Insert University logosPolymer Cluster
Towards the Affordable
Recyclable Future – Low Carbon Vehicle
TARF-LCV Seminar 17-07-2014
1
Regeneration of thermally recycled glass fibre for cost-effective composite recycling
Advanced Composites Group
Department of Mechanical & Aerospace Engineering
University of Strathclyde
Glasgow, Scotland
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TARF-LCV Seminar 17-07-2014
Towards the Affordable
Recyclable Future – Low Carbon Vehicle
Insert University logosPolymer Cluster
TARF-LCV- Liu Yang (ex RA, now Lecturer)- Durai Raghavalu Thirumalai (RA)- Peter Jenkins (PhD)- Ulf Nagel (PhD)
ReCoVeR- Chih-Chuan Kao (RA)- Eduardo Sáez-Rodriguez (PhD)- Winifred Ijomah (CI)
Advanced Composite Group Recycling Team
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TARF-LCV Seminar 17-07-2014
Towards the Affordable
Recyclable Future – Low Carbon Vehicle
Insert University logosPolymer Cluster Introduction
Strathclyde Project/Posters Overview
- Fundamentals of Fibre Strength Loss
- ReCoVeRed Fibres
- Composite Performance
Conclusions
Future Work
INDUSTRY LEADER
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GlassCarbonAramid
Global Reinforcement Fibre Usage
4300
50 40KTon/year 2011
Glass Fibre is th
e most important reinforcement
in the global composites market.
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Global Glass Fibre Demand
Source OCVhttp://investor.owenscorning.com/files/doc_presentations/2014/Q1%202014%20Presentation.pdf
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Composites in AutomotiveBMW photo as shown in Modern Plastics Magazine
ELV directive 2000/53/EC ?
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Global End-of-Life Blade Material
>10 year Exponential In
crease
EU Landfill Directiv
e 99/31/EC ?
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Available End-of-Life Glass Fibre in Thermoset Composites
Assume 60% in TS
Assume we could recycle just 10% = >100KTpa business potential today
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Glass Fibres: End-of-Life Scenario4.3 MegaTons Glass Fibre
Mainly into chopped fibre thermoplastic composites.
Intrinsically recyclable
Landfill no longer acceptable – but very difficult to recover
continuous fibre
Mainly into continuous fibre
thermoset composites
ReCoVeR and reuse as valuable chopped fibre ?
Challenging to recycle - so end-of-life = landfill ? (or zero value filler)
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Thermal Processes
Incineration Fluidized bedPyrolysis Solvolysis
• Energy recovery
• Not suitable for inorganic products
• Recover organic components
• Clean fibres and length retains
Thermo-chemical processes
Mechanical grinding
• Some energy recovery from composites
• High content of inorganic material – no longer fibrous
• Not clean fibres
• Mainly reuse as very low value filler
• Clean fibres and length retains
• Energy recovery with subsequent combustion of organic products applies
GRP Recycling Techniques
Recovered Glass Fibre has very poor
performance
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Strength after Thermo-Mechanical Treatment
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The MissionEnable the development of cost-effective, drop-in, glass fibre and composite products for lightweight automotive applications based on recycled glass fibres with regenerated mechanical performance
Regenerated Composite Value Reinforcement
13
TARF-LCV Seminar 17-07-2014
Towards the Affordable
Recyclable Future – Low Carbon Vehicle
Insert University logosPolymer Cluster
Effect of Thermal Conditioning on
Glass Fibre Strength ?
• Single Fibre Strength?
• Sizing/surface changes ?
• Bulk fibre change/relaxation ?
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Strength Loss Mechanism?
J Mater Sci (2014) submitted
• Heated 15 minutes in air• Measure Strength at 23°C• Gauge length: 20 mm• Strain rate: 1.5 %/min.• 70–100 fibres per condition
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Strength Loss Mechanisms?
Untreated
HT at 400°C
AFM carried out at Univ. of Nottingham
FE-SEM carried out at AMRL Univ. of Strathclyde
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Strength Loss Mechanisms Investigation
• Fibre strength after heat (bundle vs single fibre)
• TGA of silane film degradation
• TMA for single fibre modulus and dimension changes during conditioning
• IR analysis of silane NH2 group on fibre
• XPS surface analysis of %N on fibre
• XRD for crystal growth
• AFM & SEM of fibre surface topography
• Evolution of water
Poster - Jenkins
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Current State of Strength Loss Mechanism Investigation
Mechanism of strength loss probably involves
• sizing degradation
• surface flaws (number/severity increase)
• change/relaxation in glass structure
• removal of water/dehydroxylization
More work required for full understanding
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TARF-LCV Seminar 17-07-2014
Towards the Affordable
Recyclable Future – Low Carbon Vehicle
Insert University logosPolymer Cluster
Glass Fibres Recycled out of Composites?
• Heated Fibre vs Recycled Composite ?• Lab scale recycling of fibre out of model
composites (polyester and epoxy based)
• 1 Larger trial run on Univ. of Nottingham Fluidised Bed Reactor
• Temperature Effects?
• ReCoVeR Treatments?
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Fluidised bed process vs Lab heat treatment
Fibre characterisation•Fibre surface•Fibre strength
Material : GF-Epoxy
Bed temperature: 500°C
Residence time: 10-30 minutes
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Glass Fibres Recycled from Composites
From GF-Polyester Composite at 500°C
After additional
cleaning
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Heated vs Recycled Fibre Strengths
Posters – Kao, Yang, Durai
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HF Regenerated Fibre Strengths
Poster – Yang
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TARF-LCV Seminar 17-07-2014
Towards the Affordable
Recyclable Future – Low Carbon Vehicle
Insert University logosPolymer Cluster
Regeneration of Glass Fibre Strength after Thermal Conditioning?
• Target strength?
• What have we achieved?• Proof of concept with HF
• ReCoVeR treatments
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Target Strength for ReCoVeRed Fibre ?
Composites Part A 32 (2001) 85-90Measured BAM 1999
Average single fibre strength from commercial chopped glass products
0.0
0.5
1.0
1.5
2.0
2.5
C E I J K L M N Z
Sin
gle
Fib
re S
tren
gth
(G
Pa)
1.5-2.0 GPaGauge length = 0.3mm !
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Target Strength for ReCoVeRed Fibre ?
10 m product for GF-PA Injection Moulding applications
Measured at BAM, Berlin
Average single fibre strength from commercial chopped glass products
1.5 GPaAt 20 mm gauge length
should be sufficient
Composites Part A 32 (2001) 85-90
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Single Fibre Strength ReCoVeRy
0.0
0.5
1.0
1.5
2.0
2.5
0H
T 1 2 3 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27
Ave
. Ten
sile
Str
engt
h (
GP
a)
All APS coated 17 m Advantex with 450°C Heat Treatment
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Single Fibre Strength ReCoVeRy
• To date - 3 methods identified to regenerate single fibre strength > 1.5 GPa in glass fibres heated > 450°C
Posters – Yang, Saez, Kao, Durai
28
TARF-LCV Seminar 17-07-2014
Towards the Affordable
Recyclable Future – Low Carbon Vehicle
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Effect of Thermal Conditioning and ReCoVeR Treatment on Composite Performance?
• HF Proof of Concept
• Effect of GF Heat Treatment ?
• Effect of ReCoVeR?
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GF-Epoxy via vacuum infusion •CSM MAT92 manufactured by PPG Fibre Glass
•Bisphenol A Epoxy vacuum infusion grade
•RT cure 24h followed by post-curing at 60°C for 24h
Thermally conditioned glass fibre
Proof of Concept with HF for strength regeneration
Regenerate HT glass fibre
strength
Fibre strength
assessment
Fibre & composite processing
Composite performance
assessment
OK
Reactivate HT glass fibre
surface
Fibre-matrix interface
assessment
OK
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Regenerate fibre strength Reactivate fibre surface
-50%
60% recovery
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Results: Reuse regenerated glass fibre
CSM-Epoxy Composite
60% decrease50% recovery
Poster - Yang
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GF Heat Treatment & Composite Performance
Injection Moulded 30%GF-PP (1% MaPP)
ReCoVeR Target Zone
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ReCoVeR Composite Performance
Injection Moulded 30%GF-PP (1% MaPP)
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ReCoVeR Composite Performance
20
30
40
50
60
70
80
PP Polymer - no GF PP+GF (As Received) PP+GF (500C heattreated)
PP+GF (500C &ReCoVeR treatment)
Ten
sile
str
engt
h (
MP
a)
composite with heat treated fibre barely stronger than
polymer alone
71% composite strength ReCoVeRy
30%GF-PP
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ReCoVeR Composite Performance
0
10
20
30
40
50
60
PP Polymer - no GF PP+GF (As Received) PP+GF (500C heattreated)
PP+GF (500C &ReCoVeR treatment)
Un
not
ched
Ch
arp
y (k
J/m
^2)
87% impact strength ReCoVeRy
30%GF-PP
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Initial Results on ReCoVeR Fibre in PP Composites
72% ReCoVeRy of Composite Tensile Strength
87% ReCoVeRy of Unnotched Charpy Impact
• Non-optimized sizing on ReCoVeR fibres
• Higher potential ReCoVeRy performance to come
• Patent Application submitted Aug 2013
Poster - Nagel
37
TARF-LCV Seminar 17-07-2014
Towards the Affordable
Recyclable Future – Low Carbon Vehicle
Insert University logosPolymer Cluster C
on
clu
sio
ns
• Development of cost-effective technology to regenerate the properties of thermally recycled glass fibres will have major environmental benefits
• Glass fibres lose most of their strength after a short heat treatment above 400ºC
• Mechanism of strength loss involves both sizing degradation and changes in glass fibre structure
• Thermal conditioning glass fibres also drastically reduces end-use composite performance
• The ACG is developing treatments to ReCoVeR the strength of thermally recycled glass fibres
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TARF-LCV Seminar 17-07-2014
Towards the Affordable
Recyclable Future – Low Carbon Vehicle
Insert University logosPolymer Cluster F
utu
re W
ork
• Good progress made on fundamentals GF strength loss but more work required for full understanding
• ReCoVeR already regenerates 50-60% of fibre strength loss – more work required to achieve 100% composite performance recovery
• Similarly, post ReCoVeR surface coating (resizing) necessary to regenerate strong fibre-matrix adhesion – similar to pristine GF products
• LCA needed
• Need to move towards pilot recycling method – to define process parameters of ReCoVeR