describes the response of the
material with a thickness d related to the initial radiation
intensity I0 . It is often expressed as a percentage, which
means that T is multiplied by 100. Forming the logarithm
of T, the absorbance acŁ d is obtained, which is linear in
concentration and sample thickness (Equation 7):
acŁ d D ln I ln I0
A sample reflects light owing to various effects. For
example, light is partially reflected at phase boundaries of
different materials (e.g. air – solid sample) and from the
substrate. It is scattered at inhomogeneities, impurities,
and additives in the sample and gives rise to diffuse
reflectance. The Kubelka – Munk theory models the
diffuse reflection described in detail, e.g. by Kortüm..12/
The specular reflectance applied at small angles of
incidence is obtained from the sample surface, and is
governed by dispersion in the dielectric material. The
evaluation of the spectra obtained has to account for the
complex refractive index by applying a Kramers – Kronig
transformation.
3.2 Spectra of Plastics in the Infrared and Near-infrared
Wavelength Range
As mentioned above, plastic materials consist of the
macromolecular polymers, fillers, plasticizers, and impor-
tant additives such as flame retardants. Engineering
plastics also include fiber-reinforced composites and
polymeric resins and the organic constituents are predom-
inately composed of C, H, O, and N. The constitution of
the polymers comprises aliphatic [e.g. PE (CH2 /x , PVC]
and aromatic parts (e.g. PS) in various combinations:
Structure (1), PE; Structure (2), PS; Structure (3), PVC;
Structure (4), TBBA (tetrabromobisphenol A).
The interpretation of the spectra of complicated
molecules is based on the concept of group frequencies. It
(1)
(2)
Br
Cl Cl
HO
Cl Cl Br
(3)
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assumes that submolecular groups of atoms are coupled
weakly to other submolecular groups. The absorption
bands of these groups are called characteristic bands as
they always appear at the same wavelength position,
only slightly modified by the weak interaction with
neighboring groups. The bands characteristic of the
individual molecules are called ‘‘fingerprint’’ bands.
.7/ The most important bands of organic compounds arise
from the CH, CH2 , and CH3 groups. These vibrations are
built of the fundamental modes of motion between C and
H atoms:
ž stretching;
ž in-plane deformation;
ž out-of-plane deformation;
ž wagging;
ž twisting; and
ž rocking.
The fundamental stretching modes of CH arise near
the wavenumber 2900 cm 1 (wavelength 3.4 µm). The
symmetric and asymmetric modes of PE lie at 2930 and
2850 cm 1 . The modes of CH groups neighboring CDC
bonds are found at a higher wavenumber of 3100 cm 1
(3.2 µm), which is also valid for CH groups in aromatic
rings (e.g. PS at 3000 – 3100 cm 1 ). The wagging bands
lie between 1180 and 1350 cm 1 . In chains containing
CH2 the twisting bands appear in the same wavenumber
region. The rocking vibrations cause a characteristic band
for long chains (e.g. PE) at 720 cm 1 . The spectra of a
PE and a PS foil (5 µm thickness) in the MIR region are
plotted in Figure 5(a) and (b) respectively.
Polymers such as PA and PU contain, in addition,
NH groups. The analogous stretching modes of NH
absorb near 3300 cm 1 (3.0 µm). OH bands are found
in polymers such as cellulose acetate (CA) at 3500 cm 1
(2.8 µm) (see Figure 13).
In standard chemical analysis, the ‘‘fingerprint’’ region
begins close to 5 µm and extends to longer wavelengths
and shows a broad variety of bands of various origins,
including especially bands with other elements such as
Cl (e.g. in PVC). Important groups for identification are
those of C C, CDO, C O C, C N, etc.
Gaseous species with low molecular weight show
vibration band profiles broadened by rotation in low
resolution. At better resolution a large number of
rotational lines accompany the vibrational lines.
If the submolecular groups of polymers were to
build perfect harmonic oscillators, there would occur
CH3 only transitions between adjacent energy levels of the
Br fundamental modes. Combinations of different normal
CH3 modes would be forbidden. The inharmonicity of the
OH
molecular oscillators allows the appearance of overtones
Br
and combination bands. They arise when the energy of an
(4) absorbed photon is used for two or more energy quanta
8 POLYMERS AND RUBBERS
PE
4000 3000 2000
(a) Wavenumber (cm−1)
PS
4000 3000 2000
(b) Wavenumber (cm−1)
Figure 5 MIR transmission spectra of (a) a PE and (b) a PS
foil.
of the same normal mode or is split up for the excitation
of two or more different normal modes. However,
the absorbances of the overtones and combination
vibrations are still strongly reduced compared with the
fundamental vibrations. This effect is shown by the
transmission spectrum of a PE/PP foil in Figure 6, where
the first overtone is compared with the intensity of the
fundamental mode which is in saturation.
In the NIR wavelength region, the vibrational bands are
mainly generated by the overtones of stretching vibrations
of groups containing hydrogen and combinations of these
stretching vibrations with wagging and/or rocking vibra-
tions. This is obvious from Equation (2), which indicates
that the bands where atoms of low weight are involved
appear at shorter wavelengths in the IR spectrum. A
rough estimate of the wavenumber positions of the over-
tones and combination bands is obtained by adding the
wavenumbers of the participating fundamental modes.
The first overtone of the CH stretching mode appears
near 1.7 µm and the second near 1.2 µm. Comparable
to the fundamental vibration, the overtones are also
observed at shorter wavelengths if the CH functional
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1st overtone
band
1000
Combination
1st overtone band
band
6200 6000 5800 5600 5400
Wavenumber (cm−1)
Fundamental
1000
10 000 8000 6000 4000 2000
Wavenumber (cm−1)
Figure 6 Transmission of an industrial PE/PP foil containing
predominantly PE in the MIR/NIR spectral region, showing
weak overtones and combination bands in the NIR spectrum
(inset).
group is in the neighborhood of groups such as CDC or
in an aromatic C C bond. For example, the aromatic
CH band of PS or PMMA arises at 1.675 µm compared
with the band of PE near 1.72 µm. Combination bands
lie between the fundamental vibrations and the various
overtones (e.g. 2.3 and 1.4 µm). The first overtone of NH
is located near 1.5 µm and the second near 1.1 µm.
The basic concepts of vibrational spectroscopy are
described here rather crudely and include only aspects
to support the understanding of the classification of
the plastic materials and to emphasize advantages of
wavelength regions or measurement techniques to be
applied. Details are described in standard textbooks of
the theory of IR spectroscopy, especially of polymers [e.g.
Hertzberg,.13,14/ Steele,.15/ Siesler and Holland-Moritz,.16/
and Burns and Ciurcziak.17/ ]. An overview on the broad
variety of polymers can be obtained in collections of
spectra (e.g. Aldrich Library)..18/ The Sadtler Atlas.19/
INFRARED SPECTROSCOPY IN ANALYSIS OF PLASTICS RECYCLING 9

and the Atlas of Buback and Vögele.20/ for NIR spectra

contain only a few spectra of polymers. A comprehensive
collection of a variety of NIR spectra of polymers can PE
also be found in Siesler and Holland-Moritz..16/

3.3 The Spectra of Industrial Plastic Samples

PP
Solid samples of organic compounds, especially their
fundamental vibrations, absorb MIR radiation strongly.
In addition, an increase in the thickness of the material
to be penetrated by the radiation leads to an exponential PVC
decay of the transmitted intensity, as is obvious from
Equations (6) and (7). Therefore, in the laboratory mainly
thin films of thickness well below 100 µm or diluted
samples in inactive material, e.g. KBr, are investigated PS
to avoid saturation effects. The MIR spectral region can
be applied to materials with small penetration depths
of radiation. For example, fillers, pigments, and fibers PET
can reduce the pathlength of radiation drastically by
absorption, reflection, and scattering. This is especially 1.0 1.3 1.6 1.9 2.2
true for carbon black, which is an important filler for (a) Wavelength (µm)
black plastics, and strongly absorbs radiation of a broad
wavelength range (blackbody radiation) already close to
the surface..21 – 23/
ABS
3.4 Near-infrared Spectra
In the NIR spectral range, the overtones and combi-
nation bands absorb orders of magnitude (10 – 100) less
light when compared with the fundamental vibrations. PC
Therefore, this wavelength region between 1 and 2.5 µm
(wavenumber 10 000 – 4000 cm 1 ) is appropriate for ana-
lyzing bulky materials in reflection and transmission when PMMA
radiation penetrates a few millimeters into the material.
The situation is fairly simple in the NIR region where
mainly diffuse and partially regular reflection and super- PA
imposed transmission from substrates opposite to the
illumination can contribute to the spectrum.
There is no need to distinguish between the different
contributions to the spectra because all give rise to
a transmission-like spectrum. For identification only PU
qualitative spectra are needed. Therefore, in the figures 1.0 1.3 1.6 1.9 2.2
only transmission-like spectra are plotted. Owing to
the strongly varying conditions in real identification (b) Wavelength (µm)
measurements the ordinate is arbitrary as no clear Figure 7 NIR spectra of (a) five plastic materials mainly
correlation with the illumination I0 is possible in many present in household wastes and (b) five plastic materials
cases. These properties have attracted much attention to present in electronic product wastes, recorded with a scan speed
apply NIR spectroscopy to plastic recycling..24 – 55/ of 150 nm ms 1 .
Qualitative reflection spectra of various plastic mate-
rials are shown in Figure 7(a) and (b), recorded with band), 1600 – 1800 nm (first overtone of CH stretching
an AOTF spectrometer from engineering plastics. The mode), and 2150 – 2500 nm (combination band). The CH
polymeric samples differ in the structural composition of bands show a significant complex shape depending on
aliphatic and aromatic groups. The CH bands absorb in the molecular structures which allow a clear identifica-
the wavelength regions 1100 – 1250 nm (second overtone tion of, e.g. PE, PVC, PP, PS, ABS, PET, PC, PBT, and
of CH stretching mode), 1300 – 1450 nm (CH combination others..16,17,19,20,24 – 31,34 – 46/

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10 POLYMERS AND RUBBERS

There are only a few functional groups of molecules 120

without hydrogen which show strong NIR absorption, PE
e.g. CO. CO bands can be observed at 1900 – 2000 nm 100
and are found, e.g. in the spectra of PMMA, PET and
PC..16,17,19,20,24 – 35/ 80

Intensity
NH groups are important in polymers such as PU
and PA and the related bands appear distinctly in the 60
spectra. The first overtone dominates near 1500 nm and
overlaps the CH combination band at this position and a
40
combination band is observed near 2050 nm.
The different polymers can be distinguished clearly, as
20
proved by using multicomponent analysis. The plastics
from domestic wastes mainly consist of various types
of bottles, beakers, foils, etc. and are made of the five 0
polymers PE, PP, PS, PET, and PVC, the last being used 1.60 1.65 1.70 1.75 1.80
in decreasing amounts. Each piece is produced as a nearly (a) Wavelength (µm)
homogeneous material with thickness between 100 µm
and 1 mm, contains only few additives, and gives rise to 200
spectra of good quality and high intensity in the NIR 175 PVC
region. Dyes and prints do not substantially distort the
spectra. Therefore, they differ strongly from engineering 150
plastics. They can be reliably identified by a single band in
125
Intensity

the NIR spectrum, e.g. by the CH overtone between 1600

and 1800 nm if engineering plastic types are ignored (see 100
Figure 8). Spectra of moving bottles or beakers measured
with scan rates of 200 nm ms 1 are plotted in Figure 9(a) 75
and (b). Extending the wavelength range from 1.1 to 1.8 or
50

25
PE PP 0
1.60 1.65 1.70 1.75 1.80

(b) Wavelength (µm)

Figure 9 First overtone of CH stretching mode of bottles and
beakers passing the sensor head of an AOTF spectrometer at a
speed of 1 m s 1 (scan rate 200 nm ms 1 ). (a) PE; (b) PVC.
PS PVC

even to 2.3 µm, nonblack engineering plastics containing

fillers and additives (present in higher quantities) can also
be identified (see Figure 7). Figure 10 shows NIR spectra
in the range of 1.1 – 1.8 µm and demonstrates that a flame
retardant TBBA could be identified in a nondyed ABS
PET PMMA granulate. Also the plasticizer in soft PVC, which is often
a phthalate, can be detected owing to its aromatic band.
The processing and the surface treatment influence
the spectra to be obtained from plastic materials. Fillers
also affect the spectra strongly and can absorb, reflect,
and scatter NIR light. These effects result in baseline
1.6 1.7 1.8 1.6 1.7 1.8 shifting and twisting. The highly transparent plastics
Wavelength (µm) PMMA, PC, and PE show flat baselines. PP often contains
inhomogeneities which scatter the light. Fillers such as
Figure 8 First overtone of plastics predominantly found in glass fibers, chalk, talcum, and pigments also scatter light.
household waste. The scattering follows Mie’s law, which means that it

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INFRARED SPECTROSCOPY IN ANALYSIS OF PLASTICS RECYCLING 11

NIR spectral range is inapplicable owing to the reduced

penetration depth of radiation into these materials. The
MIR spectral range is appropriate for technical plastics
ABS + flame retardant
in cases when the plastics contain high concentrations
of glass fibers or fillers which reduce the transparency,
especially in the case of black materials..58 – 80/
The spectra are comparable to normal reflectance
spectra, revealing the bands of fundamental vibrations
of CH and NH stretching motion at 3.3 and 3.4 µm
and the highly specific bands from the ‘‘fingerprint’’
TBBA region at wavelengths above 5 µm, including also CC,
CDO, C O C and CX groups (X D end group) or
chain segments. Many spectra of samples collected
from used engineering plastics can be found in the
literature..45,58,66,67,80/ Additives for processing.81/ and
those present in higher amounts such as plasticizers
and flame retardants can also be analyzed via the MIR
ABS + 12% TBBA bands.
Carbon black is used to obtain black plastic material.
In this case the penetration depth of radiation reaches
1.3 1.4 1.5 1.6 1.7 1.8 only to the micrometer range. If thin foils are measured,
Wavelength (µm) a wave-like structure generated by internal interfer-
ences modulates the baseline of the spectrum (see, e.g.
Figure 10 NIR spectrum of ABS and the flame retardant Kampffmeyer and Pfeil.82/ ). Spectra from reflection mea-
TBBA, indicating that about 12% TBBA is present in the surements are more complicated. Different effects can
plastic.
overlap and distort the spectra (see Figure 11): The
reflected light can be composed of specular reflectance
increases strongly towards shorter wavelengths, which
from the surface, diffuse reflectance from pigments and
even allows an estimation of particle size. Blazing effects
inhomogeneities from the interior, surface scattering,
on the surface reflect light in special directions and can
and even transflectance..21 – 23/ The band peaks of the
complicate light detection. These effects also result in
specular reflectance spectra show a shape like a deriva-
baseline shift and twisting. Thin, transparent lacquers
tive spectrum, owing to refractive index dispersion.
and prints (<10 µm) do not prevent the acquisition of
A Kramers – Kronig transformation.56,57/ produces peak
useful spectra.
shapes similar to ‘‘normal’’ absorption index spectra,
which can be compared with spectra obtained by well-
3.5 Mid-infrared Spectra defined sample preparation. Spectra of two important
In the case of black plastics which are often used, for black engineering plastics are plotted in Figure 12(a)
example, in audio, video, and automotive applications, the and (b), showing derivative-like peak shapes of the raw

Specular Diffuse
reflection reflection
Transflectance

Surface
Lacquers, reflection
surface layers

Inhomogeneities

Pigments, fillers,
reinforcing materials, etc.

Matrix material
Reflecting substrate

Figure 11 Scheme of the various effects that contribute to reflection spectra.

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12
PBT
Kramers−Kronig transformed
Reflection
4000 3000 2000 1000
(a) Wavenumber (cm−1)
ABS
Kramers−Kronig transformed
Reflection
4000 3000 2000 1000
(b) Wavenumber (cm−1)
Figure 12 MIR spectra of (a) PBT and (b) ABS as examples
of industrial polymer samples.
spectra and those obtained after Kramers – Kronig trans-
formation. In addition, these diagrams show that defects
in the spectra indicate the distorting influences described
above. Figure 7(a) and (b) show the wave-like struc-
ture found in the spectra of thin foils. A comparison
of the spectra of black CA from a thin foil (5 µm) and
bulky material is shown in Figure 13 together with the
Kramers – Kronig transformation of the latter. Many spec-
tra obtained from important engineering plastics used in
cars and audio and video products can be found in the
literature..56,64,65/
If the main polymer has to be identified and if
copolymers do not have to be sorted out, the bands
near 3.4 and 3.5 µm are sufficient for identification. A
detailed analysis including the determination of additives
such as the plasticizers, special fillers such as barium
sulfate (BaSO4 ), and polybrominated flame retardants
(e.g. in PBT or ABS) requires the measurement of
the ‘‘fingerprint region’’. Also the black plastics show
more intense bands in that wavelength region. For some
blends (e.g. ABS/PC and PBT/PC) and copolymers, even
semiquantitative results can be derived. Materials of
similar composition such as PA6, PA66, and PA12 can be
distinguished.
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POLYMERS AND RUBBERS
Absorption
Kramers−Kronig
transformed
Reflection
4000 3000 2000 1000
Wavenumber (cm−1 )
Figure 13 MIR spectra of CA: absorption, Kramers – Kronig
transformed reflection, and reflection spectra.
The spectra in the MIR region are even more influenced
by pollution and lacquers than those in the NIR region.
The measurement of reliable spectra from the bulk
polymer requires surface cleaning and treatment. It is
recommended to remove the surface layer and to treat
the measuring spot of the material.
3.6 Gas-phase Spectra
The treatment of materials by various heating methods,
such as heating by contact with hot devices, flash heating,
or shock heating, produces evolved gases. These are
composed of vapors, fragments, and oxidation products
of the substance under investigation. The application of
controlled heating or pulse heating in air or in closed
sample cells is established as a method to analyze the
composition of the material and to investigate its thermal
behavior..83/ In industrial environments also vapors and
fragments of pyrolyzed pollutants, fillers, and additives
will overlap the desired gases of the main polymers. In
general, the resulting spectra should be indicative of the
polymer under investigation but detailed studies on this
technique are ongoing..84,85/
Gaseous species of low molecular weight show vibra-
tion frequencies of similar groups such as condensed
substances. The rotational lines lead to strong broadening
INFRARED SPECTROSCOPY IN ANALYSIS OF PLASTICS RECYCLING
of the vibrational lines if measured at low wavelength res-
olution. At higher resolution a large number of rotational
lines accompany each vibrational line. In air, water vapor
and carbon dioxide from the environment or from partial
oxidation often overlap or even dominate the spectra in
the MIR region. The MIR region is useful for analyz-
ing gas phases, because the low density or low species
concentration would require very long pathlengths if the
overtones or combination vibrations were applied (see
the description of the principles of IR spectroscopy).
4 IDENTIFICATION MEASUREMENT
SYSTEMS
The standard instruments to measure the NIR and
MIR spectra of solid or gaseous samples have been
widely used in laboratories for detailed chemical analysis.
Applications in chemical engineering for on-line/in-line
measurements for process control are increasing contin-
uously. The original instruments were not adequate to
work under the conditions of rapid qualitative analy-
sis in an industrial environment where the identification
systems have to be operated for recycling of plastics.
These conditions required the development of new optics,
spectrometers, photodetectors, and data evaluation algo-
rithms or at least substantial modification of standard
equipment. Appropriate components were not commer-
cially available when the activities started at the beginning
of the 1990s.
The identification of plastics from household waste
requires fast scanning techniques, especially if many
spectra are to be sampled for the identification of
one piece while moving. Full spectra, possibly of a
limited wavelength region, have to be acquired in a few
milliseconds from materials of good spectral quality at
a thickness of 100 µm– 1 mm. These constraints favor
the NIR spectral range. Although some investigations
are based on Fourier transform near-infrared (FTNIR)
spectrometers,.34 – 36/ measurement during movement of
the sample makes it difficult to apply. Mainly the following
spectrometer types are used:
ž AOTF spectrometers;.24 – 33,48,49/
ž grating spectrometers with diode arrays;.37 – 46/
ž reference sample absorbance at characteristic wave-
lengths..53 – 55/
These methods allow high scan rates of sufficient spectral
elements in the range of milliseconds and suitable
wavelength resolution. They also fulfill the criteria of
robustness in a harsh industrial environment.
The AOTF has only scarcely been used in laboratory
equipment so it is described here in more detail. It uses
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the anisotropic Bragg effect at large angles. This effect
is observed on studying birefringent crystals such as
tellurium dioxide (TeO2 )..86/ Ultrasonic waves generated
by piezoelectric transducers form a grating of different
material densities in the crystal, which diffracts incident
light to an ordinary and an extraordinary beam. If the
frequency of the acoustic wave is changed, the wavelength
changes owing to the constant sound velocity of the crystal
(650 m s 1 ). In Figure 14 the principle of light diffraction
by an AOTF crystal is plotted. The half wavelength
corresponds to the lattice distance, which causes the
Bragg diffraction. Oversimplified, a spectrum is scanned
by an AOTF by varying the distances of the ‘‘grooves’’
and measuring the different wavelengths at a fixed
angle and not rotating the grating (conventional grating
spectroscopy). A detailed theoretical description of the
effect was given by Yano and Watanabe.86/ and Chang..87/
Based on a fast-scanning AOTF spectrometer,.88 – 91/ the
first versions of plastic identification units which met
the requirements were presented at fairs (SENSORS
1988, ACHEMA 1988) and first results were published
later..24 – 27/
Other groups used diode-array spectrometers,.37 – 46/
which are commercially available. The arrays comprise
128 – 1024 diodes which acquire simultaneously the full
spectrum but the signals from the diodes are multiplexed
and fed to a single amplifier. The results obtained are
similar to those obtained by AOTF spectrometers.
The method to analyze the reflected or transmitted NIR
radiation after further transmission through reference
samples is an analogous correlation technique..54,55/ The
evaluation for identification takes into account that the
transmission through an inappropriate reference material
reduces integrated intensity more than that through an
appropriate material.
The NIR spectral range is partially covered by the
following photodetectors. The uncooled germanium (Ge)
photodiode is sensitive up to 1.8 µm and can measure the
first CH overtone at 1.7 µm. Indium gallium arsenide
(InGaAs) detectors record light up to 1.7 µm, and a
TeO2 crystal
Acoustic absorber
White light
Monochromatic (+)
diffracted beam
Traveling polarized
acoustic
wave Zero-order
beam
Acoustic
Monochromatic (−)
Variable rf source transducer
diffracted beam
polarized
Figure 14 Principle of an AOTF.
14
spectrometer using it has to work with the second
overtone and/or the combination band at 1.4 µm. InGaAs
photodetectors are available with extended wavelength
sensitivity to cover the spectral range up to 2.4 µm, but
only recently, and they are expensive, which is important if
arrays are applied. Cooling these types of photodetectors
increases strongly the signal-to-noise ratio, often referred
to as the detectivity, dŁ . Other photodiodes such as lead
sulfide (PbS) detectors are in principle appropriate for
the NIR spectroscopy but are relatively slow.
Photodetectors for the MIR spectral region are pre-
dominantly cooled. For example, the indium arsenide
(InAs) (cut-off wavelength 2.7 µm) and cooled indium
antimonide (InSb) (5.5 µm) photodiodes can also be used
for detection up to 2.5 µm. At higher wavelengths, mer-
cury cadmium telluride (HgCdTe) (14 µm) is a sensitive
detector which is often used. In addition, pyroelectrical
sensors are applied. The cooling is performed mainly by
thermoelectric effects or using Dewar vessels containing
liquid nitrogen.
A typical identification unit for plastics from packaging
materials in domestic waste has an enlarged measuring
area and allows the simultaneous observation of reflected
and transmitted light of moving samples. The light source
consists of several lamps, which illuminate the measuring
area (f D 100 mm) from different directions in order to
increase the probability that an arbitrarily positioned
moving sample reflects directly into the collecting optics,
which could be, for example, a quartz condensing lens
(Figure 15). In Figure 10(a) and (b) a series of spectra
are plotted recorded during the fall of a PE and a PVC
bottle through the sensitive area of the spectrometer.
When the plastic piece enters or leaves the sensitive area
Falling samples:
AOTF spectrometer
Halogen
lamps
AOTF
Optical
fibers
VCO
Hand-held sensor:
Halogen
lamp
Plastic
sample
Figure 15 Scheme of an AOTF spectrometer (right) iden-
tifying falling samples (upper left) and its application for a
hand-held sensor (lower left) VCO D voltage-controlled oscil-
lator.
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POLYMERS AND RUBBERS
of the spectrometer, strong arbitrary deviations of the
baseline are found. During the time interval when the
plastic covers a large area of the sensitive illuminated
zone of the detector head, spectra of similar quality are
obtained and form a bundle of the characteristic band if
plotted in one diagram. For the identification algorithm,
for example, 20 – 50 spectra are used which allow the
elimination of spectra strongly disturbed by unwanted
effects..27 – 32/ For a moving piece the different spectra
are obtained from different spots on it. This increases
the probability of obtaining most of the spectra from the
basic material and not arbitrarily from polluted material
or inactive labels. Water droplets on the sample surface
do not really distort the spectra substantially..92/
The NIR spectral range is also useful for the identifi-
cation of non-black engineering plastics..24,26 – 32,48 – 52/ In
this case, FTNIR spectrometers are also applied..40,51,52/
A typical fiber-optic detector head provides a fixed mea-
suring plane and can be moved by hand or by a robot
to the sample. The light is focused on the sample (focal
area f D 5 mm) by an appropriate optic, e.g. a quartz
condensing lens or an out-of-plane parabolic mirror. A
second optic (e.g. a quartz condensing lens, out-of-plane
parabolic or elliptical mirror or Cassegrainian optic) col-
lects the reflected light at an angle of e.g. 90° relative to the
incident light and transfers it via a fiber optic to the spec-
trometer (Figure 15). The spectra plotted in Figure 7(a)
and (b) were measured by such an identification unit.
The given examples of identification systems are not
the only versions which would work. They only represent
some comprehensive solutions which fulfill the following
requirements:
ž to account for the variable position of the sample and
sample surface;
ž to collect as much light in reflection or transflection
Photodetector of the sample as possible;
ž to deal with samples which are partially contaminated
or covered by labels or undefined materials.
Signal
processing The IR spectral range is adequate to identify engineer-
ing plastics, especially if these are black. Currently, FTIR
spectrometers are used to identify plastics in the MIR
spectral region..56 – 78/
FTIR spectrometers analyze light by measuring the
ID Fourier transformed intensity of a spectrum with the use
result
of a Michelson interferometer or modified versions of
it. The interferogram is obtained by a scanning mirror
and the spectrum obtained by a Fourier transformation.
A scheme of the basic optical configuration is shown
in Figure 16. The main advantage of this technique
arises from the fact that the photodetector receives
light from all spectral elements simultaneously at each
position of the mirror scan. In addition, the radiation
INFRARED SPECTROSCOPY IN ANALYSIS OF PLASTICS RECYCLING
IR
radiator
FTIR spectrometer
Fixed
mirror
Black
Beamsplitter
plastic Moving
part mirror
Photodetector
Figure 16 Operation scheme of an FTIR spectrometer based
on a Michelson interferometer.
to be analyzed does not have to pass an entrance slit
as in the case of a grating spectrometer. However, the
Fourier transform technique is sensitive to changes in
the spectrum during one scan because these changes are
interpreted as a contribution to the complete wavelength
range. In addition, the interferometer configuration has
to be isolated against external mechanical vibrations
or shocks, which is difficult to realize in an industrial
environment. Performing the Fourier transformation
takes time, hence FTIR spectroscopy is slow, especially
if the Kramers – Kronig transformation also has to be
applied. Typically up to 4 s are needed to obtain one
spectrum. Its application to technical plastics is possible
because these pieces are heavier and can therefore be
identified in a fixed position. They allow a throughput
sufficient for economical identification. However, the
identification takes place at one spot on the total plastic
piece. Redundant identification would require multiple
time intervals.
FTIR spectrometers are suitable instruments to identify
plastics in the MIR region, especially in the case of
black plastics, although an AOTF spectrometer was used
recently..45/ Also, if fillers and flame retardants have to be
analyzed, the MIR region, where the full range or at least
the ‘‘fingerprint’’ wavelength range has to be scanned,
gives reliable results.
Identification using FTIR spectrometers is achieved by
measuring the diffuse reflection or the specular reflection.
The sensor optics are completely built by mirrors.
Normally the parallel light beam which has already been
transmitted by the spectrometer is focused on the sample
and the reflected light is then focused on the detector.
Fiber optics are difficult to apply as the fluoride fibers
for the MIR region exhibit many disadvantages (brittle,
low transparency, limited wavelength range, expensive)
which limit their use. Hence the sensor head is normally
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positioned at a fixed position and provides a plane
sensitive area where the sample has to be placed.
The high absorbance of condensed materials in the MIR
region by the fundamental modes is of great advantage for
the identification of technical engineering plastics where
only small penetration depths are possible. However,
surface coatings, pollutants, and moisture also absorb
strongly and can prevent the acquisition of spectra from
the basic material. Lacquers often have thicknesses of
more than 10 µm and can complicate the extraction of the
desired spectrum..56,57/ Consequently, surface cleaning
and repositioning of lacquers or paints as a pretreatment
is needed at the spot of identification. Techniques used
are milling, brushing, etc.
FTIR spectroscopy is also applied to analyze the gases
evolved from pyrolyzed plastic materials..84,85/ The plastic
sample under investigation is heated by some method and
the evolved gas can accumulate in a cell directly above it or
be guided by a tube to an optical cell. The composition of
the gas is analyzed via the transmission spectra recorded
by the FTIR spectrometer. The spectra are specific for the
polymers. The spectrometer configuration can be close to
laboratory equipment.
Heavy metals and types of fillers and flame retardants
are often difficult to identify by IR techniques. Hence it
should be considered whether or not it would be a good
idea to combine the IR analysis with another technique,
e.g. LBDS..31,32,39/
5 IDENTIFICATION AND PERFORMANCE
Identification for recycling means that qualitative spectra
are compared with reference spectra and some algorithm
decides which polymer containing which main additive is
actually to be recognized. Identification by IR techniques
allows a positive sorting because the algorithms search
for the presence of patterns in the spectra definitely
assigned to a specific material. The probability of deciding
correctly can be increased by decreasing the maximum
difference between the reference pattern and the test
pattern, which is the defined upper limit for agreement.
There arises a strong coupling of the handling techniques
of the plastic pieces to be identified, allowing various
rates of throughput and user-defined purity (the quality or
contamination of the samples) of the recovered materials.
Of course, the number of plastic types to be sorted out
has to be limited to those available in the waste stream in
a sufficient volume for further economic processing.
5.1 Identification Algorithms
The identification algorithms were taken from existing
methods of pattern recognition, modeling, and statistical
16 POLYMERS AND RUBBERS

description of data. Taking into account that only
qualitative or semiquantitative information is required
at a high speed, simple algorithms such as forming
the differences of normalized spectra are sufficient
in comparing measured spectra with stored reference
spectra. The performance of microprocessors allows also
the application of more complex algorithms. The simplest
linear methods are described here in more detail.
It is assumed that a spectrum ytest .xi / is measured
at n wavelength positions (i D 1, . . . , n) and compared
with each spectrum of a set of m reference samples
yref,j .xi / .j D 1, . . . , m/. Data pretreatment can comprise
a baseline subtraction, a normalization of the spectra to
0 and 1, and a subtraction of the average of the spectrum
(Equation 8):
can define the level near 1 which is accepted to identify
positively material k and therefore define the purity of
the sorted output. In comparison with Equation (8), least-
squares procedures require a multiplication of two vectors
and of a matrix with a vector. The inverse matrix a 1
can be computed from the reference spectra before the
operation. If a is not singular, the m reference spectra
and therefore also the corresponding plastic types can in
principle be distinguished. A modified version is obtained
by assuming that the tested spectrum is composed of a
linear combination of the reference spectra (Equations 13
and 14):
X
m
y.xi / D aj yref,j .xi / i D 1, . . . , n .13/
jD1

X
n
X
n
  1
cj D jytest .xi / yref,j .xi /j j D 1, . . . , m .8/ aj D ytest .xi / yref,j .xi / j D 1, . . . , m .14/
iD1 iD1

Comparison of the sum of the norm of the difference The plastics are distinguishable if the rank of the
spectra.94/ leads to a fast algorithm which contains only n ð m matrix [yref,j .xi /] 1 is m. Blends are indicated if
additions and subtractions..30/ The decision is made on two or more aj are significantly different from 0. The
the smallest cj obtained for reference yref,j but exceeding procedures described in Equations (9 – 14) follow the
a user-defined threshold ct . Taking into account the outline of Press et al..94/ They allow one also to select the
nonideal samples of used plastics, it is obvious from this wavelength regions needed for a reliable differentiation
procedure that small values of ct produce a high purity of the reference plastics by varying them and testing
of sorted plastic materials and higher values increase the rank of the ak,j and/or yref,j . They were applied
the positively sorted material but with an increased when testing if the above-mentioned types of plastics
number of erroneously identified pieces. The algorithm is are distinguishable within selected wavelength regions.
remarkably stable and reliable also if small differences in However, such a result does not imply that these plastics
the spectra are to be detected. can be distinguished from all other plastic types under
Multilinear regression can be derived by minimizing any conditions.
the sum of squared differences (c2 function) of reference There are various methods available to model NIR
and test spectra with respect to some values aj which are and MIR data which were developed to analyze complex
obtained by differentiating c2 (Equations 9 – 12): mixtures of chemical compounds. The linear ones are
 2 summarized by the multivariate data evaluation concepts
X n X
m of chemometrics where principal component analysis
c2 D ytest .xi / aj yref,j .xi / .9/ (PCA) and partial least squares (PLS) are powerful
iD1 jD1 methods (see, e.g. Martens and Naes)..95/ These methods
  were applied to sorting plastics in household waste and
@c2 X  X
n m
0D D ytest .xi / aj yref,j .xi / yref,k .xk / also for engineering plastics. A nonlinear generalization
@aj of these linear methods using multilayers is the neural
iD1 jD1
networks,.34,35,42 – 46,65/ which have also been tested in
k D 1, . . . , m .10/ some cases together with fuzzy logic concepts..44 – 46/
X
n
In reality, the identification has to be reduced to a
ak,j D yref,j .xi /yref,k .xi /; limited number of plastic types because it is not possible
iD1 to separate all the materials possibly present in the waste
X
n
stream. Strongly contaminated, polluted, or impaired
bj D ytest,j .xi /yref,j .xi / k, j D 1, . . . , m .11/ plastic pieces are better not sorted out because these
iD1
X parts could complicate the subsequent recycling steps.
aj D aj,k1 bk j D 1, . . . , m .12/ In this case, the simple methods work reliably and run
fast enough for on-line identification. A problem arises
When testing a plastic material k, the value of ak when engineering plastics are sorted. They exist in many
should be close to 1 and all others close to 0. The user modifications which also have to be taken into account

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INFRARED SPECTROSCOPY IN ANALYSIS OF PLASTICS RECYCLING
as an extra material. The spectra are dominated not only
by the composition and structure of the polymers but
also by scattering, absorption, light reflection, baseline
variations, and other effects. The analysis then needs the
more sophisticated identification algorithms or requires
extended wavelength regions for acquiring redundant
information.
5.2 Applications
The interest in identification developed in parallel with
the beginning of activity to recycle plastic materials.
Many applications were investigated and realized on an
industrial scale. Some are described here. However, some
technical barriers had to be overcome before starting
broad applications.
In the case of household waste plastics, mechanical
separation (singulation) at adequate rates turned out
to be very difficult. Actually, mainly bottles are sorted,
which are heavier, and sorting about three pieces per
second is state of the art. Efforts are being made to
develop faster singulation, which is difficult if beakers
and damaged pieces are also included. The sorting rates
range up to 5 – 7 pieces s 1 and will increase further
if more experience is available. The NIR technique
itself is faster. As described in detail, the spectrometer
can acquire spectra with sufficient quality in 1 ms and
fast identification algorithms can keep up with it (the
identification of 10 – 12 pieces s 1 with 50 spectra per part
is no problem). In the case of bottle sorting the recovery
rates are fairly high because the material is presorted.
If samples of various sizes and shapes including beakers
from real noncleaned waste streams are sorted, the output
decreases. Labels, dyes, and inscriptions on household
waste did not disturb the identification significantly.
Erroneous identifications can lie below 0.1%. Heavy
contamination reduces the quantity of identified samples
and cleaner materials increase it. The conditions of the
samples depend strongly on the presorting treatment
and the collections, which vary considerably not only
from country to country but also from area to area,
and cannot be described adequately. The evaluation of
results obtained in a single study cannot be transferred
to a general situation. However, it can be estimated that
output results of real applications are of the same order
of magnitude of about 80 – 95%.
Automated dismantling, identification, and sorting
have been applied to medical products, predominantly
tubes and syringes. For recycling, syringes have to be
washed, disinfected and dismantled into their two base
parts: piston and case (tube). NIR spectroscopy identifies
the polymer types before separating them; they are mainly
PE, PP, and PVC..96/
The automotive industries use various types of plastics,
ranging from thermoplastic materials to composites
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17
produced by PU or reaction injection molding (RIM)
technologies. FTIR spectroscopy in the MIR range has
been applied to the identification of dismantled plastic
pieces..51,52,58 – 64,77/ These are mostly covered by lacquers.
The identification procedure requires pretreatment of
the sample surfaces, which could take about 20 s. The
identification lasts about 4 s. Studies with e.g. more than
7000 pieces revealed a purity of significantly below 1%.
The weight of sorted plastic pieces is in the region of
kilograms. Therefore, the time to identify the polymer is
adequate as, in addition, the price of engineering plastics
is higher by a factor up to five or more compared with
packaging plastics. Pyrolysis/IR spectroscopy has also
been applied with success..84,85/
The electric/electronic industries produce mass con-
sumer goods for private and industrial use which contain
plastics in many variations. Plastic housings comprise
the highest volume. In audio and video equipment
the housings are black. In this case the application
of FTIR spectroscopy in the MIR spectral region is
appropriate..58,73/ The results are similar to those for
plastic pieces in the automotive industry. Nonblack plas-
tics are often used in information technologies and data
processing where personal computers are produced in
high volumes. MIR and NIR spectroscopy identify the
polymers with sufficient accuracy and reliability. This is
illustrated by an example analyzing the cases of elec-
tric homeworker tools (not dyed black) with an AOTF
spectrometer for the NIR region..27 – 31/ The identification
error was below 1% (Table 1). The NIR technique was
also integrated into an automated dismantling and sorting
system which treated keyboards of personal computers.
There are other ongoing investigations to treat plastic
material from various industrial branches such as the
building and construction industries and cable industries.
The predominant aspects of identification are related
to the variety of materials and their modifications used
similarly as described in previous sections. Automated
sorting is the objective of many investigations and
progress suffers from the widely varying shapes and sizes
of the products, which have to be taken into account
Table 1 Statistical test of plastic identification using an AOTF
spectrometer with a hand-held sensor head in the wavelength
range 1.1 – 1.8 µm with a 300 ms identification time and
200 scans accumulated at 300 nm ms 1 :.30/ test results for a total
of 810 homeworker tools
Plastic type
PA PP ABS PC PBT Not
identified
Number of 615 16 24 81 47 36
pieces
Error 4 (D PP) 0 0 1 (D PP) 0 5
18 POLYMERS AND RUBBERS

to cover adequate volumes of plastics for economic ak,j matrix built from the spectra of the
operation. reference samples
bk,j matrix built from
the spectra of the reference and test samples
6 CONCLUSIONS c2 sum of squared differences
cj sum of normalized differences
ct threshold value
In the future plastics will be used in many products in
l wavelength (µm)
ever-increasing volumes. Their recycling saves natural
µ reduced mass
resources of raw materials and areas of deposition sites,
n frequency of molecular vibration
and recovers valuable substances.
or photons (s 1 )
NIR spectroscopy has proved to be an appropriate
nN wavenumber (cm 1 )
method to identify the plastics of packaging materials
predominantly found in domestic wastes. The spectral
quality of the plastics to be treated is high, allowing
the analysis of fast-moving pieces at various sensing ABBREVIATIONS AND ACRONYMS
positions. The identification systems can be integrated
into automated sorting lines.
The situation is more complicated in the case of ABS Acrylonitrile – Butadiene – Styrene
engineering plastics. NIR and MIR spectroscopy can solve AOTF Acousto-optic Tunable Filter
the problem of nonblack pieces but MIR spectroscopy CA Cellulose Acetate
requires a pretreatment in most cases. Black plastics DSD Duales System Deutschland
require MIR techniques. Pyrolysis/IR spectroscopy is EU European Union
also applicable to engineering plastics. Integration into FTIR Fourier Transform Infrared
automated disassembly and sorting lines is currently FTNIR Fourier Transform Near-infrared
under development and has been realized only in special IR Infrared
cases. LBDS Laser Breakdown Spectroscopy
LIPS Laser-induced Pyrolysis Spectroscopy
MIR Mid-infrared
LIST OF SYMBOLS NIR Near-infrared
PA Polyamide
ak content of material k in the test sample PB Polybutadiene
cŁ component concentration PBT Poly(butylene terephthalate)
c velocity of light (cm s 1 ) PC Polycarbonate
dŁ detectivity PCA Principal Component Analysis
Erot energy levels of rotations PE Polyethylene
Evib energy levels of vibrations PE-HD High-density Polyethylene
f force constant PE-LD Low-density Polyethylene
h Planck’s constant PE-LLD Linear Low-density Polyethylene
I radiation intensity PET Poly(ethylene terephthalate)
I0 initial radiation intensity PLS Partial Least Squares
mi mass of an atom PMMA Poly(methyl methacrylate)
n quantum number POM Poly(oxymethylene)
T transmittance PP Polypropylene
xi wavelength, wavenumber, or frequency PPE Poly(phenylene ether)
yref,j .xi / spectral intensity of reference sample j, PS Polystyrene
measured at wavelength (wavenumber, PU Polyurethane
frequency) xi PVC Poly(vinyl chloride)
ytest .xi / spectral intensity of the test sample, RIM Reaction Injection Molding
measured at wavelength (wavenumber, SAN Styrene – Acrylonitrile Copolymers
frequency) xi SB Styrene – Butadiene
I difference in intensities TBBA Tetrabromobisphenol A
x, d thickness of material TV Television
a absorptivity UV/VIS Ultraviolet/Visible

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DOI: 10.1002/9780470027318.a2011
INFRARED SPECTROSCOPY IN ANALYSIS OF PLASTICS RECYCLING
RELATED ARTICLES
Polymers and Rubbers (Volume 8)
Polymers and Rubbers: Introduction
Polymers and Rubbers cont’d (Volume 9)
Infrared Spectroscopy in Analysis of Polymer Struc-
ture – Property Relationships ž Near-infrared Spec-
troscopy of Polymers and Rubbers ž X-ray Scattering
in Analysis of Polymers
Atomic Spectroscopy (Volume 11)
Laser-induced Breakdown Spectroscopy
Chemometrics (Volume 11)
Chemometrics ž Clustering and Classification of Analyt-
ical Data
Infrared Spectroscopy (Volume 12)
Infrared Spectroscopy: Introduction ž Infrared Reflec-
tion– Absorption Spectroscopy ž Interpretation of Infra-
red Spectra, A Practical Approach ž Spectral Data,
Modern Classification Methods for ž Spectral Databases,
Infrared ž Theory of Infrared Spectroscopy
Raman Spectroscopy (Volume 15)
Raman Spectroscopy: Introduction
X-ray Spectrometry (Volume 15)
Energy Dispersive, X-ray Fluorescence Analysis ž Struc-
ture Determination, X-ray Diffraction for ž Wavelength-
dispersive X-ray Fluorescence Analysis
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