regeneration of thermally recycled glass fibre for cost ... · source - composites technology, june...
TRANSCRIPT
INDUSTRY LEADER
INNOVATION
GLOBAL VISION
SOLUTIONS
PARTNERSHIP
The ReCoVeR Project
Regeneration Of Thermally Recycled Glass Fibre For Cost-Effective, Closed-Loop, Composite Recycling in
Automotive
Jim Thomason E.Sáez, L.Yang, C.C.Kao, U.Nagel, P.Jenkins
Advanced Composites Group Department of Mechanical & Aerospace Engineering
University of Strathclyde Glasgow, Scotland
INDUSTRY LEADER
INNOVATION
GLOBAL VISION
SOLUTIONS
PARTNERSHIP
! Introduction
! ACG Recycling Projects Overview
! Some Initial Results - Fundamentals of Glass Fibre Strength Loss - ReCoVeRed Glass Fibres - Composite Performance
! Conclusions
ReCoVeR
GlassCarbonAramid
Global Reinforcement Fibre Usage
4660
50 43 KTon/year 2013
Global Glass Fibre Demand
0
1
2
3
4
5
1980 1985 1990 1995 2000 2005 2010 2015
Mill
ion
Tons
Source OCV http://investor.owenscorning.com/files/doc_presentations/2014/Q1%202014%20Presentation.pdf
Composites in Automotive BMW photo as shown in Modern Plastics Magazine
1
10
100
1,000
2010 2015 2020 2025 2030 2035
Glo
bal G
F in
EoL
Bla
des (
kT/a
)
Year
GF in End-of-Life Wind Turbine Blades
Assuming 20 year Blade Life
Source - Composites Technology, June 2008, GWEC 2013
Available End-of-Life Glass Fibre in Thermoset Composites
0.5
1.0
1.5
2.0
2.5
3.0
3.5
1980 1985 1990 1995 2000 2005 2010 2015 2020 2025 2030
Mill
ion
Tons
Gla
s Fib
re
Global Demand
15y Life
20y Life
Assume 60% in TS
Assume we could recycle just 10% = >100KTpa business potential today
ReCoVeR Glass Fibres: End-of-Life Scenario
60%
40%
4.8 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)
Thermal Processes
Incineration Fluidized bed Pyrolysis 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
GF Strength (Value) after Thermal Recycling
0
20
40
60
80
100
0 100 200 300 400 500 600 700
Gla
ss F
ibre
Str
engt
h (%
)
Conditioning Temperature (°C )
Thomason OC 1999 (E) Pickering et al 2000 (E) ACG 2008 (A) Feih et al 2009 E) Feih et al 2009 (A) ACG 2009 (A) ACG 2012 (A)
The ReCoVeR Mission Enable the development of cost-effective, drop-in, glass fibre and composite products based on recycled glass fibres with regenerated mechanical performance
– Generate fundamental understanding of the changes in glass fibres caused by thermo-mechanical conditioning (300-600°C)
– Develop cost effective treatments to regenerate the performance of thermo-mechanically treated glass fibres
– Produce examples of glass fibre and composite products using regenerated glass fibres
The Research Goals
Regenerated Composite Value Reinforcement – £1M EPSRC funding, 8 Researchers in ACG team
Strength after Thermo-Mechanical Treatment
0
20
40
60
80
100
0 100 200 300 400 500 600 700
Gla
ss F
ibre
Str
engt
h (%
)
Conditioning Temperature (°C )
Thomason OC 1999 Pickering et al 2000 ACG 2008 Feih et al 2009 E Feih et al 2009 A ACG 2009 ACG 2012
GF Heat Treatment & Composite Performance
10
20
30
40
50
30
40
50
60
70
80
0 100 200 300 400 500 600
Unn
otch
ed C
harp
y (k
J/m
^2)
Tens
ile S
tren
gth
(MPa
)
GF Preconditioning Temperature (°C)
TS UC
Injection Moulded 30%GF-PP (1% MaPP)
ReCoVeR Target Zone
Strength Loss Mechanisms Investigation
• Fibre strength after heating (or composite recycling)
• TGA of silane film degradation
• TMA for single fibre modulus and dimension changes during conditioning
• AFM/SEM analysis of surface morphology changes
• IR analysis of silane NH2 group on fibre
• XPS surface analysis of %N on fibre
• TVA of water evolution and dehydroxylisation
• XRD for crystal growth – nothing found up to 800°C
Strength Loss Mechanisms?
50
60
70
80
90
100
0 100 200 300 400 500 600 700 800
Mas
s (%
)
Temperature (°C)
Weight change of dried APS film heated in N2
TGA of cured APS film
Single Fibre Tensile Testing
0.5
1.0
1.5
2.0
2.5
0 100 200 300 400 500 600
Sing
le F
ibre
Str
engt
h (%
)
Conditioning Temperature (°C )
US APS
Composites Part A 61 (2014) 201-208
TMA Single Fibre Length Contraction
-6
-5
-4
-3
-2
-1
0
0 200 400 600 800 1000
Len
gth
Cha
nge
(µm
/mm
)
Isothermal Time (min )
500°C
300°C
400°C
J Mater Sci (2013), 48, 5768-5775
Glass fibres shrink when heated!
Strength Loss Mechanisms?
70
75
80
85
90
0 100 200 300 400 500 600
Roo
m T
emp
Mod
ulus
(GPa
)
Conditioning Temperature (°C )
J Mater Sci (2013), 48, 5768-5775
Strength Loss Mechanisms? Untreated
HT at 400°C
AFM
FE-SEM
0
1
2
3
4
5
0 100 200 300 400 500 600
RM
S R
ough
ness
Conditioning Temperature (°C )
Current State of Strength Loss Mechanisms Investigation
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
Target Strength for ReCoVeRed Fibre ? Commercial chopped strand products - Average single fibre strength
0.0
0.5
1.0
1.5
2.0
2.5
C E I J K L M N Z
Sing
le F
ibre
Str
engt
h (G
Pa)
1.5-2.0 GPa Gauge length = 0.3mm !
Target Strength for ReCoVeRed Fibre ?
0.5
1.0
1.5
2.0
2.5
0.0 0.5 1.0 1.5 2.0 2.5
Sing
le F
ibre
Str
engt
h (G
Pa)
Gauge Length (mm)
Glass 1 Glass 2
10 µm product for GF-PA Injection Moulding applications
Commercial chopped strand products - Average single fibre strength
1.5 GPa At 20 mm gauge length
should be sufficient
Glass 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 (G
Pa) All APS coated 17 µm Advantex
with 450°C Heat Treatment
Glass Fibre Strength ReCoVeRy
0.0
0.5
1.0
1.5
2.0
450 500 600
Aver
age
Fibr
e St
reng
th(G
Pa)
Glass Pretreatment Temperature (°C)
No ReCoVeR ReCoVeR 1 ReCoVeR 2 ReCoVeR 3 HF Treated
Glass Fibre Strength ReCoVeRy
0
0.5
1
1.5
2
No ReCoVeR ReCoVeR 1 ReCoVeR 2 ReCoVeR 3
Aver
age
Fibr
e St
reng
th(G
Pa)
600°C Heat Treated Fibres
Fibres Recycled from Composite at 600°C
20
30
40
50
60
70
80
PP Polymer - no GF PP+GF (As Received) PP+GF (500C heat treated)
PP+GF (500C & ReCoVeR treatment)
Tens
ile st
reng
th (M
Pa)
composite with heat treated fibre barely stronger than
polymer alone
71% composite strength ReCoVeRy
Injection Moulded 30 % GF-PP
ReCoVeR Composite Performance
0
10
20
30
40
50
60
PP Polymer - no GF PP+GF (As Received) PP+GF (500C heat treated)
PP+GF (500C & ReCoVeR treatment)
Unn
otch
ed C
harp
y (k
J/m
^2)
87% impact strength ReCoVeRy
ReCoVeR Composite Performance
Injection Moulded 30 % GF-PP
ReCoVeR Composite Performance
10
20
30
40
50
30
40
50
60
70
80
0 100 200 300 400 500 600
Unn
otch
ed C
harp
y (k
J/m
^2)
Tens
ile S
tren
gth
(MPa
)
GF Preconditioning Temperature (°C)
TS UC
1st ReCoVeR Trial
Injection Moulded 30%GF-PP (1% MaPP)
Initial Results on ReCoVeR Glass Fibres 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
Conclusions • The development of a 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 400°C
• Mechanism of strength loss involves both sizing degradation and changes in glass fibre structure
• Thermal conditioning of fibres also drastically reduces end-use composite performance
• The ACG is developing treatments to ReCoVeR the strength of thermally recycled glass fibres
New Glass Fibre Sizing Book
Available later this month
Glass Fibre Sizing A Review of Size Formulation Patents
James L. Thomason
This book contains analysis of more than 500 examples of patented size formulations many of which are probably still in use in commercial glass fibre production.
Glass Fibre Sizing Jam
es L. Thomason
Possibly the most critical component involved in the manufacture of glass fibres and their composites is the fibre surface coating (or size). Yet because of the intense level of industrial secrecy around size formulations there are very few people in the vast chain of composite materials suppliers, processors and end users who have more than a superficial understanding of these coatings. Many questions are raised about glass fibre size by
this large and growing composite community. But the most frequently asked is “what is actually in the size on this glass fibre product?” There is only one source of openly available information on commercial size formulations and that is the patents of the glass fibre manufacturers. This book contains analysis of more than 500 examples of patented size formulations many of which are probably still in use in commercial glass fibre production. The information is tabulated to allow readers to easily identify the similarities and differences between the sizes and their glass fibre products developed for different composite end-use applications, different composite processing techniques, and compatibility with different polymers. Also included is a chapter discussing how patents and their associated information can be used to gain insight into which size formulations may actually be in use in glass fibre production. !