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. !