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Abstract
The technologies for recycling thermoset composite materials are reviewed. Mechanical recycling techniques involve the use of grinding
techniques to comminute the scrap material and produce recyclate products in different size ranges suitable for reuse as fillers or partial
reinforcement in new composite material. Thermal recycling processes involve the use of heat to break the scrap composite down and a range
of processes are described in which there are various degrees of energy and material recovery. The prospects for commercially successful
composites recycling operations are considered and a new initiative within the European composites industry to stimulate recycling is
described.
q 2005 Elsevier Ltd. All rights reserved.
Keywords: A. Polymer matrix composites; A. Thermosetting; E. Recycling
1. Introduction
Thermoset composite materials are used in a wide range of
applications in industries such as automotive and construction.
They come in a variety of forms. At the cheaper end, polyester
resins are combined with short glass fibres and low cost fillers
to produce moulding compounds for applications where high
mechanical properties are not required. For more demanding
uses, continuous carbon fibres and epoxy resins are used for
critical applications in the aerospace industry. In Europe,
approximately 1 million tonnes of composites are manufactured each year [1]. Although there are many successful uses
for thermoset composite materials, recycling at the end of the
life cycle is a more difficult issue. However, the perceived lack
of recyclability is now increasingly important and seen as a
key barrier to the development or even continued use of
composite materials in some markets [2].
1.1. Problems in recycling thermoset composites
The problems in recycling thermoset composites are as
follows.
Thermosetting polymers are cross linked and cannot
be remoulded, in contrast to thermoplastics which can
* Tel.: C44 115 951 3785; fax: C44 115 951 3800.
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1359-835X/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compositesa.2005.05.030
1207
2. Recycling technologies
A number of recycling technologies have been proposed
and developed for thermoset composite materials and these
are summarised in Fig. 1. There are fundamentally two
categories of process: those that involve mechanical
comminution techniques to reduce the size of the scrap to
produce recyclates; and those that use thermal processes to
break the scrap down into materials and energy. Each will
be considered.
2.1. Mechanical recycling
Mechanical recycling techniques have been investigated
for both glass fibre and carbon fibre reinforced composites,
but the most extensive research has been done on glass fibre.
The technique used is usually to initially size reduce the
scrap composite components in some primary crushing
process. This would typically involve the use of a slow
speed cutting or crushing mill to reduce the material to
pieces in the order of 50100 mm in size. This facilitates the
removal of metal inserts and, if done in an initial stage
where the waste arises, the volume reduction assists
transport. The main size reduction stage would then be in
a hammer mill or other high speed mill where the material is
ground into a finer product ranging from typically 10 mm in
size down to particles less than 50 mm in size. Then a
classifying operation, typically comprising cyclones and
sieves, would be employed to grade the resulting recyclate
into fractions of different size [3,4,27,12].
In the mechanical recycling process, all of the
constituents of the original composite are reduced in size
and appear in the resulting recyclates which are mixtures of
polymer, fibre and filler. Typically the finer graded fractions
are powders and contain a higher proportion of filler and
polymer that the original composite. The coarser fractions
tend to be of a fibrous nature where the particles have a high
aspect ratio and have a higher fibre content. A number of
companies have been involved in developing the recycling
activity at an industrial scale, among them ERCOM in
Germany and Phoenix Fiberglass in Canada [3,12]. These
companies base their operations around the two most
common grades of thermoset glass fibre composite material:
Recycling Processes for
Thermoset Composites
Mechanical
Recycling
(comminution)
Powdered
fillers
Fibrous
products
(potential
reinforcement)
Thermal
Processes
Combustion
with energy
recovery
(and
material
utilisation)
Fluidised
bed process
Pyrolysis
Clean fibres
and fillers
with energy
recovery
Chemical
products,
fibres and
fillers
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RC1000
RC1100
RC3000
RC3101
Fibre length
(mm)
Glass content (%)
Bulk density (kg/m3)
!0.25
0.253
315
320
35
45
45
45
670
460
170
400
Table 2
Grades of SMC recyclate from phoenix fibreglass, Inc. (Ref. [3])
Recyclate grade
PHX-200 filler
fraction
MFX milled
fibres
CSX hybrid
fibres
Particle size
14 mm
z12 mm
Glass content
Filler and
organic content
13%
87%
40%
60%
30000
25000
20000
15000
10000
5000
0
0
20
40
60
80
100
1209
1210
28.3
46.7
25
1211
Table 4
Pyrolysis products from SMC (Ref. [29]), expressed as % (weight) of SMC
Temperature
400 8C
500 8C
600 8C
700 8C
Solid yield
(%)
Liquid yield
(%)
Gas yield
(%)
75.2
74.9
73.9
72.6
14.5
14.2
14.9
13.7
10.5
11.0
11.5
12.8
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Table 5
Pyrolysis products from various composites (Ref [31]), expressed as % weight of composite
Composite
Temperature (8C)
Oil/wax yield
(%)
500
45.8
45.7
8.5
500
90.2
8.8
1.0
500
550
550
550
67.4
30.0
44.8
74.4
31.3
59.4
46.8
13.0
1.2
10.6
8.4
12.6
550
83.4
15.0
1.6
Acetic acid
Pyridine-SO3 complex
Phenol
Aniline
p-Toluidine
Isoquinoline
6.1
6.1
5.1
73.9
4.4
4.3
3. Discussion
Mechanical recycling processes are suitable for scrap
composite material which is relatively clean and uncontaminated and from known origin. The technologies
developed produce powder and fibrous recyclates, which
have potential for reuse. However, the powder recyclates
have limited potential for reuse back into the thermoset
compounds from which they originated. Although they are
of lower density, there are other drawbacks to their use in
terms of ease of processing and lower mechanical properties
in the products in which they are used. The fibrous
recyclates have some potential as reinforcement materials,
but they are not as good as the virgin reinforcement, and
there are problems associated with the bonding of the
recyclate with polymers and the tendency for the larger
pieces of recyclate to be stress raisers and act as failure
initiation sites.
The thermal recycling processes have the advantage of
being able to tolerate more contaminated scrap materials.
The fluidised bed process produces a very clean fibre
product, but it is not in the same form as an existing virgin
fibre products. Development work is therefore needed to
identify the ways in which the material can be reprocessed
into cost effective new products. The same is also true of the
fibre products developed from the pyrolysis processes.
These may have varying degrees of char on the recycled
fibres, which may limit the reuse options or require further
processing to remove it. The pyrolysis processes are
generally more complex in principle than the fluidised bed
process but do produce potentially useful organic products
from the polymer. These would need further processing to
Table 8
Gaseous products from pyrolysis of epoxy carbon fibre composite (Ref.
[35])
Product
1-Propene
Water
Sulphur dioxide
Hydrogen cyanide
1-Butene
1,3-Butadiene
Bromomethane
Acetone
Acetonitrile
1,3-Cyclopentadiene
14.7
41.9
10.8
5.5
2.3
5.0
1.4
13.4
2.5
2.6
1213
4. Environmental acceptability
Although the hierarchy of waste management routes
appears to give preference to those recycling routes that
maximise material recovery, the mechanical recycling of
valuable fibres and resins as fillers does not necessarily give
the best environmental return. Pyrolysis process has the
potential to produce chemical feedstocks from the polymer
but these may be difficult to refine from the mixture of
products produced. If a pyrolysis process only produces
chemicals suitable for use as fuels then an energy recovery
process with high quality fibre recovery may be more
acceptable. Only environmental audits of the recycling
routes can identify which are the most acceptable and
although some work has been reported [39] much more
analysis of the recycling processes needs to be done.
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6. Conclusions
A considerable amount of research has been done to
investigate potential recycling techniques for thermoset
composite materials and some of the key work in the area of
mechanical and thermal recycling processes has been
described in this paper. Despite this there is no commercially viable composites recycling activity anywhere in the
world, largely as a result of markets not being available at
the right price for the recycled materials that are produced.
European legislation now requires that recycling routes are
available for composites, as other waste management
methods will not be allowed. The European composites
industry is responding with a European Composites
Recycling Concept to manage waste from composites and
stimulate recycling activities.
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