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Composite Production, Reparation and

Recycling - MEMat

Composites recycling module

2016-2017, Universidade Atlântica

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Paradox:
“Superior mechanical properties can only be gained through
complex structures such as coatings and composites, and this will
be in great conflict with the demands in good separability and
recyclability!”

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Outline
1) Introduction
2) Drivers for composite recycling
3) State of the art in composite recycling:
 Methods
 Commercial initiatives
 Advantages and disadvantages of composites recycling methods;
 r-fibers versus v-fibers; r-FRP versus v-FRP
 Composite recycling in aerospace
 Opportunities of reuse of production waste
2) Remanufacturing of recycled composites using recycled fibers
3) Companies that are recycling composites; Achievements and current issues with recycling operations
4) Recycling composites commercially
5) Challenges for better recyclable composite materials
6) A Vision for the Future…

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Classification of composite materials

Polymer-matrix composites dominate the


market, among which thermosets composites
accounts for > 2/3. However, thermoplastics
composites are growing more rapidly in
recent years.

Global composites production: 10 million tons in 2006


http://www.insee.fr/sessi/4pages/pdf/4p158anglais.pdf

Y. Yang et al., Recycling of composite materials, Chemical Engineering and


Processing: Process Intensification, Volume 51, 2012, 53–68.
http://dx.doi.org/10.1016/j.cep.2011.09.007

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Application areas of composite materials
according to the estimate for the year 2000
http://www.insee.fr/sessi/4pages/pdf/4p158anglais.pdf

FRP have been utilized for more than half a century, mainly in
high performance markets, such as the aerospace, defense,
high performance automobiles (at low volumes) and racing
vehicles.
Just more recently they are penetrating in mass market
products, such as the high volume automotive sector.
The use of composite materials in automotive
industry is increasing very rapidly (construction of body,
interiors, chassis, hoods and electrical components).

Y. Yang et al., Recycling of composite materials, Chemical Engineering and


Processing: Process Intensification, Volume 51, 2012, 53–68.
http://dx.doi.org/10.1016/j.cep.2011.09.007

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fiables

Waste material is produced by the user both during production and


at the end of the component's life.
No reliable hard numbers for advanced composites waste
generation, but already in 1997 the estimate was for ca. 853 tonnes
of scrap carbon fibre prepreg produced in industry.
Regarding the aerospace industry: the estimated manufacturing
waste is in the region of 10-40%, depending on component
complexity, etc.

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Out-of-date pre-preg rolls

Waste sources
Out-of-date pre-pregs Manufacturing cut-offs

Manufacturing cut-offs
Testing materials
Production tools
End-of-life (EoL) components

Yatch mould

EoL aircraft wings

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Cured carbon fiber waste prior to recycling

Recycling Composites Commercially, by Stella Job, REINFORCED plastics SEPTEMBER/OCTOBER 2014. Picture courtesy of ELG Carbon Fibre.

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EoL helicopter rear blade

Courtesy of INAER
Helicopter Portugal

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Why is composite recycling difficult?
 complex composition (fibres, matrix and fillers), i.e. heterogeneous nature of the
matrix and the reinforcement
 crosslinked nature of thermoset resins (which cannot be remoulded),
 their combination with other materials (metal fixings, honeycombs, hybrid composites,
etc.). very limited
industrial
operations
Most of the CFRP waste has been landfilled and the airframe of EoL vehicles has been can be found
usually disposed in desert graveyards, airports, or by landfilling
for recycling
However, these are unsatisfactory solutions … of composite
materials…
Barriers to recyclates commercialization
falta
 Lack of markets,
 High recycling cost,
 Lower quality of the recyclates versus virgin materials

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Drivers for composite recycling:
Turning CFRP waste into a valuable resource and closing the loop in the CFRP life-cycle is vital for the
continued use of the material in some applications, e.g. the automotive industry.

Environmental impact: the increasing amount of CFRP produced raises


concerns on waste disposal and consumption of non-renewable resources.
 Legislation: recent European legislation is enforcing a strict control of
composite disposal; the responsibility of disposing EoL composites is now
on the component’s manufacturer, legal landfilling of CFRP is limited, and
for instance it is required that automotive vehicles disposed after 2015 are
85% recyclable (EU 1999/31/EC; EU 2000/53/EC).
Landfill is a relatively cheap disposal route but is the least preferred waste
management option under the European Union’s Waste Framework
Directive, and opposition to it is expected to increase over the coming
years; it is already forbidden in Germany, and other EU countries are
expected to follow this route.

vertedero

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Drivers for composite recycling (cont.):

Production cost: CFs are expensive products, both in terms of energy


consumed during manufacturing (up to 165 kWh/kg) and material
price (up to 40 £/kg).
Management of resources: demand of virgin (v-) CFs usually
surpasses supply-capacity, so recycled (r-) CFs could be re-introduced
in the market for non-critical applications
Economic opportunity: recycling would convert an expensive waste
disposal into a profitable reusable material.

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Drivers for composite recycling (cont.):
global initiatives

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Drivers for composite recycling (cont.):
global initiatives

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Closed life-cycle for CFRPs
Turning CFRP waste into a valuable resource and closing the loop in the CFRP life-cycle.

v-CFRP component

v-CF CFRP waste


virgen
recycling

r-CF

r-CFRP component
re-manufacturing

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Environmental legislation will help to promote recycling, but long-term
technological developments are needed. Groundbreaking innovations
are necessary in the following three areas:
(1) Materials development for new and easy recyclable composite
materials.
(2) Materials recycling for more efficient and intensified separation and
purification technologies.
(3) Production techniques that can at least partially use the recycled
fibres instead of only new fibres.

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General recycling system
Chain of operations (dependent on one another)
1) availability of the waste composites (“old scrap” and
“new scrap”): limited availability for an economically viable
recycling due to small volume production (compared to
metals and polymers) and long-life products.
2) Collection and transport: collection of EOL vehicles
(including aircrafts) is very well organized, however, due to
their large size, EOL aircrafts need to be dismantled and cut
into smaller sizes for ease of transportation. Collections for
small electronic products and for sports and recreation
facilities is more challenging…
3) Reprocessing – recycling: the “core” of the chain
operation of the recycling system. Application of physical
(mechanical), thermal, or chemical technology, depending
on the type of the composite materials. There is a great
demand for more efficient separation technologies to meet
the requirements for product quality, environmental
regulations and operation economics (processing cost).
4) Market of the recycled products – recyclates: There is
still a lack of market for recyclates, due to the high demand
on the quality and price competitiveness compared to the
virgin composites.
Structure of recycling system for composite materials.

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Composite recycling methods
 Mechanical recycling: involves shredding and grinding followed by screening to separate
fibre-rich and resin-rich fractions for re-use.
 The method is very energy-intensive and the recyclates have relatively low quality.

 Thermal recycling: uses high temperature (between 300 and 1000 °C) to decompose the
resin and separate the reinforcement fibers and fillers. Clean fibers or inorganic fillers are re-
generated, and secondary fuel or thermal energy can be produced through pyrolysis,
gasification or combustion. Fiber
reclamation
The quality of the recovered fibers or filler materials tends to degrade. or fiber
recovery
 Chemical recycling: aims at chemical depolymerisation or removal of the matrix and from the
liberation of fibers for further recycling by using organic or inorganic solvent. composite
 Lack of flexibility and generation of waste chemicals with environmental concerns... Need to
develop cleaner processes (based e.g. on near- and super critical fluid (in particular water)
technology).

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Composites recycling
Mechanical Recycling:

Grinding materials more finely after a first crushing or shredding step into smaller pieces. After this,
different sizes of recyclates can be recovered and separated by sieving into resin-rich powders and fibres
of various lengths that are still embedded in resin.
STEPS:
1st) size reduction of the composite scrap by low speed cutting or crushing (to 50–100 mm)
2nd) further reduced down to 10 mm to 50 m through a hammer mill or other high speed millings for fine
grinding
3rd) the fine particles of the waste composites are classified with cyclones and sieves to fibrous products
(fibre-rich (coarser)) and powdered products (matrix-rich (finer) fractions).
Cutting mills give more homogeneous fiber length distribution and longer fibers than hammer mills
although the cutting blades tend to wear faster

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Thermoplastic matrix composites mechanical recycling
(similar aspects than those for recycling of non-composite thermoplastics!) According to the identification or
visual aspect. Manual task,
Mechanical Recycling: mainly.

Mechanical breakdown into granules is the most obvious Plastic Plastic Grinding
Separation and
recycling method for thermoplastic matrix composites, Product waste
washing
however, fiber breakage induced by grinding and subsequent
processing leads to devaluation of materials properties:
Resin (raw Partially
reduction of tensile strength and Young’s modulus, with
material) dried
poor surface appearance, but increased failure strain and
better moisture resistance.

The high viscosity of molten thermoplastic matrices (500– Granules Extruder Totally dried
or pellets Cooling (melting) (agglutinated)
1000 times) needs high pressure for the impregnation of
reinforcement fibers, leads to expensive product tooling and
significant energy input in heating and cooling the tooling. Compaction to reduce the volume to be sent to the extruder.
Friction occurring between the fragments and the wall of the
… New thermoplastics without such a high viscosity are being rotating equipment will result in a temperature increase and
applied in composites and will lead to a larger market a plastic mass being formed.
penetration of thermoplastic matrix composites. Additives, such as pigments, charges and lubricants can be
added at this stage.

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Thermoset matrix composites mechanical recycling
Low value applications…

 Ground composite materials will be:


 re-incorporated in new composites as:
- Fillers, at less than 10wt% (however, not commercially viable, because of the very low cost of virgin
fillers such as Ca2CO3 or SiO2)
- Reinforcements
 used in construction industry (e.g. as fillers for artificial woods or asphalt, or as mineral-sources for
cement.

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Composites recycling
Mechanical Recycling:

Novel grinding process: electrodynamic fragmentation to shred carbon fiber reinforced composites (thermoplastic
and thermoset). In this method the material is placed in water between two electrodes, and a high voltage,
between 50 and 200 kV, is then applied to fragment the material into smaller pieces.

Mechanical recycling is mostly used for glass fiber reinforced polymers (GFRPs).
There is no known grinding process exploited industrially to treat CFRCs. Other processes which allow a separation
of the fibers and the matrix (like the ones presented here after) are preferred for carbon fibres as they can be
recovered without contamination and potentially reused as reinforcement in new composites.
Fiber reclamation consists on recovering the fibers from the CFRP, by employing an aggressive thermal or
chemical process to break-down the matrix (typically a thermoset); the fibers are released and collected, and either
energy or molecules can be recovered from the matrix. Fiber reclamation may be preceded by preliminary
operations, e.g. cleaning and mechanical size-reduction of the waste.

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Mechanical recycling: commercial

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Thermoset matrix composites recycling
Fibre reclamation (Thermal and Chemical recycling techniques):

Fibre reclamation processes are particularly suitable to CFRPs: carbon fibres have high thermal and chemical
stability, so usually their excellent mechanical properties are not significantly degraded (especially regarding
stiffness). Generally, the recycled CFs (rCFs) have a clean surface and mechanical properties comparable to the
virgin (v-) precursors; nevertheless, some surface defects (pitting, residual matrix and char) and strength
degradation (especially at longer gauge lengths) have also been reported.

After reclamation, the recycled fibres are usually re-impregnated with new resin to manufacture recycled CFRPs
(rCFRPs). In addition, rCFs have also been used in non-structural applications.  REMANUFACTURING

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Mechanical recycling Fiber reclamation

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Thermoset matrix composites recycling
THERMAL RECYCLING
Thermal recycling of composites involves the processing at high temperatures.
Thermal processing of the composite waste can include 3 types of operations:
(1) Incineration or combustion for energy recovery only. Not classified as recycling
technology, although the inorganic
(2) Combustion for fiber and filler recycling with energy recovery. residues after combustion could be
(3) Pyrolysis with both fiber and fuel recovery. potentially used in the cement
industry (“recovery” vs “recycling”…)

Thermal recycling techniques allow the recovery of fibers, eventually fillers and inserts, but not always the recovery
of valuable products from the resin (i.e. monomers that could be reused to produce resins). The resin is volatilised
into lower-weight molecules and produces mainly gases such as carbon dioxide, hydrogen and methane for example,
and an oil fraction, but also char on the fibers.

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Co-processing in cement kilns
• CEMENT KILNS: the composite waste is converted into energy and into raw materials
components for the cement (fillers and fibres). However no more than 10% of the fuel input to a
cement kiln could be substituted with polymer composites reinforced with glass fibres.
Glass fibre thermoset regrind is an ideal raw material for cement manufacturing. The mineral composition of the regrind is
consistent with the optimum ratio between calcium oxide, silica, and aluminium oxide. Additionally, the organic fraction
supplies fuel for the reaction heat, right at the spot where it is needed most.
• According to the European Plastics Converters (EuPC), the European Composites Industry
Association (EuCIA) and the European Recycling Service Company (ECRC), ‘‘the European
composites industry considers the cement kiln route to be the most sustainable solution for
waste management of glass fibre reinforced thermoset parts’’.
• However at present this solution is not economically viable compared to landfill where landfill is
an option!

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Thermoset matrix composites recycling
THERMAL RECYCLING: Pyrolysis
Thermal decomposition of polymers or depolymerization at
high temperature (300-800ºC) in the (nearly) absence of O2, i.e.
in inert atmosphere (e.g. N2). The polymeric matrix is
volatilized into lower-weight molecules, while the CFs remain
inert and are eventually recovered into long, high modulus
fibres.
Control of temperature and residence time in the pyrolysis
reactor is important for the complete depolymerisation and
cleanness of the recovered fibres.
Compared to the combustion process where the polymer resins
are oxidized to CO2 and water vapour with energy release,
pyrolysis involves the break down of the networked resins into
lower molecular weight organic compounds in the form of
liquid, gas and solid carbon char product. It generates the
products with potential use as feedstock for further chemical
processing.

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Thermoset matrix composites recycling
THERMAL RECYCLING: Pyrolysis
 Recyclates:

- Solid product (50% till more than 2/3): mixture of fibre glass or carbon
fibre, filler materials, and solid carbon. Separation is needed in order to
re-use the reinforcement fibres, or fillers.

- Condensated liquid product (10–50%): mixture of complex organic


compounds with relatively high calorific value similar to fuel oil (30–40
MJ/kg), depending on the type of matrix resins.

- Gaseous products (5–15%): mixture of CO, CO2 and hydrocarbons with


relatively low calorific value (15–20 MJ/kg), and can be used as heat
source to sustain the pyrolysis process (endothermic) through
combustion.

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Thermoset matrix composites recycling
THERMAL RECYCLING: Pyrolysis

recycling the glass fibre


+ recovering of the
thermal energy

After pyrolysis, the fibers are contaminated with char residues which prevents a good bond with the new resin 
Pyrolysis + combustion (gasification, in the presence of air) to obtain clean fibers.

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Pyrolysis

Clean recycled fibers (through pyrolysis) Recycled fibers (through pyrolysis) with char residue

Clean surface Surface defects: pitting, residual matrix, char

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Thermoset matrix composites recycling
THERMAL RECYCLING: Pyrolysis

 The treatment conditions (used to clean the recovered fibers) play a great role on the resulting fibre properties.
 A compromise is thus necessary between resulting mechanical properties and the amount of remaining resin residue.
 E.g. above 600 ºC the tensile strength of the rCF was reduced by over 30%. However, high tenacity CF recovered after a
first step at 550 ºC in nitrogen during 2 h and a second step at 550 ºC in oxidant conditions retained more than 95% of
their tensile strength without resin residue on the surface  A pyrolysis temperature in the range of 500–550 ºC
appears then to be the high limit of the process in order to maintain acceptable strength for CF.
 Factors affecting the quality of r-CF:
- Temperature
- Atmosphere
- Feedstock type
calidad materia prima

 Different types of reactors such as a fixed bed reactor, screw pyrolyser, rotary kiln or fluidised-bed reactor.
Out of these the fluidised-bed and rotary kilns are most suitable as pyrolysis reactors.

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Thermoset matrix composites recycling
THERMAL RECYCLING: Microwave assisted pyrolysis
Microwave-assisted pyrolysis heats composite wastes in an inert atmosphere, degrading the matrix into
gases and oil. The r-GF suffer from 50% tensile strength reduction at 450 ºC, while the r-CF has less
degradation after the thermal treatment at 550 ºC (with 20% loss in stiffness).
The main advantage of microwaves is that the material is heated in its core so that thermal transfer is
very fast, enabling energy savings.

Wind turbine blades made of glass fibers and a thermoset resin were recycled by this method, as well:
three kg of ground materials were pyrolyzed in a 10 L reactor at 440 ºC during 90 min and an oil and
glass fibers were recovered and analyzed. A non-woven mat was then manufactured with the recycled
fibers and used in a new material by alternating these new mats with virgin glass fiber (vGF) mats.
However as the recovered fibers were coated by residual char, the adhesion with a new matrix was
unsatisfactory, which led to poor mechanical properties.

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Thermoset matrix composites recycling
THERMAL RECYCLING: Fluidized bed process
(oxidation)
Combustion of the polymeric matrix in a hot and
oxygen-rich flow (e.g. air at 450 ºC to 550 ºC).
During recycling, CFRP scrap (reduced to fragments Oxidized
molecules
approximately 25 mm large) is fed into a bed of silica and fiber
(e.g. sand) on a metallic mesh. As the hot air stream filaments

passes through the bed and decomposes the resin,


both the oxidized molecules and the fiber filaments r-fibers ~ 6–10 mm
are carried up within the air stream, while heavier
metallic components sink in the bed; this natural
segregation makes this method particularly suitable Hot air
for contaminated EoL components. The fibers are
separated from the air stream in a cyclone, and the
resin is fully-oxidized in an afterburner; energy- Fluidized Bed Process for fiber and energy recovery
recovery to feed the process is feasible. The reactor is operated at 450 ºC for polyester resin
composites and up to 550 ºC for epoxy resin composites.

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Thermoset matrix composites recycling
THERMAL RECYCLING: Fluidized bed process (oxidation)
It can treat mixed and contaminated materials, with painted surfaces or foam cores in composites of
sandwich construction or metal inserts  particularly suitable for EoL waste, however it has not largely
been applied to reclaim fibers, in particular carbon fibers.
The r-GF suffer from 50% tensile strength reduction at 450 ºC, while the r-CF has less degradation
after the thermal treatment at 550 ºC (with 20% loss in stiffness).
Does not allow recovery of products from the resin apart from gases, whereas pyrolysis can enable
the recovery of oil containing potential valuable products. Carbon fibers seem to be more damaged
than with pyrolysis; however the process has not been optimized. In addition to the high temperature,
attrition by the fluidized sand might also damage the fibers.
For GF composite scrap recycling, this process could only be economical if a processing capacity of
above 10,000 tonnes/year can be reached. For CF the plant scale can be smaller due to the higher
market value of the CF. [S.J. Pickering, Thermal methods for recycling waste composites, in: V. Goodship (Ed.), Management, Recycling
and Reuse of Waste Composites, WP and CRC Press, Cambridge, UK, 2010, pp. 65–101.]

fibra de vidrio recicladas

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Mechanical properties (tensile strength) of r-fibers

El mejor proceso de reciclaje es x pirolisis simple

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Composites recycling
CHEMICAL RECYCLING: Solvolysis
Se utiliza disolvente

Solvolysis consists of a chemical treatment using a solvent to degrade the resin. There is partial or total breakage of
plastics into monomers in the presence of glycol/methanol and water. This technique was first considered about 30
years ago and applied to unsaturated polyesters (UP) and sheet moulding compounds in general.
A reactive solvent, sometimes in mixture with a co-solvent or with a co-reactive solvent, diffuses into the composite
and breaks specific bonds. It is therefore possible to recover monomers from the resin and to avoid the formation
of char residues. enlaces
Offers a large range of possibilities thanks to a wide range of solvents, temperature, pressure and catalysts.
Depending on the nature of the resin, more or less high temperatures and pressures are necessary to degrade the
resin: polyester resins are generally easier to solvolyse than epoxy resins and so require lower temperatures to be
degraded.
Reactors can become expensive as they have to withstand high temperatures and pressures, as well as corrosion
due to modified properties of the solvents, especially when supercritical conditions, of water for example, are
reached.

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Composites recycling
CHEMICAL RECYCLING: Solvolysis

Process for chemical depolymerisation or removal of the matrix by using chemical dissolution reagents for liberation of
fibers, under low temperature (typically <350ºC).
The chemical recycling process can re-generate:
-clean fibers and fillers;
- depolymerized matrix in the form of monomers or petrochemical feedstock.
Quite used to recycle CFRPs.
The dissolution process is often called solvolysis, and depending on the solvent can be further classified as: hydrolysis
(using water), glycolysis (glycols), and acid digestion (using acid).
• When using alcohol or water, high temperature and high pressure are normally used under either sub- or supercritical
conditions to gain a faster dissolution and a higher efficiency. (environmentally relatively clean)
• When using acid digestion, atmospheric conditions are normally applied but the reaction rate could be very slow. Acidic
catalysts have been mainly used to degrade more resistant resins, for example PEEK, or to degrade epoxy resins at low
temperatures.
• Often it is used with alkaline catalysts like sodium hydroxide (NaOH) or potassium hydroxide (KOH), but the removal of
the used catalyst salt at the end of the process is still a challenge, due to the high viscosity of the recovered oil.

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Solvolysis applied to:
E.g.
Polyurethane foam: the foam is hydrolyzed to diamine, polyol and CO2 under high pressure steam
and high temperatures (232–316 ◦C), (General Motors in the 1970s).
CFRP: use of supercritical fluids at temperatures of 250–400 ºC and a pressure of 4–27 MPs for
water, and at temperatures of 300–450 ºC and a pressure of 5–17 MPa for alcohols (methanol,
ethanol, 1-propanol and acetone), in the presence of an alkaline catalyst (e.g. KOH):
• supercritical water: resin elimination efficiency of over 90%; recovered CF with only 2–10% degradation in the
mechanical strength.
• supercritical alcohol: resin elimination efficiency of over 98%; recovered CF with 1–15% degradation in the mechanical
strength.

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CHEMICAL RECYCLING

If the environmental and cost issue could be resolved, there will be a


great potential in commercial application of the chemical recycling
technology, since the recycled fiber is not significantly degraded, and
the de-polymerized resin could be made to new resin again.

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Mechanical properties (tensile strength) of r-CF
Uniaxial strength
of the fiber Interfacial shear
(tensile) strength

Solvolisis

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COMPARISON BETWEEN PYROLYSIS, FLUIDISIZED BED AND CHEMICAL RECYCLATES

Mechanical properties of recycled carbon-fibers and their virgin precursors


(a) Young´s modulus
(b) Strength
(c) Interfacial shear strength with epoxy resin

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desventajas

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Advantages and disadvantages of some recycling methods

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Overview of recycling technologies for
Thermoplastic-matrix composites

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Overview of recycling technologies for
Thermoset-matrix composites

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Overview of recycling technologies for
Metal-matrix composites

Mainly aluminum alloy matrix Discontinuously reinforced composites: remelted back to the new composite for
composites (automotive direct reuse, and the quality of the recycled composite is only marginally
industry degraded.
as engine parts). Typically
reinforced (at <30%) with short
fibers, whiskers, or particulates Continuously reinforced composites: normally only aluminum or its alloys are
such as SiC, Al2O3, graphite, recovered through re-melting, and leaving the reinforcement materials as wastes
boron, boron carbide, and for landfill.
titanium carbide.

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Overview of recycling technologies for fiber metal
laminates
Mechanical separation – cryogenic liberation and eddy current separation

Fibre metal laminates Thermal delamination: in an open furnace at 220 ºC, or in a fluidized bed to
(aluminum sheets and aramid destroy the epoxy resin, but the delaminated aluminum was still covered with
fibre/epoxy prepreg), used in solid residues which required mechanical treatment such as sand blasting.
the fuselage of
the Airbus A380.
Thermal delamination: in an open furnace at 500 ºC: clean fibers and aluminum
plates are generated.

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Recycling in the aerospace industry?

Typically unrecyclable largely based on the inability of the industry to utilize the
individual components that make up the composite materials: retired aircraft are
left parked in the desert mainly due to a variety of economic reasons, while the
aircraft owners were largely unaware of the material value still represented in
these airframes.

inconscientes

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Recycling in the aerospace industry?

Both commercial aircraft manufacturers Boeing and Airbus have been involved with research efforts into carbon
fiber recycling over the past several years.

For the past several years, Boeing has been working with a number of third-party technology firms on the
recycling of aerospace grade composites (by pyrolysis). Recent tests involved primary composite scrap material
from the 777 and 787. Boeing’s goal is to achieve 90–95% recyclability of the world’s fleet with the materials
recovered in these recycled aircraft directed toward high-value commercial manufacturing applications.
The studies suggested that the costs for manufacturing are $15–$30 per pound (lb) with the amount of energy
consumed during the process of 25–75 kWH/lb against $8–$12/lb and 1.3–4.5 KWH/lb for recycled carbon fiber.

In 2005, Airbus established its process for advanced management of EoL aircraft (PAMELA) consortium with the
objective to increase the amount of aircraft recycled material from the current 70–75% upwards to 90% in the
coming years.

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Remanufacturing of r-CFRP
All fiber reclamation processes result in a short
length fiber and filamentized, random, low-density
packing (fluffy) form. With no sizing anymore…

The entangled and unsized rCF form requires


existing methods to be adapted. Re-impregnating
non-woven mats with a new matrix is one of the
most effective methods in terms of the mechanical
performance of the composites.

Further technical developments in re-manufacturing


technologies are still needed:
-inducing fiber alignment,
-increasing fiber content,
-decreasing fiber damage during processing.

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Observations in remanufactured rCF composites
Extensive breakage of fibers during re-manufacturing led to
a considerable degradation of tensile strength at the
composite level.

Dispersed phase

Fiber bundle
125 m
manojo

Fiber bundles — held together by minimal amounts of residual


matrix not completely pyrolysed — increase the in-plane
1 mm
fracture toughness of the material

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Remanufacturing of r-CFRP
Injection moulding:
Mixture of resin (typically a thermoplastic), rCFs
(short or milled) and fillers/additives is pre-
compounded into pellets, which are subsequently
injected into a mould (at 10 MPa to 100 MPa).

e.g. maleic anhydride grafted PP to improve fiber-matrix


adhesion; 25% less stiffer than with vCF

Bulk moulding compounding compression:


BMCs are intermediate products made by mixing
resin (typically a thermoset), rCFs, fillers and curing
agents into bulky charges; this premix is subsequently
compression moulded (under 3.5 MPa to 35 MPa)
into a component.

Compression moulding of intermediate Compression moulding of aligned rCF


non-woven products Fiber alignment improves the mechanical performance of
Production and subsequent re-impregnation composites manufactured with discontinuous rCFs (along
of 2D or 3D rCF non-woven dry products preferential fiber direction). Also, manufacturing requires
(with a short and random reinforcement lower moulding pressures and smoother fiber-to-fiber
architecture). Compression moulding with interactions. Techniques: centrifugal alignment rig; yarn
resin layers or re-impregnated through a spinning technique, fiber dispersion by blowing with
liquid process. compressed air.

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r-CF alignment in composite

r-CF pull-out from PP matrix

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Remanufacturing of r-CFRP (Summary)

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Remanufacturing of r-CFRP
Woven rCFRP
tejido
Preservation of the reinforcement architecture of the waste, from large woven
items, e.g. out-of-date prepreg rolls, EoL aircraft fuselage, or pre-preg trimmings
from large components.
By re-impregnation (through e.g. resin transfer moulding (RTM) or resin infusion)
of the recycled weave fabrics, it will be possible to produce the woven rCFRPs.

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Remanufacturing of r-CFRP (Summary)

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Remanufacturing of r-CFRP
Demonstrators manufactured with rCFs
Crashworthy and secondary components for the automotive industry, components for aircraft interiors, and tooling

Aircraft seat arm-rest (3-DEP process)

rCFRPs might be incorporated back


Wing mirror covers (BMC compression) Rear of WorldFirst F3 car into non-critical aeronautical
(woven re-impregnation) applications in a foreseeable future.

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Remanufacturing of r-CFRP
Demonstrators manufactured with rCFs

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Remanufacturing of r-CFRP: potential structural applications

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Estimated values for the cost of CFs

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Companies that
are recycling
composites (CFRP
and GFRP) into
marketable
products

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Reprocover, Belgium (case study)
Reprocover break, grind and sieve thermoset (and reinforced
thermoset) industrial waste into 6 mm granules. A similar
recycling process is carried out on dry glass fiber waste.
These are mixed with each other in a ratio of approx. 30% of
glass fiber flakes to 70% thermoset granules. The dry mixture is
then mixed with polyols and isocyanate (at 8-10%) and poured
out into moulds and pressed under 200 tonne presses, triggering
off a chemical reaction (cold pressure process) whereby the
chemicals polymerize into a polyurethane resin, binding the
granules and glass fibre flakes.

The result is a very hard and strong material which is resistant to


fire, extreme temperature variations, UV and chemicals. It
does not corrode, has good slip resistance and is lightweight.
The material is 100% closed loop recyclable in the same process,
as the thermoset resins do not lose strength when recycled over
and over again as thermoplastics do.

Ludo Debergh invested €6 million in capital in Reprocover, in


addition to further investment from other sources. The company
is on track to break even by the end of 2015.
They charge a gate fee to take waste that would otherwise go to
landfill.
Level crossing panels including recycled GRP and phenolics from car parts.
(Picture courtesy of Reprocover.)

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ELG Carbon Fiber, UK (case study)

The world’s
first commercial carbon fiber
recycling company

Pyrolysis process
2000 tonnes/year recovered carbon fiber output

Recyclate market:
Chopped/milled/pelletised carbon fibre.
Carbon fibre random mats and discontinuous
fiber yarns. Preforms.

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Near
commercial
composites
recycling
services

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Composites waste management strategies

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Number of research projects by type of composites
waste management strategies
growing trends in composites
recycling technologies

(based on 56 projects identified from journals and white papers*)

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Composites recycling projects by recycling
technique

Growing trends in composites recycling technologies.


Pyrolysis, solvolysis and mechanical grinding are the most uptaken recycling practices.

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Technology readiness level assessment

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Technology readiness level assessment

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Allocation of composites
recycling technologies on
TRL scale.

Most advanced process:


-For GF: mechanical
grinding
-For CF: pyrolysis

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QUESTION TO ADDRESS:
How to find a low cost, efficient recycling technology to separate and recycle the current in-use composite
materials?

MAJOR CURRENT CHALLENGE TO CFRP RECYCLING OPERATIONS:


Establishment of a sound CFRP recycling chain supporting the effective commercialization of recycling
processes and products.

MAJOR ISSUES TO OVERCOME:


1.Global strategy: organised networks for CFRP recycling
2.Incentives for recycling: (e.g. penalties for non-recyclers (e.g. landfilling taxes) direct privileges (e.g. carbon
credits) for companies recycling their CFRP waste)
3.Implementing suitable legislation: Logistics and cooperation in the supplying chain: supplying the waste in a
continued and suitable form, providing the recyclers with material certificates and ensurance, by the recyclers,
that materials and components supplied will not undergo reverse engineering.
4.Market identification and product pricing: (i) characteristics and properties of different rCFRPs are known,
(ii) their processing times and costs are assessed, and (iii) the value for the recycled label is established.
5.Life-cycle analysis, to assess cost effectiveness and environmental impact of using rCFs.
6.Market establishment: recognition by leading researchers, CF recyclers, CF users and analysts.

…So, rCFs are accepted as an environment-friendly and cost-effective material.

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A Vision for the Future…
1) The fundamental contradiction between the heterogeneity and recyclability would become
less critical, by using newly developed reinforcement materials which will have much more
similarity with the matrix materials in their chemical nature.
2) The use of non remeltable thermoset matrix will be significantly replaced by thermoplastics.
3) Recycling technology will become much more mature to either separate the reinforcements
from the matrix materials most likely based on clean chemical recycling technology such as
super critical water, or recycle the (re-meltable) matrix together with reinforcements.
4) The high cost of composite recycling will be compensated by legislation for forbidding the
landfill and incineration of composites waste and EOL products, and by increasing production
cost of virgin composite constituents (reinforcement fibres and polymer matrix).

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This study material was based mainly on the following papers:

• Géraldine Oliveux, Luke O. Dandy, Gary A. Leeke, Progress in


Materials Science 72 (2015) 61–99.
• Yongxiang Yanga, Rob Boom, Brijan Irion, Derk-Jan van Heerden,
Pieter Kuiper, Hans de Wit, Chemical Engineering and Processing 51
(2012) 53– 68.
• Soraia Pimenta, Silvestre T. Pinho, Waste Management 31 (2011)
378–392.
• S.J. Pickering, Composites: Part A 37 (2006) 1206–1215.
• J. Rybicka et al., Journal of Cleaner Production 112 (2016) 1001-1012.

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