CHEM-E2200: Polymer blends and composites

Reinforcement processes

Mark Hughes
21st September 2020
Today’s topics

• A little more about stress transfer

• Reinforcement by slip
• Conditions for fibre fracture
• The effect of fibre behaviour on composite
micromechanics
Elastic stress transfer: interfacial shear stresses

• Interfacial shear stress ( i) operates at

the interface, parallel to the fibre
surface
• Using a force-balance approach it can
be shown that:
d f 2 i

dx r
Where: x is the axial distance from the fibre mid-point
r is the fibre radius (Source: Hull & Clyne 1996)

• The model assumes that there is no slippage at the interface,

i.e. the system behaves elastically
Shear stress distribution
Max interfacial shear
stress, τi
10
aspect ratio = 5
interfacial shear stress (MN m-2)

aspect ratio = 25
aspect ratio = 100
5

0
Stress
transfer
-5
region

-10
SSMG-ITALY - Laboratory for Physical Modelling of Structures and Photoelasticity
(University of Trento, Italy)
-300 -200 -100 0 100 200 300
position along fibre (arbitary units)

• Maximum interfacial shear stress at the fibre ends

 Fibre-matrix debonding
• Highest interfacial shear stresses are at the fibre ends
• Debonding is clearly visible due to a change in the
refractive properties of the interface
• This is particularly visible in fragmented fibres
Debonded length

Interface breakdown
Debonded fibre ends in fragmented fibre (flax-epoxy SFC)
Reinforcement by slip
• If the interfacial shear stress exceeds
some critical value (the interfacial
shear strength), then the interface
will breakdown leading to a loss in
adhesion
• Reinforcement may still take place
through frictional forces at the
interface and a process analogous to Model of stress transfer by slip
the Cox shear-lag mechanism will (Piggott, 1980)
operate
– (Note: 𝐹𝑚𝑎𝑥 = 𝜇𝑠 𝐹𝑛 for static friction)
• Assuming that the frictional
interfacial shear stress is constant at
the ends of the fibre, a model of the
axial fibre stress is as shown opposite

Photoelastic response in an epoxy matrix

at fibre ends
 Stress transfer aspect ratio
Stress transfer aspect ratio
• Whether by elastic stress transfer, or
by friction, the axial fibre stress 250

increases from the ends of the fibre

200
towards the mid-point

fibre axial stress (MN m-2)

• Over the stress transfer length, the
150
aspect ratio = 5
aspect ratio = 25
aspect ratio = 100
fibre is not being fully effective as 100

reinforcement 50

• If the aspect ratio, s, is too small, then 0

the fibre axial stress will not reach a position along fibre (arbitary units)
-300 -200 -100 0 100 200 300

maximum and thus is not acting

efficiently
• There will therefore be an aspect ratio, where the fibre axial stress just
reaches a maximum value, for the applied composite strain. This is
known as the stress transfer aspect ratio
Conditions for fibre failure

Whether by elastic stress transfer, or by friction, the axial

fibre stress increases from the ends of the fibre towards
the mid-point
Over the stress transfer length, the fibre is not being fully
effective as reinforcement
 Fibre axial stress
400

• As the composite is deformed,

the maximum value of axial fibre 350

stress will increase (although the 300

stress transfer profile will be the 0,5% strain

Fibre axial stress (MPa)

0,1% strain
same) 250
0,25% strain

• When the fibre axial stress 200

0,75% strain

reaches the tensile strength of

the fibre, it will fail 150

• The fibre aspect ratio will 100

decrease
50

• As the strain on the composite

increases, the axial stress in the -400 -300 -200 -100
0
0 100 200 300 400
remaining section will continue Position along fibre (arbitary units)

to increase, leading to further Theoretical build up of fibre axial stress

fibre failure following a Cox type shear lag mechanism
(Ef = 50 GPa; Em = 3.5 GPa; s = 50)
Fibre fracture

• As longer fibres are progressively shortened, the maximum

axial tensile stress in the fibre that can be generated will
reduce, to a point below which further fracture cannot
occur. I.e. the interface fails before the fibre
• This is known as the critical fibre length

Fragmented flax fibre in an epoxy matrix SFC

Critical fibre aspect ratio

• A critical aspect ratio ( Sc ) can thus be identified.

This is the point where the central axial stress in
the fibre equals the ultimate tensile strength of
the fibre ( fu). It can be shown that if stress
transfer by slip (friction) is considered then:
 fu
Sc 
2 i*

Where τi* is in the interfacial shear stress

Fibre strength

• Is the strength of the

fibre going to be the
same along its entire
length?
• Unlikely! Particularly with
natural fibres with many
defects…

Fibre defects in flax fibre; points of weakness, seen under polarised light
Composite behaviour & relationship to
micromechanics
• Lower fibre aspect ratio, lower composite stiffness
• Theory predicts that the stress-strain relationship will
be linear
• Non-linear behaviour will occur when microstructural
damage commences. For example, if there is matrix
yielding, or if interfacial failure occurs, leading to a
reduction in ‘efficiency’ of stress transfer. If the fibre
fractures, then it is unable to provide as effective
reinforcement and therefore the composite stiffness
will reduce
Interfacial failure

Interfacial debonding
Interfacial failure and matrix yielding

Matrix cracking
(Hughes et al 2000)
Matrix yielding
Effect of aspect ratio on composite stiffness
s=1000
160
s=100

120 s=10
Stress (MN m )
-2

80 s=5

40

0
0.00 0.05 0.10 0.15 0.20 0.25 0.30
Strain (%)
 Case study: the use of plant fibre as
composite reinforcement

17
Composite behaviour
• What is the influence of
changing the degree of 340
320
UnM
interfacial bonding? 300
MeA
PrA
• Three forms of flax fibre-
280
E-glass
260

Tensile stress (GPa)

reinforced unsaturated 240
220
polyester composite 200
investigated: 180
160
– No fibre treatment 140

– Hydrophobic fibre 120

100
surface (increased 80
wetting) 60
40
– Chemical bonding 20 (Hughes et al 2007)
• Stress-strain (and failure) 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
characteristics altered Strain %
Properties of polymer-matrix composites
based on natural fibres (hemp)
• Generally good stiffness - similar to glass-fibre
reinforced material, especially on a specific basis
• Adequate strength for many commonplace
applications, if not too demanding
• Poor toughness - order of magnitude lower?
• Yielding at low stress levels, making the working
range of loading quite limited
Stiffness
Young's modulus (GPa) 12

0
0 10 20 30 40 50
fibre volume fraction (%)
hemp csm Linear (hemp)
Strength
100
tensile strength (MPa)

80

60

40

20

0
0 10 20 30 40 50
fibre volume fraction (%)
hemp csm Poly. (hemp)
Toughness (Chapy impact strength)

100
Charpy impact strength (kJ m -2)

80

60

40

20

0
0 10 20 30 40 50
fibre volume fraction
hemp csm Poly. (hemp)
Polarised light

Unprocessed Mechanically processed

hemp fibre hemp fibre
 Fibre structure
• Highly aligned structure
leads to excellent tensile
properties in fibres such as
flax, hemp, jute, ramie, etc.
• But: prone to compressive
failure through the
formation of kink-bands,
affecting either the cell wall
or the entire fibre
• This affects the behaviour of
the fibre
(Baley 2004)
• Failure in wood and
non-wood fibre in
compression is
analogous to the
compression failure
seen in polymer
composites, or
synthetic fibre such
as Kevlar 49

(DeTeresa et al, 1984)

 (DeTeresa et al, 1984)

• Kevlar 49 fibre without defects exhibits Hookean behaviour

• Fibre containing kinks induced by compressive failure, exhibit significant
non-linear behaviour initially, before strain hardening
• In subsequent cycles the fibre exhibits nearly linear behaviour
Kink bands in flax fibre

(Baley 2004)
Stress-strain behaviour of fibres

• Stress-strain behaviour strongly influenced by the microfibril angle

Tensile stress-strain behaviour of elementary
flax fibre

(Charlet et al, 2010)

Tensile stress-strain behaviour of elementary
flax fibre

Analogous “S”
shaped form to the
stress-strain
behaviour
FE model proposed by Nilsson & Gustafson (2007)

(Nilsson & Gustafson 2007)

Modelled tensile behaviour

(Nilsson & Gustafson, 2007)

Effect of the extent of damage

• Increasing levels of damage in flax

fibre ultimates results in a lowering
of the stiffness of the fibre
• This implies that the fibre undergoes
greater strain at the defect
• This has been verified
experimentally by Mott et al (1996),
who showed that fibre defects acted
at strain concentrators
• The same conclusion was reached
by Eichhorn et al (2000)
(Davies & Bruce, 1998)
Effect of fibre damage (dislocations) in
hemp fibre-epoxy composites

Shear stress distribution in an

epoxy matrix adjacent to a
defect in a strained specimen
at small deformation
Matrix shear stress post fracture

Polarised light micrograph of a failed single filament composites showing

fibre-matrix de-bonding in regions of high shear-stress concentration
adjacent to fibre defects (and fracture)
 Model for a fibre containing dislocations

(Hughes et al. 2007)

• Continuous fibre acts as a series of shorter fibres or segments

• Dislocations act as the loci of microstructural failure, resulting in
– fibre fracture
– fibre-matrix de-bonding
– matrix cracking
Matrix shear stress distribution

Fibre defects

C
B Single flax fibre composite
A

(Eichhorn et al 2001)
How are composite properties affected?

• Unidirectional composites manufactured from flax fibre in an

epoxy matrix
• Fibres modified to improve fibre-matrix adhesion
• Various fibre volume fractions
• Tensile properties investigated
Deformation behaviour
A - Initial linear region
B - Yield point
400 C - Reduced stiffness
E
D - Strain hardening
E - Failure
300
D
Tensile stress (MPa)

200

C
(UD composite of ca. 55% volume fraction)
100 B

A
0
0.0 0.5 1.0 1.5 2.0
Strain (%)
 Irreversible (plastic) deformation
10000
0-3 0 - 9.6dB
200

Cumulative AE events count -N

4-5 9.6 - 14.4dB 180
6-7 14.4 - 19.2dB
1000 160
8-10 19.2 - 26.4dB

Tensile stress (MPa)

11-14 26.4 - 36dB 140
15-17 36 - 43.2dB 120
18-24 43.2 - 60dB
100 100
25 60+dB
90
Stress 80
80 60
10
Tensile stress (MPa)

70 B 40

60 20

50
1 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
40
Strain (%)
30 A
20
10
0
0.2 0.4 0.6 0.8
Strain (%)
Fracture behaviour

Increased adhesion reduces

interfacial de-bonding and
results in a change in the
fracture behaviour: ductile to
brittle
Effect of changing interfacial properties
350 UnM ~V f 57.6%
325 MeA ~V f 59.6%
300
Tensile stress (MPa)

PrA ~V f 55.2%
275 E-glass ~V f 42.4%
250
225
200
175
150
125
100
75
50
25
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8
Strain (%)

Table VV: Analysis of the influence of fibre-matrix adhesion upon yielding behaviour

Reinforce-
Modulus Yield point
ment type
Young’s Tangent Differ- Yield Yield
Modulus modulus ence strain Stress
(GN m-2) (GN m-2) (%) (%) (MN m-2)
UnM 28.96 (1.72) 13.82 (0.98) 52 0.12 (0.01) 35.89 (3.55)
PrA 27.41 (2.26) 18.56 (3.23) 32 0.18 (0.02) 51.32 (6.61)
MeA 26.69 (2.52) 18.10 (3.00) 32 0.18 (0.06) 50.47 (13.73)
Effective fibre aspect ratio

s=1000
160
s=100

120 s=10
Stress (MN m )
-2

80 s=5

40

0
0.00 0.05 0.10 0.15 0.20 0.25 0.30
Strain (%)
Other considerations about
reinforcement
Regenerated cellulose fibre-based composites

• Continuous fibres
• Regular cross-section
• Significantly less variability than natural fibres
• Defect free?
• Potential for modification
• Various manufacturing options: conventional matrices (epoxy,
unsaturated polyesters etc.) or single polymer composites
(“all-cellulose composites” - ACC)
Tensile behaviour of hemp fibre
Stress-strain behaviour of regenerated
cellulose fibre
(Gindl et al 2007)

• High strain to failure can provide good ductility

• Pronounced yield point
Compliance vs orientation

Greater orientation leads to stiffer fibre – good for composite reinforcement

(Gindl et al 2007)
 Natural vs Lyocell fibre
• Epoxy matrix composites

(Santamala et al (2016). Composites Part A-Applied Science

and Manufacturing. 84: 377-385)
Ioncell-epoxy composites
100
60 wt%
80 40 wt%
30 wt%
Stress (MPa)

20 wt% 10 µm
60

40 Neat epoxy

20
20 µm
0
0 0.01 0.02 0.03
Strain
Fibre Young’s Tensile Yielding Yielding Strain at

loading modulus strength strength strain (%) break (%)

(wt%) (GPa) (MPa) (MPa)

0 2.2 ± 0.4 50.2 ± 6.5 13.3 ± 4.9 0.66 ± 0.4 4.1 ± 0.5

20 3.0 ± 0.5 58.3 ± 12 22.4 ± 3.4 0.86 ± 0.25 2.8 ± 1.2 (Unpublished data)
30 4.5 ± 0.5 72.5 ± 7.7 36.7 ±16.1 0.88 ± 0.36 2.1 ± 0.2

40 4.9 ± 1.2 62.7 ± 16.5 39.5 ± 1.6 0.7 ± 0.17 1.6 ± 0.4

60 7.2 ± 0.8 102.8 ± 28 30.3 ± 11 0.49 ± 0.14 4.0 ± 1.8

Traditional matrix vs ACC
• ACCs can be prepared by ‘selective
dissolution’ of fibre or by mixing of
reinforcement in dissolved cellulose,
followed by regeneration
• Various cellulose solvents have been
investigated
• Unidirectional fibre reinforced
composites prepared from Lyocell or
flax fibre with either epoxy or
‘cellulose’ matrix
• Clearly very different microstructures
created when selective dissolution
employed
• Failure of epoxy-matrix composites
dominate by matrix properties
(Gindl-Altmutter et al (2012). Compos. Sci. Technol. 72(11): 1304-1309)
ACCs via solvent infusion processing (SIP)
• Woven Cordenka® fibre textile
• Solvent: NaOH/urea
• Dissolution time/temperature
varied

(Dormanns et al (2016) Composites Part A-Applied Science and Manufacturing 82: 130-140 )
 References and further reading
• Aslan M, Mehmood S, Madsen B, Goutianos S (2010) The effect of processing on
defects and tensile strength of single flax fibres. In: Proceedings of 14th European
Conference on Composite Materials, 7-10 June 2010, Budapest, Hungary
• Baley C (2002) Analysis of the flax fibres tensile behaviour and analysis of the tensile
stiffness increase. Compos Part A-Appl S 33(7):939 -848
• Baley C (2004) Influence of kink bands on the tensile strength of flax fibers. J Mater
Sci 39:331-334
• Davies GC, Bruce DM (1998) Effect of environmental relative humidity and damage
on the tensile properties of flax and nettle fibers. Text Res J 68(9):623-629
• Desch, HE and Dinwoodie, JM (1981). Timber: Its Structure, Properties, and
Utilisation, Sixth edition. Macmillan, London; New York
• DeTeresa SJ, Allen SR, Farris RJ, Porter RS (1984) Compressive and torsional
behaviour of Kevlar 49 fibre. J Mater Sci 19:57-72
• Dinwoodie, JM (2000). Timber: Its nature and behaviour
 References and further reading
• Dinwoodie JM (1968) Failure in timber part 1: microscopic changes in cell-wall
structure associated with compression failure. J Inst Wood Sci 21:37-53
• Dormanns, JW, Schuermann, J, Mussig, J, Duchemin, BJC and Staiger, MP (2016).
Solvent infusion processing of all-cellulose composite laminates using an aqueous
NaOH/urea solvent system. COMPOSITES PART A-APPLIED SCIENCE AND
MANUFACTURING 82: 130-140 (DOI: 10.1016/j.compositesa.2015.12.002)
• Eichhorn, S.J., Baillie, C. A. and Zafeiropoulos, N., Mwaikambo, L.Y. and Ansell, M.P.,
Dufresne, A., Entwistle, M., Herrera-Franco P.J., and Escamilla, G.C., Groom, L.,
Hughes M. and Hill, C., Rials, T.G., Wild P.M. (2001). Current International Research
into Cellulosic fibres and Composites. J. Mat. Sci. 36: 2107-2131
• Eichhorn SJ, Hughes M, Snell R, Mott L (2000) Strain induced shifts in the Raman
spectra of natural cellulose fibres. J Mater Sci Lett19(8): 721-723
• Gindl, W., Reifferscheid, M., Adusumalli, R.B., Weber, H., Roder, T., Sixta, H. and
Schoberl, T. (2008). Anisotropy of the modulus of elasticity in regenerated cellulose
fibres related to molecular orientation. Polymer 49(3): 792-799 (DOI:
10.1016/j.polymer.2007.12.016)
 References and further reading
• Gindl-Altmutter, W., Keckes, J., Plackner, J., Liebner, F., Englund, K. and Laborie, M.P.
(2012) All-cellulose composites prepared from flax and lyocell fibres compared to
epoxy-matrix composites. Composites Science and Technology. 72(11): 1304-1309
(DOI: 10.1016/j.compscitech.2012.05.011)
• Hull, D. and Clyne, T.W. (1996). An Introduction to Composite Materials. Cambridge
University Press, Cambridge, UK
• Hughes, M., Hill, C.A.S., Sèbe, G., Hague, J., Spear, M. and Mott, L. (2000). An
Investigation into the Effects of Microcompressive Defects on Interphase Behaviour
in Hemp-Epoxy Composites Using Half Fringe Photoelasticity. Composite Interfaces
7(1): 13-29
• Hughes, M., Carpenter, J. and Hill, C. (2007). Deformation and Fracture Behaviour of
Flax Fibre Reinforced Thermosetting Polymer Matrix Composites. J. Mat. Sci.
42(7):2499-2511
• Hughes, M. (2011). Defects in natural fibres – their origin, characteristics and
implications for natural fibre reinforced composites: a review. Journal of Materials
Science
 References and further reading
• Hughes M, Hill CAS, Sèbe G, Hague J, Spear M, Mott L (2000) An investigation into the
effects of microcompressive defects on interphase behaviour in hemp-epoxy composites
using half fringe photoelasticity. Compos Interface 7(1):13-29
• Hughes M, Carpenter J, Hill C (2007) Deformation and fracture behaviour of flax fibre
reinforced thermosetting polymer matrix composites. J Mat Sci 42(7):2499-2511
• Mott L, Shaler SM, Groom LH (1996) A technique to measure strain distributions in single
wood pulp fibers. Wood Fiber Sci 28(4):429-437
• Nilsson T, Gustafsson PJ (2007) Influence of dislocations and plasticity on the tensile
behaviour of flax and hemp fibres Compos Part A-Appl S 38(7):1722-1728
• Piggott, M.R. Load Bearing Fibre Composites, Pergamon.
• Santamala, H., Livingston, R., Sixta, H., Hummel, M., Skrifvars, M. and Saarela, O. (2016)
Advantages of regenerated cellulose fibres as compared to flax fibres in the processability
and mechanical performance of thermoset composites. Composites Part A-Applied
Science and Manufacturing. 84: 377-385 (DOI: 10.1016/j.compositesa.2016.02.011 )
• Wardop, A.B. and Dadswell, H.E. (1947). Contributions to the Study of the Cell Wall. 5.
The Occurrence, structure and Properties of Certain Cell Wall Deformations.
Commonwealth of Australia C.S.I.R. Bulletin No. 221.