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Traditional engineering design focusses on the load-bearing capabilities of materials, and develops functionality by adding the structure. However, hybridising with functional materials allows non-load bearing capabilities to be integrated, that simplify the design. Material anisotropy can effect this multi-functionality in complimentary ways, however its effects need to be understood.
The aims of this study were to produce tailored anisotropy in elastomers, and to investigate the resulting mechanical and magnetic performance. Hence, a combination of experimental testing, and numerical & constitutive modelling were used to analyse the mechanical behaviour.
The placement of fibres with a homogeneous magnetic field is demonstrated and described by a simple model. The resulting transversely isotropic elastomers, reinforced by short nickel-coated carbon fibres, are compared to a number of numerical and constitutive mechanical models. Current methods for describing the behaviour of aligned reinforcements assume an inherent anisotropy, analogous to continuous fibre reinforcement, rather than discontinuous reinforcements. However, it is demonstrated that a simple constitutive model can adequately describe the behaviour up to moderate strains (<30%). In addition, a simplified numerical model is shown to represent the behaviour, and could be adapted to investigate complex effects, such as failure and interfacial properties.
In addition, the specimens actuate in a magnetic field, due to the nickel-functionalised fibres. The actuation is dependent on the reinforcement angle and is described by a simple model; furthermore, the combination of the magnetic and mechanical models allows the complimentary behaviour of these properties to be described.
The multi-functional material could be envisaged in a number of high performance applications, such as the active surface of micro-swimmers & -controllers. However, there are a number of challenges in experimental testing of anisotropic materials that require further investigation. Never-the-less, the orientation of reinforcements could be used to produce bespoke fibre alignments or for through-thickness composite repair.

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You are on page 1of 232

David C. Stanier

requirements for award of the degree of Doctor of Philosophy in the Faculty

of Engineering

May 2016

Abstract

develops functionality by adding the structure. However, hybridising with functional materials allows non-load bearing capabilities to be integrated, that simplify the design. Material

anisotropy can effect this multi-functionality in complimentary ways, however its effects

need to be understood.

The aims of this study were to produce tailored anisotropy in elastomers, and to investigate the resulting mechanical and magnetic performance. Hence, a combination of experimental testing, and numerical & constitutive modelling were used to analyse the mechanical

behaviour.

The placement of fibres with a homogeneous magnetic field is demonstrated and described by a simple model. The resulting transversely isotropic elastomers, reinforced by

short nickel-coated carbon fibres, are compared to a number of numerical and constitutive

mechanical models. Current methods for describing the behaviour of aligned reinforcements assume an inherent anisotropy, analogous to continuous fibre reinforcement, rather

than discontinuous reinforcements. However, it is demonstrated that a simple constitutive

model can adequately describe the behaviour up to moderate strains (<30%). In addition,

a simplified numerical model is shown to represent the behaviour, and could be adapted to

investigate complex effects, such as failure and interfacial properties.

In addition, the specimens actuate in a magnetic field, due to the nickel-functionalised

fibres. The actuation is dependent on the reinforcement angle and is described by a simple

model; furthermore, the combination of the magnetic and mechanical models allows the

complimentary behaviour of these properties to be described.

The multi-functional material could be envisaged in a number of high performance applications, such as the active surface of micro-swimmers & -controllers. However, there are

a number of challenges in experimental testing of anisotropic materials that require further

investigation. Never-the-less, the orientation of reinforcements could be used to produce

bespoke fibre alignments or for through-thickness composite repair.

Publications

In the following, the reader is directed to a list of publications produced during the course of

this Research Project. In particular, the author would like to acknowledge that Section 2.2

reuses work published in [1 ], [6 ] and [7 ], Section 2.3 contains results from [2 ] and [3 ],

whilst Section 3.3 and Section 3.4 use work from [4 ] and [3 ], respectively. Section 4.3

uses work from [2 ], whilst [8 ] contains work from Section 2.3, Section 4.2 and Section

4.3.

Journal Publications

[1 ]

Stanier, D.C., Patil, A., Sriwong, C., Rahatekar, S., and Ciambella, J. (2014). The

reinforcement effect of exfoliated graphene oxide nanoplatelets on the mechanical and viscoelastic properties of natural rubber. Composites Science and Technology, 95:59-66.

Conference Proceedings

[2 ]

Stanier, D. C., Ciambella, J. and Rahatekar, S. (2015). Magnetic Response of

aligned nickel coated carbon fibres in a PDMS matrix. In Proceedings of the 9th European

Conference on Constitutive Models for Rubbers (ECCMR IX), Prague.

[3 ]

Ciambella, J. and Stanier, D.C. (2014). Orientation Effects in Short Fibre-Reinforced

Elastomers. In Proceedings of ASME 2014 International Mechanical Engineering Congress

and Exposition, Montreal. American Society of Mechanical Engineers (ASME).

[4 ]

Stanier, D.C. and Ciambella, J. (2014). Multi scale Modelling Nano-Platelet Reinforced Composites at Large Strain. In Proceedings of ECCM 16th European Conference on

Composite Materials, Seville. European Society for Composite Materials (ESCM).

[5 ]

Stanier, D.C., Patil, A.J., Rahatekar, S.S., and Ciambella, J. (2013). Microstructure

Evolution in Graphene Oxide Reinforced Elastomers. In Proceedings of the 7th International Nanoscience Student Conference (INASCON), London.

[6 ]

Stanier, D.C., Ciambella, J., Rahatekar, S., Patil, A.J. and Mann, S. (2013). The

Reinforcement Effects of Graphene Oxide on the Mechanical and Viscoelastic Properties of

Natural Rubber. In Proceedings of the 8th European Conference on Constitutive Models for

Rubbers (ECCMR VIII), San Sebastian.

Internal Publications

[7 ]

Stanier, D.C., Ciambella, J., Rahatekar, S., Patil, A.J. and Mann, S. (2013) The Reinforcement Effects of Graphene Oxide Nanoplatelets on the Mechanical and Viscoelastic

Properties of Natural Rubber. University of Bristol (internal unpublished document).

Pending Publications

[8 ]

Stanier, D.C., Ciambella, J. and Rahatekar, S. Bending and Twisting Actuation of

Nickel Coated Carbon Fibres and Elastomer Composites using Low Magnetic Field. Composites Part A, Under Review 2016.

[9 ]

Ciambella, J., Stanier, D.C., and Rahatekar, S. Magnetic Alignment of Short Carbon

Fibres in Curing Composites by Uniform and Non-Uniform Fields. To be submitted in 2016.

Acknowledgements

This thesis has been realised thanks to the contributions of a number of individuals.

I would like to acknowledge the assistance of my supervisors. In particular, I have been

extremely lucky to have such a dedicated and passionate supervisor as Jacopo, who was able

to respond to my enquires and concerns so promptly, even when a thousand miles away. He

has given me an enormous amount of freedom, and given me the opportunity to experience

so much.

I wish to express my gratitude for the unerring belief and support of my parents and

close family, and the encouragement of my friends. I am also indebted to Iryna, who has

been closest during the most difficult periods; offering continued patience and optimism that

I hope to repay.

Finally, I must thank the Engineering and Physical Sciences Research Council, for providing the funding which has made all of this possible.

Declaration

I declare that the work in this dissertation was carried out in accordance with the requirements of the Universitys Regulations and Code of Practice for Research Degree Programmes

and that it has not been submitted for any other academic award. Except where indicated by

specific reference in the text, the work is the candidates own work. Work done in collaboration with, or with the assistance of, others, is indicated as such. Any views expressed in

the dissertation are those of the author.

SIGNED:................................................................................ DATE:....................................

Table of contents

Table of contents

xiii

List of figures

xvii

List of tables

xxix

Acronyms / Abbreviations

xxxii

Introduction

1.1

Motivations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.2

Technical Challenges . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.3

Objectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.4

2.1

2.2

2.3

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

2.1.1

10

2.1.2

15

20

2.2.1

20

2.2.2

21

2.2.3

24

2.2.4

Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . .

34

36

2.3.1

36

2.3.2

37

2.3.3

40

2.3.4

Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . .

49

xiv

3

Table of contents

Numerical Modelling

3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . .

3.1.1 Literature Review . . . . . . . . . . . . . . . . . . . .

3.2 Constitutive Modelling . . . . . . . . . . . . . . . . . . . . .

3.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . .

3.2.2 The Transversally Isotropic Neo-Hookean Model . . .

3.3 Numerical Homogenisation . . . . . . . . . . . . . . . . . . .

3.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . .

3.3.2 Homogenization Procedure . . . . . . . . . . . . . . .

3.3.3 Description of the RVE . . . . . . . . . . . . . . . . .

3.4 Results of the FE Analysis for Fibre Reinforced Elastomers . .

3.4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . .

3.4.2 Numerical Methods . . . . . . . . . . . . . . . . . . .

3.4.3 Results of the SFRVE FE Analysis . . . . . . . . . . .

3.4.4 Results of the MFRVE FE Analysis . . . . . . . . . .

3.4.5 Discussion . . . . . . . . . . . . . . . . . . . . . . .

3.5 Results of the FE Analysis for Platelet Reinforced Elastomers

3.5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . .

3.5.2 Numerical Methods . . . . . . . . . . . . . . . . . . .

3.5.3 Results of the FE analysis . . . . . . . . . . . . . . .

3.5.4 Discussion . . . . . . . . . . . . . . . . . . . . . . .

3.6 Concluding remarks . . . . . . . . . . . . . . . . . . . . . . .

Magnetic Response

4.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . .

4.1.1 Manufacturing Tailored Reinforced Networks . . . . .

4.1.2 Stimuli Responsive Elastomers . . . . . . . . . . . . .

4.2 Magnetically tailoring the orientation of reinforcements . . . .

4.2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . .

4.2.2 Materials characterization and experimental techniques

4.2.3 Magnetic Experimental Setup and Discussion . . . . .

4.3 Magnetic Actuation . . . . . . . . . . . . . . . . . . . . . . .

4.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . .

4.3.2 Experimental Techniques . . . . . . . . . . . . . . . .

4.3.3 Magnetic Response in a Static Homogeneous Field . .

4.3.4 Results and Discussion . . . . . . . . . . . . . . . . .

4.4 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . .

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Table of contents

5

xv

Conclusions

157

5.1 Original Contributions . . . . . . . . . . . . . . . . . . . . . . . . . . . . 157

5.2 Further Perspectives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160

References

163

183

A.1 The Stress-Strain Curve for Reinforced PDMS . . . . . . . . . . . . . . . . 183

Appendix B Supplementary Material - Chapter 3

B.1 Comparison of the RVE to the Constitutive Model - Plane Stress . . . . . .

B.2 Comparison of the RVE to the Constitutive Model - Plane Strain . . . . . .

B.3 Comparisons of the SPRVE and MPRVE - Plane Strain . . . . . . . . . . .

185

185

191

197

199

C.1 The Magneto-Mechanical Experimental Data . . . . . . . . . . . . . . . . 199

List of figures

1.1

2.1

2.2

2.3

2.4

2.5

2.6

The fibril structure at the spruce tree branch joint (Adapted from [27]). (c)

Venuss Fly Basket Euplectella Aspergillum [235], and (d) A section of the

mineralized skeletal cage of Euplectella Aspergillum (Adapted from [172]).

(e) The marine mussel, anchored by the byssus [93], and (f) A Byssal thread,

with a soft fibrous core and protective cuticles (Adapted from [218]). . . . .

Schematic representation of two types of crystallisation encountered in rubber materials. (a) Static crystallisation. (b) Strain-induced crystallisation. .

(b) A homogeneous distribution of the fillers with an increased dispersion. .

The effect of particle size on the interfacial area. (a) Large particles of

diameter, d. (b) Small particles of diameter, d/2. Particles of equivalent

area have an interfacial zone over twice the size when the diameter is halved.

The inter-particle spacing is also decreased. . . . . . . . . . . . . . . . . .

10

medium. The blue arrow shows the path of least resistance for, e.g. water

molecules travelling through a permeable material. . . . . . . . . . . . . .

15

The crack path for aligned anisotropic fillers. The blue arrow indicates the

crack path. (a) parallel to the loading direction, (b) perpendicular to the

loading direction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

17

Schematic structure of (a) graphene and (b) graphene oxide. Adapted from

[150]. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

20

xviii

2.7

2.8

2.9

List of figures

(a) AFM images of the GO platelets reveal the delaminated sheets to be

1-1.4 nm in thickness, consistent with completely exfoliated single layer

GO; (b) TEM image of GO platelet reveals ultra-thin flat sheet between 500

nm and 1 lm in size; (c) Fourier-transform spectra of GO, graphite, natural rubber and NR-GO nanocomposites containing 1.00 wt% GO; and (d)

SEM images of fractured 1.00 wt% NR-GO specimens reveal homogeneous

dispersions of filler particles. . . . . . . . . . . . . . . . . . . . . . . . . .

22

increasing in GO conc. up to 1.00 wt% on the right. (b) The petri dish

arrangement from which specimens are cut, showing a pure NR material. .

23

Uniaxial tensile test results of NR-GO specimens (a) The stress-strain curve

up to failure. (b) The small-strain fitting of the Mooney-Rivlin model (Eq. 2.1)

up to 30% strain. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

2.10 Uniaxial tensile testing results of cycling specimens up to 1.4 MPa, in between 24 hour rests. (a)&(d) 0.00 wt%, (b)&(e) 0.25 wt%, (c)&(f) 0.50

wt%. (a)-(c) Stress-strain curves. (d)-(f) Mooney plots. . . . . . . . . . . .

min1

27

102 ).

(strain rate of 5.55

(a) Strain versus time; (b) stress versus time for 0.25 wt.% against the constitutive model in Eq. 2.1; (c) stress versus strain at 50 mm\min. The model

for 0.00 wt.%, 0.25 wt.% and 0.50 wt.% are represented by the solid, dashed

and dash-dot lines respectively. . . . . . . . . . . . . . . . . . . . . . . . .

29

2.12 (a) Normalised dissipated energy D during cyclic tests estimated through

Eq. 2.2.b normalised with respect to dissipation of the natural rubber sample

(i.e. 0.00 wt.%). (b) Ratio between the dissipated and stored energies during

the cyclic test (estimated through Eq. 2.2.b). . . . . . . . . . . . . . . . . .

30

at 50, 100 and 200 mm min-1 for specimens v = 0.00 wt.%(continuous line),

0.25 wt.% (dashed line) and 0.50 wt.% (dash-dotted line). . . . . . . . . . .

31

2.14 (a) Stress-time plot of the relaxation tests for the different GO concentrations. The specimens were loaded at 100 mm min1 up to 50% strain, then

held fixed for 600 seconds. (b) The stress-time plot, without the initial loading ramp, normalised against the maximum stress. . . . . . . . . . . . . . .

32

specimen strain cycle. (b) NR stress-strain cycle up to failure. (c) The first

30 seconds of the NR-GO specimen (1.00.wt%) strain cycle. (d) The NRGO

(1.00wt.%) stress-strain cycle up to failure. . . . . . . . . . . . . . . . . .

33

List of figures

xix

2.16 The evolution of the maximum strain reached at the peak of each stress cycle

during stress-ratcheting between 0.15 MPa and 0.30 MPa of specimens of

NR-GO with concentrations of GO between 0 wt% and 1.00 wt%. . . . . .

34

2.17 (a) The neodymium magnetic setup for aligning magnetic fibres in viscous

PDMS solution, and (d) The dispersion of fibres through the thickness of

the specimen, observed by SEM on a fractured specimen. . . . . . . . . . .

37

2.18 The dumbbell test specimen according to ASTM D1708, and an inset showing the alignment of the fibres within a small central sample of the specimen

(Highlighted fibres shown for illustrative purposes only). . . . . . . . . . .

38

2.19 The fibre distributions from a specimen aligned between the four Neodymium

N52 magnets. (a) The fibre orientation distribution, fitted to Eq. 2.3 (b=4.3),

(b) The fibre length distribution, fitted to Eq. 2.4 (c=23.0, d=1.59). The averaged values of 6 specimens are b= 4.5 0.57, c=25.7 4.9 and d=1.61

0.15. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

39

2.20 Interface of the fractured PDMS specimens. (a) A poor interface showing

fibres without matrix attached [96]. (b) Trapped rubber between bundles of

fibres. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

39

2.21 Large strain tensile experimental results of magnetically aligned fibre reinforced PDMS, up to 60% strain. (a) Reinforcement angles 0 , 30 , 60

and 75 , (b) Reinforcement angles 15 , 45 and 90 . The 90% confidence

bars, calculated from 6 tested specimens at each angle, are shown at strain

intervals for each specimen. . . . . . . . . . . . . . . . . . . . . . . . . . .

42

2.22 Large strain tensile experimental results compared to the transversally isotropic

constitutive model, Eq. 2.5, up to 60% strain. Markers indicate the experimental results, lines indicate the constitutive model fitting. (a) Reinforcement angles 0 , 30 , 60 and 75 , (b) Reinforcement angles 15 , 45 and

90 . The 90% confidence bars, calculated from 6 tested specimens at each

angle, are shown at strain intervals for each specimen. . . . . . . . . . . . . 44

2.23 Small strain behaviour of the material, averaged from all specimens and

showing the standard deviation. The model (Eq. 2.10) fitting is shown to fit

the behaviour well. ( = 0.252, = 1.85). . . . . . . . . . . . . . . . . . .

44

at different strain levels. . . . . . . . . . . . . . . . . . . . . . . . . . . . .

45

2.25 The experimental rotation of the fibres compared to the rotations predicted

h

i

by the model, obtained through Nansons formula, i.e. = tan1 3/2 tan(0 ) . 45

xx

List of figures

2.26 The lateral stretch, 2 vs longitudinal stretch, 1 of selected specimens of

each reinforcement angle, compared to the theoretical plane stress (dashed

line) prediction, i.e. 2 = 10.5 . . . . . . . . . . . . . . . . . . . . . . . .

46

2.27 (a) The COMSOL Multiphysics (ver. 5.0, 2014) dumbbell numerical model,

compared to the idealised constitutive behaviour, for angles 0 , 30 , 60 &90

(=0.252 MPa & =1.85). Dashed lines refer to the idealised constitutive

behaviour, markers refer to the behaviour of a dumbbell according to ASTM

D1708. (b-c) The deformation of the 45 dumbbell numerical model, indicating the lateral misalignment between the top and bottom of the gauge

length, at 20% strain for parametric values (b) =0.252 MPa & =1.85

(Lateral misalignment = 0.31mm) and (c) =0.252 MPa & =18.5 (Lateral

misalignment = 0.58mm). The parameter x refers to the lateral misalignment in millimetres, compared to the undeformed configuration. . . . . . .

47

3.1

3.2

3.3

3.4

3.5

3.6

The transverse isotropy of a fibre. Indicating the plane of isotropy orthogonal to the principal fibre direction. . . . . . . . . . . . . . . . . . . . . . .

59

The smallest section of the material microstructure that can model the properties of the overall composite is called the representative volume element.

An assumption of periodicity in the microstructure allows a further simplification to a unit-cell. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

63

multiple fibre RVE, assuming plane stress in the through thickness direction.

In addition, a platelet reinforced elastomer can be assumed to have plane

strain in the through thickness direction, if the thickness is much greater

than the length, i.e. t >> L. In both cases, a further simplification to a

single reinforcement RVE can be made if an assumption of periodicity and

dilute inclusions is made. . . . . . . . . . . . . . . . . . . . . . . . . . . .

66

E1 ,E2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

69

3D RVE to the single platelet one. In each case, the model is simplified

further. (a) The platelet reinforced elastomer block, (b) The fibre reinforced

thin elastomer specimen. . . . . . . . . . . . . . . . . . . . . . . . . . . .

82

A thin elastomer (length much greater than the thickness) with fibres restricted to a single plane (E1 , E2 ) can be modelled as a 2D plane stress

structure. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

85

List of figures

3.7

xxi

multiple aligned fibre RVE model for 0 = 30 (2D-MFRVE). The inset

shows the mesh surrounding a reinforcement. (b) The single fibre reinforced

RVE model for 0 = 30 (2D-SFRVE). The inset shows the mesh around the

inclusion edge. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

86

The distribution of the fibre angles, as defined by the parameter b in Eq. 3.75.

The images show an arrangement whereby the fibres are aligned around the

0 = 0 configuration. The fibre distributions of the 2D-MFRVE are shown

for b = 5 and the aligned configuration. . . . . . . . . . . . . . . . . . . .

87

Cauchy stress 11 against stretch for simple tension in terms of reinforcement orientations 0 = {0 , 25 , 45 , 65 , 90 }. In all cases, (r) = 2 MPa,

f = 1000, AR = 40 and vol = 1.2%. . . . . . . . . . . . . . . . . . . . . .

87

3.10 (a) The tangent modulus during tensile loading of initial reinforcement angles 0 = {0 , 25 , 45 , 65 , 90 }. (b) The fibre change of orientation during

simple tension for different initial configuration of the reinforcement 0 =

{0 , 25 , 45 , 65 , 90 } plotted against the predicted behaviour, Eq. 3.69. In

all cases the parameters of the RVE are: AR=40, vol%=1.2, (r) = 2 MPa

and f = 1000. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

89

3.11 Cauchy stress, 12 , against shear, , for simple tension in terms of reinforcement orientations 0 = {0 , 25 , 45 , 65 , 90 }. In all cases, (r) = 2 MPa,

f = 1000, AR = 40 and vol = 1.2%. . . . . . . . . . . . . . . . . . . . . .

89

3.12 (a) The tangent modulus during simple shear loading of initial reinforcement angles 0 = {0 , 25 , 45 , 65 , 90 }. (b) The fibre change of orientation during simple tension for different initial configuration of the reinforcement 0 = {0 , 25 , 45 , 65 , 90 } plotted against the predicted behaviour,

Eq. 3.69. In all cases the parameters of the RVE are: AR=40, vol%=1.2,

(r) = 2 MPa and f = 1000. . . . . . . . . . . . . . . . . . . . . . . . . .

90

3.13 The change in initial modulus during simple tension for different initial

configuration of the reinforcement 0 = {0 90 }, (r) = 2 MPa and

f = 1000 against Eq. 3.69 . . . . . . . . . . . . . . . . . . . . . . . . . .

91

3.14 A comparison between the uniaxial cauchy stress of the multiple and single

fibre 2D plane stress RVE models up to 60% strain. . . . . . . . . . . . . .

92

3.15 The variation of the stress-strain curves with varying amounts of fibre distribution for different angles. (a) 0 , (b) 30 , (c) 60 , (d) 90 . . . . . . . . .

93

3.8

3.9

xxii

List of figures

3.16 The small strain effects of a distribution of fibres in the RVE. (a) The reduction in transverse isotropy is shown by the reduction in the stiffness difference between longitudinal and lateral directions, (b) Show the effect of

increased alignment on the stiffness for each angle. . . . . . . . . . . . . .

93

3.17 The transverse isotropy of the model is shown by the close fitting to Eq. 3.22

for different values of the heterogeneity contrast (a) f = 10, (b) f = 100 (c)

and f = 1000. The other values are 0 = 35 , (r) = 2 MPa, AR = 40

and = 0.8%. The planes show the constitutive model fitted to the data.

The plotted dots show the numerical values of the strain energy function as

computed by Abaqus for simple tension/compression (red dots) and simple

shear (magenta dots). . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

95

3.18 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 0 , (c)-(d) 0 = 45 and

(e)-(f) 0 = 75 . The other values were (r) = 2 MPa and f = 1000. The

remaining angles can are found in the Appendix B.1 . . . . . . . . . . . . .

96

wherein the thickness is much greater than the length, can be modelled by a

2D plane strain assumption. . . . . . . . . . . . . . . . . . . . . . . . . . .

98

3.20 The two RVE configurations in the undeformed configurations. (a) The

3D multiple aligned platelet RVE model for 0 = 30 (3D-MPRVE). The

inset shows the mesh surrounding a reinforcement. (b) The single platelet

reinforced RVE model for 0 = 30 (2D-SPRVE). The inset shows the mesh

around the inclusion edge. . . . . . . . . . . . . . . . . . . . . . . . . . .

99

3.21 Comparisons between the 3D-MPRVE and 2D-SPRVE for the cauchy stress

difference (11 33 ) against strain for simple tension and compression,

and the cauchy shear stress (12 ) against the shear strain. Displayed for

reinforcement orientations, (a) 30 , (b) 45 , (c) 75 , (d) 90 . . . . . . . . . 101

3.22 Cauchy stress difference against stretch for (a) simple compression and

(b) tension in terms of reinforcement orientations, 0 = {0 , 25 , 45 , 65 , 90 }.102

3.23 (a) Tensile tangent modulus against stretch in terms of reinforcement orientations, 0 = {0 , 25 , 45 , 65 , 90 }. (b) The platelet change of orientation for different initial configurations of the reinforcement against Eq. 3.38.

The absence of points for large tensile and compressive strains both at 0

and 90 is caused by the premature failure of the FE simulation. . . . . . . 103

List of figures

xxiii

3.24 Shear stress against (a) negative and (b) positive shear strain in terms of

reinforcement orientations 0 = {0 , 25 , 45 , 65 , 90 }. . . . . . . . . . . . 104

3.25 (a) Tangent shear modulus against shear strain in terms of reinforcement

orientations, 0 = {0 , 25 , 45 , 65 , 90 }. (b) The platelet change of orientation during simple shear for different initial configuration of the reinforcement against Eq. 3.38. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105

3.26 The transverse isotropy of the model is shown by the close fitting to Eq. 3.22

for different values of the heterogeneity contrast (a) f = 10, (b) f = 100 (c)

and f = 1000. The other values are 0 = 35 , (r) = 2 MPa, AR = 40

and = 1.2%. The planes show the constitutive model fitted to the data.

The plotted dots show the numerical values of the strain energy function as

computed by Abaqus for simple tension/compression (red dots) and simple

shear (magenta dots). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106

3.27 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 25 , (c)-(d) 0 = 45 and

(e)-(f) 0 = 90 . The other values were (r) = 2 MPa and f = 1000. The

remaining angles can are found in the Appendix B.2 . . . . . . . . . . . . . 107

3.28 Effective shear modulus c in terms of platelet orientations 0 for various

heterogeneity contrast {1, 10, 100, 1000} against Eq. 3.43. The other parameters were (r) = 2 MPa, = 1.2% and AR = 40. Note that the case

f = 1 corresponds to the homogeneous solution. . . . . . . . . . . . . . . . 108

3.29 Dependence of the constitutive parameters (a) & (c) and (b) & (d) on the

heterogeneity contrast, f , the aspect ratio, and the volume fraction against

the model introduced in [160] and the one introduced with Eqs. (3.76)-(3.78). 109

4.1

Examples of magnetic actuation and locomotion in the literature. (a) Inchworm like motion of a composite sample by varying the magnetic field on

a ratchet strip [132], (b) Modular, finger-like actuator responsive to a magnetic field [202], (c) A modular micro-actuator, in which each module has

a different reinforcement direction and responds to a magnetic field accordingly [127], (d) A soft cellular elastomer with embedded magnets that collapses in a magnetic field [236]. . . . . . . . . . . . . . . . . . . . . . . . 124

4.2

NiC fibre characterisation under SEM. (a) good fibre (b) agglomeration of

fibres (pre-cure) (c) uneven nickel coating (d) Broken fibre (e) broken interface (g) almost fully broken interface of small fibre. . . . . . . . . . . . . . 129

xxiv

List of figures

4.3

(a) The fibre length distribution, fitted to Eq. 2.4 (c=23.0, d=1.59). The

averaged values of 6 specimens are c=25.7 4.9 and d=1.61 0.15 (b) Micrograph image of the aligned fibres, showing the variation in length and

orientation (Selected fibres highlighted in white). . . . . . . . . . . . . . . 129

4.4

(a) The curing PDMS specimen during the alignment procedure between

the coils of the Electromagnet (Newport Instruments Electromagnet Type

C), (b) The fibre distribution after 24 hours under various magnetic fields

(|B0 | = {0.01, 0.03, 0.05, 0.08} T), fitted to the fibre distribution function,

Eq. 2.3 (b=0.44, 0.92, 1.58, 2.95). . . . . . . . . . . . . . . . . . . . . . . 131

4.5

Orientation distribution of the fibre as predicted by the model (4.10) at different times, tr , for (a) = 5 and (b) = 0.5. A random orientation of the

fibres is assumed at tr = 0. . . . . . . . . . . . . . . . . . . . . . . . . . . 134

4.6

(eq. 4.13) to have 90% of the fibres oriented at 5 deg. B0 min is plotted

against (a) the initial curing rate 0 = 0 /c and the fibre aspect ratio AR

(for a = 2.20 103 ), and (b) the initial curing rate 0 = 0 /c and the

fibre magnetic susceptibility a (for ar = 25). The labels show the magnetic

filed intensity in Tesla. The dashed red area represents the region where B0

is higher than 1 T. Due to the increasing viscosity of the solution, the results

are shown for the steady state (i.e. cured) condition. . . . . . . . . . . . . . 135

4.7

The effect of fibre damage and fibre morphology on the magnetic susceptibility. Orientation of different fibre aspect ratios after 60 minutes under the

homogeneous magnetic field of an electromagnet at a field strength of 0.08T.

Fitted to Eq. 2.3 (a) Orientation of fibres of aspect ratio: {0 < AR 12.7},

b=0.7 (b) {12.7 < AR 24.1}, b=1.4 (c) {24.1 < AR}. b=37.7. . . . . . . 136

4.8

the fitting of Eq. 4.10. (a) One value of is fitted to the interval data,

o1 = 15.4. (b) Three characteristic orientation times improve the fitting of

the data, o1 = 20.2, o2 = 15.7, o3 = 12.6 . . . . . . . . . . . . . . . . . . 137

4.9

(a) The Neodymium magnetic set-up to create an approximately homogeneous field for alignment of the reinforcement, (b) The magnetic field

strength (0.07-0.08T) approximation calculated using FEMM (ver.4.2), (c)

The cured specimen; the arrow indicates the in-plane direction of the reinforcement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138

List of figures

xxv

4.10 (a) The post-cure fibre distribution from a specimen aligned between the

four Neodymium N52 magnets, fitted to Eq. 2.3 (b=4.3). (b) Manufactured

defects and fibre interaction during the curing process cause some agglomerations to form. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139

4.11 (a) The neodymium magnetic set-up to create an out-of-plane reinforcement, (b) The magnetic field strength approximation calculated using the

FEMM software [170], (c) The cured specimen; the arrow indicates the inplane direction of the reinforcement. The centre dot indicates the fibres are

oriented orthogonal to the viewed plane. . . . . . . . . . . . . . . . . . . . 140

4.12 The out-of-plane cured specimen has a fibre reinforcement angle that varies

along the length of the specimen. The length along the specimen is shown

in each image. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140

4.13 (a) The non-homogeneous neodymium magnetic set-up to create an, inplane, variable angle reinforcement, (b) The magnetic field strength approximation calculated using FEMM (ver.4.2), (c) The cured specimen; the arrow indicates the in-plane direction of the reinforcement. . . . . . . . . . . 141

4.14 Experimental setup of the electromagnet for static actuation of the specimens, with the magnetic field directed orthogonal to the plane of the fibres.

Inset: A sample specimen of 0 = 90 , actuated in the static magnetic field. 143

4.15 Static Actuation of specimens with reinforcement angles, 0 , at 0 , 30 , 60

& 90 . Specimens of length 27.5mm, width 7mm and thickness 0.5mm are

presented to a homogeneous magnetic field. A transition from pure bending

for 0 , to pure twisting for 90 is observed. For the orientation of the axes

see Fig. 4.18. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145

4.16 Static bending/twisting actuation of specimens with different fibre alignments; (a) 0 = 0 , (b) 0 = 15 , (c) 0 = 30 , (d) 0 = 45 , (e) 0 = 60 ,

(f) 0 = 75 , (g) 0 = 90 . The dominant actuation angle (bending or twisting) is recorded in each case. . . . . . . . . . . . . . . . . . . . . . . . . . 146

4.17 The magneto-mechanical properties of the magnetically responsive specimens, in a homogeneous magnetic field of maximum strength 0.09 Tesla.

(a) The perpendicular arrangement, whereby 0 is orthogonal to the field.

(b) The transverse arrangement, whereby the field lines are in the plane of

the reinforcements. At 0 = 90 the field is parallel to the field lines. . . . . 147

4.18 Schematic representation of the beam model. (a) The undeformed beam

showing the reinforcement angle in the x-z plane, 0 . (b) The twisting angle,

. (c) The bending angle, . . . . . . . . . . . . . . . . . . . . . . . . . . 148

xxvi

List of figures

(crit)

tion becomes unstable, assuming the model (4.21). (Parameters: E(0 ) and

G(0 ) taken from the results of the mechanical testing (i.e. = 0.252MPa, =

1.85), I = 1.261013 (m4 ), J = 4.771013 (m4 ), L = 27.5103 (m), a

= 2.20103 and f = 6 %). The black dots with error bars represent the results of the experiment carried out by the authors for specimens with fibres

at 0 = {0 , 15 , 30 , 45 , 60 , 75 , 90 }. . . . . . . . . . . . . . . . . . . . 151

4.20 The bending and twisting angles achieved for an imposed orthogonal magnetic field at a field strength just greater than at the occurrence of instability

(crit)

(i.e. 1.01By ), assuming the model (4.19). (Parameters: E(0 ) and G(0 )

taken from the results of the mechanical testing (i.e. = 0.252MPa, =

1.85), I = 1.261013 (m4 ), J = 4.771013 (m4 ), L = 27.5103 (m), a

= 2.20103 and f = 6 %). The orange dots and purple dots, represent the

bending and twisting experimental results, respectively, for specimens with

fibre angles at 0 = {0 , 15 , 30 , 45 , 60 , 75 , 90 }. The solid line represents the model (4.19). The error bars represent the experimental prediction

of the actuation angle, when extrapolated from the magnetic field 1% before and after the occurence of the instability (Given by the dashed line in

Fig. 4.16). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152

A.1 The stress-strain behaviour of 7 selected specimens of NiC fibre reinforced

PDMS samples, shown up to mechanical failure. . . . . . . . . . . . . . . 183

B.1 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The plots represent (a)-(b) 0 = 5 . The other values were (r) =

2 MPa and f = 1000. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 185

B.2 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 10 , (c)-(d) 0 = 15 , and

(e)-(f) 0 = 20 . The other values were (r) = 2 MPa and f = 1000. . . . . 186

B.3 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 25 , (c)-(d) 0 = 30 , and

(e)-(f) 0 = 35 . The other values were (r) = 2 MPa and f = 1000. . . . . 187

List of figures

xxvii

B.4 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 40 , (c)-(d) 0 = 50 , and

(e)-(f) 0 = 55 . The other values were (r) = 2 MPa and f = 1000. . . . . 188

B.5 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 60 , (c)-(d) 0 = 65 , and

(e)-(f) 0 = 70 . The other values were (r) = 2 MPa and f = 1000. . . . . 189

B.6 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 80 , (c)-(d) 0 = 85 , and

(e)-(f) 0 = 90 . The other values were (r) = 2 MPa and f = 1000. . . . . 190

B.7 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 0 , and (c)-(d) 0 = 5 .

The other values were (r) = 2 MPa and f = 1000. . . . . . . . . . . . . . 191

B.8 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 10 , (c)-(d) 0 = 15 , and

(e)-(f) 0 = 20 . The other values were (r) = 2 MPa and f = 1000. . . . . 192

B.9 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 30 , (c)-(d) 0 = 35 , and

(e)-(f) 0 = 40 . The other values were (r) = 2 MPa and f = 1000. . . . . 193

B.10 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 50 , (c)-(d) 0 = 55 , and

(e)-(f) 0 = 60 . The other values were (r) = 2 MPa and f = 1000. . . . . 194

B.11 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 65 , (c)-(d) 0 = 70 , and

(e)-(f) 0 = 75 . The other values were (r) = 2 MPa and f = 1000. . . . . 195

B.12 Comparison between model (3.22) and FE results for different values of the

orientation angle in terms of strain energy vs. strain and stress vs. strain

curves. The different plots represent (a)-(b) 0 = 80 , and (c)-(d) 0 = 85 .

The other values were (r) = 2 MPa and f = 1000. . . . . . . . . . . . . . 196

xxviii

List of figures

B.13 Comparisons between the 3D-MPRVE and 2D-SPRVE for the cauchy stress

difference (11 33 ) against strain for simple tension and compression,

and the cauchy shear stress (12 ) against the shear strain. Displayed for

reinforcement orientations, (a) 0 , (b) 15 , (c) 60 . . . . . . . . . . . . . . 197

C.1 The cyclic testing of a 0 specimen. The specimen is cycled 10 times, to

10% strain at a loading rate of 10mm min1 . . . . . . . . . . . . . . . . . . 199

List of tables

2.1

2.2

2.3

4.1

and 1.0 wt%. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

Youngs modulus, E, calculated from based on the fitting of the Mooney

Rivlin formulation (Eq. 2.1) to the stress-strain response up to 30% strain,

alongside an estimate of the strain value at which the upturn in stress occurs

(associated with the onset of SIC [37]), which is estimated from a Mooney

plot. The testing consisted of the first uniaxially stretching the specimen up

to 1.4MPa and then resting it, followed by again testing to 1.4 MPa after

24 hours; resulting in two sets of results. . . . . . . . . . . . . . . . . . .

The average mechanical results of specimens tested to failure, standard deviations shown in brackets. Indicating, the Youngs modulus, E, calculated

from based on the fitting of the Transversely Isotropic constitutive model

(Eq. 2.10) to the stress-strain response up to 30% strain, the strain-to-failure

and the strength of the specimens. . . . . . . . . . . . . . . . . . . . . . .

25

26

41

The percentage of fibres aligned to the magnetic field direction in experimental testing. The model fittings are shown in square brackets, when considering three characteristic orientation times (o1 = 20.2, o2 = 15.7, o3 =

12.6). . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 137

Acronyms / Abbreviations

AFM Atomic Force Microscopy

CB

Carbon Black

FE

Finite Element

FT IR Fourier transform infrared spectroscopy

GE

Graphene

GO

Graphene Oxide

H T Halpin-Tsai

LAA

MPRV E Multiple Platelet Volume Element

NR

Natural Rubber

RV E Representative Volume Element

SAXS Small angle x-ray scattering

SEM Scanning electron microscopy

SFRV E Single Fibre Representative Volume Element

SIC

Strain-Induced Crystallisation

xxxii

Acronyms / Abbreviations

T EM Transmission electron microscopy

Tg

Chapter 1

Introduction

1.1

Motivations

Optimisation in the design of engineering structures is a vital requirement. The optimisation can involve consideration of many variables that include, e.g. time, cost and weight.

However, this is not possible without (1) a good understanding of the processes involved

and (2) a knowledge of the design space available. Research is continually involved in the

expansion of both of these areas, and often takes inspiration from nature [61, 62]; which has

had many thousands of years to optimise its behaviour to its environment.

The mechanical properties are generally regarded as of primary concern in the majority of structural applications, however there is also great interest in other properties such

as electrical conductance [15] and magnetic responsiveness [202]. In fact, it is possible to

control multiple properties simultaneously to develop multi-functionality. In composite materials, major advances are being made to develop novel and multi-functional materials, for

instance morphing structures [234] and self-healing composites [123].

In elastomer materials, the design space can be expanded to consider the large strain

behaviour, although the continuous fibre reinforcements used in composite materials are not

suitable for withstanding large strains. Hence, discrete reinforcements such as carbon black

(CB) are commonly used to reinforce the material, although anisotropic reinforcements are

increasingly used due to the excellent excellent physical and mechanical properties of the

resulting elastomers [14]. However the reinforcing potential of anisotropic reinforcements is

rarely maximised due to the homogenous distributions that are typically used. To maximise

their potential, deliberate placement of the reinforcement can be considered that will create

an anisotropic material that optimises it to, for example, carry load or resist damage.

There are many of example in nature of optimising the architecture of the constituents

to achieve high performance. Trees construct their architecture in such a manner by ori-

Introduction

Fig. 1.1 Examples of anisotropic architecture in nature. (a) A spruce tree, and (b) The fibril structure at the spruce tree branch joint (Adapted from [27]). (c) Venuss Fly Basket

Euplectella Aspergillum [235], and (d) A section of the mineralized skeletal cage of Euplectella Aspergillum (Adapted from [172]). (e) The marine mussel, anchored by the byssus

[93], and (f) A Byssal thread, with a soft fibrous core and protective cuticles (Adapted from

[218]).

enting the fibrils, and tailoring the response of the material [59]. In this way, rather than

homogenising the material properties, the strain field can be homogenised; subsequently reducing the stress concentrations and delaying failure around features such as branch stems

[178] (See Fig. 1.1a&b). Similar examples include the Venuss Fly Basket (Euplectella Aspergillum), which makes use of low strength and brittle glass to create a stable structure

that is able to withstand ocean currents [51] (See Fig. 1.1c&d) and the byssus of marine

mussels, that has a hard protective coating that withstands strains as high as 100% [94] (See

Fig. 1.1e&f).

1.2

Technical Challenges

Control of the reinforcements in elastomer materials, in terms of orientation and spatial position, could provide potential weight savings, increased performance and maximum use

of multi-functional capabilities (e.g. electrical conductance, magnetic susceptibility). In

this study, an understanding of the stress-strain behaviour will generally only be considered

up to moderate strain values (defined here as 60%); due to the technical challenges that

remain unresolved in this strain range, and the large number of applications that operate

within this range.

The identified key technical challenges and unanswered questions are highlighted below:

Despite the recent interest in nano-dimensioned fillers, many aspects of the effects of

anisotropic nano-reinforcements on the mechanical and viscoelastic properties of elastomers

remain unclear. This is particularly relevant to its acceleration of formed stiffening networks

compared to spherical particles, and the induced anisotropic behaviour that may occur at

large strain. Anisotropic reinforcements are known to cause instabilities under compression,

however the rotation of the reinforcement is also expected to affect the large strain behaviour

by changing the stress transfer mechanism.

A transversely isotropic material has properties which are identical in one plane, with

different properties in the direction normal to this plane. This is the simplest form of

anisotropy, and is often used in industrial applications. However the manufacture of these

materials with dis-continuous fillers is challenging, as it requires the alignment of the reinforcement in a single plane. Further complications exist when spatial change in the alignment angle exists. A number of strategies exist that can help to predict and control the

alignment of fillers in a viscous solution, however the lack of experimental data to validate the approaches raises questions regarding the extend to which such models are able to

predict the behaviour.

Modelling the behaviour of these dis-continuous filler reinforced elastomer materials

can also be challenging at large strain. Complex models are often required, particularly

when considering material phenomenon, such as strain-induced crystallisation, that result

in highly non-linear behaviour. However these models can be computationally expensive

and unstable. A simple model is generally preferred, however it is important to be aware

of the limitations of each approach and assess the degree to which it is able to describe the

material behaviour.

Magnetic fibres are added to an elastomer material, and so the resultant material is responsive to a magnetic field. When the fibres are aligned, the magnetic responsiveness and

Introduction

mechanical properties both depend upon the fibre orientation, and are expected to behave

in a complimentary manner, i.e. the mechanical properties affect the magnetic response. It

is expected that interesting actuation behaviour can be achieved by careful consideration of

the reinforcement direction, in relation to the magnetic field direction.

1.3

Objectives

that these benefits will be most apparent when the reinforcements are aligned.

To demonstrate the controlled manufacture of aligned reinforcements.

To understand the mechanical behaviour up to moderate strains (60%).

To see how best to model the behaviour and understand the limitations of each method.

To demonstrate the usefulness of anisotropic behaviour in the context of actuation,

and the complimentary manner in which mechanical/magnetic response will interact.

1.4

This thesis discusses the benefits of anisotropic reinforcements on the mechanical and multifunctional response of elastomers, and is organised into three distinct sections. Each section

has a self-contained literature review that is intended to focus the reader on the relevant literature concerning the chapter ahead. It is organised as follows:

In the second chapter, "Experimental Mechanical Characterisation", the experimental

results of elastomers containing anisotropic reinforcements are discussed. In particular, the

effects of the orientation and rotation of the reinforcements is explored. This chapter introduces the reader to the mechanical properties of the anisotropic materials, and shows that

a simple constitutive model is unable to describe the material behaviour at larger strains.

A literature review is included at the beginning of the chapter to give the reader a general

introduction to rubber technology and a number of its physical characteristics.

In the third chapter, "Numerical Modelling", a set of representative volume elements

are used to explore the constitutive models applicability to the specific problem of discontinuous fibres in an elastomer. The numerical model considers the micro-scale behaviour

of the constituents, and the constitutive model acts as an intermediary step towards the experimental testing of chapter 1. Only strain effects up to 60% are considered. A literature

review at the beginning of the chapter discusses the progress of numerical modelling towards describing complicated non-linear effects at large strain; illustrating the difficulties

and limitations of both constitutive modelling and numerical modelling.

In the fourth chapter, "Magnetic Response", the effects of the magnetically responsive

fibres are discussed in the material when the PDMS matrix is uncured and cured (i.e. during

alignment, and the subsequent actuation of the material upon cure). As such, a literature

review is included at the beginning of the chapter to display the state-of-the-art in this field,

and the projected applications which it is intended for.

Chapter 2

Experimental Mechanical

Characterisation

2.1

Introduction

dissipation and the ability to deform to large strain [42], that see it used in applications that

range from car tyres to vibration mounts to artificial hearts [162].

It is able to recover quickly to its approximate original shape after large deformations

[241], which is a quality shared by a number of materials, that includes some biological

tissues. The behaviour is as a result of the long chains in the material, and the unique way

in which they interact. For example, in natural rubber (NR) there are three main characteristics of the chemical structural composition that are thought to be most responsible for this

behaviour, and differentiate it from a viscous liquid [241]: (1) the presence of long polymer

chains with freely rotating links, (2) weak secondary forces between polymer chains that

allow it to take a variety of statistical configurations without being massively impeded by a

large number of primary bonds (e.g. covalent bonds), (3) a limited 3D network formed by

the interlocking of molecules at certain points, allowing it to return to its original shape.

This interlocking 3D network is the result of a cross-linking agent added to the elastomer. In natural rubber it is known as vulcanisation and typically involves the addition of

sulphur to form cross-links, although in unvulcanised NR there is no direct 3D network, and

instead it is thought that the chain entanglements and end-linking networks help to form a

pseudo network [4].

An important phenomenon of NR, and some other rubbers, is the ability to crystallise at

temperatures approaching 0 C, which involves a gradual reordering of the polymer chains

to form crystalline regions (see Fig. 2.1a). This change in structure is a first order transition,

and is therefore accompanied by an increase in density and the release of latent heat [241].

It can result in the ordering of up to 30% of the polymer chains, after which the motion of

polymer chains is restricted, resulting in a hardening/reinforcing of the material analogous

to filler reinforcement. The rate of crystallisation is much slower in vulcanised NR than in

unvulcanised NR because of the relative decrease in chain motion possible.

A related, but independent, type of crystallisation that occurs due to the ordering of

the chains in the direction of an applied stretch is strain-induced crystallisation (SIC) (see

Fig. 2.1b). This reinforces the material in the direction of the applied strain (analogous to

transversely isotropic fibre reinforcement), causing a stiffening of the material at high strain

that can be observed as an upturn in stress on the stress-strain curve [226] (1) . However,

upturns in stress are observed in non-crystallising rubber such as PDMS due to the effects

of limited extensibility of the polymer chains. The overall result can be a toughening of the

rubber, whereby the initial softening protects the material and reduces stress concentrations,

but as strain hardening occurs it protects areas from damage and further deformation [252].

Fig. 2.1 Schematic representation of two types of crystallisation encountered in rubber materials. (a) Static crystallisation. (b) Strain-induced crystallisation.

The rubbery behaviour of elastomers is temperature dependent, and due to them operating above the glass transition temperature, Tg. The behaviour depends on the random

thermal motion of polymer chains by the rotation of single bonds, an effect that is partially

restricted in the materials. However, the addition of thermal energy aids this motion. Con1 The

upturn in stress is an indication of SIC rather than a direct measure of it, and does not necessarily

indicate the initiation point of SIC.

2.1 Introduction

versely, however, by restricting the thermal energy to the system it is possible to reach a

temperature at which the material cant behave as such, and effectively behaves as a solid,

i.e. glassy. The Tg alters depending on the materials internal structure, but there is no

change in density, volume or in fact any geometrical structural change within the material

during the transition, and so it is termed a secondary phase transition. It does however involve an increase in the elastic properties (i.e. stiffness) as well as a change in the expansion

coefficient [241].

The addition of filler materials to rubber is the general method of improving the mechanical properties, and in fact the reinforcements are almost ubiquitous to rubbers (i.e. consider

that rubber is generally thought of as black, which is the case only because of the addition

of large quantities of carbon black). The primary purpose of filler materials is to reinforce

and improve the mechanical and physical properties of a material, however non-reinforcing

fillers can also be used to bulk out a material. For instance, the use of CB in rubbers also

reduces both the cost and weight of the material.

The effectiveness of reinforcements is largely dependent on the state of dispersion and

distribution of the fillers. A good distribution of the fillers requires that they are evenly

spaced in the material to give a homogenous mechanical response, but to maximise the surface interaction to the elastomer it is important to separate agglomerations and maximise

dispersion [265] (See Fig. 2.2). In this way it is possible to avoid defect sites, voids and

stress concentrations; all of which will reduce the mechanical properties and lead to premature failure [198].

Fig. 2.2 Distribution vs Dispersion. (a) A homogeneous distribution of the fillers, (b) A

homogeneous distribution of the fillers with an increased dispersion.

The morphology of the filler can also have a significant effect upon the properties, and

can be separated into three main categories: (1) Equi-axed (spherical) [9, 156], (2) fibres

such as carbon fibres [66] and carbon nanotubes (CNT) [13], and (3) platelets such as

10

graphene (GE) [226] and layered clays [76]. The choice of reinforcements generally depends upon the ease of manufacture and material cost, however anisotropic reinforcements

can be tailored to give a controlled anisotropic response to the material [52] and have a

higher specific surface area than equi-axed particles. The surface area, in particular, is

a well considered advantage of a reinforcement and has led to an explosion in the use

of nano-dimensioned materials [14, 262], particularly since the discovery of methods to

produce graphene [182] and CNTs [109]. Their large specific surface area and excellent

physical properties give the engineer a large amount of control over the bulk properties of

the material, if they can control the transfer of stress between the matrix and reinforcement.

The extent of this increase can be seen in Fig. 2.3, which shows that a reduction of the particle size leads to an increase in the specific surface area and a reduction in the inter-particle

spacing. This effect is further exacerbated by an increase in the aspect ratio of the particle

towards a fibre or platelet morphology. This has led to an enormous amount of research

on improving the interface of nano-reinforcements, as a small change in the interface has a

comparatively large effect compared to micro reinforcements and can help to improve the

dispersion of the fillers (2) .

Fig. 2.3 The effect of particle size on the interfacial area. (a) Large particles of diameter,

d. (b) Small particles of diameter, d/2. Particles of equivalent area have an interfacial zone

over twice the size when the diameter is halved. The inter-particle spacing is also decreased.

2.1.1

The mechanical benefits of elastomers reinforced by stiff filler materials are well documented. The benefit is dependent on both the mechanical properties of the reinforcement,

2 The

interfacial region is the region of altered properties, in comparison to the main constituent parts, that

surround the fillers due to, for example, chain mobility, altered chemistry or crystallinity [2].

2.1 Introduction

11

and its adhesion to the elastomer i.e. the interfacial properties. Hence, the recent interest in nano-dimensioned materials in elastomers is unsurprising [34, 100, 264], as their

large surface areas and excellent physical properties [262] help to form an excellent transfer

mechanism between the elastomer and the reinforcement. In order to affect these property

enhancements, it is important to carefully control both the processing techniques and the

interfacial properties of the materials. It is generally considered that a good dispersion of

reinforcements is advantageous, as shown in [265] where a better dispersion is achieved

by sonication of an aqueous dispersion of NR and Graphene Oxide (GO), followed by insitu reduction to GE. However, by carefully controlling the formation of the reinforcement

networks within the rubber, it is also possible to improve the small-strain mechanical properties, as well as the electrical and thermal conductivity, at the expense of the large strain

ability to withstand rupture [196]. In this case, the strong inter-particle links at small strain

become stress concentrations at large strain. Although, in general it is agglomerations which

have a significant effect on the large strain performance due to the formation of cracks and

voids [15].

In addition to the processing of the reinforced rubber, the interface between the constituents is equally important. Reduced GO (i.e. GE) can be produced with defects and

chemical bonding sites that reduce the property of the platelet, but improve the interfacial

properties by creating extra bonding sites and mechanical interlocking, and which help to

enhance the cross-linking process [100]. In fact, the interfacial chemistry is very similar in

most reinforcing materials and involves forming an immobilized region of rubber around

the reinforcement; the effects of which can stretch far into the polymer chains of the rubber

if the functionalization of the reinforcement is good [200]. However, this is only possible when the interface between the rubber polymer and the reinforcement is good. This

can be achieved by modification of the reinforcement prior to mixing [23, 143], although

advantages in dispersion have been demonstrated with in-situ functionalization [200].

The result is that incredible improvements in rubber mechanical properties (e.g. stiffness and strength) can be achieved by the addition of only a small amount of nano-filler

[13, 196]. The consequence, however, is that for heavy polymers, as elastomers typically

are, the use of cheap fillers such as CB have the effect of reducing not just the price but also

the weight of the final material. It is for this reason that there is also work involving the

combination of cheap conventional fillers, such as CB, with nano-fillers such as GE. This

combination has been shown to produce beneficial effects in the properties of NR, showing

an appreciable increase in the dynamic, thermal and mechanical properties of the material

[164].

12

One of the advantages of using discontinuous reinforcements, in contrast to, for example, continuous carbon fibres used in conventional composite materials, is that they allow

the rubber to achieve the large strains that are synonymous with rubbers and are a major

advantage in many of their applications. This has significant effects upon the large strain

performance of reinforced elastomers, which is evidenced particularly in the upturn in stress

at large strain, which occurs at lower strains due to strain amplification effects of the reinforcements (3) [13, 15, 265].

The reinforcement of NR with CB has been shown to affect this change [186], and

although the exact mechanism is uncertain [239], it is clear that the reinforcement promotes

an early formation of SIC due to a strain amplification effect. However, the final percentage

of SIC is independent of reinforcement concentration, suggesting that the reinforcement

merely initiates SIC earlier and does not help to directly promote its growth [186]. Whilst

wide angle X-ray diffraction (WAXD) is able to directly measure the onset of crystallization

[240], the use of a mooney-plot is able to give a useful representation of the stress-strain

curve that more clearly indicates the upturn in stress [265]; this upturn is associated with

the onset of SIC [186]. SIC is also found to delay rupture in elastomers, as evidenced by

the dramatic decrease in tensile strength when SIC is suppressed by testing at an elevated

temperature [79].

A similar upturn in stress at high strain can be observed in non-crystallizing elastomers,

such as PDMS. In this case the limited extensibility of short chains causes an upturn in

stress, whilst longer chains in the network help to delay rupture; in this way it can be described as a bimodal network [252]. It results in a less pronounced increase in the tangent

modulus than SIC in NR, however it is unaffected by temperature.

Whilst crystallization can have significant large strain effects in some elastomer materials, the direct effect of anisotropic reinforcements can also be evidenced. Whilst CB shows

little to no evidence of orientation at large strain, GE has been observed to orient by small

angle X-ray scattering (SAXS) [186] due to its anisotropic morphology. This orientation

can assist in the formation of crystallites, as demonstrated by CNTs oriented at large strain

in NR [14, 250], or in a breakdown of the electrical networks [14]. However it has been

demonstrated that, by careful knowledge of the mechanisms that form the networks, repeated loading of CNT reinforced epoxy can demonstrate improvements in mechanical and

electrical properties by creating a transversely isotropic network of CNTs [248].

3 Strain

amplification: The local strain of an elastomer around a rigid reinforcement often considerably

exceeds that of the macroscopic strain, due to the matrix bearing the entire deformation. The effect in filled

elastomers can be that phenomenon such as strain-induced crystallization occur at a reduced global strain

level.

2.1 Introduction

13

In vulcanized NR, such permanent orientations are not easily possible, however with the

use of unvulcanized NR it is thought that some permanent deformation of the reinforcement

could be achieved due to the viscous effects of the entangled polymer chains; and the resulting behaviour of the material could provide further understanding of the material networks.

Viscoelasticity

The viscoelastic properties of rubber materials can be advantageous (e.g. dissipation in

car tyres) or disadvantageous (e.g. the creep in plastic shopping bags when full). Therefore it is important to understand the viscoelastic effects, particularly as they are further

complicated by the addition of reinforcements [142].

The viscoelasticity of filled elastomers is often investigated under stress-relaxing conditions. An investigation of the effects of fillers has shown that in crystallizing elastomers,

i.e. NR, the fillers act as nucleation sites for crystallization resulting in an increase of the

relaxation rate due to a relaxation of the amorphous phases [205]. A similar increase in

relaxation rate with the addition of fillers in non-crystallizing materials has also been investigated and could be attributed to the strain amplification effect [49, 141], as well as a

loss of cross-linked network and breakdown of the molecular weight of the polymer during

processing, due to the presence of the fillers [43]. In unvulcanised specimens however, the

presence of fillers slow down the relaxation rate due to the increased viscosity and additional

entanglements provided by a large amount of CB (up to 46 wt%) [43].

Closely related to these relaxation effects are the dynamic moduli. When a viscoelastic

material is stretched at a given strain rate, the response of the material will not be instantaneous; in fact the stress lags behind the strain and allows the elastic and viscous quantities to

be separated mathematically, which are known as the storage and loss moduli respectively.

The ratio of these quantities, referred too as the loss tangent (4) , is representative of the

damping ability of a material.

The addition of reinforcing fillers to rubber has the effect of simultaneously increasing both the storage modulus and the loss tangent, although by different mechanisms. The

storage modulus is representative of the stiffness of a material at a dynamic strain (i.e. nonstatic) and is typically increased by the inclusion of reinforcements because of the stress

transfer between the rigid fillers and bulk matrix [16]. However, the reinforcements also increase friction, due to polymer/filler interactions as well as particle interlayer sliding [148].

This, accompanied by measurement of the glass transition temperature [173], can provide

information on the interfacial interactions of the material.

4 The

tan :=

loss tangent, also referred to as tan , is the ratio of the loss modulus to the storage modulus i.e.

G ()

G ()

14

Fatigue

Rubbers are typically required to be a high performing materials that can withstand high

strain and have the ability to dissipate large amounts of energy efficiently. This makes it an

ideal material for use in tyres, seals, vibration isolators, belts and hoses, structural bearings,

boat engine impellers, impact dampers, footwear, among other applications. However, this

also means that in its life-time the material is expected to withstand repeated static and timevarying strains, making the fatigue life of vital importance. This can be especially difficult

in elastomer materials when effects such as strain-induced crystallization become important.

Whilst the nucleation and growth of cracks is of primary importance when considering

the life of rubber materials in service [166], and in fact nano-reinforcing materials have

been shown to stunt the growth of cracks, the prohibition or delay of this nucleation is

also advantageous. Crystallization is a known mechanism in NR that helps to delay fatigue

failure, particularly in reinforced elastomers where the amount of crystallization at a given

strain level is amplified [12, 146, 216]. In these cases however, the loading conditions are

particularly important due to their relation to crystallization. Non-relaxing load conditions

favour the formation of large crystallites [216], especially if the minimum strain is above

the crystallite melting strain ratio, which help to halt the growth of cracks [146]. Even at

moderate strains ( 30%), reinforced elastomers are able to accelerate the formation of SIC

around the highly strained crack tip and reduce its effect [259].

In contrast, non-crystallizing rubbers are typically not as fatigue resistance [11] although

similar mechanisms can still enhance the property. For instance, strain-induced anisotropy

helps to split the cracks and spread their energy; an effect that anisotropic inclusions can aid

[188]. Therefore, the amplitude of the applied strain and the minimum strain are important

in the same way as they are for NR [1]. Reinforcements can also roughen the surface

of cracks, causing crack pinning and deflection [19, 188]. However, without appropriate

dispersion and distribution, fillers can cause agglomerations which reduce the fatigue life

by causing cracks to propagate from stress concentrations [128].

To mitigate this risk, the proper inclusion of reinforcements is necessary. By distributing

them homogeneously and with a good dispersion, a strain amplification can occur whereby

a smaller strain is necessary to reach an equivalent stress. This reduces the growth of stressconcentrations into cracks by reducing the maximum stress the material operates at. As this

effect is directly related to the fatigue performance of a material, it is possible to predict the

long-term performance of a material through the use of relatively short-term testing such as

stress-ratcheting [263]. By cycling the material between fixed stress values and observing

the evolution of strain, it is possible to predict the fatigue performance [48] and even gain

2.1 Introduction

15

Elastomeric Networks Created by Anisotropic Reinforcements

The formation, and subsequent breakdown, of filler networks is also an important area of

research. Whilst there has been a lot of work on the advantages of equi-axed nanoparticles

[34, 107], one of the biggest advantages of elongated fillers such as fibres and platelet, is

their ability to orient and form effective networks within the material that can enhance, for

example, the mechanical and electrical properties.

The improvement of these networks is typically achieved by superior dispersion and distribution of the fillers [265], however a better network can be formed by careful processing,

as Ref.[196] demonstrated by the formation of a web-like network structure that enhanced

the mechanical, electrical and thermal properties when compared to an even dispersion of

the same filler.

In fact, the positioning of fillers, coupled with their morphology, can create a tortuous

path that retards the advancement of, for example, cracks [188] or improves permeability

[204]. This tortuous path can be further supplemented by the flat elongated morphology of

GE platelets [264] (See Fig. 2.5).

Fig. 2.4 The tortuous path caused by aligned anisotropic reinforcements in a matrix medium.

The blue arrow shows the path of least resistance for, e.g. water molecules travelling through

a permeable material.

2.1.2

The effects of anisotropy upon material properties are extensively dealt within industry and

research: often this is incidental anisotropy produced as a result of manufacturing processes,

such as induced anisotropy in mylar sheets produced by roll milling [110], or the anisotropic

behaviour of NR induced by large strain deformation [237].

The reinforcement of materials by the addition of filler particles is typically applied to

improve the material properties, and often the use of anisotropic fillers is employed because

16

of their increased interface. However the addition of these fibres can produce anisotropy,

even when the material is initially isotropic, due to the rotation of the fibres at large strain

[206].

By careful consideration of the spatial and orientational distribution of these reinforcements it is possible to tailor the anisotropic properties to give exceptional properties that

are not attainable in isotropic materials. The anisotropy can be attained in 3-dimensions,

giving a large design space and allowing optimisation of the constituent materials within the

composite. However, anisotropic materials can be highly non-linear and so it is important to

understand the behaviour, the factors that affect it and be able to predict it. It is also possible

to further utilise this anisotropy for other material properties such as the electrical [264],

magnetic [131] and permeability [220] properties.

Transversely Aligned Reinforcements

The orientation of reinforcing materials is a technique used extensively in nature, for

example the fibril angles of spruce tree branches are oriented to optimise the structure to the

loading encountered by the tree and can even adapt to changing loading conditions during

its growth. Due to the small size, and subsequently low moment of inertia of young branch

stems, they are unable to withstand high wind loads; therefore the fibrils of the spruce

are initially oriented away from the loading direction where they give low stiffness and

high toughness. As the tree branch grows, it creates stiffer deposits of material on the top

tension side of the branch, by gradually orienting the fibril angle until it is parallel to the

loading direction [59].

The advantages of orienting reinforcements in polymer systems have been demonstrated

by many researchers [52, 53, 154]. This is especially true for nano-dimensioned materials,

which can bring significant property improvements with small amounts of reinforcing material. For example, a 48% (415MPa to 615MPa) increase in stiffness has been obtained

by randomly dispersing CNTs in an epoxy matrix. However by aligning the CNTs, a 102%

(843MPa) increase in the stiffness can be obtained parallel to the fibres with only a small decease in the perpendicular direction (575 MPa) [248]. Similar increases in strength are also

observed, and a 74% increase in strength is obtained when orienting the fibres compared to

a random dispersion.

Platelets have the advantage that they can reinforce in two principle directions because

of their morphology, and control of both axes can be obtained using magnetic fields. In

Ref.[154] longitudinal alignment of alumina platelets has resulted in a 124% increase in

the flexural stiffness compared to the pristine epoxy, with a moderate increase in stiffness

when the platelets are oriented transversely. However, whilst a 10% increase in strength is

2.1 Introduction

17

also obtained when the platelets are oriented longitudinally to the loading direction, transverse alignment induces stress concentrations, fails to stop the propagation of cracks and

ultimately results in the onset of brittle fracture (See Fig. 2.5).

Fig. 2.5 The crack path for aligned anisotropic fillers. The blue arrow indicates the crack

path. (a) parallel to the loading direction, (b) perpendicular to the loading direction.

At this stage it is worth discussing the difficulties in experimental testing of anisotropic

materials, which has led to very little reliable experimental data being available in the literature; particularly for more complicated modes such as bi-axial and shear deformations [24].

A transversally isotropic lamina can be characterised to some degree by tensile tests of 0 ,

45 and 90 configurations [115]; however it is important to consider the large strain behaviour and the behaviour of different deformation gradients [24, 46]. This can be difficult

due to the oblique angle of anisotropy which is known to cause shear forces and bending

moments in standard grips, resulting in stress concentrations [45]. When the anisotropy is

weak, it may be appropriate to neglect the effects, however when the anisotropy between

principal directions is an order of magnitude different (such as in Ref.[256]) it is necessary

to use, e.g. oblique test fixtures, that clamp at the angle of anisotropy [256]. At large strain

this is not possible due to the rotation of the principal axes, and so rotating test fixtures are

needed.

Anisotropy has had beneficial effects to a number of other properties, for example, the

hardness of the material has been found to be highest when the platelets were oriented

vertically to the surface, compared to a very low hardness when the platelets were oriented

parallel or randomly to the surface [154]. This arrangement of the outer layer in a material

to give protective properties can be observed in mollusc shells.

The outer layer of mollusc shells consists of perpendicularly oriented calcite prisms that

18

increase the wear resistance [215]. The wear of material consists of the development of

shear stresses at the surface that remove particles from this area, however particles perpendicularly aligned to the surface are harder to remove. Beneath this layer, the mollusc shell

is designed so that any cracks that do initiate are met by a layer of parallel layered aragonite

platelets that create a tortuous path and hinder crack propagation [215].

Polyurethane reinforced with magnetite coated alumina platelets have shown a 77%

increase in the wear volume when oriented vertically out of the surface, compared to longitudinally oriented platelets [52]. This increase in wear resistance is an important quality of

many materials, particularly those expected to be in service for extended periods, however

vertical alignment of the platelets is also accompanied by a reduced in-plane stiffness. In

order to achieve an optimised material that combines the best qualities of both materials, it

is possible to produce a layered material.

Reinforcements Distributed in a Layered Arrangement

Layered materials make it possible to combine the properties of multiple constituents,

and utilise the constituents in optimal configurations throughout a structure to strengthen

it. For example, teeth consist of a 3D multi-layer structure; primarily consisting of a hard

enamel shell built to withstand mastication loads and a dentine core that is very tough and

helps to stop cracks propagating [61].

The use of mismatched expansion ratios in material layers has been demonstrated to

create actuating capabilities, with the mode and degree of actuation controlled by the orientation of the constituent layers. Erb et al. [53] oriented super-paramagnetically activated

aluminium oxide platelets in a hydrogel, with the orientation of the platelets controlling

the swelling expansion ratios in water (because the in-plane swelling ratio is reduced with

respect to the out-of-plane direction). Multiple layers can be manufactured by adding successive material on top of the cured layer, and then applying a different magnetic field; the

result is that bending/twisting effects can be produced as one layer swells more than the

other.

Three-dimensional Spatial Distribution of the Reinforcements

Conventional composites typically consist of layered configurations of fibre reinforced

resin. However a difficulty with layered materials is in the stress concentrations that arise at

tapered sections of a structure. Tapering can consist of ply-drops which contain resin rich

areas; the structural and mechanical gradient at this point causes a stress concentration and

can initiatDe failure of the material [245].

Stress concentrations arise in structures when there are geometric or mechanical dis-

2.1 Introduction

19

which developed cracks due to the formation of stress concentrations at the window corners resulting in the catastrophic failure of two of its aircraft [47]. The human body also

has to deal with many mechanical gradients, for example, the interface between ligaments

and bone includes a large discrepancy in the moduli of around 2 magnitudes; to overcome

this challenge the body uses mechanical and structural gradients that gradually smooth the

transition of stress between the two constituents [253].

Libanori et al. [155] have shown that by combining micro-dimensioned and nanodimensioned platelets, it is possible to reduce the formation of stress concentrations within

a material. This hierarchical strategy allows the material to be sufficiently ductile, for the

inclusion of large concentrations of reinforcements. Similarly, a mechanical gradient can

be formed by the sequential layering of material with increasingly large stiffness so that the

through-thickness stiffness changes by as much as five magnitudes, whilst still being able

to achieve reversible stretching of up to 300% strain [153].

An alternative to layered structures is the spatial positioning and orientation of the reinforcement. Magnetically responsive reinforcements can be oriented in a 3D magnetic field,

with the alignment of the reinforcement controlled by the direction of the field lines. For

example the use of low strength permanent magnets has been used to vary the orientation of

platelets along a material, creating local stiffening effects that are visible as a wavy pattern

upon the swelling of the material [52]. However, by using a non-homogeneous magnetic

field it is also possible to control the position of reinforcements. Erb et al. [52] demonstrate

the possibilities of controlled positioning in the vicinity of a structural defect (e.g. a hole);

the reinforcing platelets aggregate towards the hole in a radial pattern to strengthen it and

prevent a stress concentration from forming. The consideration of reinforcing structurally

weak areas is a requisite of creating efficient structures, however this is usually achieved by

only considering geometrical changes (i.e. additional material) rather than by considering

more efficiently utilising the material constituents.

20

2.2

2.2.1

The addition of fillers into elastomers can add further improvements to the mechanical

[203], viscoelastic[186] and magnetic properties [29] of the material, among others[136,

149]. The improvement of these properties depends on a number of factors that include, but

is not limited to: particle morphology, size, aspect ratio, dispersion and surface structure

[65, 196]. Therefore, due to their large specific surface area, excellent physical properties

and increasing availability, there is currently significant interest engaged in the exploitation

of nano-dimensioned fillers (such as nanoclays [49], graphene [164, 186, 262], and carbon

nanotubes (CNT) [14]).

Since the discovery of single layer graphene [182], there has been increasing interest in

elastomer-graphene nanocomposites to improve on existing material solutions. Graphene

is nano-dimensioned, with an exceptionally large surface area due to its large aspect ratio

[39]. It also has very high in-plane stiffness, out-of-plane flexibility, high electrical and

thermal conductivity [147] and can be functionalized to further improve or customise the

properties; and increase the surface interaction with different polymer matrices [78]. Any

improvements in the properties of a nanocomposite material are often very dependent upon

the physiochemical interaction of the graphene and matrix [139], and so functionalization is

very important. Graphene Oxide is often used as a precursor material in the production of

graphene [265]; however the many oxygenated reaction sites on its structure (See Fig. 2.6)

can provide reaction sites for further functionalization [78], and are expected to increase

both the physical and chemical reactions with a matrix material. The result is expected to

be an increase in the bulk properties of an elastomer.

Fig. 2.6 Schematic structure of (a) graphene and (b) graphene oxide. Adapted from [150].

Among the most commonly used industrial elastomer materials is natural rubber (NR),

which is usually extracted in the form of a latex, consisting of a colloidal suspension of

21

latex particles, non-rubber impurities and water [69]. Natural rubber is characterised by

its ability to deform to large strain, damping performance and durability; qualities that are

improved by cross-linking of the polymer chains through the vulcanization process (5) . Nonvulcanised NR shares many of the characteristics of vulcanised NR, in that the long polymer

chains entangle and create enhancements in the residual forces (van der waals) [241] and

additional functional groups at the end of polymer chains are able to interact with non-rubber

components to form a natural pseudo network [241].

NR demonstrates a characteristic upturn in the stress at high strain (typically 100%) due

to SIC, caused by the alignment of polymer chains at high strain to form crystalline regions

[42] and involves structural change, an increase in density and a release of latent heat [241]

(See Section 2.1).

The addition of morphologically anisotropic fillers (e.g. graphene and CNTs) provides

significant mechanical advantages to NR (see for example [186], [164] and [206]). Their

large surface area and aspect ratio are thought to accelerate the formation of a stiffening

filler network, compared to spherical particles [206].

In this section, the effects of GO nano-platelets upon the mechanical and viscoelastic

properties of unvulcanised NR are investigated; both of which are affected by the stress

transfer and dissipative properties of the fillers. At large strain, new insights into the material

behaviour are seen; where a possible rotation of the nanoplatelets occurs in the direction of

the applied load.

2.2.2

Materials Characterization

Natural Rubber (NR, 60% high ammonia, Chana Latex Co., Ltd., Thailand) Latex was obtained from a private source and used as received and without further modification. Fouriertransform (FTIR) spectra of graphite, graphene oxide, natural rubber and NR-GO nanocomposites are shown in Fig. 2.7c. The FTIR spectra of natural rubber showed signature peaks

at 2960 cm1 , 2920/2855 cm1 , 1447/1376 cm1 , 1086 cm1 and 838 cm1 corresponding

to cis-isoprene units [81].

Graphene Oxide (GO) was prepared from graphite according to the Hummers-Offeman

method described in [189]. TEM and AFM analysis of the GO precursor were performed

by air drying the aqueous GO solution on carbon coated copper grids and freshly cleaved

5 Vulcanisation

is the process of cross-linking the polymer chains in natural rubber and other similar polymers. Sulphur is predominantly used as the cross-linking agent but others can be used, such as peroxides. The

form and amount of additives has a large effect upon the material properties and can be used to customise the

properties [42]

22

Fig. 2.7 (a) AFM images of the GO platelets reveal the delaminated sheets to be 1-1.4 nm

in thickness, consistent with completely exfoliated single layer GO; (b) TEM image of GO

platelet reveals ultra-thin flat sheet between 500 nm and 1 lm in size; (c) Fourier-transform

spectra of GO, graphite, natural rubber and NR-GO nanocomposites containing 1.00 wt%

GO; and (d) SEM images of fractured 1.00 wt% NR-GO specimens reveal homogeneous

dispersions of filler particles.

mica sheets respectively. Tapping mode AFM study showed the presence of delaminated

sheets that were 1-1.4 nm in thickness (Fig. 2.7a), which is consistent with the formation of

completely exfoliated single layer GO platelets. TEM images (Fig. 2.7b) indicate the size of

the largest platelets to be 500 nm to 1 m in length. FTIR analysis (Fig. 2.7c) of graphite and

GO exhibited features at 3446 cm1 , 2925/2852 cm1 and 1627 cm1 corresponding to OH, C-H and C=C stretching vibrations from absorbed water, alkyl groups at the edges and the

graphitic sp2 hybridised network. Additional peaks were present for the GO sample, with

peaks at 3378 cm1 , 1718 cm1 and 1225 cm1 indicating hydroxyl, carbonyl/carboxylic

acid and epoxide groups respectively [190].

The NR-GO nanocomposites were prepared by latex-mixing of the NR latex with an

aqueous dispersion of GO platelets. This involved the addition of 3 g of NR latex to a petri

dish, followed by 3ml of aqueous GO platelets (wherein the aqueous concentration of GO

is controlled to give the required wt%). The solution is then agitated on a vibrating plate

to achieve a homogeneous dispersion, and finally left to dry for 48 hours. The resulting

23

nanocomposite showed no FTIR vibration peaks characteristic of GO, due to the strong

presence of symmetric and asymmetric stretching frequencies of isoprene units. However,

SEM images (Fig. 2.7d) indicated a homogeneous dispersion present throughout the fracture surface. Characterisation of the nanocomposites by Differential Scanning Calorimetry

(DSC) showed only a small increase in the glass transition temperature (Tg) of 0.7C

between concentrations of 0 wt% and 1.0wt%, indicating that the presence of GO lowers

the quantity of polymer that is fluidified at the Tg; a result previously reported in similar

nanocomposite systems [164, 186, 192, 206].

Nanocomposite concentrations of 0, 0.25, 0.50, 0.75, 1.0 wt% were produced and tested.

Testing Techniques

All tests were performed at room temperature, with rectangular specimens of dimensions

5.0 mm width, 1.0 mm thickness and approximately 17.5 mm length. The nominal stress is

determined as the ratio of the measured force to the original specimen cross-sectional area,

whilst the strain is determined as the ratio of the extension to the original distance between

the clamps.

Fig. 2.8 (a) Specimens of NR-GO used in experimental testing. Pure NR on the left, increasing in GO conc. up to 1.00 wt% on the right. (b) The petri dish arrangement from which

specimens are cut, showing a pure NR material.

Mechanical testing was performed with an Instron testing machine, unless otherwise

stated, on two batches of nanocomposite specimens.

The first set of specimens (batch one) are tested 6 weeks after synthesis to investigate

the effects of GO concentration on the stiffness, strength and strain-to-failure by applying

displacement control (100 mm min1 ) until rupture.

A second series of specimens from batch one are tested 2 weeks after synthesis, to

investigate the strain rate dependency of the nanocomposites. This involved cyclically load-

24

ing/unloading the specimens to 30% strain; incrementally increasing the displacement rate

so that rates of 10 mm min1 , 50 mm min1 , 100 mm min1 , 150 mm min1 and 200 mm

min1 were applied.

A third set of specimens from batch one were used to investigate the relaxation and

fatigue properties of the nanocomposite. This involved stretching one set of specimens

to 50% strain, then holding them for a period of 10 minutes to observe the relaxation of

the applied force. An initial displacement rate of 100 mm min1 was applied. Another

set of specimens were stress-ratcheted between 0.3 MPa and 0.15 MPa for 200 cycles at a

displacement rate of 100mm min1 to observe the evolution of strain values between cycles.

Batch two was used for two separate series of experiments, tested at 2 and 6 weeks

after synthesis respectively, in order to examine the NR-GO networks and the effects of the

naturally occurring pseudo network [4]. The testing consisted of applying a stress of 1.4

MPa via displacement control (100 mm min1 ), before releasing the stress for 24 hours and

then again re-testing to 1.4 MPa. The stress value is chosen based on preliminary testing;

assuming the need to maximise disruption to the polymer networks, whilst ensuring the

specimen did not rupture.

Those specimens tested to high strain (> 400%) showed, upon retraction of the loading

force, a permanent deformation: when tested to 1.4 MPa, the permanent deformation for

pure NR was 30%; which decreased monotonically with the addition of GO to 10% at

a concentration of 1.0 wt%. The application of lower strains (i.e. 50%) resulted in the

complete recovery of the initial length with no residual deformation.

2.2.3

The stress-strain results of uniaxial tensile testing, at constant strain rate, on specimens of

natural rubber reinforced with graphene oxide can be seen in Fig. 2.9. It displays the S

shape behaviour typical of rubber behaviour [241], displaying the upturn in stress at high

strain associated with SIC.

At moderate strain levels it is possible to fit the non-linear behaviour with the MooneyRivlin model [175, 208], often used for filled elastomers [13, 163, 226]. This allows the

small strain properties to be more easily determined. The Mooney-Rivlin relationship is

given by,

N11 = 2(C10 +C01 / )( 2 )

(2.1)

where N11 is the nominal stress parallel to the loading direction (i.e. force over reference

25

2.5

2

0.5

0.00

0.25

0.50

0.75

1.00

wt%

wt%

wt%

wt%

wt%

1.5

1

0.5

0

0

(a)

100

200

300

400

500

600

0.4

0.3

0.00 wt%

0.25 wt%

0.50 wt%

0.75 wt%

1.00 wt%

Model

0.2

0.1

0

0

(b)

5

10

15

20

25

30

Strain (%)

Strain (%)

Fig. 2.9 Uniaxial tensile test results of NR-GO specimens (a) The stress-strain curve up to

failure. (b) The small-strain fitting of the Mooney-Rivlin model (Eq. 2.1) up to 30% strain.

area), is the elongation ratio (i.e. deformed length over original length) and the parameters

C10 and C01 are phenomenologically determined material constants determined by comparison to the experimental data. The Youngs modulus of the nanocomposites can then be

related to the model parameters by E = ( / ) 1 = 6(c10 + c01 ).

The fitting at low strain can be seen in Fig. 2.9b, showing the accuracy of the fitting up

to 30% strain.

Table 2.1 NR-GO nanocomposite tensile properties at concentrations between 0.0 wt% and

1.0 wt%.

GO (wt%)

0.00

0.25

0.50

0.75

1.00

Strain-to-failure (%)

598 (39)

546 (33)

516 (03)

501 (24)

473 (23)

Strength (MPa)

2.34 (0.17)

2.30 (0.18)

2.87 (0.18)

3.12 (0.36)

3.13 (0.24)

1.58 (0.10)

1.85 (0.28)

2.09 (0.24)

2.18 (0.37)

2.33 (0.15)

The results in table 2.1 show that with the addition of GO: the stiffness increases, the

strength increases and the strain-to-failure decreases.

The significant effects seem to be at low strain (indicated by the increase in the Youngs

Modulus) which have a knock-on effect to the large strain results; at large strain the nanocomposites behave very similar, although there is a slight increase in the tangent modulus

(Fig. 2.9a). Two reinforcing mechanisms are thought to act on the small strain response:

reinforcement by the filler [13] and the reinforcement from the polymer network of intercalating polymer chains; which itself consists of end-linking pseudo-networks and entanglements [186].

26

At large strain, for increasing concentrations of GO, Fig. 2.9a shows a decrease of the

strain at which the upturn in stress occurs. This upturn in stress has been associated with

SIC in filled and unfilled natural rubber [186]; and the decrease of the strain level at which

it occurs is due to the presence of the filler and trapped rubber increasing the crystallisation

rate for a given level of macroscopic strain [196].

To further understand these effects, and additionally the effects of the naturally occurring pseudo network, supplementary tests were performed at 2 and 6 weeks after synthesis.

Specifically this will allow the effects of the cross-linking density to be investigated, which

is known to increase with time, in relation to the concentration of GO. It will also allow the

effects of large strain deformation upon the NR-GO networks to be investigated, and their

resulting effect upon the SIC, by subjecting each specimen to a non-destructive stress level

of 1.4 MPa before resting it for 24 hours and again testing to 1.4 MPa.

The results of this testing, that can be seen in Fig. 2.10 and Table 2.2, show that for

all specimens on the second cycle; both the Youngs Modulus and the strain at which the

upturn in stress occurs (calculated from a Mooney plot, see Fig. 2.10) are decreased. The

Mooney plot allows the upturn in stress (defined as the point at which the tangent of the

modulus begins to increase), and considers the reduced stress as a function of the inverse

.

stretch, where the reduced stress is defined by force

1

2

Table 2.2 Youngs modulus, E, calculated from based on the fitting of the Mooney Rivlin

formulation (Eq. 2.1) to the stress-strain response up to 30% strain, alongside an estimate

of the strain value at which the upturn in stress occurs (associated with the onset of SIC

[37]), which is estimated from a Mooney plot. The testing consisted of the first uniaxially

stretching the specimen up to 1.4MPa and then resting it, followed by again testing to 1.4

MPa after 24 hours; resulting in two sets of results.

GO (wt%)

0.00

0.25

0.50

0.75

1.00

First cycle

E (MPa)

upturn (%)

1.03 (0.03) 211 (4.9)

1.44 (0.04) 177 (10.6)

1.69 (0.01) 164 (10.1)

1.78 (0.09) 149 (15.6)

1.89 (0.13) 158 (6.9)

Second cycle

E (MPa)

upturn (%)

0.79 (0.09) 141 (20.9)

0.99 (0.10) 133 (5.0)

1.00 (0.11) 107 (21.4)

1.09 (0.10) 108 (13.3)

1.08 (0.03) 116 (12.0)

It is well understood that both entanglements and the pseudo network play an important

role in the Youngs modulus of unvulcanised NR [4]; therefore the fact that the Youngs

modulus decreases on the second cycle suggests there is a breakdown in many of the polymer networks and a reduction in the number of entanglements, that is not recovered in 24

hours. The percentage reduction in the Youngs modulus also increases with higher concentrations of GO due to the presence of more filler-matrix interactions that can be disrupted.

27

0.6

0.4

0.2

0.6

1st cycle

2nd cycle

1.25

2.5

3.75

Stretch,

(d)

0.4

0.3

1st cycle

2nd cycle

0.2

0.25

0.8

0.6

0.4

0.2

0.6

0.5

0.5

0.75

Inverse Stretch, 1/

1st cycle

2nd cycle

0

0

1.25

2.5

3.75

Stretch,

1

0.8

0.6

0.4

0.2

0.6

0.5

0.4

0.3

1.2

1st cycle

2nd cycle

0.25

0.5

0.75

Inverse Stretch, 1/

1st cycle

2nd cycle

0

0

(e)

0.2

1

0.8

(c)

1.2

0

0

(b)

(a)

1.2

1.25

2.5

(f)

0.5

0.4

0.3

1st cycle

2nd cycle

0.2

1

3.75

Stretch,

0.25

0.5

0.75

Inverse Stretch, 1/

Fig. 2.10 Uniaxial tensile testing results of cycling specimens up to 1.4 MPa, in between

24 hour rests. (a)&(d) 0.00 wt%, (b)&(e) 0.25 wt%, (c)&(f) 0.50 wt%. (a)-(c) Stress-strain

curves. (d)-(f) Mooney plots.

The decreased strain level at which the upturn in stress occurs on the second cycle is

a peculiarity that is not adequately explained by residual crystallisation. It is anticipated

that a small amount of reconfiguration will occur in the sample, especially as it is unvulcanised natural rubber (i.e. no permeant cross-linking exists) and so the presence of oriented

regions upon full retraction of the load in the first cycle is possible[4, 240], however the

amplification of this effect with increased GO concentration, i.e. a decrease in the strain of

the upturn with increased GO wt% (See Fig. 2.10), suggests the possibility of some permanent orientation of the GO platelets towards the direction of the applied load during the first

cycle.

The rotation of platelet-like reinforcements has previously been observed (see e.g. [186,

206]), and indeed the permanent orientation of CNTs after large strain cyclic loading has

28

been observed [229]. This would potentially increase the effectiveness of the reinforcement

(due to GO in-plane stiffness being much higher than the bending stiffness [229]), and have

significant effects upon the large strain performance, as we observe here.

The permanently cross-linked network in Vulcanized Rubber prevents polymer chain

movement, and would therefore return the platelet to its original orientation. However, nonvulcanised NR does not have this permanent network and so small configurational changes

could occur internally, even if there are no obvious visible signs. The result would be

increased reinforcement in the direction of the applied load, which would account for the

further effects that are observed on the second load cycle with increasing GO concentration.

The specimens were subjected to uniaxial tension loading at varying strain rates. The results

at 50 mm min1 for three different concentrations (0.00, 0.25 and 0.50 wt%) can be seen in

Fig. 2.11, with the strain and stress evolutions in time shown in Fig. 2.11a and Fig. 2.11b

respectively.

Two major effects of increasing the concentration of filler can be observed from Fig. 2.11c:

an increase in the Youngs modulus and an increase in the area within the stress-strain

curves; the latter hysteresis indicating an increase in the dissipated mechanical energy. The

increase in the Youngs modulus can be attributed to the action of entanglements and interactions between the rigid filler and polymer chains; hence, as the GO concentration increases,

the short strain response should closely resemble the effect of an increasingly cross-linked

network [43]. At high strain the platelets could slide across the matrix, and the large interface of the GO platelets means increased polymer/filler friction, resulting in the increasing

hysteresis as the GO concentration increases.

To discern between these two effects, i.e. the increases in Youngs modulus and hysteresis, the value of the dissipation, D(6) , and the ratio between the dissipated and stored

energies, D/S( 7) , are calculated by quantifying the area within the stress-strain curve (see

Fig. 2.12). The results, assuming a loading ramp duration of tR /2 and an entire cycle of tR ,

6A

non-viscous material would have loading and un-loading paths that would coincide, indicating that

al the mechanical energy provided to deform the specimen was completely recovered and so the dissipated

energy, D, would be zero.

7 The ratio between the dissipated and stored energies, D/S, is related to tan ; obtained from dynamic

mechanical analysis (DMA).

29

Fig. 2.11 Loading\unloading cyclic test at 50 mm min1 (strain rate of 5.55 102 ). (a)

Strain versus time; (b) stress versus time for 0.25 wt.% against the constitutive model in

Eq. 2.1; (c) stress versus strain at 50 mm\min. The model for 0.00 wt.%, 0.25 wt.% and

0.50 wt.% are represented by the solid, dashed and dash-dot lines respectively.

can be estimated by

Z tR

D=

(t) (t)dt;

0

Z tR /2

S=

(t) (t)dt

(2.2.a)

(2.2.b)

The dissipative contribution of the NR specimen (0.00 wt%) has been normalised, so as

to highlight the contribution of the filler. For all concentrations of GO, the dissipated energy

increases monotonically with the applied displacement rate of the loading ramp: from 1.5

at 50 mm min1 to 2.3 at 200 mm min1 for the 0.25 wt% specimen and from 2.2 at 50 mm

min1 to 4.1 at 200 mm min1 for the highest GO concentration (1.00 wt%). However, it

should be noted that the highest dissipation is observed in the 0.75 wt% specimen and does

not increase for the 1.00 wt% specimen; this saturation effect has also been observed for the

Youngs modulus (see Table. 2.1).

Contrary to the dissipative properties, the ratio D/S monotonically decreases with loading rate but increases with filler content. It is well known that low strain rates favour the

dissipative aspects of material behaviour, whilst higher strain rates favour the elastic properties of materials [142]; however its relationship with filler content is less easy to predict

due to its dependence on a number of factors such as the interfacial strength between the

30

Fig. 2.12 can give an indication of the different effects of the platelets upon the high

and low strain rate responses: at low strain rate the ratio, D/S, increases with increased GO

concentration; indicating the predominant effect of the platelets upon the dissipative energy

due to friction between the polymer chains and GO. However, as the strain rate is increased,

the elastic energy increases faster at a given concentration of filler due to the difficultly in

disentangling the polymer chains. The notable feature is that even at higher strain rates, the

GO platelets increase the ratio D/S; indicating that the platelets have a predominant effect

upon the dissipative properties of the material.

D/D

NR

(a)

5

4

3

0.25 wt%

0.50 wt%

0.75 wt%

1.00 wt%

2

1

50

(b)

0.2

D/S

0.15

0.1

100

150

Velocity (mm min1)

Dissipated Energy / Stored Energy

200

0.00 wt%

0.25 wt%

0.50 wt%

0.75 wt%

1.00 wt%

0.05

50

100

150

Velocity (mm min1)

200

Fig. 2.12 (a) Normalised dissipated energy D during cyclic tests estimated through Eq. 2.2.b

normalised with respect to dissipation of the natural rubber sample (i.e. 0.00 wt.%). (b)

Ratio between the dissipated and stored energies during the cyclic test (estimated through

Eq. 2.2.b).

The effect of the GO platelet fillers can be further understood by observing the loading

ramps at different strain rates (see Fig. 2.13). The results show that a higher stress is reached

at 30% strain as the concentration of filler is increased, and independently as the strain rate

is increased; both phenomenon well understood. However the sensitivity to the strain rate is

also effected by the filler concentration, which can be indicated by the maximum stress at the

end of each cycle (Fig. 2.13): for NR the stress increases from 0.204 MPa at 50 mm min1

to 0.225 MPa at 200 mm min1 , a 10.2% increase, for the 0.50 wt% specimen the stress

increases from 0.332 MPa at 50 mm min1 to 0.370 MPa at 200 mm min1 . This increased

sensitivity of the strain rate with the addition of filler has been observed in other elastomer

systems [203], and is caused by the entanglements between polymer chain networks; an

31

effect that GO and immobilised rubber may contribute to by creating effective cross-links.

0.4

0.35

50 mm/min

100 mm/min

200 mm/min

0.3

0.25

0.2

0.15

0.1

0.05

0

0

10

15

20

25

30

Strain (%)

Fig. 2.13 Comparisons of the stress-strain plots at different cross-head speeds. Tested at 50,

100 and 200 mm min-1 for specimens v = 0.00 wt.%(continuous line), 0.25 wt.% (dashed

line) and 0.50 wt.% (dash-dotted line).

Relaxation

It has been seen that the addition of GO nanoplatelets to NR increases the stiffness of the

nanocomposite by providing a stiff network for the transfer of stress; a well known phenomenon in reinforced materials [142, 205]. However, prolonged loading of the composite

causes the network of entanglements and end-links to slowly breakdown over time [241];

resulting in the phenomena known as creep and relaxation. Here we report the results of

relaxation testing (see Fig. 2.14a), which involves loading the specimen to 50% strain at a

loading rate of 100 mm min1 , and holding it for 10 minutes.

The results show that at short times, the increased stiffness of the material, provided by

the presence of the stiff GO reinforcements, increases the maximum stress that is reached at

50% strain. At longer times, as the stress is unloaded, the rate of relaxation increases with

GO concentration; a result that has been observed in unfilled [239] and filled elastomers

[205], and even elastomers at much higher concentrations [141].

When the applied initial strain is large (i.e. >200%), any change in the relaxation times

can be associated to the formation of crystallites; which are themselves amplified by the

presence of fillers and immobilised rubber [239]. However, when the applied deformation

is lower (as in this case), the rate of crystallisation is known to be too low to justify this

increase in the relaxation rate. In Ref.[43] a similar increase was observed in swollen carbon

black filled synthetic rubber, and is thought to be due to a breakdown in the molecular

0.5

0.4

0.00wt.%

0.25wt.%

0.50wt.%

0.75wt.%

1.00wt.%

(a)

0.3

0.2

0.1

0 1

10

10

10

Time (s)

10

32

(b)

0.9

0.8

0.7

0.6

0.00wt.%

0.25wt.%

0.50wt.%

0.75wt.%

1.00wt.%

1

10

10

Time (s)

Fig. 2.14 (a) Stress-time plot of the relaxation tests for the different GO concentrations. The

specimens were loaded at 100 mm min1 up to 50% strain, then held fixed for 600 seconds.

(b) The stress-time plot, without the initial loading ramp, normalised against the maximum

stress.

weight of the polymer during processing, produced by the presence of the filler. However

the procedure used in this study, i.e. "latex-mixing", is unlikely to produce any significant

breakdown of the polymer chains.

The large surface area of the GO nanoplatelets is likely to have two effects relevant to

the relaxation rate: firstly to reduce the number of entanglements within the rubber as the

chains lie flat against the platelet, and secondly to increase the maximum stress; of which

both effects would increase the relaxation rate with the addition of GO. To discern between

these two effects, the normalised unloading curves are shown in Fig. 2.14b. The results

indicate that, after normalising the stress, the relaxation rate still increases with increasing

GO content; suggesting that the polymer chains are less entangled, with more freedom to

reconfigure.

Fatigue

Fatigue in materials is a result of repeated cyclic loading; propagating damage to weaken

the material and often causing failure to occur at a value much lower than the strength of the

material. However, the addition of reinforcements has been shown both to increase these

effects by creating stress concentrations [128] and to decrease these effects by strengthening

polymer networks [49], especially in nano-dimensioned materials [262].

Fatigue is considered a long-term material behaviour, however it has been shown that

relatively short-term stress-ratcheting between fixed values of stress can be used to give

an indication of the fatigue resistance of a material [49].

33

Strain (%)

60

40

20

(a)

0

0

10

20

Time (s)

Stress (MPa)

The testing involved cycling the specimens between 0.3 MPa and 0.15 MPa for 200 cycles at a displacement rate of 100 mm min1 ; a rapid evolution in the strain values between

cycles gives an indication of fatigue failure. Fig. 2.15 indicates the significant difference in

the fatigue resistance of the material with the addition of 1.00 wt% of GO; this is likely to

be due to the increased stiffness of the material because of the stiff network imparted on the

material by the presence of GO, meaning that the specimen is cycled between lower values

of strain (see Fig. 2.15a & 2.15a). The result is that the polymer chains of the NR within the

material are lower, meaning less breakdown of the network and a higher fatigue resistance.

(c)

0

0

10

20

Time (s)

30

Stress (MPa)

Strain (%)

30

10

0.2

0.1

(b)

0

0

30

20

0.3

50

100

Strain (%)

0.3

0.2

0.1

(d)

0

0

50

100

Strain (%)

Fig. 2.15 Stress-ratetching of NR-GO specimens. (a) The first 30 seconds of the NR specimen strain cycle. (b) NR stress-strain cycle up to failure. (c) The first 30 seconds of the

NR-GO specimen (1.00.wt%) strain cycle. (d) The NRGO (1.00wt.%) stress-strain cycle up

to failure.

By calculating the maximum strain of each cycle, it is possible to observe these effects

based on the concentration of GO; this is shown in Fig. 2.16. An increase in the fatigue

resistance is shown as the GO concentration increases up to 0.75wt%; the fatigue resistance

at 1.00wt% is slightly decreased, likely due to a similar saturation effect to that observed

for the Youngs Modulus. Similar reductions in the reinforcement effectiveness have been

observed in [49] for larger concentrations of nanoclay blends. There is a significant impact

due to the inclusion of even 0.25wt% GO compared to the pure NR specimen; showing the

increased fatigue resistance provided by a small amount of nano fillers due to their large

surface area and resulting strong internal network of polymer chains and fillers.

34

200

Strain (%)

150

0.00

0.25

0.50

0.75

1.00

wt%

wt%

wt%

wt%

wt%

100

50

0

0

50

100

150

200

No. of cycles

Fig. 2.16 The evolution of the maximum strain reached at the peak of each stress cycle

during stress-ratcheting between 0.15 MPa and 0.30 MPa of specimens of NR-GO with

concentrations of GO between 0 wt% and 1.00 wt%.

2.2.4

Concluding Remarks

Graphene oxide reinforced natural rubber elastomers have been produced by latex-mixing

in a simple process that requires no additional heat or chemical input. Characterisation of

the specimens confirms that homogeneous specimens are produced, containing a regular

size distribution of oxidised graphene of single layer thickness.

Observations show that the introduction of the nano reinforcements increases the stiffness and strength of the material, indicating an increased stress transfer through the material.

The decrease of the strain-to-failure with increasing concentration indicates the stiffness increase is more significant than the strength. The increase in strength suggests that the GO is

well dispersed, as confirmed by the mechanical tests carried out on specimens cut along different directions of the same batch. The significant increase in the Youngs Modulus, even

for low filler content (e.g., +55% @ 0.75 wt%) illustrates the reinforcing effect, and suggests the presence of rubber trapped within the filler network. This is in part confirmed by

Tg measurements that showed only a marginal increase with increasing GO concentration.

The effect of the strain rate in experimental testing is known to be a relevant factor, and

is shown to be particularly relevant for nanocomposites, not only in increasing the Youngs

Modulus but also in the dissipative properties of the material. The ratio between dissipated

and stored energies has been calculated in cyclic tests and is shown to increase as the GO

concentration increases; presumably due to the increased friction caused by the presence of

high aspect ratio GO platelets. However, as the strain rate increases the ratio between the

35

dissipated and stored energy decreases for a given GO concentration; due to the reduced

time given for the mechanism to take place.

Relaxation tests also show that the stress reduces more quickly with the addition of GO

because of strain amplification effects and a reduction in the number of entanglements. The

strain amplification effects also help to improve the short cycle fatigue testing behaviour as

the GO concentration is increased.

Interestingly, orientation of the GO platelets is thought to take place at high strain, which

subsequent testing on the material suggests is permanent to some degree. This is evidenced

by the reduction of the strain level at which the upturn in the stress-strain curves occurs when

the same specimen is subsequently retested after 24 hours rest; and effect that increases at

higher GO concentrations.

This effect would require further investigation which could be carried out by Small Angle Neutron Scattering on pristine and stretched samples, however the underlying behaviour

suggests the interesting properties of aligned anisotropic reinforcements in an elastomer that

is deformed to large strain.

36

2.3

2.3.1

PDMS reinforced by Carbon Fibres

giving better utilisation of the constituent materials by strengthening in positions where they

can provide critical reinforcement. In conventional composites these challenges are often

met by careful orientation of the composite layers, for example anisotropy can help in aeroelastic applications [122, 140]. In elastomer materials the consequences of this orientation

effect, because of the large strain potential, have effects upon both the large and small strain

response. At large strain additional non-linear effects have been observed (Section 2.2 and

Ref.[226]) in discontinuous filler reinforced elastomers. Due to the potential complexities of

designs possible with 3D spatial reinforcement, it is important to understand this behaviour,

its effects upon the material behaviour and to understand the mechanisms underpinning its

behaviour, plus be able to model the behaviour.

The challenges in controlled orientation of materials have been considered using a number of different manufacturing methods, for example, shear forces [223], ultrasonic waves

[219], electrical currents [167] and magnetic alignment [31, 52, 131, 134, 197]. Some of

the advantages of magnetic alignment include:

The magnetic field provides a contactless volume force that orients the magnetically

anisotropic materials along field lines into 3D spatial configurations [52]

Permanent magnets and electromagnets are readily available and produce strong enough

fields to orient the reinforcements. In fact, surprisingly weak field strengths can orient

reinforcements when the size and shape is carefully considered [52]

Compared to electric fields, magnetic fields do not produce currents and are not sensitive to surface charge and pH [207].

There are found to be many factors affecting the orientation of anisotropic fillers in

a viscous solution. Firstly it is important to consider the magnetic field, in particular its

strength [134], field direction [52] and homogeneity [225]. Secondly, it is important that the

reinforcement morphology and magnetic functionalization compliment the magnetic field

[52]. By controlling these factors, it is possible to predict the distribution and configuration

of the reinforcing fibres within the host matrix [41], and hence provide spatial reinforcement

that can have delicate consequences upon the mechanical properties.

In this section, we take inspiration from some of natures solutions and apply these concepts to the large strain behaviour of elastomer materials reinforced with discontinuous

37

fibres. The focus of this investigation is understanding the behaviour of the material when

the short fibres are oriented in a transversely isotropic configuration. It is expected that the

orientation of the discontinuous fibres will have consequences upon both the small strain behaviour, as has been shown in such a material previously, however the rotation of the fibres

at large strain is also expected to contribute to additional non-linear effects. An understanding of these effects, and the many other factors that control the mechanical behaviour of

such a material is critical to fully utilising its potential as a novel and innovate solution to

elastomeric reinforcement.

Motivated by the potential benefits of such a material, a transversely isotropic constitutive model is compared to the experimental data in order to gain an understanding of the

behaviour. Its performance at understanding the large strain behaviour is considered.

2.3.2

Material Preparation

PDMS (Sylgard 184) elastomer is used without further modification and reinforced with

nickel coated carbon fibres (Ni/C 40/60 wt.% chopped to 0.25 mm, diameter 4.8m) purchased from Marktek Inc. The PDMS fibre reinforced elastomers are made by direct mixing

of the two compounds under the influence of a magnetic field (in a process described later in

section 4.2); which includes strategies to achieve a homogeneous dispersion of oriented fibres with few agglomerations at a concentration of 6 wt% NiC fibres. This is later confirmed

by micrographs of the fractured surfaces (Fig. 2.17b).

Fig. 2.17 (a) The neodymium magnetic setup for aligning magnetic fibres in viscous PDMS

solution, and (d) The dispersion of fibres through the thickness of the specimen, observed

by SEM on a fractured specimen.

Once cured, the specimens are cut into dumbbell specimen shapes ready for mechanical

38

Fig. 2.18 The dumbbell test specimen according to ASTM D1708, and an inset showing the

alignment of the fibres within a small central sample of the specimen (Highlighted fibres

shown for illustrative purposes only).

testing according to ASTM D1708 (see Fig 2.18). The resulting specimens have distributions in the fibre lengths and orientations that can be seen in Fig. 2.19; this is expected to

influence the mechanical properties [66], hence they are documented in order to make comparisons between the experimental results and theoretical/numerical methods, it also allows

the repeatability of the results to be assessed.

To characterise the fibre angle distribution and to aid in comparisons, the following

distribution function is applied:

ebcos(2 )

( ) = R

/2

bcos(2 ) d

e

/2

(2.3)

where b is a coefficient to be determined. This function is found to better describe the experimental results than expressions considered previously [63] and will be used later (Chapter 3.4) to understand the effects of fibre angle distribution the numerical environment. The

fitting of this function for a sample is shown in Fig. 2.19a.

Meanwhile, a normal distribution function is found to describe the length distribution of

the fibres better than alternative expressions presented in the literature to [63].

1

(L d)2

exp(

)

h(L) =

(2c2 )

( 2 c)

(2.4)

where c and d are coefficients to determine, and the fitting is shown in Fig. 2.19b.

The interfacial properties between the fibre and matrix are also of importance to the

39

Probability Density

1.5

Distribution

Distribution Function

0.5

(a)

0

90

45

45

Fibre Angle, ( )

90

Probability Density

Distribution

Distribution Function

6

(b)

0

0

0.1

0.2

0.3

0.4

0.5

Fig. 2.19 The fibre distributions from a specimen aligned between the four Neodymium N52

magnets. (a) The fibre orientation distribution, fitted to Eq. 2.3 (b=4.3), (b) The fibre length

distribution, fitted to Eq. 2.4 (c=23.0, d=1.59). The averaged values of 6 specimens are b=

4.5 0.57, c=25.7 4.9 and d=1.61 0.15.

overall material properties [262]. It is generally assumed in numerical and constitutive

models that the interface is ideal, i.e. that there is perfect stress transfer between the fibre and

the matrix. The result is that the composite is optimally strengthened by the stiff reinforcing

fibres, however in reality this is rarely the case and efforts are undertaken to improve the

interfacial properties [260]. Due to the lack of functional reactive groups on either the

PDMS or nickel-coated carbon fibres the interface is unlikely to be optimal, illustrated by

the clean fibre-pull out observed on fractured specimen surfaces (Fig. 2.20a); although some

trapped rubber is observed in-between fibre bundles that have agglomerated (Fig. 2.20b).

Fig. 2.20 Interface of the fractured PDMS specimens. (a) A poor interface showing fibres

without matrix attached [96]. (b) Trapped rubber between bundles of fibres.

40

Experimental Techniques

All mechanical testing was performed at room temperature, according to ASTM D1708

on specimens of approximate thickness 0.5 mm. The nominal stress is determined as the

ratio of the measured force to the original specimen cross-sectional area, whilst the strain

is the ratio of the deformation between two points in the gauge length, compared to the

original distance. This is calculated by digital image correlation (DIC), by spray painting

the specimen with a very light speckle pattern and choosing distinct points either side of the

mid-point of the specimen at an approximate distance from each other of 10mm. Due to

the very small size of the specimens, this distance is kept consistent to ensure the resolution

does not affect the results, or that the end-tabs do not interfere with the strain field in this

region. Testing is performed on an Instron testing machine, applying displacement control

(10 mm/min) until failure to 6 specimens for each angle tested (i.e. 0 , 15 , 30 , 45 , 60 ,

75 , 90 ).

Microscope images of each specimen are taken prior to mechanical testing using a Carl

Zeiss Jenavert optical microscope; the post-processing of these images involved analysing a

60 mm x 40 mm section of each petri dish. Image software is used to create an image layer

onto which the fibres are drawn; this layer is then imported to the MATLAB (ver.2012b)

Image Processing Toolbox and information on the fibre position, orientation and size can

be determined. Fibres that interact/overlap are added to a separate image layer so that they

can be treated as two distinct fibres. The fibres are selected based on them in being in clear

focus and completely intact (i.e. not half cut from the image). Further microscopy is undertaken on identical specimens during uniaxial mechanical testing up to 60% strain to analyse

the rotation of fibres in-situ and therefore verify the applicability of the assumed deformation gradient used in constitutive modelling. SEM (JSM-IT300) images of the fractured

specimen surfaces are taken to analyse the interface between the matrix and fibres, and the

dispersion of fibres.

2.3.3

The results of the uniaxial tensile testing are shown in Table 2.3, and indicate a significant

correlation between the angle of alignment and the elastic modulus; a maximum is observed

when the reinforcement is aligned parallel to the loading direction (i.e. 0 ), with a minimum

modulus at 60 . The variation of the modulus in this manner can be explained by making

comparisons to a transversely isotropic hyperelastic model, which will be discussed later.

The strength and strain-to-failure are also similarly correlated; the strength is minimised

at 60 due to the reinforcement reorienting its body rather than transferring stress, which

41

results in the strain-to-failure being at its maximum. Conversely, when the reinforcement is

oriented towards the loading direction it efficiently transfers stress and restricts the deformation of the specimen.

Table 2.3 The average mechanical results of specimens tested to failure, standard deviations

shown in brackets. Indicating, the Youngs modulus, E, calculated from based on the fitting

of the Transversely Isotropic constitutive model (Eq. 2.10) to the stress-strain response up

to 30% strain, the strain-to-failure and the strength of the specimens.

0 ( )

0

15

30

45

60

75

90

E (MPa)

2.10 (0.35)

1.90 (0.37)

1.56 (0.29)

0.71 (0.28)

0.71 (0.13)

0.86 (0.01)

0.83 (0.27)

Strain-to-failure (%)

93 (2.4)

96 (11.6)

88 (15.6)

113 (9.4)

118 (5.6)

108 (5.8)

113 (6.6)

Strength (MPa)

0.65 (0.05)

0.71 (0.11)

0.70 (0.13)

0.65 (0.22)

0.55 (0.10)

0.58 (0.06)

0.60 (0.13)

The nominal stress-strain behaviour of PDMS displays a weak S shaped curve (See

Appendix A.1) due to the limited extensibility of the elastomer chains (in comparison to the

S shaped stress-strain curve of Natural Rubber, e.g. see Fig. 2.9a). However due to (1)

the variability of test results that continue to diverge at high strains, (2) the applicability of

moderate strains to many elastomer applications and (3) the increased difficulty in identifying a constitutive behaviour at large strains, particularly when additional non-linearities

are present due to limited chain extensibility, comparisons between the specimens are made

only up to 60% strain.

The results of the large strain tensile tests are shown in Fig. A.1 for selected specimens

of each orientation up to 60% strain, and include confidence intervals calculated from the

average stress-strain curve of all specimens of each reinforcement angle. The stress-strain

curves highlight the different stress transfer mechanisms that take place for different orientations of the reinforcements. When the fibres are oriented towards the loading direction

(0 -30 ) they are able to carry the majority of the load and a high modulus is achieved; on

the contrary, low moduli correspond to configurations where the fibres are almost orthogonal

to the loading (60 -90 ).

It is interesting to note the effects of the reinforcement reorientation during deformation

and its effects upon the stress, which can be evidenced when comparing the reinforcement

at 0 and 30 in Fig. A.1a. The initial modulus of 0 is higher, but at = 1.35 the rotation

of the fibre towards the loading direction causes the 30 tangent modulus to decrease less

and the stress to rise above the other. A similar occurrence is not observed at higher angles

0.6

00

30

60

75

0.5

0.4

0.3

0.2

(a)

0.1

0

1

1.1

1.2

1.3

1.4

1.5

1.6

42

0.6

15

45

90

0.5

0.4

0.3

0.2

(b)

0.1

0

1

1.1

Stretch,

1.2

1.3

1.4

1.5

1.6

Stretch,

Fig. 2.21 Large strain tensile experimental results of magnetically aligned fibre reinforced

PDMS, up to 60% strain. (a) Reinforcement angles 0 , 30 , 60 and 75 , (b) Reinforcement

angles 15 , 45 and 90 . The 90% confidence bars, calculated from 6 tested specimens at

each angle, are shown at strain intervals for each specimen.

(e.g. between the 60 and 75 specimens), however this is most likely due to the relatively

moderate change in modulus that a rotation of the fibres would cause at these angles (see

Fig. 2.23).

The behaviour described is highly non-linear, especially at large strain, however by comparing the behaviour with a transversally isotropic hyperelastic model, it will allow further

understanding of the material behaviour and allow the constitutive behaviour to be applied

to further modelling.

The strain energy, M , of the model has the following form,

M (I1 , I4 ) =

2

(2.5)

with

1

g(I4 ) = ( I4 1)2 ( I4 + 2)

I4

(2.6)

with the stress-strain relationship derived under the assumption of a uniaxial deformation gradient, i.e.

0

0

1

FM = 0 2

0 ,

1

0

0 2

(2.7)

This form of strain energy is essentially the Neo-Hookean model [241] with an addi-

43

tional contribution to account for the transversely isotropic distribution of fibres, represented

by the dimensionless parameter, . I1 and I4 represent the 1st and 4th strain invariants, defined in section 3.1.1. A more detailed description to the model can be found in section 3.2.

However, the nominal stress can be derived as:

2

1

N11 = 2 +

cos (0 )

(2.8)

(1 + )2 (1 + )(2 + )

+

=

2 2

2

(1 + )2 (2 + ))

2 3

(2.9)

Comparisons of the constitutive model to the experimental data, assuming uniaxial tension loading, can be seen in Fig. 2.22. At strains above 30% the model begins to struggle

to capture the highly non-linear behaviour observed in the experimental data. Therefore a

more complex form of the constitutive parameters 1 , 2 and 4 may be considered, such

as those seen in [165] but with such complicated models it is difficult to gain an understanding of the underlying mechanics of the material behaviour. Instead, the model here is applied

with the limitations understood, and attempts will be made to understand the reasons for the

difficulty in defining a constitutive model. Even still, it will be shown that even with deformations below 30% strain it is possible to observe significant non-linear behaviour which is

highly dependent upon the reinforcement direction.

The accurate fitting at small strain suggests the applicability of the model to small deformations, and so the expression for the effective elastic modulus E11 is obtained (Details

in Section 3.2),

E11 (0 ) =

3

(16 + 5 + 8 cos (20 ) + 3 cos (40 ))

16

(2.10)

As expected the effective elastic modulus depends on the fibre orientation. In particular

E11 has a minimum for 0 = 65.9 ; in this configuration the fibre provides the least amount

of resistance to the uniaxial forces imposed upon it. On the contrary, for 0 = 0 or 0 = 90 ,

the effective modulus is a local maxima. The maximum at 0 = 0 being significantly larger

than at 0 = 90 . However, the limiting value at 0 = 90 is interesting as it indicates

the potential importance of the lateral constraint of the reinforcement in an incompressible

system, a phenomenon that is experimentally observed (See Fig. 2.23).

0.6

00

30

60

75

0.5

0.4

0.3

0.2

(a)

0.1

0

1

1.1

1.2

1.3

1.4

1.5

44

15

45

90

0.6

0.5

0.4

0.3

0.2

(b)

0.1

0

1

1.6

1.1

1.2

Stretch,

1.3

1.4

1.5

1.6

Stretch,

Fig. 2.22 Large strain tensile experimental results compared to the transversally isotropic

constitutive model, Eq. 2.5, up to 60% strain. Markers indicate the experimental results,

lines indicate the constitutive model fitting. (a) Reinforcement angles 0 , 30 , 60 and 75 ,

(b) Reinforcement angles 15 , 45 and 90 . The 90% confidence bars, calculated from 6

tested specimens at each angle, are shown at strain intervals for each specimen.

2.5

2

1.5

1

0.5

0

20

40

60

80

Reinforcement Angle, 0 (o )

Fig. 2.23 Small strain behaviour of the material, averaged from all specimens and showing

the standard deviation. The model (Eq. 2.10) fitting is shown to fit the behaviour well.

( = 0.252, = 1.85).

gradient. To analyse the applicability of the applied uniaxial tensile loading in the constitutive model, the rotation of the fibres is observed, in-situ, during tensile testing at strains

values up to 55% (see Fig. 2.24). This has allowed the rotation of individual fibres from the

centre of each specimen to be captured and compared to rotations predicted by the model,

which is obtained by using Nansons formula (see, e.g., Ref.[184]). 0 is the direction of the

45

fibre in the undeformed configuration, thus its direction is given by N = (cos(0 ), sin(0 ), 0),

whilst the direction normal to the platelet is A = ( sin(0 ), cos(0 ), 0). The current normal vector a is a = FT A1 FT A , that in view of the imposed deformation gives the

current orientation

of the fibre,

h

i , in terms of the original angle, 0 , and the stretch, , i.e.,

= tan1 3/2 tan(0 ) .

The results of the fitting with this formula are shown in Fig. 2.25a for five specimens

with initial angles 0 , 15 , 45 , 75 and 90 . A remarkably close agreement between the

rotation predicted by the model and the actual rotation of the fibres is apparent up to 55%

of deformation for fibres observed in the centre of the specimens, which suggests that discontinuous reinforcements are well approximated as continuous fibre reinforcements in this

context.

Fig. 2.24 Experimental micrographs of a reinforcing fibre during uniaxial tensile tests at

different strain levels.

Fig. 2.25 The experimental rotation of the fibres compared tohthe rotations predicted

by the

i

1

3/2

model, obtained through Nansons formula, i.e. = tan

tan(0 ) .

46

However, as shown in Fig. 2.22, there are significant discrepancies in the experimental

data at large strain that can not be described by the model and suggest that the angle of

isotropy may be significant. There are a number of possibilities that could help to explain

the deviation from the assumed transversally isotropic model:

Whilst the rotation of the fibre reinforcements helps to validate the plane stress assumption of the model, Fig. 2.26 shows that the lateral constraint of the reinforcement may cause

discrepancies as the reinforcement angle increased (i.e. 90 ). This has been analysed

by digital image correlation (DIC) on each specimen, that tracks the deformation and calculates the stretch components parallel and perpendicular to the applied force. The results

in Fig. 2.26 show that for specimens with the reinforcement aligned towards the loading

direction (i.e. 0 - 30 ), the specimens are well described by the deformation gradient (2.7)

8 . As the reinforcement angle increases towards 90 , there is a gradual reduction of in

2

comparison to 1 ; which is further assessed in the following.

Lateral Stretch, 2

1

0.95

0.9

0.85

0.8

1

00

15

30

45

60

75

90

1.2

1.4

Longitudinal Stretch, 1

1.6

Fig. 2.26 The lateral stretch, 2 vs longitudinal stretch, 1 of selected specimens of each

reinforcement angle, compared to the theoretical plane stress (dashed line) prediction, i.e.

2 = 10.5

This demonstrates that the lateral constraint of the reinforcement has an effect upon the

deformation and in fact at angles between 0 and 90 a shearing of the sample occurs due

to a shift in the stress transfer of the reinforcement (See Fig. 2.27b). A discussion of this

effect in experimental testing of transversely isotropic materials in the literature is included

in section 2.1.2, and discusses the difficulty in these experimental tests; particularly at large

strain. However the effects are dependent upon the angle of isotropy and the strength of the

transversely isotropic effect (i.e. the value of in Eq. (2.5)) and so a quantification of these

8 This

confirms the well known results in non-linear elasticity that simple tension implies (2.7) only if the

fibres are aligned in the direction of the load.

47

Fig. 2.27 (a) The COMSOL Multiphysics (ver. 5.0, 2014) dumbbell numerical model, compared to the idealised constitutive behaviour, for angles 0 , 30 , 60 &90 (=0.252 MPa &

=1.85). Dashed lines refer to the idealised constitutive behaviour, markers refer to the

behaviour of a dumbbell according to ASTM D1708. (b-c) The deformation of the 45

dumbbell numerical model, indicating the lateral misalignment between the top and bottom of the gauge length, at 20% strain for parametric values (b) =0.252 MPa & =1.85

(Lateral misalignment = 0.31mm) and (c) =0.252 MPa & =18.5 (Lateral misalignment =

0.58mm). The parameter x refers to the lateral misalignment in millimetres, compared to

the undeformed configuration.

In order to assess this inhomogeneity, the constitutive behaviour is compared the behaviour of a dumbbell specimen with clamped tab boundary conditions (according to ASTM

D1708) modelled in the commercial FE software COMSOL Multiphysics (ver. 5.0, 2014).

The results, shown in Fig. 2.27a, confirm that the 0 specimen matches the constitutive behaviour, as no shear deformation is developed. However, at angles greater than 0 there

is an S-shaped deformation that occurs due to the development of shear, indicated by a

lateral misalignment between the top and bottom of the gauge length (See Fig. 2.27b&c).

The result on the stress-strain relationship is that the material is effectively softened at low

0 due to the shear modulus being considerably lower than the Youngs modulus (See the

15 and 30 specimens in Fig. 2.27a, compared to the predicted constitutive behaviour).

This illustrates the effect of the boundary conditions during the experimental testing. If

the degree of transverse isotropy were increased (i.e. a greater , relative to ) or the gauge

length were decreased, then the deviation from the constitutive behaviour would become

more pronounced.

The degree to which this S-shape develops depends on the ratio of the In-plane and

shear moduli. The shear modulus has a maximum at 45 degrees, whilst the Youngs modulus

48

has a minimum at 65.9 degrees (See Section 3.2.2 for details). The consequence is that,

although the shear moduli at 30 degrees and 60 degrees are identical; there is a much more

evident S-shape for the 30 specimen because the Youngs modulus is higher and forces the

specimen to shear along the reinforcement direction (see Fig. 2.27b and Fig. 2.27c).

At larger angles however, the behaviour results in the dumbbell specimen being initially

stiffer (See e.g. the 60 specimens in Fig. 2.27a). At higher strains, due to the rotation of the

angle of isotropy, the constitutive behaviour eventually increases above these stresses. The

switch in these behaviours (i.e. when the initial modulus of the constitutive and experimental

models is identical) is found to occur at = 56.8 , although it depends on the relationship

between the shear modulus and the tensile modulus.

Whist it is shown that the deformation field causes some discrepancies in experimental

testing of transversally isotropic materials, the behaviour is marginal for the experimental

specimens (See Fig. 2.27b). However, if the strength of the transversely isotropic effect were

to increase (i.e. an increase in ) this effect would become prominent (See Fig. 2.27c). At

such a point, it would become important to consider better clamping and test fixtures that

allow the angle of isotropy to be tracked. A discussion of test fixtures for transversely

isotropic materials is given in section 2.1.2.

These effects do not explain the discrepancies at 0 or the stress increase at 30 , that are

observed in the experimental tests, whereby it increases above that of the 0 specimen at

= 1.35 (See Fig. A.1). In fact, the induced shear response would be expected to cause a

softening of the material at 30 .

Indeed, the increase in stress at large strain for the 30 specimen, compared to 0 , suggest the possible influences of snubbing friction (9) , which is the friction that results from

the fibre being pulled from the matrix at an oblique angle to the loading direction, and is

independent of the fibre-matrix interfacial properties. The evidence of fibre pull-out from

the matrix in Fig. 2.20 supports this idea and the phenomenon has been observed and numerically accounted for previously [63, 251] and can have the effect of increasing the stress

transfer as the angle of the reinforcement is oriented away from the loading direction.

Additionally, the upturn in stress (due to the limited extensibility of the PDMS elastomer

chains) could also be affected by the rotation of the fibres (as has been seen for SIC in NR

[226]), causing the strain at which this behaviour occurs to vary. Such effects would generally require an extension of the constitutive model to include additional parameters; a logical

extension to the constitutive behaviour would be to a transversally isotropic Mooney-Rivlin

model (i.e. containing one additional parameter, dependent on the invariant I2 ) however it

is shown in Ref.[40] that it is unable to satisfactorily improve the model fitting.

9 Snubbing

49

Further additional parameters would likely yield better fitting of the constitutive equations, however their addition complicates the understanding of the parameters and is beyond

the scope of this research, and in fact, many models are mostly motivated by improved constitutive fitting rather than a desire to directly model the mechanics of materials.

2.3.4

Concluding Remarks

PDMS reinforced with aligned nickel-coated short carbon fibres have been produced by

magnetic alignment during the pre-cure phase. Characterisation of the specimens confirms

that a homogeneous distribution is achieved with the degree of alignment easily assessed

by optical microscope; additionally allowing the fibre position and length distribution to be

recorded.

Observations show that the introduction of aligned fibres modifies the mechanical properties, and is dependent upon the alignment angle in comparison to the direction of the

applied load. Two observed stiffening effects are observed at 0 and 90 , termed longitudinal and lateral stiffening respectively. Similar, albeit weaker, correlations are observed in

the strength and strain-to-failure which show that a minimum of the strength occurs at 60

due to the reinforcement realigning rather than transferring the stress. This also causes the

strain-to-failure to be a maximum at this point.

The assumption of plane stress deformation is reasonable, although the lateral constraint

of the reinforcement can cause difficulties when the reinforcement is laterally oriented. Even

so, the rotation of the fibres within the elastomer is well described up to 60% strain.

A neo-hookean transversely isotropic model can fit the experimental data up to 30%

strain. Discrepancies at larger strains are likely primarily caused by the weak interface that

is shown to exist between the PDMS and reinforcing fibres.

Chapter 3

Numerical Modelling

3.1

Introduction

Long continuous reinforcements are ubiquitously found in natural materials such as softtissues and plants, and the mimicry of this behaviour is a major challenge in the optimisation of engineering design. Glass or carbon-fibre reinforced epoxy are examples of artificial

materials that try to mimic the behaviour of a natural composite and to exploit the load carrying capability offered by the continuous reinforcement. On the contrary, the mechanical

properties of composites are decreased when the reinforcements are discontinuous but they

do give a number of advantages such as increased ductility, formability and process-ability.

The understanding and prediction of this material behaviour is a key requirement in

engineering design, however many challenges exist; particularly in understanding the large

strain behaviour of materials. The anisotropy of the reinforcement has little effect on the

material behaviour at the macroscale if a homogeneous and isotropic dispersion is achieved,

but by deliberately controlling the orientation of the reinforcement it is possible to exploit

the anisotropic behaviour. The behaviour of anisotropically reinforced elastomers can be

highly non-linear, as seen in section 2.3, due to a number of factors that include:

The material heterogeneity contrast of the constituents.

The morphology and shape of the fillers [157].

The initial orientation and subsequent rotation of fillers during deformation.

The variable length and orientation of the fillers [64].

The condition of the filler coating and the subsequent interfacial strength [65].

52

Numerical Modelling

The distribution and dispersion of the fibres [201].

A fundamental problem with particle reinforced composites is to predict their overall behaviour in terms of the mechanical properties of the constituents, particularly the anisotropic

response at large strain. Most papers in the literature have focused on macroscopically

isotropic composites with a random or nearly random distribution of reinforcements. At

small strains, the Guth-Gold equation is used to predict the dependence of linear moduli on

filler/matrix mechanical properties for spherical and rod shaped filler particles [206]. Halpin

and Tsai developed a semi-analytical approach based on Hills "self-consistent" method to

predict the elastic modulus of composites reinforced with a variety of filler geometries ranging from spheres to long fibres (see, e.g. Ref. [91]). Whilst these methods have been successfully applied for a variety of different materials, Finite element analysis is required for

more advanced morphologies and distributions [157].

At large strain, the analytical approach is made difficult by the presence of geometrical

and constitutive nonlinearities. The pioneering works of Hill [102] and Hill & Rice [103]

have shown that it is possible to find an effective strain energy function able to describe

the overall behaviour of the composite. This has led to the development of a number of

approaches [85]. In fact, efforts to understand many of the effects that control the large

strain performance of reinforced materials can be found in the literature [104, 160]. In

particular, Gasser et al. [72, 187] developed a constitutive model to look at the effects of

fibre angle distribution on the large strain behaviour of arterial walls.

The benefit of such a model is the relatively small computational cost compared to alternative methods such as the finite element method and molecular dynamics. However it is

difficult to develop a model that can account for even relatively simple configurations, and

often only particular boundary value problems are considered [158]. More general settings

require the use of the finite element method, and accompanying numerical homogenisation of a representative volume element. Recently, numerical homogenisation was used by

[86], [176] and [88] to study the large strain behaviour of Incompressible Particle Reinforced neo-Hookean composites (IPRNCs). In particular Guo et al. [88] simulated the 3D

reinforcement of a representative volume element (RVE) with multiple spherical-shaped inclusions. The authors have shown that when both the filler and the matrix are neo-Hookean

the overall response is still neo-Hookean and the apparent shear modulus can be predicted

through the Halpin-Tsai equation.

In this chapter, motivated by the need to understand the highly non-linear behaviour of

anisotropic particle reinforced elastomers, we use a numerical homogenisation approach to

investigate the mechanical behaviour of the composite at large strain under general boundary

conditions. The numerical model is a simplified representation of the reinforced elastomers

3.1 Introduction

53

introduced in section 2.2 and section 2.3, and allows the assumptions of the constitutive

model can be explored. In this way, the validity of the constitutive equation to describe the

experimental behaviour can be assessed. The numerical results show that the orientation

of the platelet induces an anisotropic response that can be adequately described by a generalised neo-Hookean model in which the stiffness depends on the fibre stretch, when both

the reinforcement and the matrix are assumed to behave like incompressible neo-Hookean

solids.

The combination of a constitutive model, a finite element (FE) model and the experimental results of section 2.3, allow for greater understanding of the material behaviour

of anisotropic dis-continuous fibre reinforced elastomers and indicate to what extent the

transversally isotropic neo-Hookean constitutive model can be applied, and give an assessment of the degree to which a simplified FE model can describe the non-linear composite

behaviour.

3.1.1

Literature Review

The understanding and prediction of the behaviour of engineering materials is a prerequisite

of design and in the development of new materials. To address this, many different models

have been proposed that vary in complexity in the assumptions of the constituents, the loading conditions and the information extracted. The essential goal is to define a relationship

between the stress and strain, which for a linear elastic material can be related by an average

stiffness tensor for a composite, ie. = C.

One of the fundamental approaches which has been adapted in later models is the equivalent inclusion theory of Eshelby [55], which considers the effect of an ellipsoidal inclusion

in an infinite elastic body. The theory considers an initially homogeneous stress-free body,

from which an ellipsoidal inclusion undergoes a transformation. If it were a separate body

to the infinite medium then it would undergo a uniform strain T , however, due to the bond

between the inclusion and medium, the composite actually develops a strain field, C . The

relationship between the two strain tensors is then given by c = E Eshelby T where E Eshelby

is known as the Eshelby tensor, which depends on the inclusion aspect ratio and matrix

elastic properties.

A second scenario is considered where the inclusion undergoes no transformation, but

has a different stiffness. By subjecting both bodies to a uniform strain, Eshelby was able to

find a strain concentration tensor to relate the average strain in the composite to the strain

in the inclusion. The tensor, A, can then be used to relate the stiffness of the constituents to

54

Numerical Modelling

is the strain-concentration tensor, Em and E f are the stiffnesses of the matrix and fibres,

respectively, and v f is the fibre volume fraction. A more detailed derivation can be found

in the literature [108, 180]. However the theory only considers dilute composite materials

(low concentrations) and no particle interactions.

Mori-Tanaka [177] developed a model from Eshelbys theory that considered the effect

of multiple identical inclusions, whose derivation is methodically explained by Benveniste

[8]. Whilst the equivalent inclusion theory calculated a tensor to relate the strain in the

inclusion to that of the composite, i.e. f = AEshelby , Mori-Tanaka assume that multiple

fibres would relate to the average strain of the matrix instead, i.e. f = AEshelby m . The

result is an alternative extension of the Eshelby strain-concentration tensor,

AMT = AEshelby [(1 v f )I + v f AEshelby ]1 .

(3.1)

This theory is commonly used in the literature [58, 98], and has been further developed

to consider effects such as fibre distribution [35].

Alternatively to the equivalent inclusion theories, a self-consistent method has been developed, originally by Hill [101] and Budiansky [25]. In this scheme, the inclusion is assumed to be embedded in an infinite medium that has the average properties of the composite. In this way, the transversely isotropic properties tensor of short-fibre reinforced

composites can be calculated by an iterative process [145]. A generalised self-consistent

model has also been developed , in which Hermans [99] considered that both the fibre and

matrix are embedded in an infinite medium. From this work, the Halpin-Tsai equations were

developed [91] by finding a common form for expressing the moduli of composites, i.e.

1 + v f

(E f /Em ) 1

E

=

where, =

.

Em

1 v f

(E f /Em ) + 1

(3.2)

In this form, E represents one of a number of different moduli and is chosen based

on the particular moduli being considered. The Halpin-Tsai equations are commonly used

to estimate the mechanical properties of composites based upon knowledge of the material

constituent properties (See e.g. [58, 108]) however the many experimental variables in

testing mean the accuracy varies, so an alternative method is to set bounds upon the material

properties.

The first models of this type are the Voigt and Reuss bounds, which assume the fibre

and matrix have the same uniform strain or stress, respectively. The Voigt bound is then

found by minimising the potential energy, and calculates an upper bound to the stiffness.

55

3.1 Introduction

Alternatively the Reuss bound finds the maximum of the energy, and calculates a lower

bound of the composite stiffness. The results assume an isotropic composite, with very

wide bounds; but by giving a reference material either infinite or zero stiffness, the upper

and lower bounds can be tightened [97] and extended to anisotropic materials [246].

Bounding methods are useful because of the difficulty in predicting the material properties of composites due to the uncertainty in the material properties caused by, for example,

the dispersion of fibres and distributions in their lengths. However they give wide bounds

that are difficult to design from. In consideration of the effects of fibre length and angle distribution, Fu and Lauke [64, 67] developed a theory based on the laminate analogy approach

(LAA), which used distribution functions to represent the variability in the microstructure

of the fibres and its effect upon the elastic response. The method can be used to consider

many variables within a composite such as particle size, interface and vol% [65], and shows

reasonable agreement to experiments when the fibres are well aligned [119].

However, in order to describe the behaviour of an elastomer material it is important to consider its non-linear behaviour. Moreover it is important, in general, that any model should be

capable of describing a material when subject to any feasible deformation gradient. For example Gumbrell et al. [82] obtained significantly different results, inconsistent with theory,

under equi-biaxial extension, although tension data fitted the model well. The difficulty in

defining a constitutive theory for generalised strain, that is based on the material molecular

and microstructural composition, is evident from the comparative number of phenomenologically based models that are derived based on observations of their stress-strain behaviour

from an entirely mathematical point of view. From this context, it is important to introduce

the strain invariants that are used in the majority of phenomenological models.

To quantify the deformation of a body, it is convenient to consider the deformation

gradient, F, which is the derivative of each component of the deformation vector, x, with

respect to its undeformed counterpart, X, so that,

x1

X1

xi

x

= 2

F=

X j X1

x3

X1

x1

X2

x2

X2

x3

X2

x1

X3

x2

X3

x3

.

X3

(3.3)

The eigenvalues of the deformation gradient are known as the principal stretches, given

56

Numerical Modelling

by 1 , 2 and 3 . Rivlin [208] considered that even powered functions of these three principal stretch ratios would satisfy the constraints of a material strain energy density function, ,

that was assumed isotropic and incompressible. An alternative notation is made by choosing

these principal stretches to represent the basic variants of the right and left stretch tensors

(U and V, respectively). However, the calculation of U and V is generally mathematically

inconvenient.

However, the square of the stretch tensors provide the right and left Cauchy-Green deformation tensors (i.e. C and B, respectively),

C FT F = U2

B FF T = V 2

(3.4)

which are easier to calculate, and from this it is possible to calculate the three invariants of

an isotropic material, which are independent of the choice of coordinate axes and are called

strain invariants,

I1 = tr(C) = 12 + 22 + 32

I2 = tr(C1 ) = 22 32 + 32 12 + 12 22

(3.5)

I3 = det(C) = det(B) = 12 22 32

where tr and det indicate the trace and determinant of a matrix, respectively. For an incompressible material, I3 is constant and equal to 1. As the majority of elastomers are

incompressible, in the following only incompressible constitutive models are considered.

One of the simplest theories to describe the behaviour of elastomers is the neo-Hookean

model, which is equivalent to the statistical theory of networks, Eq. 3.6. The statistical

theory of networks is a physically-based model that considers the effect of a number of longchain molecules linked together at discrete points (e.g. vulcanisation) to form a 3D network

and provides a good approximation of the behaviour of rubber under different types of strain.

The strain energy density, i.e. the work in deforming the elastomer, can be expressed as,

1

= NkT (I1 3)

2

(3.6)

where, N is the number of network chains per unit volume, k is the Boltzmann constant

and T is the absolute temperature. The physical basis of the model has led to its critical

assessment, and the range of its validity explored. Whilst the theory is useful for a first

57

3.1 Introduction

approximation of the behaviour of a rubber material within a general strain context, at large

strains the statistical network theory underestimates the stresses due to the upturn in stress

caused by SIC and chain extensibility [241].

An extension of this theory that considers the dependence of the behaviour on the invariant I2 as well, was developed by Mooney [175] and commonly referred to as the MooneyRivlin equation due to the work of Rivlin [208] in expanding the theory. It is derived under

the assumption that Hookes law is obeyed in simple shear, which is known to be true up to

moderate strains of around 100% [82].

= C10 (I1 3) +C01 (I2 3)

(3.7)

When considering only simple extension, the Mooney-Rivlin equation gives a better

approximation of the non-linear behaviour than the neo-Hookean model, however the theory

is unable to satisfactorily improve upon the neo-Hookean model when additional strain types

are considered [241].

More complex even powered functions of i can be expressed in terms of the three

variants, and so Rivlin [208] showed that the strain energy function of an incompressible

isotropic elastic material may be expressed as the sum of a series of terms,

(3.8)

i=0, j=0

For i=1 and j=0 we get the neo-Hookean model, which is the simplest form of the series.

i=0, j=1 can be used, but this part of the series has no physical basis for rubber on its own

but can be added to form the Mooney-Rivlin equation.

However, the difficulty of these models to describe the large strain behaviour (such as

the upturn in stress), without the addition of many parameters, has led to a number of different elastomer material models being developed. A few notable models that describe the

behaviour up to relatively large strain, for general strain, will be presented.

Rivlin and Saunders [209] proposed that the dependency on I2 should be a function

decided by experimental testing, rather than a constant as in the Mooney-Rivlin equation,

i.e. C01 = f (I2 3). From this Gent and Thomas [74] proposed the following form of strain

energy,

= C1 (I1 3) + k ln(I2 /3)

(3.9)

that has a non-linear dependence on I2 and requires only two parameters to be fitted.

By considering the limited extensibility of polymer chains and the resulting observed

58

Numerical Modelling

non-linear behaviour, Hart and Smith [95] suggested a non-gaussian 3 parameter formula to

account for the rapid increase in stress at high strain.

k2

2

(i)

= G exp k1 (I1 3) (ii)

=G

I1

I2

I2

(3.10)

The use of the invariants is only for mathematical convenience. Therefore, Ogden [183]

ignored the restriction to even powers of extension ratios and wrote a power series for an

incompressible rubber that is qualitatively similar to the Mooney-Rivlin model but is able

to model the strain-hardening effect at large strain more effectively.

=

n

n N

( + 2N + 3N 3)

n 1

(3.11)

It has been shown that, for simple extension and pure shear, 4 parameters can be used

to match experimental data, but when additionally considering equi-biaxial extension 6 parameters were required to match the data up to 600% strain [241].

Arruda and Boyce [6] proposed a model that assumes a unit sphere with a distribution of

chains in eight directions along the vertices of a cube, and due to the central junction of the

chains and the symmetry that results, the deformation is related to the first invariant. The

integration of the stain energy is difficult to compute, although it can be presented in the

polynomial form as,

1

1 2

11

(I1 ) = G (I1 3) +

(I1 9) +

(I13 27)

2

2

20N

1050N

(3.12)

19

519

4

5

+

(I 81)+

(I 243)...

7000N 3 1

673750N 4 1

where N is the number of rigid links composing a single chain. The model is physically

based, as the parameter G is the same as in the statistical theory of networks, i.e. G = nkT ,

and requires only 2 parameters to fit to experimental data.

Many more constitutive equations are available that can describe isotropic materials,

that are either mathematically motivated (see e.g. the Gent [75] and Alexander [3] models)

or physically motivated (see e.g. the Yeoh [261], extended-tube [121] and van der Waals

[124] models). A comparison of these methods, and others, can be found in the literature

[21, 117, 165]. However, in general, it is necessary to include a large number of parameters

to describe the full stress-strain curve of an elastomer and so much of the physical interpretation is lost. Up to moderate strain levels ( 60%) the neo-Hookean model is generally

considered a good choice, due to the good fitting of the physically motivated function with

59

3.1 Introduction

only one parameter [165].

When the elastomer material is anisotropic there is generally a requirement for more complicated models, especially when considering the application of complex strain. A special

case of anisotropy is found when the properties of the material are aligned to 3 orthogonal

directions in the material; such a material is labelled orthotropic. If two of these directions

have equal properties then the material can be considered as transversely isotropic; such a

material might be an aligned fibre reinforced elastomer (See Fig. 3.1).

Fig. 3.1 The transverse isotropy of a fibre. Indicating the plane of isotropy orthogonal to the

principal fibre direction.

The transversely isotropic assumption leads to a significant simplification of the constitutive relationship, although the ability to describe a material successfully in an experimental

context can still be challenging. A strategy to simplifying the derivation of a stress-strain

relation is to have an additional term in the strain energy function that is decoupled from

the isotropic contribution, i.e. (C) = Isotropic + Anisotropic . Within this strain energy

function two additional invariants can be added,

I4 = A CA

I5 = A C2 A

(3.13)

where A is the axis of transverse isotropy in the reference configuration, i.e., the initial orientation of the platelet shown in Fig. 3.1. The dot product, , is defined as A B ni=1 Ai Bi .

A is a vector in the direction of the transverse isotropy in the reference configuration,

indicating the initial orientation of the reinforcement shown in Fig. 3.1, I4 is related to the

60

Numerical Modelling

square of the stretch in the direction of A, i.e. f2ibre , whilst I5 has no direct physical meaning

but can be related to fibre/matrix shear interaction [191].

A resulting form of the strain energy, assuming decoupling of the isotropic and anisotropic

components, can be given as,

(I1 , I4 , I5 ) = Isotropic (I1 , I2 , I3 ) + Anisotropic (I4 , I5 )

(3.14)

and the Cauchy stress tensor for an incompressible material is given by [45],

= pI + 21 B 22 B1 + 24 a a + 25 (a Ba + Ba a)

(3.15)

FA. is used to indicate the tensor product defined by (a b)i j = ai b j . However due to

the computational difficulty in such an equation, especially in the dependence on I5 , the

form of the strain energy is typically reduced to depend on only I1 and I4 for mathematically

simplification. A common model of this form is the so-called standard reinforcing model,

c

2

(I1 , I4 ) = I1 3 + (I4 1)

2

(3.16)

constant to measure the effectiveness of the reinforcement, and used in [45, 181].

It is important to carefully consider the whole deformation response from the constitutive model, for instance, at large values of the material can show a non-monotonic relationship between the stretch and stress (i.e. for a compressive uniaxial load at > 4.961

[199]). Hence, Guo et al. [87] modified the standard reinforcing model in order that it gives

monotonic behaviour in compression.

Similar models that depend on the fibre stretch, I4 , for the anisotropy material behaviour

have been developed (See e.g. [105, 106]), however it is also possible to construct a strain

energy dependent on I4 that considers the effects of fibre/matrix interaction [85, 249]. An

equivalent form of the standard reinforcing model has also been investigated by Merodio &

Ogden that depends on I5 , rather than I4 due to the dependence of I5 on the shear behaviour

[171],

c

2

(I1 , I4 ) = I1 3 + (I5 1)

2

(3.17)

however no significant advantage of this strain energy function is evident, and similar nonmonotonic behaviour can be observed in compression due to the finite strain energy in compression.

3.1 Introduction

61

describes the anisotropic behaviour under general loading conditions has led to many different models being developed. One of the most common formulations is that developed

by Holzapfel et al. [104], who developed a phenomenological transversally isotropic constitutive model to describe the mechanical response of arterial tissue, commonly referred

to as the Gasser-Ogden-Holzapfel model. Whilst the underlying behaviour of arterial walls

is similar to that of fibre-reinforced elastomers, the double layered material means that the

model considers the effects of two fibre families, given by the vectors a1 and a2 . In this way

there are additional available invariants, where I4 is the strain invariant in the direction a1 ,

and I6 is the equivalent invariant in the a2 direction.

n

o

k1

c

2

exp

k

(I

1)

= iso (I1 ) + aniso (I4 , I6 ) = (I1 3) +

1

2 i

2

2k2 i=4,6

(3.18)

parameter in the fibre direction, whilst k2 is a dimensionless parameter. The exponential

form of the strain energy density is motivated by the behaviour of collagen fibrils, which

show a strong stiffening effect at high strain, analogous to strain-induced crystallization.

Despite being intended to describe the behaviour of arterial walls, the model is found

to describe many transversely isotropic materials, and the extension to this theory, that considers fibre angle distributions (Ref. [72]), has been implemented in the commercial FE

software ABAQUS (ver. 6.12). A further extension of this theory, that is intended to give

a more accurate representation of the fibre distribution by including higher order terms, has

been presented in Ref. [187], whilst other models that include the effects of fibre angle

distribution can be included [32, 33].

The accuracy of a model usually depends on an inherent knowledge of the underlying

constituents of a material which can be particularly difficult for phenomenologically motivated models. Guo et al. [87] attempted to make some quantitive parameters in terms of the

homogeneity contrast and vol% of the constituents, although in general a homogenisation

scheme is required. Homogenisation schemes at small strain have been discussed, however at large strain additional geometric and constitutive non-linearities exist that make the

constitutive approach difficult.

However, it is shown by the pioneering work of Hill [102] and Hill & Rice [103] that an

effective strain energy function can be found to describe the overall constitutive behaviour

of a composite material of more than one constituent, i.e. the Hill-Mandel condition. Upper

and lower bounds on the strain energy, of the Voigt and Reuss types, were later found by

62

Numerical Modelling

Various research has since focused on particular boundary value problems, for instance,

Lopez-Pamies et al. [158] used an iterative homogenization technique to show that for

two-phase neo-Hookean composites with particulate microstructure the overall behaviour

is neo-Hookean for axisymmetric loading conditions. In Ref. [161], the constituents of a

composite are assumed to take a layered configuration and shows the effect of varying the

angle of transverse isotropy on the large strain behaviour. An advantage of a homogenisation

scheme can be the ability to relate the microstructure of a material directly to the constitutive

behaviour (i.e. size, shape, orientation and mechanical properties of the constituents). Lopez

et al. used the homogenisation theory of Ref. [159], to develop a constitutive homogenised

model of oriented reinforcing fibres in a hyperelastic matrix. The model is able to relate the

strain energy function of the overall composite to the fibre volume fraction, fibre angle and

heterogeneity contrast of the constituents,

( I4 + 2)( I4 1)2

(I1 , I4 , c0 , i ) = (I1 3) +

2

2

I4

(3.19)

where and are both functions of the volume and the properties of the constituents.

The attraction of such methods is the relation of the constituent properties to the overall composite behaviour, whilst phenomenological models are usually designed firstly for

mathematical convenience. The majority of constitutive models are developed for biological

tissues (See e.g. [104, 105, 249]), and then subsequently find applicability in similar material systems. However, particular elements of the material behaviour are often different and

require more specific models to be developed, and homogenisation schemes are difficult to

develop and generally only applicable to a specific range of material behaviour and loading.

An alternative approach is to develop a constitutive model directly from the experimental

behaviour [24]. Whilst generally a number of parameters are needed for the models of this

type found in the literature (See e.g. [111] which fits 6 parameters to describe the nylon fibre

reinforced rubber compound used in an industrial v-belt), care must be taken to ascribe the

parameters to any deformation or loading condition not explicitly considered in the original

experimental data.

The difficulty to obtain experimental data for isotropic rubber has already been discussed, and obtaining reliable data for an anisotropic material is only made more difficult.

It is said that a transversely isotropic laminate can be characterised by an experimental

tension test of the material when the fibre is aligned at 0 , 45 and 90 from the tensile direction [115], however it is inevitable that, for example, the compressive, bi-axial and shear

responses of an anisotropic material will behave very differently than that predicted by just

an examination of the tensile performance. Limited experimental data is therefore available

3.1 Introduction

63

to validate any constitutive equation (See e.g. Table 1 of Ref.[24]) due to the difficulties in

accurate experimental testing, some of which is discussed in section 2.3. To assist in the

accumulation of experimental data, it is possible to supplement it with analyses of materials

in the finite element environment.

Identification of the constitutive behaviour from the mechanical response of an RVE

The homogenisation of materials in a finite element environment, when considering the microstructure of the constituents, typically consists of a unit-cell or representative volume

element (RVE) of the material (Fig. 3.2). A unit-cell is a model that represents some periodic feature of the microstructure, whilst an RVE is the smallest representative volume of

microstructure information that can represent the overall behaviour of the macroscopic material [73]. Whilst the terms may be interchangeable in some instances, the unit-cell would

be unable to capture the effects of, for example, fibre dispersion and distribution.

Simplicity in the design of the RVE is advantageous, both in reducing the computational

cost and in simplifying parametric studies of a model; however it is important that it can

capture the realistic behaviour of the material (within the limits required of the model). A

consideration of randomness and variance is usually found to be important in the behaviour

of materials.

Fig. 3.2 The smallest section of the material microstructure that can model the properties

of the overall composite is called the representative volume element. An assumption of

periodicity in the microstructure allows a further simplification to a unit-cell.

The behaviour of many materials can often be predicted by a consideration of a single

reinforcement [36, 255], particularly when low concentrations of filler are considered, so

64

Numerical Modelling

that the effects of fibre-fibre interactions are minimised. However, when the interaction of

randomly distributed reinforcements becomes significant, as a result of processing or due to

an increase in concentration, either multiple RVEs or an RVE with multiple reinforcements

are required. Sheng et al. [221] showed that the effects of particle interaction played a

role in the efficiency of platelet reinforcements in a 2D plane strain RVE, resulting in a

reduced modulus when a platelet is shielded from the strain field by another platelet. This

can mean that the effective aspect ratio of the reinforcements reduces, due to stacking of the

reinforcements [98].

It has been shown that a platelet reinforced model predicts a slightly stiffer material than

when assuming 2D plane stress [98]; although the plane stress assumption may contribute

to this effect due to the lateral stiffening expected of a platelet reinforcement, that a plane

strain assumption would consider. The small strain effects of alignment and reinforcement

angle are also of particular interest to anisotropic materials [116, 247], as are the effects

of reinforcement geometry [247]. At large strain, however, the effects can become more

important; especially as the reinforcement mechanism can change during the deformation.

Kouznetsova et al. [137] showed that the difference between a single void RVE and a

multiple void RVE is minimal at small strain for an elasto-visco-plastic matrix. However, as

the strain is increased, the results begin to deviate slightly due to development of additional

plasticity between the voids. Similar results are found in Ref. [113] using the hyperelastic Gent model [75] to model CB reinforced rubber at large strain, which show that the

boundary conditions become very important at large strain, and multiple reinforcements are

required to ensure the RVE doesnt overestimate or underestimate the stress.

The results obtained from finite element analysis (FEA) can often be useful to explore

the mechanisms of a composite material, and can be used as a method to efficiently explore

the design space of the constituents in a controlled environment, especially when the loading

conditions and constituents of experiments are difficult to apply and control. However, they

also assist in the validation of less computationally expensive constitutive models. Guo et

al. [83, 84] investigated the effects of circular voids on the mechanical properties of an RVE

subject to different loading conditions, and were able to report the ability of a transversally

isotropic constitutive relationship to fit the data. Similarly, it has been shown that when a

filler and matrix are both neo-Hookean, the overall response is also neo-Hookean and the

apparent shear modulus can be predicted by the Halpin-Tsai equation.

The case of a fibre or platelet reinforcement is expected to differ significantly to that of

a spheroid reinforcement, mainly due to the effects orientation and rotation that will affect

the performance of the composite during deformation. Efforts to describe the behaviour of

fibre reinforced composites has shown that a transversely isotropic model can fit the nu-

3.1 Introduction

65

merical simulations well in general loading conditions up to 20-30% strain, and that the

transversely isotropic model can be related to the constituents of the RVE [44] or that the

Halpin-Tsai can be fitted well to the small strain results, and used to predict some features

of the large strain behaviour [86]. Both studies considered a unit-cell to represent the material behaviour, however the effects of fibre orientation, rotation during deformation and

dispersion/distribution are not possible to explain from such a model; in this case an RVE is

required.

A 3-dimensional multiple fibre reinforced slightly compressible RVE, developed in Ref.[77],

shows the effect of a random distribution of aligned fibres on the transversely isotropic behaviour of the model, which is compared to hyperelastic constitutive relationships. The

stress-stress relationship is investigated up to 20% strain, and is able to use the periodic

boundary conditions to model multiple reinforcement angles with one RVE model. A parametric study of the reinforcement angle is undertaken for an RVE with randomly dispersed,

perfectly aligned fibres of length/width ratio 20 and a heterogeneity contrast between the

matrix and reinforcement of 25. The volume content of the fibres is varied between 10 and

25 vol%, and shows that a transversely isotropic form of the strain energy can represent the

material behaviour well up to 10-20% strain.

66

3.2

3.2.1

Numerical Modelling

Constitutive Modelling

Introduction

is an active area of research [165], particularly when the micro-structure presents interesting features to the overall behaviour (See, e.g., the mechanical and stability response of

fibre-reinforced elastomers [160]). However, experimental testing of materials can often be

challenging [256] and so the constitutive models are compared to FE simulations to determine the limitations of the models in different loading conditions [86].

Fig. 3.3 A fibre reinforced thin elastomer specimen (t << L) can be simplified to a multiple

fibre RVE, assuming plane stress in the through thickness direction. In addition, a platelet

reinforced elastomer can be assumed to have plane strain in the through thickness direction,

if the thickness is much greater than the length, i.e. t >> L. In both cases, a further simplification to a single reinforcement RVE can be made if an assumption of periodicity and

dilute inclusions is made.

In this section, a transversally isotropic model is introduced that is expected to describe

the behaviour of composites with aligned, reinforcing filler particles. The deformation of an

67

elastomer reinforced by an aligned fibre (reinforced in 1-dimension) is expected to be modelled by a simplification of the constitute behaviour to plane stress, i.e. the stress through the

thickness is assumed to be negligible and equal to zero due to the very thin specimen thickness and lack of lateral constraint, Fig. 3.3. Such an equation has shown that is can successfully model the behaviour of a fibre reinforced PDMS elastomer up to 30% strain, subject to

aligned reinforcement in the range 0 = {0 , 90 }. At higher strains, above 60-100% strain,

additional non-linear effects, such as strain-induced crystallisation and inextensibility of the

polymer chains, make identification difficult. A neo-Hookean based transversally isotropic

model should be able to describe the behaviour up to moderate strains (<60%), see e.g.

[165], but the inability of the model to describe the behaviour in the strain range 30%-60%

suggests that the aligned dis-continuous reinforcements cause non-linearities that are not

described well by a transversally isotropic material model that assumes the reinforcement is

continuous.

In contrast to fibre reinforcements, the morphology of a platelet reinforces a material

in 2-dimensions and therefore provides a lateral constraint (See Fig. 3.3); this means the

through thickness stress is not negligible. In addition, if the platelets are very long in the

through thickness direction, and the specimen thickness is much greater than the length,

i.e. t >> L, then a plane strain assumption can be enforced. A constitutive model is also

presented for this microstructure.

A real composite would behave somewhere between these two extremes.

These models will later be compared to FE simulations to determine the applicability

of the constitutive model to describe the microstore under consideration, i.e. that of an stiff

aligned dis-continuous reinforcement in an elastomer matrix.

3.2.2

When the reinforcing particles have uniform orientation distribution, the overall behaviour

of the composite is isotropic and the corresponding stress-strain relationship at the macroscale

would follow the behaviour of the constituents [160]. On the contrary, when the composite

is reinforced with anisotropic inclusions oriented in a preferred direction, it is reasonable to

expect that their orientation has an effect on the overall mechanical response. The intent of

our analysis is to show in what limit of the aspect ratio of the platelet and the size of the RVE

the overall composite can be actually described as transversally isotropic. These models are

usually employed to describe the behaviour of materials reinforced with continuous fibres

that span the entire length of the body. When the inclusions are discontinuous, one has to

assess the predicting capabilities of the models against numerical results.

In the following it is assumed that the platelet oriented in a preferred direction cause the

68

Numerical Modelling

the set of invariants pertinent to incompressible materials introduced earlier are used, with

the added subscript M henceforth referring to the macroscopic quantity,

I1 = tr(CM ) ,

1

I2 = tr(CM

)

2

I4 = A CM A , I5 = A CM

A

(3.20)

In the most general case, the strain energy function of an incompressible transversely

isotropic material depends on all the invariants defined in (3.20): two isotropic, I1 and I2

and an additional two, I4 and I5 used to account for anisotropic effects. However, we focus

the attention on the subclass of materials whose strain energy depends only on the two

invariants I1 and I4 . This choice is motivated by the behaviour of the constituents, whose

constitutive response has been assumed to depend only on I1 m (see Eq. 3.74). The additional

dependence on I4 allows the effect of the stretch in the direction of the platelet to be weighed.

Such a form of the strain energy has been largely and successfully used in the literature to

model soft-tissues, gels and reinforced elastomers (see, e.g., [40, 45]).

Under this assumption, the macroscopic Cauchy stress, M , is given by,

M = p I + 2 1 BM + 2 4 a a ,

(3.21)

and is derived from the following strain energy density function, M ,

M (I1 , I4 ) =

2

(3.22)

with

1

g(I4 ) = ( I4 1)2 ( I4 + 2)

I4

(3.23)

The model (3.22) was introduced in [44] and used in [86] and [160]. The strain energy

function, , is the sum of two different contributions: the energy associated with the overall

stretch of the composite, i.e., I1 3, plus the energy associated with the stretch along the

fibre direction, i.e., g(I4 ). This decomposition is based on the assumption that the strain

energy stored in the fibres depends only on the fibres elongation, given by I4 (see [44]).

The isotropic neo-Hookean model is recovered for = 0. Note that, in general, with this

formulation the constitutive parameter loses its significance as the shear modulus of the

composite.

69

Additionally it is well known that the effective shear modulus of the composite can be

estimated from the mechanical properties of the constituents in terms of shear moduli of the

filler, (p) , of the matrix (r) and the corresponding volume fractions (p) and (r) (such

that (p) = 1 (r) ). Among several formulations available in the literature, the HalpinTsai equation has been successfully used to predict the in-plane and transverse shear moduli

of composites reinforced with unidirectional inclusions [91]. Therefore when the fibre is

aligned in the direction E1 , i.e., 0 = 0 , Halpin-Tsai equation gives the following relationship between the composite shear modulus, c (0 ) = , and those of the constituents

f + 1 + (r) ( f 1)

f + 1 (r) ( f 1)

(3.24)

where f = (p) / (r) is the so-called heterogeneity contrast. Transversally isotropic materials require an additional parameter, defined as , to capture the effect of the alignment

angle, 0 (See Fig. 3.4). Formulations to describe in terms of the constituents are available in the literature for continuous reinforcement, see e.g. Ref.[160] and Ref.[86], and an

assessment of these formulations will be made in the context of dis-continuous platelet-like

reinforcements.

Fig. 3.4 A schematic representation of the RVE in the cartesian coordinates plane E1 ,E2 .

70

Numerical Modelling

Plane Strain

The plane strain deformation in the E1 , E2 plane of a Cartesian coordinate system has the

following form,

F11 F12 0

FM = F21 F22 0 ,

0

0 1

(3.25)

B11 B12 0

BM = B12 B22 0 ,

0

0 1

(3.26)

where B33 = F33

11

11

12

2

2

B12 = F11 F21 + F22 F12 and B22 = F22 + F21 .

Since the material is incompressible, the following relationship between the strain components holds,

B11 B22 B212 = 1 ,

(3.27)

that shows that only two components of the deformation can be controlled independently

when an incompressible material is constrained to a plane strain deformation.

If 0 is the orientation of the axis of isotropy in the reference configuration, i.e., the

platelet orientation, (see Fig. 3.4), then A = (cos(0 ), sin(0 ), 0)T while its spatial counterpart is a = (a1 , a2 , 0)T where,

a1 = F11 cos(0 ) + F12 sin(0 ) ,

a2 = F21 cos(0 ) + F22 sin(0 ) .

(3.28)

I1 = B11 + B22 + 1

I4 = a21 + a22

and from (3.21) the components of the Cauchy stress immediately follows as

(3.29)

71

11 = p + 2 1 B11 + 2 4 a21

(3.30)

22 = p + 2 1 B22 + 2 4 a22

(3.31)

33 = p + 2 1

(3.32)

12 = 2 1 B12 + 2 4 a1 a2

(3.33)

by subtracting the stress in the E3 direction, 33 , from (3.30) and (3.31) one obtains the

following stress differences,

11 33 = 2 1 (B11 1) + 2 4 a21

(3.34)

22 33 = 2 1 (B22 1) + 2 4 a22

(3.35)

that are independent of p and together with (3.33) are used to compare analytical and numerical results.

Incidentally, the chosen form of M , i.e., M (I1 , I4 ), represents the largest class of

transversally isotropic materials that can be fully identified through plane strain deformations. I.e. The previous equations involve two unknown functions, 1 and 4 , and two

independent components of the deformation, B11 and B12 . In a displacement controlled test,

one can vary them to characterise completely the macroscopic strain energy function M .

Indeed, if M were dependent also on I2 or I5 , additional unknowns would have appeared

in (3.30)-(3.32) causing them to be not identifiable uniquely in plane strain.

The following plane strain deformation is here considered,

1 0

1 0

0 0

FM = 0 1 0 = 0 1 0 0 1 0 ,

0

0

1

0 0 1

0

0 1

(3.36)

Given (3.36), it is easy to calculate the invariants

I1 = 2 + 2 + 2 + 1

I4 = ( sin (0 ) + cos (0 ))2 + 2 sin2 (0 ) .

(3.37)

The direction normal to the platelet in the reference configuration is N = ( sin(0 ), cos(0 ), 0)T

1 T

(see Fig. 3.4), whereas the current normal vector is n = FT

M N FM N; in view of (3.25)

72

Numerical Modelling

the current orientation of the platelet in terms of the original angle 0 and the deformation

components and is given by,

1 cos(0 )

1

= tan

.

2

cos(0 ) sin(0 )

(3.38)

The expressions of the non-dimensional Cauchy stress,

deformation components , and the orientation of the platelet 0 , can then be obtained

from (3.21),

2

e11

e33 = 2 1 + sin (0 ) + 2 cos (0 )

(3.39)

1 + 2

1 + sin2 (0 )

2

(3.40)

e22

e33 =

e12 = + sin (0 ) sin (0 ) + 2 cos (0 )

(3.41)

3/2

= ( 2 + 1) sin2 (0 ) + 2 sin(20 ) + 4 cos2 (0 )

(3.42)

In section 3.5.4, the cauchy stresses (3.39)-(3.41) are compared with the FE simulations

of the RVE.

To assure the compatibility with small strain linear elasticity it is useful to recover the

expression of the effective shear modulus c from (3.41). This can be done by assuming

that the the RVE is deformed in simple shear with no overimposed stretch, i.e., = 1 and

= 0, in which case c is given by c = 12 / for 0, that is,

3

c (0 ) = 1 + (1 cos(40 )) .

8

(3.43)

and as expected, depends on the fibre orientation. In particular c has a maximum for

0 = 45 in which case the platelet is aligned along the principal direction of the deformation

and is either stretched or compressed; as such it provides the maximum resistance to external

forces that in turn results in the maximum effective shear modulus. On the contrary for

0 = 0 or 0 = 90 , the effective modulus is minimum and equal to .

These two limit values can be used to identify the constitutive parameters and from

the numerical results of the small strain analysis. Through Eq. 3.43 these are given by,

= c (0 ),

4

=

3

c (45 )

1 .

c (0 )

(3.44)

73

which show that, if a composite is described by the strain energy function (3.22), full characterization of the nonlinear response requires only two small strain tests: a shear test with

the fibres oriented at 45 and another one with the fibres at 0 . As a result, and are

uniquely determined.

Plane Stress

For the plane stress deformation in the E1 , E2 plane of a Cartesian coordinate system, the

macroscopic deformation gradient has the following form,

F11 F12 0

FM = F21 F22 0 ,

0

0 F33

(3.45)

B11 B12 0

BM = B12 B22 0 ,

0

0 B33

(3.46)

Since the material is incompressible, the following relationship between the strain components holds,

B33 (B11 B22 B212 ) = 1 ,

(3.47)

that shows that only two components of the deformation can be controlled independently

when an incompressible material is constrained to a plane stress deformation (As B11 , B22

and B33 are coupled).

If 0 is the orientation of the axis of transverse isotropy in the reference configuration, i.e., the fibre orientation, (see Fig.3.4), then A = (cos(0 ), sin(0 ), 0)T while its spatial

counterpart is a = (a1 , a2 , 0)T , where

a1 = F11 cos(0 ) + F12 sin(0 ) ,

a2 = F21 cos(0 ) + F22 sin(0 ) .

(3.48)

I1 = B11 + B22 + B33

I4 = a21 + a22

and from (3.21) the components of the Cauchy stress immediately follows as,

(3.49)

74

Numerical Modelling

11 = p + 2 1 B11 + 2 4 a21

(3.50)

22 = p + 2 1 B22 + 2 4 a22

(3.51)

33 = p + 2 1 B33

(3.52)

12 = 2 1 B12 + 2 4 a1 a2

(3.53)

As expected, the only component independent of the pressure field is 12 , although the

plane stress assumption means that 33 = 0 and so,

p = 2 1 B33

(3.54)

(3.55)

(3.56)

12 = 2 1 B12 + 2 4 a1 a2

(3.57)

33 = 0

(3.58)

The previous equations involve two unknown functions, 1 and 4 , and two independent components of the deformation, B11 and B12 . As with plane strain, in a displacement

controlled test, one can vary them to characterise completely the macroscopic strain energy function M . The chosen form of M , i.e., M (I1 , I4 ), represents the largest class of

transversally isotropic materials that can be fully identified through plane stress deformations, and in fact, if M were dependent also on I2 or I5 , additional unknowns would have

appeared in (3.55)-(3.58) causing them not to be uniquely identifiable in plane stress.

Considering a plane stress deformation given by,

1

0

0

2

0

1 0

1

1

FM = 0 2

0 ,

0 = 0 1 0 0 2

1

1

0 0 1

0

0 2

0

0

2

(3.59)

75

easy to calculate the invariants,

2

+ 2 + 1

2

I4 =

sin (0 ) + cos (0 ) + 1 sin2 (0 )

I1 =

(3.60)

eM = M /() in

that gives the following expression of the non-dimensional Cauchy stress,

terms of the deformation components , , , and the initial orientation of the fibre, 0 ,

sin (0 ) 2

1

e11 = + cos (0 ) +

1/2

1 + 2 1

e

22 =

+ 1 sin2 (0 )

sin (0 )

1/2

1/2

e12 = +

sin (0 ) cos (0 ) +

1/2

2

(3.61)

(3.62)

(3.63)

(1 + )2 (1 + )(2 + )

+

=

2 2

2

(1 + )2 (2 + ))

2 3

(3.64)

sin (0 ) 2

sin2 (0 )

=

+ ( cos (0 ) +

)

1/2

1/2

(3.65)

In section 3.4.5, the cauchy stresses (3.61)-(3.63) are compared with the FE simulations

of the RVE, whilst in section 2.3, comparisons have been made to experimental results.

To assure the compatibility with small strain linear elasticity it is useful to recover the

expression of the effective shear modulus c from (3.63). This can be done by assuming

that the the RVE is deformed in simple shear with no overimposed stretch, i.e., = 1 and

= 0, in which case c is given by c = 12 / for 0, that is,

3

c (0 ) = 1 + (1 cos(40 )) .

8

(3.66)

which is the same form as for plane strain i.e. it depends on the fibre orientation, c has a

maximum for 0 = 45 and a minimum for 0 = 0 and 0 = 90 .

76

Numerical Modelling

Similarly, these two limiting values can be used to identify the constitutive parameters

and from the numerical results of the small strain analysis. Through Eq. 3.66 these are

given by

= c (0 ),

4

=

3

c (45 )

1 .

c (0 )

(3.67)

which show that, if a composite is described by the strain energy function (3.22), full characterization of the nonlinear response requires only two small strain tests: a shear test with

the fibres oriented at 45 and another one with the fibres at 0 . As a result, and are

uniquely determined.

Additionally, in order to make comparisons to the small strain elasticity of uniaxial

extension experimental results, it is useful to recover an expression for the effective elastic

modulus, E11 , from (3.61). This can be done by calculating the derivative of the stress, and

taking the value at which there is no imposed stretch or shear, i.e., = 0, in which case E11

is given by E11 = 11 / for 1, that is,

E11 (0 ) =

3

(16 + 5 + 8 cos (20 ) + 3 cos (40 ))

16

(3.68)

As expected the effective elastic modulus depends on the fibre orientation. In particular

E11 has a minimum for 0 = 65.9 ; in this configuration the fibre provides the least amount

of resistance to the uniaxial forces imposed upon it.

On the contrary for 0 = 0 or 0 = 90 , the effective modulus is a local maxima. The

maximum at 0 = 0 being significantly larger than at 0 = 90 . However, the limiting value

at 0 = 90 is interesting as it indicates the potential importance of the lateral constraint of

the reinforcement in an incompressible system, an observation that has been experimentally

observed and will be discussed in section 2.3.

Finally, it is useful to derive the expression of the fibre orientation in terms of the deformation components and . The direction normal to the fibre in the reference configuration is N = ( sin(0 ), cos(0 ), 0)T (see Fig. 3.4), whereas the current normal vector is

n = FMT N1 FMT N; in view of (3.45) the current orientation of the fibre, , in terms of

the original angle, 0 , and the deformation components and is given by:

"

= tan1

#

1/2 sin(0 )

.

cos(0 )

(3.69)

The previous equation allows comparisons to be made between the orientation of the

fibre as predicted. As it is shown in the next section, the mismatch between the numerical

results and the analytical model increases for increasing values of the stretch . This effect

77

is thought to cause the mismatch between the stress values obtained by ABAQUS and the

ones from (3.61)-(3.63).

78

Numerical Modelling

3.3

3.3.1

Numerical Homogenisation

Introduction

to capture the behaviour of a material up to moderate strains (30-100% strain) has been

demonstrated previously. On the contrary, a transversally isotropic hyperelastic models

are usually employed to describe the behaviour of materials reinforced with continuous

fibres that span the entire length of the body and so it is important to assess the predicting

capabilities of the models against numerical results when using discontinuous fibres. The

intent of our analysis is to show the extent to which such a model accurately describes the

behaviour of both the RVE and experimental results.

In order to investigate the applicability of constitutive models, it is important to validate

the model with respect to a comprehensive set of experimental data. In light of the difficulty

to experimentally test anisotropic materials (See e.g. the experimental difficulties in section 2.3 and Ref.[256]), an alternative is to simulate the material behaviour in the context of

a representative volume element (RVE).

Three RVE configurations are considered in determining the behaviour of an elastomer

material reinforced by aligned fibres up to moderate strains (i.e. <60%): (1) A 3D, multiple

reinforcement RVE as a benchmark for the real material behaviour, (2) A 2D, multiple

reinforcement RVE, and (3) A 2D, single reinforcement RVE. The 2D RVEs are investigated

to determine their ability to describe the behaviour of the elastomer composite at a reduced

computational cost.

The constituents of the RVE (i.e. the matrix, and the reinforcement) are both modelled as

neo-Hookean materials with a heterogeneity contrast in the neo-Hookean parameter, C10 , i.e.

(p) / (r) . The justification for assuming the constituents behave as neo-Hookean materials

is based on the knowledge that:

An elastomer matrix (e.g. NR or PDMS) can be described as neo-Hookean up to

moderate strains (<100%) [165].

When the heterogeneity contrast between the constituents is large, the fibre is expected

to be approximated well by a neo-Hookean model.

The neo-Hookean model requires one parameter to be defined (i.e. C10 ), which simplifies any parametric study.

The addition of a moderate amount of compressible filler particles (<10%) to an

nearly-incompressible elastomer is not expected to increase the compressibility much

79

[24].

It has been shown that a composite with a matrix reinforced by spherical fillers, both

neo-Hookean, can be successfully described by a neo-Hookean constitutive equation

[88].

It has further been shown that when the reinforcement is a fibre, the overall behaviour

can be described by a transversely isotropic constitutive equation [86].

Despite the research on transversely isotropic materials, including both constitutive and

numerical studies, there are still many unanswered questions that an RVE of the type discussed in the literature is unable to answer:

The models available in the literature only consider reinforcement configurations 0

and 90 , and therefore fail to consider the effects of the reinforcement angle and the

subsequent rotation of the reinforcement during deformation.

The effects of fibre angle distribution have been investigated in a constitutive context

[72, 187], however a constitutive model makes a number of assumptions (e.g. no fibre

interaction) that could change the behaviour. The effects of fibre angle distribution

could significantly change the behaviour of the composite.

It is difficult to assess the mechanical performance of transversely isotropic materials

in certain loading conditions (See e.g. [256]), hence there is a limited amount of

experimental data available from which to validate constitutive models. An RVE can

be used to assess the effects of different loading conditions that are difficult to assess

experimentally (e.g. The compression of a specimen, reinforced by obliquely aligned

reinforcements).

Furthermore, the extent to which a simplified single reinforcement RVE (Fig. 3.4) can

model the behaviour of an elastomer, reinforced by aligned particles, is unclear. The benefit

of such a model would be the simplification of a parametric study to investigate effects

of, e.g., the particle aspect ratio, filler vol% and constituent heterogeneity contrast. This

would also be performed at a greatly reduced computational cost. The model could also

be used as the basis for further investigation into the effects of the matrix/reinforcement

interface, failure criteria and an investigation of the large strain effects with more advanced

constitutive behaviour.

80

3.3.2

Numerical Modelling

Homogenization Procedure

The macroscopic behaviour of the composite can be determined from the mechanical response of a Representative Volume Element (RVE). The accurateness of the solution depends critically on the ratio between the size of the RVE and inclusion. In general, for reinforced composites, it can be assumed that the microstructure characteristics are such that

the dimensions of the filler are on a completely different length scale to the macroscopic

dimensions of the body.

In the following, we denote xm as the current position of a microscopic particle, and Xm

as the position in the reference configuration of the RVE, that is assumed to be stress free.

The subscript "M" refers to a macroscopic quantity, while the subscript "m" will denote a

microscopic quantity. The motion is a one to one mapping (Xm ,t), that assigns to each

point, Xm , belonging to the reference configuration the position xm at time t, i.e. xm =

(Xm ,t). As such, the deformation gradient Fm is defined through Fm = / Xm . If both

the constituents are hyperelastic, one can postulate the existence of a strain energy function

m that depends upon the deformation gradient Fm , the position Xm , i.e, m (Fm , Xm ), and

satisfies objectivity and material symmetry.

The homogenisation procedure allows previous microstructural quantities to be related

to the macroscopic response of the body in terms of average deformation and stress. These

are defined by,

1

1

F dV =

xm N dS,

FM =

|0 | 0

|0 | 0

Z

Z

1

1

PM =

P dV =

tm X dS,

|0 | 0

|0 | 0

Z

(3.70)

where 0 is the volume occupied by the RVE in the reference configuration, |0 | its meaR

sure, i.e., 0 dV , xm and tm represent the position and traction on the boundary of the RVE

and N denotes the outward normal to the boundary of the RVE.

One can introduce the macroscopic strain energy function, M , that is in relation with

the average stress and deformation,

1

M (FM ) :=

|0 |

m (Fm ) dV = PM FM ,

(3.71)

also known as the Hill-Mandel condition. Here and henceforth indicates the inner product.

Considering the form of the strain energy given in (3.22), The previous equation implies

that for an incompressible material, i.e. (3.22), the first-Piola Kirchhoff stress is calculated

81

as,

PM =

M (FM )

.

FM

(3.72)

The volume average of the macroscopic quantities does not hold for the Cauchy stress

(see, e.g., [138]); however once the first-Piola Kirchhoff stress is calculated the usual relationship between the stress measures means the macroscopic Cauchy stress could be defined

as,

M = p I +

M (FM ) T

FM .

FM

(3.73)

The problem of defining the constitutive response of the homogenised hyperelastic material is hence reduced through (3.72) or (3.73) to finding the macroscopic strain energy

function, M . Unfortunately, the derivation of an analytical expression is often challenging even for very simple microstructures due to geometrical and constitutive nonlinearities.

Therefore, to find the homogenised model one has to use the finite element solution obtained

by applying the proper average deformation gradient, FM , to the RVE.

3.3.3

by the addition of stiff discontinuous reinforcements. Either a plane strain or plane stress

deformation can be applied to the 2D RVE; in this way the reinforcement can be considered

as either a fibre reinforcement or platelet reinforcement, respectively.

Owing to the geometry of the specimens and reinforcements, it is possible to reduce the

full 3D model to a 2D one by enforcing a plane stress/strain deformation. As such, four

numerical models are considered in this study. To model the behaviour of an elastomer

block reinforced by platelets (See Fig. 3.5a): A 3D multiple platelet RVE (3D-MPRVE) is

reduced to a 2D single platelet RVE (2D-SPRVE) under the assumption of plane strain. To

model the behaviour of a thin fibre reinforced elastomer specimen, a 2D multiple fibre RVE

(2D-MFRVE) is adopted under a plane stress assumption (Fig. 3.5b). This model is reduced

to a 2D single fibre RVE (2D-SFRVE), again under the assumption of plane stress.

The reduction of the models to a single reinforcement model (i.e. 2D-SPRVE or 2DSFRVE) is likely to be valid under the hypothesis of dilute inclusions (low wt%) and that the

overall behaviour of both composites (i.e. fibre and platelet reinforced) can be inferred from

a single reinforcement model with significant advantages in terms of computational cost

and accuracy of the solution, however the degree to which this simplification is applicable

82

Numerical Modelling

is unclear.

Fig. 3.5 A schematic representation of the different models examined: from the full 3D

RVE to the single platelet one. In each case, the model is simplified further. (a) The platelet

reinforced elastomer block, (b) The fibre reinforced thin elastomer specimen.

Both the matrix and the filler are assumed to behave like incompressible neo-Hookean

materials with the strain energy functions given by,

()

(I1 m 3) p() (Jm 1) ,

(3.74)

2

where = {r, p} indicates the matrix and the filler, respectively. Here, , is the shear modulus of the constituents and I1 m = tr(Fm FTm ) and p() is the Lagrange multiplier associated

with the incompressibility constraint.

()

m (I1 m ) =

83

For the numerical simulations, the shear modulus of the matrix was chosen as (r) =

2 MPa, and the heterogeneity contrast between the constituents, i.e. (p) / (r) , in the range

(p) / (r) = {1, 10, 100, 1000}; p() is determined from the boundary conditions.

Parametric simulations were run with the FE software ABAQUS (ver. 6.12) for different values of the constituents parameters and orientation of the reinforcement 0 [0, 90].

In particular, seven different orientations were considered for the 3D and 2D multiple reinforcements model (0 = 0 , 15 , 30 , 45 , 60 , 75 , 90 ). For the 2D single reinforcement

model, the reinforcement orientation was investigated at 5 intervals, between 0 and 90 ,

giving a total of 19 unit-cells.

The single reinforcement model is generated through a combination of ABAQUS input

file and python script, which allows the orientation of the platelet to be accurately controlled

and varied. In this case, the mesh was automatically generated through the Abaqus input

file. In contrast, the 3D multiple reinforcement RVE and 2D multiple reinforcement RVE are

meshed in the ABAQUS CAE environment. The multiple reinforcements are positioned and

oriented in a semi-random manner, by firstly assigning an orientation to each reinforcement

in correspondence to a prescribed distribution (eq. 3.75). The reinforcements are positioned

by initially considering a uniform distribution, and then applying a random displacement,

to the reinforcement (i.e. x < < x), where x is the distance between the reinforcements. The procedure is repeated until a configuration is achieved without reinforcements

overlapping each other, or the boundary of the RVE.

The number of elements was established through a convergence check and it was seen

that a good accuracy/convergence was reached with about 200,000 elements for the 3D

model, 26,000 elements for 2D multiple platelets and 4000 elements for the single reinforcement RVE. The *Hyperelastic, neo hooke model in ABAQUS was used for both

the matrix and the platelet with bulk modulus k = 104 , that makes the material nearly incompressible. For all simulations a *Static analysis with nonlinear geometry was carried

out.

The affine boundary conditions were enforced on the RVE through the Abaqus *DISP

subroutine. The average stress PM was computed from the resulting forces on the boundary

through (3.70). The effective incremental moduli are obtained by constructing the numerical

tangent through a linear perturbation analysis after each step of the nonlinear analysis.

For all simulations the ratio between the height and the length of the RVE is kept fixed

and equal to 1, i.e., a square RVE. The ratio t between length and thickness of the fibre is

t = 40, unless otherwise stated, and corresponds to a volume fraction of 1.2 vol%. The overall geometry and assumptions in the numerical model are comparable to the experimental

materials in section 2.3 and is also typical of the values used in nanocomposites [226].

84

3.4

3.4.1

Numerical Modelling

Introduction

The addition of anisotropically aligned reinforcements can significantly increase the properties of composites [52], with the directions of alignment being chosen to produce a tailored

response [40]. When fibre reinforcements have only one referred plane of orientation, the

composite can be described as transversally isotropic. At large strain, the effects of the

anisotropic reinforcement and rotation are expected to complicate the response of the material, however the behaviour of nickel-coated short carbon fibre reinforced PDMS has been

shown to be described well by a transversally isotropic hyperelastic incompressible model

up to approximately 30%. At strains greater than 30%, the model is unable to capture the

highly non-linear behaviour of the material.

The intent of our analysis is to develop a numerical model to assist in understanding the

behaviour of a transversally isotropic composite that is reinforced by dis-continuous fibres.

The models are usually employed to describe the behaviour of materials reinforced with

continuous fibres that span the entire length of the body, however, when the inclusions are

discontinuous and dispersed, one has to assess the predicting capabilities of the models.

When the reinforcements are oriented in a 3 dimensional arrangement it is expected that

this behaviour would require a full 3D analysis and a consideration of the angular and spatial distribution of the reinforcements. The computational cost of such a model is large,

and restricts the possibility to parametrically explore the design space of the composite.

However, when the fibres are restricted to an orientation within a single plane and the specimen thickness is very thin, as in our case, (Fig. 3.6), it is expected that the model can

be simplified to a 2D plane stress model. In fact, it is further proposed that the behaviour

may be described by a single reinforcement. The extent to which a 2D-SFRVE can model

the transversally isotropic material requires assessment, however its implementation would

greatly reduce the computational cost of the numerical analysis, reduce the variables in a

parametric study and allow a basis to consider other microstructural features, e.g. into the

effects of the matrix/reinforcement interface.

Never the less, it is known that the distribution of fibres, and the distribution of fibre

angles, can have a significant effect upon the behaviour of the composite. In order to investigate these effects, a 2D RVE consisting of 100 randomly distributed fibres (2D-MFRVE)

is created with the distribution of the fibre orientation carefully controlled to give a bespoke

distribution.

85

Fig. 3.6 A thin elastomer (length much greater than the thickness) with fibres restricted to a

single plane (E1 , E2 ) can be modelled as a 2D plane stress structure.

3.4.2

Numerical Methods

The numerical study consists of assessing the behaviour of a 2D-SFRVE (Fig. 3.7b) and

comparing it to the transversally isotropic constitutive model, Eq. 3.22. The model consists

of 4000 CPS4R elements, subject to plane stress deformation. A single reinforcement represents the behaviour of a dis-continuous fibre, which has an aspect ratio of 40, i.e. AR = L/t ,

a volume of 0.8% and a shear modulus of (r) = 2000 MPa, therefore giving a heterogeneity

contrast between the reinforcement and matrix of, (p) / (r) = 1000. The reinforcement is

aligned at 5 intervals between 0 = 0 and 0 = 90 . The RVE is compared to the transversally isotropic hyperelastic constitutive model up to 60% strain in tension and shear; in such

a way the RVE is fully characterised under the plane stress assumption for an incompressible

material.

To assess the ability of the 2D-SFRVE to model aligned reinforcements, a 2D-MFRVE

is developed (Fig. 3.7a); consisting of 100 aligned reinforcements of equivalent properties,

i.e. AR = 40, vol% = 0.8 and heterogeneity contrast, (p) / (r) = 1000. The reinforcements

are then aligned at the required angles, 0 . The number of elements required is increased

to 26,000, using the same plane stress elements, i.e. CPS4R. The reinforcement of the

platelets is considered at 15 intervals, at angles 0 = {0 , 15 , 30 , 45 , 60 , 75 , 90 }.

An additional parametric study is undertaken on the 2D-MFRVE, to investigate the effects of fibre angle distribution. The angle is varied in accordance with the distribution given

by,

86

Numerical Modelling

Fig. 3.7 The two RVE configurations in the undeformed configurations. (a) The multiple

aligned fibre RVE model for 0 = 30 (2D-MFRVE). The inset shows the mesh surrounding

a reinforcement. (b) The single fibre reinforced RVE model for 0 = 30 (2D-SFRVE). The

inset shows the mesh around the inclusion edge.

1

ebcos(2 )

( ) = R

bcos(2 ) d

0 e

(3.75)

By varying the parameter b at values b = {2, 5, 8} a set of MFRVEs with varying angle

distribution are created (See Fig. 3.8). The values are chosen based on the experimental

results of section 2.3, in which b = 4.5. The results of the five configurations, i.e. b = 2,

b = 5, b = 8, the perfectly aligned 2D-MFRVE and the 2D-SFRVE, are compared and the

ability of the hyperelastic model to capture the behaviour is assessed in each case, for each

angle, in uniaxial tension up to 60% strain. A total of 10 numerical specimens are created for

each MFRVE configuration, each with a randomly created distribution of fibre alignments

defined by Eq. 3.75, in order to quantify the resulting variability of fibre position and angle.

3.4.3

The reinforcement is expected to increase the overall stiffness of the RVE; whilst the transversely isotropic properties that result from the oriented fibres are expected to have significant effects upon the large strain behaviour due to the initial orientation of the fibre and its

subsequent rotation as the RVE is stretched. However, the dis-continuous morphology of the

reinforcement may result in discrepancies to the hyperelastic model due to its assumption

of a continuous, inherent, reinforcement.

The results of the simple tension tests are shown in Fig. 3.9 in the range [1, 1.6] for

different initial orientations of the reinforcement, 0 = {0 , 25 , 45 , 65 , 90 } and hetero-

87

Probability density

1.5

b=2

b=5

b=8

Model Fit

1

0.5

0

0.5

0

0.5

0

90

60

30

30

60

90

Reinforcement angle, 0

Fig. 3.8 The distribution of the fibre angles, as defined by the parameter b in Eq. 3.75.

The images show an arrangement whereby the fibres are aligned around the 0 = 0 configuration. The fibre distributions of the 2D-MFRVE are shown for b = 5 and the aligned

configuration.

0.5

geneity contrast, f = (p) / (r) = 1000 ( (r) = 2 MPa). The maximum stretch is chosen to

reflect the ability of a neo-Hookean material to model a rubber up to strains of at least 50%,

and in general are unlikely to be subjected to much larger deformations in most applications.

0

25

45

65

90

1.5

(a)

0.6

0.7

0.8

Stretch,

0.9

0

25

45

65

90

0

1

(b)

1.1

1.2

1.3

1.4

1.5

1.6

Stretch,

Fig. 3.9 Cauchy stress 11 against stretch for simple tension in terms of reinforcement

orientations 0 = {0 , 25 , 45 , 65 , 90 }. In all cases, (r) = 2 MPa, f = 1000, AR = 40

and vol = 1.2%.

The effects of the initial orientation of the fibre 0 can be seen from Fig. 3.9, in which

the 0 orientation has the higher stiffnesses, whereas the 65 RVE displays the lowest initial

stiffness, with the 90 RVE only marginally stiffer initially. For the 65 configuration the

stress applied on the boundary is transferred by the fibre predominantly by shear forces and

hence the lower tensile modulus. At larger tensile stretches, the 65 RVE becomes stiffer

88

Numerical Modelling

due to the reorientation of the fibres towards the loading direction (See Fig. 3.10a). Such a

rotation does not occur for the 90 RVE, as is seen in Fig. 3.10b, due to no shear stresses

being formed that rotate the fibre. The 0 RVE in compression has a much larger stress

response, partially due to the boundary effects of the specimen that is unable to rotate and

results in an instability at large strain; hence a similar instability is not seen in e.g. the 25

RVE.

This result illustrates the two distinct types of stiffening that the model shows at small

strain: longitudinal stiffening due to the stress transfer from the matrix to the fibre (most

prominent when the fibre is oriented parallel towards the loading axis i.e. 0 = 0 ), and

lateral stiffening due to the Poissons effect (when the fibre is oriented perpendicular to the

loading direction i.e. 0 = 90 ). At large strain the lateral stiffening effect is seemingly

reduced and the contribution of the longitudinal stiffening becomes more important to the

overall behaviour of the RVE. The fact that the stiffness at 0 = 65 is higher at larger tensile

stretch than 0 = 90 (shown clearly in Fig. 3.10a) shows that the longitudinal stiffening

effect is stronger at high stretches; and that the rotation of the fibre during stretching will

have a significant effect upon the large strain behaviour of the material.

The evolution of the fibre orientation in terms of the overall stretch, , has been plotted

in Fig. 3.10b against Eq. 3.69. When the fibres span the entire RVE, Eq. 3.69 gives the exact

expression of the current reinforcement angle; however in the present case, the movement

of the fibre is not constrained to the boundary that causes Eq. 3.69 and can not be assumed

equivalent. However, the error in comparing the predicted rotation and actual RVE rotation

is limited, with larger error for the 25 angle. Apparently, due to the geometry of the RVE,

at 0 and 90 no reorientation of the fibre takes place. On the contrary, when the angle, 0 >

and 0 < 90, the fibre aligns itself to the direction of the applied load, i.e., the 1-axis. For

instance, the fibre initially oriented at 65 reaches the orientation of 40 at = 1.6 that

corresponds to a rotation of 25 . Interestingly, the rotation of the fibre will add a non-linear

effect. For instance, for an initial fibre angle of 35 the stiffness contribution of the fibre

will increase with deformation due to the change in fibre angle. At an initial angle of 75 ,

the rotation of the fibre would be expected to decrease the stiffness of the RVE as it rotates

towards the softest response of 65.9 ; further rotation would then subsequently increase the

stiffness as it rotates towards the loading direction.

The RVE subjected to a simple shear deformation, i.e. Eq. 3.59 with = 1, shows a similar dependence upon the initial orientation and subsequent orientation. The corresponding

results are shown in Fig. 3.11. With these boundary conditions, the RVE has the stiffest response when the fibre is orientated at 45 ; in this configuration the reinforcement is aligned

along the principal direction of deformation and is either stretched or compressed and thus

89

20

Reinforcement Angle, ( )

0

25

45

65

90

15

10

5

1

(a)

1.1

1.2

1.3

1.4

1.5

1.6

0

25

45

65

90

Model

80

60

40

20

(b)

0

0.6

0.8

1.2

1.4

1.6

Stretch,

Stretch,

Fig. 3.10 (a) The tangent modulus during tensile loading of initial reinforcement angles

0 = {0 , 25 , 45 , 65 , 90 }. (b) The fibre change of orientation during simple tension

for different initial configuration of the reinforcement 0 = {0 , 25 , 45 , 65 , 90 } plotted against the predicted behaviour, Eq. 3.69. In all cases the parameters of the RVE are:

AR=40, vol%=1.2, (r) = 2 MPa and f = 1000.

provides the maximum resistance. In this latter configuration the platelet is compressed for

< 0 which in turn causes numerical problems, hence the results are only shown up to

= 0.42.

0

25

45

65

90

0.5

1.5

0.6

(a)

0.5

0.4

0.3

0.2

Shear Strain,

0.1

1.5

0

25

45

65

90

0.5

0

0

(b)

0.1

0.2

0.3

0.4

0.5

0.6

Shear Strain,

Fig. 3.11 Cauchy stress, 12 , against shear, , for simple tension in terms of reinforcement

orientations 0 = {0 , 25 , 45 , 65 , 90 }. In all cases, (r) = 2 MPa, f = 1000, AR = 40

and vol = 1.2%.

The effects of the fibre on the overall composite response are minimal for 0 = 0 due

to the fact that fibres parallel to E1 are unstretched under simple shear and behave approximately like the bulk matrix; therefore the thinner the platelet, the lower its influence on the

90

Numerical Modelling

composite response. At 90 the reinforcement effect is also minimal at small strain, due to

the fact that the height of the RVE does not change and the fibre initially rotates around its

position. However, as the shear strain increases the rotation of the fibre causes the RVE to

stiffen compared to the responses of the matrix behaviour and that of the 0 RVE. These

rotation effects can be seen by observing the tangent modulus, as shown in Fig. 3.12a. For

larger stretches, the tangent modulus at 90 becomes larger than 0 = 0 and for > 0.4

it even overcomes the 0 = 25 configuration. This effect can be justified by looking at

the evolution of the orientation in terms of shown in Fig. 3.12b. The platelet initially at

0 maintains its orientation and therefore has the lowest shear modulus. On the contrary,

the platelet initially at 90 rotates and aligns with the principal direction of deformation,

furnishing a stiffening response.

3

2.8

0

25

45

65

90

2.6

2.4

2.2

2

1.8

0

(a)

0.1

0.2

0.3

0.4

Shear Strain,

0.5

0.6

Reinforcement Angle, ( )

The effect of the re-orientation for the 45 RVE, is that the specimen becomes softer

than the 65 one for > 0.33, due to the 65 RVE rotating towards 45 whilst the 45 RVE

rotates towards the softer configuration (i.e. 0 ) and in fact has rotated by about 30 at 60%

strain. For all angles Figure 3.12b gives a close fit to the actual orientation of the platelet

computed through numerical simulations, with a slight deviation for the 45 specimen due

to the divergence of the solution.

0

25

45

65

90

Model

120

100

80

60

40

20

(b)

0

0.6

0.4

0.2

0.2

0.4

0.6

Shear Strain,

Fig. 3.12 (a) The tangent modulus during simple shear loading of initial reinforcement angles 0 = {0 , 25 , 45 , 65 , 90 }. (b) The fibre change of orientation during simple tension

for different initial configuration of the reinforcement 0 = {0 , 25 , 45 , 65 , 90 } plotted against the predicted behaviour, Eq. 3.69. In all cases the parameters of the RVE are:

AR=40, vol%=1.2, (r) = 2 MPa and f = 1000.

Complimentary to these results is the small strain behaviour shown in Fig. 3.13, demonstrating clearly the predominant longitudinal stiffening of the RVE at 0 < 60 and as well

as the complimentary lateral stiffening at 0 > 60 . The minima at 60 could be utilised

91

8.5

Abaqus Model

Theory

8

7.5

7

6.5

6

5.5

15

30

45

60

75

90

Reinforcement angle,

Fig. 3.13 The change in initial modulus during simple tension for different initial configuration of the reinforcement 0 = {0 90 }, (r) = 2 MPa and f = 1000 against Eq. 3.69

in the design of small strain applications, and could be further considered in respect to the

stiffening/softening effects achieved as the reinforcement orients at large strain. Interestingly, the theoretical hyperelastic model is fitted to the behaviour (i.e. Eq. 3.68) and shows

a minimum stiffness configuration of 65.9 as opposed to the mimimum of around 60 for

the RVE; this suggested the dis-continuous fibre reinforcement transfers the stress differently to that assumed by the inherent transverse isotropy of the hyperelastic model. The

RVE also demonstrates a more pronounced transversely isotropic effect, as shown by the

larger stiffness increases at 0 and 90 compared to the softest configuration. In particular,

Eq. 3.68 shows very little lateral stiffening effect.

3.4.4

A comparison between the results of the 2D-SFRVE and the 2D-MFRVE shows the very

close agreement between the RVEs and validate the choice of a single reinforcement to

model the reinforcing behaviour of a fibre reinforced hyperelastic material up to 60% strain

in uniaxial tension (Fig. 3.14). However, in order to observe the effects of distribution in the

fibre angles, it is required to consider multiple reinforcements.

Figures 3.15 (a-d) display the results of the MFRVE with varying distributions of the

fibre angle, and show that the overall behaviour remains consistent, i.e. there are no additional non-linear effects at the macroscale caused by the multiple reinforcements. It is

observed that, although the distribution has an effect upon the macro-response of the RVE,

the response is dependent upon the primary angle of the reinforcement. For instance, the

0 RVE shows an expected increased in the stiffness with increased alignment of the fibres

92

Numerical Modelling

0 - SFRVE

30 - SFRVE

60 - SFRVE

90 - SFRVE

0 - MFRVE

30 - MFRVE

60 - MFRVE

90 - MFRVE

4.5

4

3.5

3

2.5

2

1.5

1

0.5

0

1

1.1

1.2

1.3

1.4

1.5

1.6

Stretch ()

Fig. 3.14 A comparison between the uniaxial cauchy stress of the multiple and single fibre

2D plane stress RVE models up to 60% strain.

(The inset of Fig. 3.15a shows a stress increase of 0.3 MPa at = 1.6). However, the

60 RVE decreases in stiffness as the alignment of the fibre increases. A explanation can

be found by a consideration of Fig. 3.13 and the relationship of the reinforcement configuration to the modulus, i.e. Eq. 3.68; the 0 configuration is the stiffest response and so

any deviation of the reinforcement angle will soften the response. However, any deviation

of the softest configuration, 60 , results in an increase of the stiffness. Incidentally, the

30 configuration lies on a slope between the stiffest and softest configurations and so the

angle distribution has had a minimal effect upon the tensile response (0.075 MPa stress

difference at = 1.6).

The effect of the fibre angle distribution is also evident on the small strain response.

Fig. 3.16a indicates that, as the alignment increases, the transverse isotropy of the RVE also

increases; as illustrated by the increased difference at 0 and 90 when compared to the

softest RVE response. This softest configuration was found to be approximately 60 for the

SFRVE, however Fig. 3.16a suggests this may change as the distribution increases. This

is due to the stiffening effect that mis-aligned fibres would have in stiffening the response,

especially when they are aligned towards 0 , which is greatest when b = 2 (See Fig. 3.8).

The effects of the fibre alignment upon the individual small strain responses of each

angle can be seen in Fig. 3.16b, and show a prominent effect of the alignment on the 0

RVE compared to the other configurations due to the significant decrease in stiffening effect

offered by misaligned angles compared to a perfectly aligned fibre in this configurations

(See Fig. 3.13).

93

b=2

b=5

b=8

Aligned

= 0

0

1

1.1

1.2

1.3

1.4

1.5

1.6

3.8

ne

ig

Al

3.75

b=

ne

Al

ig

b=

b=

4.2

4.4

b=2

b=5

b=8

Aligned

= 30

0

1

1.1

1.2

b=2

b=5

b=8

Aligned

1

0.5

= 60

0

1

1.1

1.2

1.3

1.4

1.6

1.5

1.38

1.37

8

ig

ne

d

b=

1.5

1.36

Al

Al

1.5

1.5

(d)

1.39

b=

8

ig

ne

d

b=

b=

3.1

1.4

2.5

3.2

(c)

b=

2.5

1.3

Stretch,

Cauchy Stress, 11 (MPa)

3.3

b=

Stretch,

3

(b)

3.85

b=

b=

(a)

b=

b=2

b=5

b=8

Aligned

1

0.5

1.6

= 90

0

1

1.1

Stretch,

1.2

1.3

1.4

1.5

1.6

Stretch,

8.5

b=2

b=5

b=8

Aligned

SFRVE

8

7.5

7

6.5

6

(a)

0

15

30

45

60

75

Reinforcement Angle, 0 ( )

Fig. 3.15 The variation of the stress-strain curves with varying amounts of fibre distribution

for different angles. (a) 0 , (b) 30 , (c) 60 , (d) 90 .

=0

=30

=60

=90

6

Decreasing Alignment

(b)

90

b=2

b=5

b=8

Aligned

SFRVE

Fig. 3.16 The small strain effects of a distribution of fibres in the RVE. (a) The reduction in

transverse isotropy is shown by the reduction in the stiffness difference between longitudinal

and lateral directions, (b) Show the effect of increased alignment on the stiffness for each

angle.

94

Numerical Modelling

3.4.5

Discussion

Due to the geometry of the reinforcement, and the material properties of the constituents,

the composite is assumed to behave as a transversally isotropic material that is closely modelled by an incompressible hyperelastic transversally isotropic constitutive model, such as

Eq. 3.22. The model has shown it is effective is describing the behaviour of nickel-coated

short carbon fibres in a PDMS matrix up to about 30% strain (Section 2.3), however a

neo-Hookean type model can typically describe isotropic reinforced elastomers up to much

larger strains (<100%) [165], and even an extension of the current model to a Mooney-Rivlin

type transversally isotropic model has shown minimal improvement in the fitting [40].

The underlying assumption of these models is that the transverse isotropy is from continuous fibres that span the length of the composite. Hence, rather than consider more complicated constitutive models, it is deemed important to explore the mechanics of a transversally

isotropic composite when it is reinforced by discontinuous fibres, and test the validity of this

assumption.

The strain energy, Eq. 3.22, is linear with respect to both I1 3 and g(I4 ) and means

that a plane is formed within these axes which should be matched by the numerical RVE

results. To validate this hypothesis, the strain energy, , is compared to the one computed

by ABAQUS for the 2D-SFRVE: for all angles, Eq. 3.22 is fitted against the strain energy

data for simple shear and simple tension by using the Matlab lsqnonlin function (nonlinear

least square method). As a result, a set of values of the constitutive parameters and are

identified for each RVE (i.e. one set of parameters to describe all reinforcement angles for

an RVE of equivalent material properties).

The results for 0 = 25 , 45 , 90 are shown in Fig. 3.17. The coloured plane is Eq. 3.22,

that is linear with respect to both I1 3 and g(I4 ), which is defined in Eq. 3.23. The

ABAQUS results are shown by dotted red lines for simple tension/compression and by dotted magenta lines for simple shear. The accurateness of the fitting confirms that the overall

behaviour of the RVE can be modelled with the constitutive equation (3.22) and hence that

the assumption of transverse isotropy is acceptable for the considered platelet geometry.

Note that all the numerical points lie on the model plane; the same results were obtained for

all the angles.

The corresponding values of and were

= 2.018 MPa,

= 0.165,

To further assess the capabilities of the model, the fitting of the strain energy function is

shown in Fig. 3.18 in the vs. strain plane for different angles {0 , 45 , 75 }. The match

95

Fig. 3.17 The transverse isotropy of the model is shown by the close fitting to Eq. 3.22 for

different values of the heterogeneity contrast (a) f = 10, (b) f = 100 (c) and f = 1000.

The other values are 0 = 35 , (r) = 2 MPa, AR = 40 and = 0.8%. The planes show

the constitutive model fitted to the data. The plotted dots show the numerical values of the

strain energy function as computed by Abaqus for simple tension/compression (red dots)

and simple shear (magenta dots).

of the model with the data is excellent for both simple tension/compression and simple

shear. In Fig.3.18 (b), (d) and (f), the constitutive parameters and identified from the

fitting of the strain energy are used to predict through, Eqs. (3.61)-(3.63), the corresponding

stress-strain curves. For the 45 and 75 RVEs up to 60% strain, the model matches the

numerical results very closely for both uniaxial and shear loading conditions. The 0 RVE

matches the model very well in all loading conditions up to 20% strain, however in uniaxial

compression the model and the numerical curves start to diverge due to instabilities used

by the compression of the reinforcement. In all other loading conditions, the 0 RVE fits

the model remarkably well. Simiar instabilities are caused in uniaxial tension for a 90

RVE configuration, again due to the instability of the reinforcement under compression.

Similar compression of the reinforcement occurs for the 45 RVE in compressive shear,

however the geometry of the reinforcement does not have this confining effect; however

larger reinforcement geometries may expect this to be encountered.

96

Numerical Modelling

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 0

1

0.5

0

60

11 , 12 (MPa)

1.5

20

20

40

2

1

0

1

(a)

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

(b)

2

60

60

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 45

1

0.5

0

60

20

20

40

1

0

(d)

40

20

20

40

60

Strain (%)

0.5

11 , 12 (MPa)

Strain Energy,

60

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

0 = 75

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain (%)

1.5

20

(c)

40

Strain (%)

11 , 12 (MPa)

1.5

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

0

60

(f)

(e)

40

20

20

Strain (%)

40

60

2

60

40

20

20

40

60

Strain (%)

Fig. 3.18 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 0 , (c)-(d) 0 = 45 and (e)-(f) 0 = 75 . The other values were

(r) = 2 MPa and f = 1000. The remaining angles can are found in the Appendix B.1

3.5

3.5.1

97

Introduction

When platelet-like reinforcements, such as Graphene, have uniform orientational distribution, the overall behaviour of the composite is isotropic and the corresponding stress-strain

relationship at the macroscale would follow the behaviour of the constituents [160]. However, when the anisotropic reinforcements are oriented in a preferred direction, it is reasonable to expect that their orientation has an effect on the overall mechanical response. When

the reinforcements are suspended within a 2D single plane, the behaviour can be described

as transversally isotropic.

The intent of our analysis is to show in what limit the large strain behaviour of the

overall composite can be accurately described as transversally isotropic. The models are

usually employed to describe the behaviour of materials reinforced with continuous fibres

that span the entire length of the body, however, when the inclusions are discontinuous and

reinforce in 2 directions, one has to assess the predicting capabilities of the models against

numerical results.

Attempts in the literature to describe the behaviour have focused on fibre reinforced

materials [44, 86]; even so, the models do not consider the effects of the reinforcement

rotation at large strain, which is expected to effect the behaviour and to depend on the

loading conditions. It may be expected that a consideration of this behaviour would require

a full 3D analysis and a consideration of the random distribution of the reinforcements (in

orientation and position). The computational cost of such a model is large, and restricts the

possibility to parametrically explore the design space of the composite. However, when the

platelets are restricted to an orientation within a single plane (Fig. 3.19), it is expected that

the model can be significantly simplified whilst still allowing much of the behaviour to the

explained and for a parametric study to be possible.

It has been shown that a greatly simplified 2D-SFRVE (single fibre RVE) can model

the behaviour of a fibre reinforced composite (Section 3.5). It is expected that a similar

model can be used to describe a reinforcement by platelet-like reinforcements, although

plane strain is applied to account for the platelets oriented in a block elastomer (Fig. 3.19).

The extent to which a 2D-SPRVE can model the transversally isotropic material requires

assessment, however its implementation would greatly reduce the computational cost of the

numerical analysis and would provide a basis for further investigation, e.g. into the effects

of the matrix/reinforcement interface, aspect ratio and vol%.

For small deformations, the mechanical behaviour of a neo-Hookean material is comparable to a material with linear elastic behaviour. Thus it is possible to consider an effective

98

Numerical Modelling

Fig. 3.19 Long Platelets oriented in a single plane (E1 , E2 ) of a block elastomer, wherein the

thickness is much greater than the length, can be modelled by a 2D plane strain assumption.

stiffness of the composite, and use it to estimate the strain energy for the shear deformation and extend the procedure to large deformations. This effective stiffness has been

explored extensively and various formulations are available, including the semi-analytical

Halpin-Tsai (H-T) equations that are found to fit experiments well (Eq. 3.76). However, the

2D-SPRVE allows a uniquely controlled environment that is not possible in experimental

testing; as such, comparisons can be made between the predictions of the SPRVE and the

H-T equations.

In [160] and [86] the Halpin-Tsai (H-T) equations [91] are used to predict the value of

in terms of the properties of the constituents. However, in those papers the reinforcements

were assumed to span the entire RVE (i.e. long fibres) and hence the morphology of the

reinforcement was not taken into account. When the filler has a platelet-like shape, the

following expression of the H-T equation can be used (See e.g., [10, 226]):

= (r)

2 f 2( + 1) + f

+ f (1 ) 2

(3.76)

where the additional parameter is introduced to take into account the aspect ratio of the

platelet. This equation is useful in predicting the properties of aligned reinforcement composites, although does not predict the effects on the transverse isotropy of the material, given

by . For what concerns the constitutive parameter , in [160] the following expression has

99

been derived,

=

(1 ) ( f 1)2

.

1 + ( f 1) + f

(3.77)

the H-T equations to the full set of orientational configurations, i.e. 0 = 0 to 0 = 90 .

However its usability to dis-continuous reinforcing platelet-like reinforcements is unknown.

It is important for a semi-empirical model, such as the H-T equations, to validate the design

space considered; otherwise the predictive capabilities of the model are limited. As such, a

parametric study shows the fitting of the small strain response to Eqs. (3.76) and (3.77).

3.5.2

Numerical Methods

The numerical study consists of initially capturing the behaviour of a 3D MPRVE (multiple

platelet RVE) and comparing it to the transversally isotropic constitutive model, Eq. 3.22.

The model consists of 200,000 C3D8R elements, subject to plane strain deformation, and

contains 30 aligned and randomly distributed platelets of aspect ratio 40, i.e. AR = L/t , of

total volume 1.2% and shear modulus (r) = 2000 MPa, therefore giving a heterogeneity

contrast between the reinforcement and matrix of, (p) / (r) = 1000. The reinforcement of

the platelets is considered for the angles 0 = {0 , 30 , 60 , 90 }.

Fig. 3.20 The two RVE configurations in the undeformed configurations. (a) The 3D multiple aligned platelet RVE model for 0 = 30 (3D-MPRVE). The inset shows the mesh

surrounding a reinforcement. (b) The single platelet reinforced RVE model for 0 = 30

(2D-SPRVE). The inset shows the mesh around the inclusion edge.

i.e. AR = 40, vol% = 1.2 and heterogeneity contrast, (p) / (r) = 1000. However the

100

Numerical Modelling

model consists of one reinforcement, oriented at a defined angle, 0 . The number of elements required is greatly reduced to 4000, using the plane strain elements CPE4RH. The

reinforcement of the platelets is considered at 5 intervals for angles between 0 = 0 and

0 = 90 .

In the case of both RVEs, the models are compared to the transversally isotropic hyperelastic constitutive model up to 60% strain in tension and shear; in such a way the RVE is

fully characterised under the plane strain assumption for an incompressible material.

An additional parametric study is undertaken on the 2D-SPRVE, to investigate the effects of filler volume, aspect ratio and heterogeneity contrast. The parameters are adjusted to

consider the volume in the range vol%= {0.4, 0.8, 1.2}, the aspect ratio in the range, AR=

{1, 10, 20, 40} and the heterogeneity contrast in the range (p) / (r) = {1, 10, 100, 1000}.

From this, comparisons are made to the Halpin-Tsai equations, and an alternative formulation is proposed that better fits the numerical data.

3.5.3

The inclusion of a stiff platelet reinforcement is expected to increase the overall stiffness of

the RVE; whilst the transversely isotropic nature of the material means that the results are

affected by the orientation of the platelet. For materials subject to large deformations, such

as rubber, this transversely isotropic behaviour is expected to have significant effects upon

the large strain behaviour due to the initial orientation of the platelet and its subsequent

rotation as the RVE is stretched.

Here we report the results of the large strain FE analysis carried out with ABAQUS.

All the results, unless otherwise stated, assume (r) = 2 MPa, heterogeneity contrast f =

(p) / (r) = 1000, aspect ratio of the platelet AR = 40 and volume fraction = 1.2%. The

maximum and minimum stretches were chosen by considering that composites are very

unlikely to be subjected to deformations larger than 50% for most practical applications.

The results of simple compression/tension tests for the 3D-MPRVE and the 2D-SPRVE

are shown in Figs. 3.21 (a)-(d) in the range [0.6, 1.6] for different initial orientations

of the reinforcement, 0 = {30 , 45 , 75 , 90 }. The results from the two numerical models

considered are remarkably close, although divergence for 0 = 45 in compressive shear

at large strain show boundary effects of the large single platelet. Similar discrepancies at

0 = 90 in tension are caused by convergence issues due to the compressive forces acting

on the platelet of the 2D-SPRVE; in those cases the results are only shown to = 1.3. In

shear, the RVEs generally show much closer agreement due to the reduction in converging

issues caused by the compressing of the reinforcement. The complete set of results for

0 = {0 , 15 , 30 , 45 , 60 , 75 , 90 } are available in Appendix B.3. The results suggest

101

2D-SPRVE Uniaxial

2D-SPRVE Shear

3D-MPRVE Uniaxial

3D-MPRVE Shear

Model Uniaxial

Model Shear

0 = 30

11 33 , 12 (MPa)

11 33 , 12 (MPa)

single-platelet plane strain numerical model, in certain circumstances.

2

60

(a)

40

20

20

40

60

2D-SPRVE Uniaxial

2D-SPRVE Shear

3D-MPRVE Uniaxial

3D-MPRVE Shear

Model Uniaxial

Model Shear

2

60

(b)

40

2D-SPRVE Uniaxial

2D-SPRVE Shear

3D-MPRVE Uniaxial

3D-MPRVE Shear

Model Uniaxial

Model Shear

0 = 75

2

60

(c)

40

20

20

Strain (%)

20

20

40

60

Strain (%)

11 33 , 12 (MPa)

11 33 , 12 (MPa)

Strain (%)

4

0 = 45

40

60

2D-SPRVE Uniaxial

2D-SPRVE Shear

3D-MPRVE Uniaxial

3D-MPRVE Shear

Model Uniaxial

Model Shear

0 = 90

2

60

(d)

40

20

20

40

60

Strain (%)

Fig. 3.21 Comparisons between the 3D-MPRVE and 2D-SPRVE for the cauchy stress difference (11 33 ) against strain for simple tension and compression, and the cauchy shear

stress (12 ) against the shear strain. Displayed for reinforcement orientations, (a) 30 , (b)

45 , (c) 75 , (d) 90 .

The results of simple compression/tension tests for the 2D-SPRVE are shown in Figs. 3.22

(a) & (b) in the range [0.6, 1.6] for different initial orientations of the reinforcement,

0 = {0 , 25 , 45 , 65 , 90 }. The effects of the initial orientation, 0 , are apparent from the

stress-strain curves and from the tangent modulus in Fig. 3.23a: 0 and 90 orientations confer to the RVE the higher stiffnesses whereas the 45 RVE has the initially softer response.

In this latter configuration the stress applied on the boundary of the RVE is transferred by

the platelet predominantly by shear forces and hence the tensile modulus at small strain is

very close to the one of the matrix, i.e., 6 MPa. These results are indeed in accordance with

the linear laminate theory that predicts identical stiffnesses at 0 and 90 (and minimum

stiffness at 45 ) (see, e.g., [90]). Interestingly, the two complementary angles 25 and 65

102

Numerical Modelling

have the same small strain longitudinal modulus but, as the stretch increases, the 65 one

becomes softer and by about = 1.22 is even softer than the 45 RVE.

0.5

0

25

45

65

90

0

25

45

65

90

11 33 (MP a)

11 33 (MP a)

3

2

1

(a)

1.5

(b)

0

0.6

0.7

0.8

Stretch,

0.9

1.1

1.2

1.3

1.4

1.5

1.6

Stretch,

Fig. 3.22 Cauchy stress difference against stretch for (a) simple compression and (b)

tension in terms of reinforcement orientations, 0 = {0 , 25 , 45 , 65 , 90 }.

These results illustrate the two distinct types of stiffening that the model shows: longitudinal stiffening due to the stress transfer from the matrix to the platelet (most prominent

when the platelet is oriented parallel towards the loading axis i.e. 0 = 0 ), and lateral stiffening due to the Poissons effect (when the platelet is oriented perpendicular to the loading

direction i.e. 0 = 90 ). It is seen that this lateral stiffening is partially driven by the geometry of the platelet in the 2D SPRVE, as the multiple platelet RVEs do not show such

prominent stiffening effects for 0 = 90 . The two stiffening effects also cause the divergence of the 25 and 65 configurations at large strain, due to the way the stress transfer

mechanism evolves. At 0 = 65 , the platelet rotates towards the softest configuration, i.e.

45 (See Fig 3.23b). However, the 25 specimen rotates towards the longitudinal reinforcing

direction.

For moderate strains the 90 in tension and the 0 RVEs in compression (2D SPRVE) are

actually much stiffer than the other configurations; this is due to the geometry of the problem

and by the geometrical constraint that the rigid platelet imposes on the movement of the RVE

edges. The stiffer response of 0 = 90 can be partially mitigated by the use of a smaller

reinforcement or multiple platelets that reduce the boundary effects of the reinforcement.

To further analyse these effects, the evolution of the platelet orientation in terms of the

overall stretch is shown for the 2D SPRVE in Fig. 3.23b against Eq. 3.38. When the

fibres span the entire RVE, Eq. 3.38 gives the exact expression of the current reinforcement

angle; however in the present case, the movement of the platelet is not constrained to the

boundary and hence Eq. 3.38 gives only approximate results. The error in terms of the

103

0

25

45

65

90

14

12

10

8

(a)

6

1.1

1.2

1.3

1.4

Stretch,

1.5

1.6

Reinforcement Angle, ( )

0

25

45

65

90

Model

80

60

40

20

(b)

0

0.6

0.8

1.2

1.4

1.6

Stretch,

Fig. 3.23 (a) Tensile tangent modulus against stretch in terms of reinforcement orientations, 0 = {0 , 25 , 45 , 65 , 90 }. (b) The platelet change of orientation for different initial

configurations of the reinforcement against Eq. 3.38. The absence of points for large tensile

and compressive strains both at 0 and 90 is caused by the premature failure of the FE

simulation.

actual orientation of the platelet is however limited, with larger errors occurring for the 25

and 65 angles at large strain. Apparently, due to the geometry of the RVE, at 0 and 90

no reorientation of the platelet takes place. On the contrary, when the angle, 0 > 0 and

0 < 90, the platelet aligns itself in the direction of the applied load, i.e., the 1-axis. For

instance, the platelet initially oriented at 65 reaches the orientation of 40 at = 1.6 that

corresponds to a rotation of 25 . Interestingly, during the deformation, the RVE assesses

the state of minimum stiffness that causes an effect in terms of the stress-strain curves, e.g.,

the tangent stiffness of the 65 RVE becomes softer than the 45 ones.

The same analysis was carried out for the RVE subjected to a simple shear deformation,

i.e., Eq. 3.36 with = 1; the corresponding results are shown in Figs. 3.24 (a) & (b). With

these boundary conditions, the RVE has the stiffest response when the platelet is orientated

at 45 (see Fig. 3.25a): in this configuration the reinforcement is aligned along the principal

direction of deformation and is either stretched or compressed providing the maximum resistance. In this latter configuration the platelet is compressed for < 0 which in turn causes

numerical problems, hence the results are only shown up to = 0.42. This is shown as a

divergence of the solution compared to the 3D-MPRVE (See Fig. 3.21 (b)), whilst the other

results show very close agreement.

The effects of the platelet on the overall composite response are minimal for 0 = 0 due

to the fact that fibres parallel to E1 are unstretched under simple shear; therefore the thinner

the platelet, the lower its influence on the composite response. At 90 the reinforcement

104

Numerical Modelling

effect is also minimal at small strain, due to the fact that the height of the RVE does not

change and the platelet initially rotates around its position. The effect of the re-orientation

that takes place at large strain, for the 45 RVE, is that the specimen becomes softer than

the 65 ones for > 0.33, due to the 0 = 65 configuration rotating towards 45 .

0

25

45

65

90

0.5

(a)

1.5

0.6

0.5

0.4

0.3

0.2

Shear Strain,

0.1

1.5

0

25

45

65

90

0.5

(b)

0

0

0.1

0.2

0.3

0.4

0.5

0.6

Shear Strain,

Fig. 3.24 Shear stress against (a) negative and (b) positive shear strain in terms of reinforcement orientations 0 = {0 , 25 , 45 , 65 , 90 }.

This rotation effect can be seen by observing the effective shear modulus, as shown

in Fig. 3.25a, from which it is seen that at both 0 and 90 the tangent modulus of the

overall composite is close to the shear modulus of the matrix, i.e., (r) = 2 MPa. For

larger stretches, the tangent modulus at 90 becomes larger than 0 = 0 and for > 0.4

it even overcomes the 0 = 25 configuration. This effect can be justified by looking at

the evolution of the orientation in terms of shown in Fig. 3.25b. The platelet initially at

0 maintains its orientation and therefore has the lowest shear modulus. On the contrary,

the platelet initially at 90 rotates and aligns with the principal direction of deformation,

furnishing an increasingly stiffer response. The 45 RVE rotates up to about 30 at 60%

strain. For all angles, Fig. 3.25b gives a close fit to the actual orientation of the platelet

computed through numerical simulations.

3.5.4

Discussion

Due to the geometry of the reinforcement, the overall composite response is assumed to

follow the transversely isotropic constitutive model (3.22) with the axis of isotropy given by

the orientation of the platelet. To validate this hypothesis, the strain energy, , is compared

to the one computed by ABAQUS for the 2D-SPRVE: for all angles, Eq. 3.22 is fitted against

the strain energy data for simple shear and simple tension by using the Matlab lsqnonlin

105

0

25

45

65

90

2.5

2

0

(a)

0.1

0.2

0.3

0.4

0.5

0.6

Reinforcement Angle, ( )

120

0

25

45

65

90

Model

100

80

60

40

20

0

0.6

(b)

0.4

0.2

0.2

0.4

0.6

Shear Strain,

Shear Strain,

Fig. 3.25 (a) Tangent shear modulus against shear strain in terms of reinforcement orientations, 0 = {0 , 25 , 45 , 65 , 90 }. (b) The platelet change of orientation during simple

shear for different initial configuration of the reinforcement against Eq. 3.38.

function (nonlinear least square method). As a result, a set of values of the constitutive

parameters and are identified for each RVE (i.e. one set of parameters to describe all

reinforcement angles for an RVE of equivalent material properties).

The results for 0 = 35 are shown in Fig. 3.26 for different values of the hetereogenity

contrast f = 10 (a), f = 100 (b) and f = 1000 (c). The coloured plane is Eq. 3.22, that is

linear with respect to both I1 3 and g(I4 ), which is defined in Eq. 3.23. The ABAQUS

results are shown by dotted red lines for simple tension/compression and by dotted magenta

lines for simple shear. The accurateness of the fitting confirms that the overall behaviour

of the 35 RVE can be modelled with the constitutive equation (3.22) and hence that the

assumption of transverse isotropy is acceptable for the considered platelet geometry. Note

that all the numerical points lie on the model plane; the same results were obtained for all

the angles.

The corresponding values of and were

10 = 2.019 MPa,

100 = 2.020 MPa,

1000 = 2.028 MPa,

10 = 0.08,

100 = 0.313,

1000 = 0.405,

(where the subscript refers to the heterogeneity mismatch) and indicates that the inclusion

rigidity has a predominant effect on the parameter rather than . Indeed, is a measure of

the transverse isotropy of the RVE with = 0 corresponding to the isotropic neo-Hookean

model; and its effects are reflected by the increasing slope with respect to the g(I4 ) axis of

106

Numerical Modelling

Fig. 3.26 The transverse isotropy of the model is shown by the close fitting to Eq. 3.22 for

different values of the heterogeneity contrast (a) f = 10, (b) f = 100 (c) and f = 1000.

The other values are 0 = 35 , (r) = 2 MPa, AR = 40 and = 1.2%. The planes show

the constitutive model fitted to the data. The plotted dots show the numerical values of the

strain energy function as computed by Abaqus for simple tension/compression (red dots)

and simple shear (magenta dots).

the plane in Fig. 3.26. On the contrary, the effect of the platelet stiffness on the equivalent

modulus, , is rather limited due to the low volume fraction considered, i.e., = 1.2%.

To further assess the capabilities of the model, the fitting of the strain energy function is

shown in Fig. 3.27 in the vs. strain plane for different angles {25 , 45 , 90 }. The match

of the model with the data is excellent for both simple tension/compression and simple

shear at both 25 and 45 . In Fig. 3.27 (b), (d) & (f), the constitutive parameters and

identified from the fitting of the strain energy are used to predict through, Eqs. (3.39)-(3.41),

the corresponding stress-strain curves. Up to 30% strain, the model matches the numerical

results with small errors for both uniaxial and shear loading conditions. When the strain is

larger, the model and the numerical curves start to diverge; a similar behaviour was observed

for the platelet orientation. In fact, at large strain the model does not accurately reproduce

the actual orientation of the platelet which in turn causes some error in the stress-strain

diagrams.

At 90 the RVE is much stiffer in tension than the one predicted by the constitutive

model. This feature was already observed at high strain (see Fig. 3.22) and it is caused

by the geometrical constraint that the rigid platelet imposes on the top and bottom bases;

a thought that is supported by the results of the multiple platelet RVEs. On the contrary,

simple shear does not have this confining effect and a closer match with the numerical

results is achieved.

Whilst the orientation of the platelet is important in determining the large strain results

of the RVE, the small strain response of the material also shows very clearly the effect of the

initial platelet orientation, 0 , on the effective shear modulus of the composite (Fig. 3.28)

and can help predict the large strain behaviour of the composite [87]. These results were

107

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 25

1

0.5

0

60

(a)

40

20

20

40

11 33 , 12 (MPa)

1.5

3

2

1

0

1

(b)

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 45

1

0.5

0

60

(c)

40

20

20

40

4

3

1

0

1

(d)

(e)

20

20

Strain (%)

40

60

11 33 , 12 (MPa)

Strain Energy,

0.5

40

60

40

20

20

40

60

Strain (%)

0

60

40

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

0 = 90

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain (%)

1.5

Strain (%)

11 33 , 12 (MPa)

1.5

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

(f)

2

60

40

20

20

40

60

Strain (%)

Fig. 3.27 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 25 , (c)-(d) 0 = 45 and (e)-(f) 0 = 90 . The other values were

(r) = 2 MPa and f = 1000. The remaining angles can are found in the Appendix B.2

obtained by running a perturbative analysis on the undeformed configuration. For the considered boundary conditions and RVE geometry, the shear response of the platelet offers

the maximum resistance when oriented at 45 whereas at 0 and 90 it remains almost unstressed; this is mostly noticeable from the limited influence that the increase in the ratio

f has on the effective shear modulus at 0 = 0 with all the curves almost overlapping in

Fig. 3.28a (note that the case f = 1 corresponds to the homogeneous RVE). Note that, as

confirmed by Eq. 3.43 whose fitting is shown in the figure, angles reciprocal with respect to

108

Numerical Modelling

(a)

2.4

2.2

2

0

15

30

45

60

75

Reinforcement Angle, 0 ( )

90

AR = 1

AR = 20

AR = 40

Model

2.6

(b)

2.4

2.2

2

0

15

30

45

60

75

90

Reinforcement Angle, 0 ( )

f=1

f = 10

f = 100

f = 1000

Model

2.6

45 give the same value of the composite shear modulus, e.g. c (30 ) = c (60 ).

vol = 0.4%

vol = 0.8%

vol = 1.2%

Model

2.6

(c)

2.4

2.2

2

0

15

30

45

60

75

90

Reinforcement Angle, 0 ( )

Fig. 3.28 Effective shear modulus c in terms of platelet orientations 0 for various heterogeneity contrast {1, 10, 100, 1000} against Eq. 3.43. The other parameters were (r) =

2 MPa, = 1.2% and AR = 40. Note that the case f = 1 corresponds to the homogeneous

solution.

The accurate fitting of Eq. 3.22 in Figs. 3.27 and the small strain fitting of Figs. 3.28

suggest that, by using Eq. 3.44, the values of c at 0 and 45 can be used to identify the

constitutive parameters and . These are shown in Fig. 3.29 in terms of the heterogeneity

contrast, f , and different values of the filler volume fraction; as expected from the addition

of stiffer and larger inclusions, both and monotonically increase for increasing f and .

As already seen in Fig. 3.26, the increase in f has a prominent effect on that passes from

being almost 0 when f = 10 (soft inclusion) to 0.42 when the platelet is much stiffer than the

matrix ( f = 1000). In the same figure the fitting of with Eq. 3.76 is shown. It is apparent

that this modified form of the H-T equation gives a remarkably good fitting being able to

assess the dependence either on f and on . The corresponding value of the volume fraction,

, for which this fitting was achieved was 1.2%. On the contrary Eq. 3.77 used in [160] and

in [89] does not provide the same accuracy of fitting for (see Fig. 3.29b) due to the lack of

an additional parameter to account for the aspect ratio of the platelet. Hence the following

alternative empirical expression is here considered, (3.78), which provides a much better

fitting of the numerical results that depends upon heterogeneity contrast, volume fraction

and the additional parameter which is optimised to = 4.93 for an aspect ratio of 40,

and = 2.27 for an aspect ratio of 20. The relationship shows the strong influence of

the parameter with respect to the aspect ratio and reinforcement volume. Additionally

it shows the logarithmic relationship of the heterogeneity contrast with the parameter ,

which is not captured by Eq. 3.77 and similar forms based on continuous fibres [86].

= (1 ) log( f );

(3.78)

109

1.5

0.25

vol = 0.4%

vol = 0.8%

vol = 1.2%

H-T

AR=20

0.2

vol = 0.4%

vol = 0.8%

vol = 1.2%

Eq.(3.79)

Eq.(3.78)

AR=20

0.15

1

/(r) 1 (%)

0.1

0.5

0.05

(a)

0 1

10

(b)

0 1

10

10

10

Heterogeneity Contrast, f

10

0.5

vol = 0.4%

vol = 0.8%

vol = 1.2%

H-T

AR=40

0.4

vol = 0.4%

vol = 0.8%

vol = 1.2%

Eq.(3.79)

Eq.(3.78)

AR=40

0.3

/(r) 1 (%)

10

Heterogeneity Contrast, f

1.5

0.2

0.5

0.1

(d)

(c)

0 1

10

10

Heterogeneity Contrast, f

10

0 1

10

10

10

Heterogeneity Contrast, f

Fig. 3.29 Dependence of the constitutive parameters (a) & (c) and (b) & (d) on the heterogeneity contrast, f , the aspect ratio, and the volume fraction against the model introduced

in [160] and the one introduced with Eqs. (3.76)-(3.78).

110

Numerical Modelling

3.6

Concluding remarks

plane stress/strain deformations, has been analysed.

The motivation for investigating the RVE models lies in understanding the non-linear

behaviour of elastomers at large strain, when reinforced with aligned fibres and platelets.

In particular, it has been shown that the ability of a constitutive model to describe the

experimental data of a fibre reinforced PDMS elastomer extends only to 30% strain (See

section 2.3), even though a neo-Hookean based transversally isotropic model would be expected to describe the behaviour up to higher strains (<60%), see e.g. [165]. The inability of the model to describe the behaviour in the strain range 30%-60% suggests that the

aligned dis-continuous reinforcements cause non-linearities that are not described well by

a transversally isotropic material model that assumes the reinforcement is continuous. As a

result, the constituents of the simulation are chosen to model those of the fibre reinforced

elastomer.

A study of the behaviour of the RVEs has been carried out and has shown that the response of the fibre and platelet reinforced materials can be adequately described by single

reinforcement RVE models, which work at a greatly reduced computational cost compared

to multiple reinforcement RVE models. Furthermore, in the case of the fibre reinforced

model, there is a close match between the numerically computed strain energy function and

the transversally isotropic neo-Hookean model up to 60%, whilst for the platelet reinforced

elastomer block, the transversally isotropic neo-Hookean model matches the behaviour to

40%; this slight reduction is thought to be due to the difficulty of the model to accurately

capture the rotation of the platelet, due to the lateral constraint. In all cases, care is required

to consider the instabilities that develop as a result of the compressive forces on the reinforcements in certain configurations (e.g. A 0 = 90 specimen in uniaxial compression).

This behaviour is not captured by the model, and inaccuracies occur; particularly at large

strain.

The advantage of a simplified RVE model, compared to the constitutive model, is that it

could be used to model many complex effects such as fibre interaction, matrix/fibre interfacial properties, and even material fracture behaviour.

Never-the-less, the considered transversally isotropic neo-Hookean model has some remarkable properties:

it is dependent on I1 and I4 only, and has the most general transversely isotropic form

that can be uniquely identified in plane stress. A dependency on an additional invari-

111

ant would require (e.g.) biaxial loading, which is not possible for an incompressible

material in plane strain.

the model has demonstrated that one value of each parameter, and , can simultaneously represent the properties of 19 angular configurations of the RVE, (i.e. at 5

intervals between 0 and 90), in all deformation gradients possible for the hyperelastic

incompressible material.

only two simple shear tests at small strain are actually necessary to identify the nonlinear constitutive parameters and : one with the platelets oriented at 0 and another

with 45 orientation.

The consequence of anisotropic reinforcements at short strain is evident in the stiffness

that is observed to depend strongly on the reinforcement orientation; although in the case

of a thin fibre reinforced elastomer transverse stiffening effect is not as significant, due to

the plane stress boundary conditions. In this case (plane stress), the constitutive model

considers the effect, although it is less pronounced. An investigation on the effects of fibre

mis-alignment at low wt% (when fibre interaction is reduced) has involved studying the

properties of a multiple fibre RVE (2D-MFRVE), which indicates that a reduction in fibre

alignment causes a reduction in these stiffening effects at 0 and 90 , reducing the transverse

isotropy. As a consequence of the misalignment, the angle of minimum stiffness is also

found to alter, in accordance with the fibre angle distribution.

A parametric study has been undertaken to investigate the effect of the heterogeneity

contrast and volume fraction of the platelet reinforced specimen. The results show that the

form of the Halpin-Tsai equation derived in the literature to describe [160] overestimates

the effect of the heterogeneity contrast and an alternative form of the Halpin-Tsai equation

is presented to illustrate the logarithmic relationship that the RVE predicts. As a result, the

values of the two parameters, and , can be estimated from the mechanical properties of

the constituents with the modified forms of the Halpin-Tsai equation introduced.

As a result of these analyses, it is suggested that for moderate strain up to 60%, fibre

reinforced thin composites are modelled as transversally isotropic solids. Whilst, platelet

reinforced elastomer blocks are modelled as transversally isotropic solids up to 40% strain.

Larger deformations are likely to require more advanced models that consider non-linear

material behaviours such as chain inextensibility, or a multiscale analysis to correctly match

the stress-strain behaviour of the composite and the interaction of reinforcements during

deformation.

Chapter 4

Magnetic Response

4.1

Introduction

The advantages of reinforcing networks (Discussed previously in section 2.1) are numerous, and ubiquitous in natural systems. This has led to significant research effort in the

orientation of anisotropic reinforcements in materials; partly due to the highly desirable

engineering materials they can create, which expand the design space, but also due to the

current difficulty in making such anisotropic and hierarchical structures without dramatically increasing the cost.

The remarkable properties of such materials are typically the result of biomimicry. For

example, consider the mineralised outer layer of many fish scales that create an aerodynamic

and protective coating [61] or the lamellar structure of seashells that arrest crack growth with

mechanical gradients [61]. Alternatively, see the microfibril angle of cellulose in spruce

trees, which varies to tailor the response of the material to the expected loading conditions

[59], and is individually tailored to reduce mechanical gradients and homogenise the strain

field to reduce stress concentrations [178].

Conventional composite materials attempt to utilise the advantages of anisotropic materials by using long stiff fibres in a softer matrix. The fibre geometry, volume and geometrical

arrangement can then be tailored to control the properties of the overall material, although

typically the fibres are only be oriented in a 2-dimensional plane and quasi-isotropic material properties are most common. Never-the-less, anisotropic laminates have demonstrated

advantageous properties in terms of, for example, aeroelastic tailoring [122] and are used

in helicopter blades to optimise flight performance [140]. Furthermore, relatively new advances are being made in the use of variable angle tow composite panels, that change the

orientation of fibres within a composite layer [125]; the advantages of which include the

potential for increasing the stability of plates by redistributing structural loads.

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Magnetic Response

The majority of these applications need only to consider the small strain behaviour of a

planar arrangement of continuous fibres, i.e. conventional composites. However, elastomers

are large strain performing materials that would additionally allow the consideration of 3dimensional orientation of reinforcements; this expands the design space considerably for

an engineer, but also increases the associated manufacturing difficulties. Thus a thorough

understanding of the technical challenges is required.

In addition, in order to achieve spatial orientation it is often necessary to functionalize the reinforcements. For example, magnetic orientation requires the filler to develop a

magnetic torque. The result is that, once the elastomer has cured, the magnetic torque is

transferred to the bulk matrix. The material is now magnetically responsive, with mechanical and magnetic properties that are complimentary.

4.1.1

Manufacturing Techniques

Shear Processing

The manufacture of bespoke reinforced materials in 3-dimensions is challenging and

many different techniques are available. Perhaps most prevalent is the orientation of fibres

by shear processes, often incidentally as an unavoidable consequence of extrusion or injection moulding, as demonstrated in Ref. [68], where short fibres are oriented towards the

flow direction. Nano-fillers can also be oriented by shear forces, GE [120] and CNTs [30]

have both provided enhanced thermal properties when oriented. Greater flexibility of the

orientation can be achieved by the use of a converging channel that orients the fibres in the

flow direction [119] or by additive layer manufacturing, which allows tracks to be draw

with the oriented fibre mixtures [233]. In this way, 3D constructions of oriented fibres can

be made.

More direct analogues to conventional composites can be seen in tape casting, where

a slurry of polymer is swept under a blade and shear-stresses orient the fillers [155]. The

resulting material is advantageous for its easy operation, stack-ability and therefore scalability. Similar layered nanocomposites can also be achieved by a similar layer-by-layer

technique [17]. More viscous melts can be oriented by the assistance of hot-pressing, which

orient them in a 2D plane [18].

Mechanical Deformation

Similar orientation of the reinforcements can be achieved by mechanical deformation of

4.1 Introduction

115

the final composite specimen. Wang et al. [248] demonstrated, in CNT reinforced epoxy,

that repeated stretching caused the CNTs to rotate in the direction of the applied deformation, whilst Jin et al. [114] used an elevated temperature in a thermoplastic composite to aid

the process.

Freeze casting

The orientation does not have to be achieved in-situ of the polymer matrix. Freeze casting can be implemented, which involves freezing a suspension of fillers in a medium to create a controlled structural order. This technique has demonstrated controlled suspension of

ceramic platelets [179]. The orientation of the fillers can be controlled by the ordered formation of ice crystals, and then the polymer matrix is later added to form the final anisotropic

composite.

Remote orientation

In contrast to many methods of filler orientation, particularly shear processing, there are

also methods that require no physical contact with the constituents once a homogeneous

dispersion is achieved. For example, the use of ultrasonic waves has been demonstrated to

create semi-oriented assemblies of fibres, positioned in discrete pathways along the ultrasonic wave lines [219]. Similarly, networks of filler can be created by the use of electrical

currents, which has shown positive results in successfully orienting CNTs in uncured epoxy

[167].

Magnetic orientation

However, the potential for magnetic orientation is increasingly being realised. It is a

non-contact method that gives orientational and spatial control of the reinforcement within

a matrix. The direction of the magnetic field determines the alignment direction of the

fillers, the magnetic field strength controls the degree of alignment and spatial control can

be obtained by controlling the homogeneity of the field. Moreover, this is all achievable in a

3-dimensional space without the use of electrodes or shear operations that could externally

affect the matrix material.

There have been many reports of magnetic orientation of filler particles within matrices, this can involve the formation of filler networks for applications such as, for instance,

magnetorheological dampers [151]. However, the benefits of oriented continuous fibres in

conventional composites has attracted research into the orientation of discontinuous fibres

[52, 114, 154, 232], driven by the exciting potential of an increased design space. By using a

static magnetic field, aided by an intermittent rotating magnetic field, it has been shown that

116

Magnetic Response

short carbon fibres can be oriented in a viscous fluid [133]. The incorporation of orienting

reinforcements into conventional manufacturing processes is attractive, as it would further

enhance the material properties. This has been attempted by Takahashi et al. [231], who

applied a 2.4T magnetic field during a hot-press operation of carbon fibres in polycarbonate and found increased alignment as a result. A demonstration of radial alignment with a

permanent magnet has also been conducted, in which carbon fibres were aligned in a 0.75T

field to create a bending actuator [131].

Recent interest in nano-dimensioned materials [14, 149, 262], has also been accompanied by attempts to magnetically align them. However, this often requires very high magnetic fields. For instance Kimura et al. [129] oriented CNTs in a polyester matrix under a

field of 10T, before polymerizing the dispersion after alignment. Stronger magnetic fields

of 25T have also been used to align CNTs in epoxy, in order to create filler networks that enhance the electrical conductivity [38]. Magnetic fields of up to 40T have also been tested to

investigate the effect of pulsed magnetic fields [232]; as pulsed fields provide an economical

method of producing a high field strength in a large space.

A solution to counter the requirements for large magnetic fields is to use magnetically

responsive fibres, such as Ni/Co coated CNTs, which have been aligned in polystyrene by

a magnetic field of 5T [222]. Lower magnetic fields of 0.3T have also achieved alignment

by coating CNTs with nanoparticles [126], which is a low enough magnetic field strength

to utilise permanent magnets [197]. The addition of superparamagnetic nanoparticles to

alumina platelets allows alignment in a rotating field of around 0.1T [154]. Alignment in

this latter case was aided by the combination of a magnetic field and mechanical vibration;

the vibration helps to overcome steric hindrance, particularly at high filler volume fractions.

The vibration or sonication of samples before alignment also has the effect of improving the

dispersion of the fillers [31, 134, 220], whilst its use during magnetic orientation has been

shown to improve the alignment of fillers [154].

The morphology of the reinforcement also has a large effect upon the alignment, for example it has been shown that curved CNTs do not align as easily as straight-pristine CNTs

[112]. However, by appropriate choice of the morphology of the filler (e.g. size, aspect

ratio, morphology and magnetic properties), alignment of fillers can be achieved with magnetic fields orders of magnitude lower than previously seen. Erb et al. [52] demonstrated

this, by theoretically predicting the geometry of filler that would give an ultra-high magnetic

response; the result was the alignment of alumina platelets coated with super-paramagnetic

nanoparticles in a magnetic field of just 0.08mT.

4.1 Introduction

117

Orientation schemes

Control of the matrix and filler properties, as well as the processing conditions, has been

shown to be important to the quality of the produced material; especially in its ability to

disperse and align the reinforcements. However, careful control of the magnetic field is

equally important. It can be used to locally and globally control the orientation and concentration of fillers in 3-dimensional space. For instance, magnetic alignment typically orients

the primary axis of fibres towards the direction of the magnetic field, however platelets

have 2 principle axes and so the application of a rotating magnetic field is able to bi-axially

align the platelets. The rotational speed of the magnets is important: at low frequency and

low viscosity, the platelets continuously rotate, but at high frequency and high viscosity the

platelet will bi-axially align. It has been shown that by considering the viscous, magnetic

and gravitational forces, a critical frequency for bi-axial alignment can be calculated [54].

A similar concept is to use a uniform field to orient one of the principal axes, and then use

a rotating magnetic field to orient the other [53].

By using a hydrogel with aluminium platelets coated with superparamagnetic nanoparticles, alternately oriented layers can be created [53]. The anisotropic swelling of each layer

then causes either bending or twisting, depending on the orientation of the platelets. Similar

actuating devices that directly use the magnetic responsiveness of the fillers have also been

produced by the radial orientation of fibres, which allow the specimen to bend under the influence of a magnetic field [131]. In fact, a similar arrangement has demonstrated its ability

to walk using the intermittent application of the magnetic field [132].

Spatial orientation is also a useful tool for engineering design for mechanical performance, for example Erb et al. used it to create vertically aligned platelets along a polyurethane

surface to increase the abrasion resistance, whilst platelets within the material were oriented

in-plane to increase the overall strength and toughness [52]. In addition to spatial orientation, the concentration of magnetic fillers can be controlled locally with the application of

a non-homogeneous magnetic field. This creates mechanical gradients, concentrating reinforcing materials to areas of particular interest, in a similar manner to natural systems such

as tree wood [52].

Knowledge of the dispersion and orientation of fibre reinforced composites can be critical

to understanding the underlying mechanical behaviour of a material. Indeed, many models

have sought to include the effects of orientation distribution on the small strain [64, 119]

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Magnetic Response

and large strain behaviour [72, 187]. Hence, it is important that methods are available to

verify the state of orientation and distribution. For example, Kimura et al. [131] used a

cylindrical magnet to orient short fibres in a radial configuration in a composite strip. The

use of short carbon fibres of micro-scale dimensions meant that optical microscopy could

be used to verify the results.

In addition to the overall spatial orientation of the fibres, the distribution of the orientation can also be a useful quantity which can vary due to the number of different factors,

for instance the anisotropy of oriented chopped carbon fibres has been shown to be directly related to the strength of a magnetic field [134]. The collection of such information

can be very useful in understanding the material behaviour and in making comparisons to

constitutive/numerical models, however the collection of this data is often difficult and time

consuming. To improve this process, contrast techniques have been employed such as: etching the matrix with oxygen ions to roughen its surface in comparison to the fibres [174] and

the use of penetrative dyes that illuminate the glass fibres in an epoxy matrix [118]. These

methods make identification of the fibres from the matrix easier, and so automatic image

analysis can be undertaken with the appropriate software, however this is more challenging

when nano-scale fibres are employed.

Nano-dimensioned materials require the use of SEM to be able to view the reinforcements, however only small portions of the material can realistically be analysed and the

quality of the image depends on the conductivity of the consituent materials. Despite this,

Kim et al. [126] recorded the orientation of around 100 CNTs in epoxy after analsysis with

SEM in order to view the distribution. Alternatively, X-ray diffraction has been successfully used to indirectly assess the anisotropy of filler particles by taking diffraction patterns

of the specimens and recording the relative intensity, the intensity can then be related to

the orientation state of the material microstructure [4, 154]. This has been demonstrated

with CNTs in polycarbonate [231] and a thermoplastic composite [114], as well as platelet

shaped particles in epoxy [154].

The prediction of particle alignment in the presence of a magnetic field can be useful in

the design of materials with controlled architectures, and a number of methods have been

used in the literature [52, 134]. However, the accuracy of any solution depends on careful

consideration of a number of quantities such as: the filler geometry, orientation, aspect ratio,

magnetic susceptibility, matrix viscosity and the curing rate of the matrix. Even considering

all these factors, discrepancies can still occur due to a number of factors which are difficult

4.1 Introduction

119

to account for, such as movement of the matrix, magnetic coupling of fibres, mechanical

fibre interaction, matrix evaportation and matrix shrinking. Hence, experimental validation

is a vital tool in assessing the predictive capabilities of the models, although limited data is

available in practice due to the difficulty in recording the orientation of a sufficient quantity

of filler particles.

It is possible to construct a model by consideration of the thermal and magnetic energies

of a particle. At thermal equilibrium, a randomised orientation of particles is achieved

that can be given by Boltzmann statistics, however when the magnetic energy of the filler

is greater than the thermal energy, it is possible to achieve orientation if the geometry of

the filler produces an anisotropic magnetic response; the probability function of alignment

can then be calculated [134]. Erb et al. [52] also considered the gravitational energy, in

addition to a direct consideration of the geometry of the filler (1D fibre/2D platelet). The

addition of the gravitational energy takes into account that large particles will be dominated

by gravitational effects, but very small particles are dominated by thermal effects; in doing

so, it was shown that an optimum particle size exists at which high magnetic response can

be achieved. An accompanying distribution function, similar to that seen in Ref. [134],

determined the probability that 90% of the fibres, based on their geometry and magnetic

properties, would be aligned to within 15 degrees of complete alignment.

The previous studies considered a homogeneous steady magnetic field, however a rotating magnetic field has also been employed to biaxially align platelet-like reinforcements

[53, 54]. This has shown that at low frequency and low viscosity the platelets continuously

rotate, but as the frequency and viscosity are increased, the viscous torque begins to dominate and alignment of the platelets occurs. By consideration of the viscous, magnetic and

gravitational torques it has been determined that a critical frequency exists for a given viscosity at which alignment of the platelets occurs [54], and which has been used to bi-axially

align magnetised alumina platelets in an epoxy matrix [154].

120

4.1.2

Magnetic Response

When the tailored magnetic reinforcements, discussed previously in their capacity to control

the mechanical properties of a material, are locked in position within the material, it is no

longer possible for them to rotate or translate in the presence of a magnetic field. However,

the force is now transferred to the matrix to cause deformation and locomotion of the material. This stimuli responsive behaviour of a material is ubiquitous in nature, particularly

in the form of biological muscles [238] and plants [168]. The range of actuation varies

hugely, from mechanical changes, to physical changes, to the rapid release of elastic energy

for propulsive purposes.

For example, differential swelling in pinecone bilayers causes them to open as they

dry. During rain, water is then collected by the pine and travels rapidly to the centre, is

transported to the inner scales and closes the pine again to prevent the seeds from spreading

in humid conditions [224]. Differential swelling is similarly adapted in spruce tree branches

by varying the cellulose fibril angles in the wood [60]. When the fibril is parallel to the long

axis of the branch, the wood is stiffest and restricts swelling; this results in a strong branch

that curves upwards and resists collapse.

However, these processes are generally relatively slow acting. In many applications

it is necessary to enact rapid or propulsive actuation, for example sphagnum moss is also

activated by dehydration which causes a rapid propulsion of spores into the air [168]. As

the moss drys, the cell walls of the capsule begin to collapse laterally, forming a cylindrical

shape with an increased internal pressure; at a critical level, the cap breaks free and the

spores are explosively released [168]. Similarly, the bunchberry bogwood flower has an

interesting pollen dispersal mechanism reminiscent of a catapult. Stimulated by the force of

a large insect or strong wind, the flower opens up in under 0.5ms and accelerates the pollen

at up to 2200g before quickly reaching terminal velocity [80, 168]; this gives it the best

chance of cross-pollination.

The venus fly trap is a well known example of an actuating plant that uses a bi-stablility

in the leaf to rapidly close and capture its prey [80]. The process consists of sensory and

actuating mechanisms: firstly the active sensory process is initiated by a loss of pressure

in the motor cells caused by the prey. This then triggers an elastic response in the form

of a switch in the stable configuration, trapping the prey by closing the leaf [266]. This

has inspired an electromagnetically actuated bi-stable composite plate that replicates this

change in stability under the action of a magnetic field [266]. Novel devices such as this

could potentially lead to solutions for engineering design in areas such as morphing wings,

hinge mechanisms and other deployable structures.

Indeed, the creation of new, exciting materials and structures is a challenging task in

4.1 Introduction

121

engineering, and has attracted considerable interest in recent years [228, 234]. The examples

found in nature concerning the actuation of materials to various stimuli have encouraged

many other novel designs that efficiently use multi-functionality to achieve shape change

through elegant design [26].

The actuation of structures in engineering is typically driven by mechanical forces, however a number of different stimuli have been demonstrated to cause actuation. For example,

Li et al. [152] demonstrated the temperature dependent actuation of gel blends into various

shapes by controlling the composition of bi-layers. The position of the temperature responsive material is varied within the structure to create junctions that act as shape-memory

hinges. This memory effect is also shown in a pH responsive elastomer [254], which slightly

changes its elastic properties in different pH environments. Here, the cellulose whisker reinforced polyurethane can be stretched in distilled water and held until dry. It will then

indefinitely hold its shape until immersion in water again.

These stimuli owe the shape of the deformed material to a combination of the undeformed structural architecture and the configuration of the material constituents, however

this behaviour can also be coupled to the directional properties of the stimuli, e.g. the electric field. Fehr et al. [57] showed the alignment of TiO2 particles in a PDMS gel, under

the action of an electric field. The resulting material is responsive to an electric field, and

can be made to bend into an undulating pattern by changing polarities of neighbouring electrodes [57] or elongate due to the electrostriction of a dielectric elastomer [257]. Similarly,

Varga et al. [242] showed the alignment of particles in different fields (i.e. electric and

magnetic), however they subsequently showed that there is a coupling between the field response and the mechanical properties. This depends on both the anisotropy of the material

and the direction of the applied field, and in a PDMS gel can additionally affect the swelling

behaviour. The maximum elastic modulus is found when the field and particles are aligned

[242].

However, an electric field requires physical contacts (i.e. electrodes) that are not ideal

in many applications. Infrared-triggered actuation offers an alternative by providing contactless stimulation. Liang et al. shows that thermally active polyurethane can be infrared

active with the addition of photoactive graphene reinforcements; in this case the graphene

increases the mechanical performance and means infrared light is absorbed by the graphene,

causing the polyurethane matrix to contract. This reversible actuation has also been applied

to bi-layer hinges [135]. By reinforcing one layer with CNT reinforced silicone, and leaving

the other as a passive silicone layer, the hinge can bend reversibly; the result is an inchworm

walker that can travel.

Many other types of stimuli have also been successfully demonstrated, such as thermal

122

Magnetic Response

[152], solvent [80] and visible light [26], and are generally characterised by their comparatively weak mechanical response on the structure, which means they are most suited to the

actuation of soft elastomers, for applications as diverse as soft actuating valves [236], artificial muscles [238], tuneable dampers [217] and micro-swimmers [71, 193]. Therefore, due

to the comparatively low elastic modulus of such materials, the effect of the reinforcements

on the mechanical properties is heightened, and magnitude increases in the mechanical properties are possible [13, 16]. Additionally, as shown by the work of Varga et al. [242] the

mechanical and stimuli properties can be coupled, therefore it is very important to consider

the configuration of the material constituents.

A lot of interest surrounds the potential of carefully controlling the alignment of the

constituents [52, 53, 134], particularly as the advantages are clearly demonstrated in nature

(e.g. the varying orientation of fibrils in tree branches along their lengths [228]). Erb et al.

[53] shows the various swelling behaviours of hydrogels, which create different twisting and

bending configurations dependent on the alignment and configurations of the reinforcing

platelets. The platelets are oriented by low magnetic fields, meaning the resulting hydrogel

is also responsive to a magnetic field.

This magnetic field response has been used to control actuation, and has shown a number

of advantages over other stimuli.

First and foremost is its ability to actuate remotely, i.e. without the need for electrode contacts, batteries or particular environmental conditions, which increases its

usefulness in biomedical applications, e.g. inside the human body.

In addition, the field can be controlled in strength, direction and homogeneity in 3dimensional space, creating a variety of responses.

This response can be reversible, repeatable and almost instantaneous. By turning an

electromagnet on and off, an oscillating response has been demonstrated up to 40Hz

[270], with no phase shift.

The mechanical and magnetic behaviour are coupled, and in fact the elastic modulus

can be increased substantially in the presence of an increasing magnetic field [20].

This potential for magnetic actuators has attracted a number of studies on the properties

of magneto-elastomers. Most prominent is the work of Zrnyi et al. concerning magnetic

polymer gels, in particular the dependence of elongation on the non-uniform magnetic field

intensity [230, 267269]. The application of a load to a gel causes it to elongate, however

the addition of spherical superparamagnetic particles to a gel reinforces the material and

4.1 Introduction

123

reduces this effect. Furthermore, the magnetic response of the material under a magnetic

field is to contract and subsequently further reduce the effects of the load [267], in a process

analogous to the motion of a muscle. This contraction is caused by the magnetic locomotion

of the superparamagnetic particles, which attract to each other in a field and increase the

mechanical properties.

For this reason, the mechanical-magnetic properties of homogeneous magneto-elastomers

have been investigated by a number of researchers (See, e.g. [20]), and have shown an increase in the elastic modulus [243] that is proportional to the field intensity and important

to consider in the derivation of theoretical models concerning actuation [268, 269]. The

specimen resists any imparted deformation, and has, for example, shown increases in the

compressive modulus when in a magnetic field [56]. This enhancement in the properties

is immediate in the presence of a magnetic field, and can show dynamic behaviour when

coupled to the actuating behaviour. For instance, Zrnyi et al. [270] showed the actuating

in-phase response up to a oscillating magnetic field of 40 Hz.

The actuation of anisotropic materials is also of interest, especially as the anisotropy can

be produced in a magnetic field prior to curing the specimen. In this case, particle-particle

interactions cause the spherical particles to form chain-like structures in the material that

provide anisotropic properties [213, 242]. In the case of anisotropic magneto-elastomers,

the coupling between the mechanical and magnetic properties is now further complicated;

firstly by the direction dependent behaviour of the mechanical behaviour, and secondly by

the behaviour in each direction, which is dependent on the direction of the applied field.

Varga et al. [242, 243] showed that maximum elastic moduli are obtained when the load,

field and reinforcements are all aligned parallel, although when the field and reinforcements

are parallel but perpendicular to the load, there is still a significant increase in elastic modulus due to the resulting lateral constraint. For homogeneous materials, the increases in

elastic properties are not as great; although not significantly dependent on the field direction. Other configurations of field, load and reinforcement alignment are possible and many

of these are considered in Ref. [244].

However, in general only perpendicular arrangements of magnetic field, mechanical

loading and reinforcement anisotropy are considered due to the complexity of other systems. Never-the-less, the benefits of such arrangements are known and constitutive models

to predict the behaviour are being developed [28, 29, 213]. Among the many effects are

differential stiffening, which can result in, for example, localised swelling of polyurethane

reinforced with magnetite coated alumina platelets [52]. Bending of polymer films is possible by the creation of bi-layers, with the bending dependent on the mechanical gradients,

reinforcement concentrations, stimuli strength and a number of other factors [80]. Alterna-

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Magnetic Response

tively, anisotropic reinforcement can create interesting actuating behaviour: Kimura et al.

[131] radially oriented short carbon fibres with a circular permanent magnet. The resulting

material aligns its reinforcing fibres to the lines of a magnetic field, and creates a bending

actuation effect. This arrangement can be used to create an actuating and walking elastomer

[132] (Fig. 4.1a). Similar variation of the reinforcement angle is demonstrated by Kim et

al. [127] to create a crawling movement (Fig. 4.1c). The material is made of modules of

transversally isotropic material, each with a different angle of isotropy that creates a zigzag pattern in a magnetic field. This is a direct improvement on the work of Ramanujan et

al. [202], who also use a modular arrangement of ferrogels to create a finger-like actuating

prototype (Fig. 4.1b); although the modules are magnetically homogeneous and limit the

motion.

Fig. 4.1 Examples of magnetic actuation and locomotion in the literature. (a) Inch-worm

like motion of a composite sample by varying the magnetic field on a ratchet strip [132],

(b) Modular, finger-like actuator responsive to a magnetic field [202], (c) A modular microactuator, in which each module has a different reinforcement direction and responds to a

magnetic field accordingly [127], (d) A soft cellular elastomer with embedded magnets that

collapses in a magnetic field [236].

Utilising this actuation to the locomotion of the material would be of interest to a number

of applications, including drug delivery and biological exploration, and has led to attempting

to find suitable actuation and locomotion mechanisms for this purpose. These are often

4.1 Introduction

125

the intended applications [193]. They can be optimised to a number of situations, making

use of the dimensions and morphology of the propulsive surfaces [71]. However, larger scale

applications can be envisaged. Larsen et al. [144] have developed a magneto-rheological

foam that can, under the action of a magnetic field, vary in shape and mechanical properties.

A novel material such as this could be of interest as an actuator or a damper. Tipton et al.

[236] showed that a cellular array of elastomer material (similar to a honey-comb material)

with embedded permanent magnets could deform and eventually buckle in a magnetic field,

and could have application as a valve or pump (Fig. 4.1d).

126

4.2

4.2.1

Magnetic Response

Introduction

The demand for highly innovative, multi-functional, and lightweight structures continues to

increase (see for example the book by Leng and Leu [147]). This demand can be realised,

partly through the use of self-assembly of reinforcements to produce bespoke material architecture.

The self-assembly of fibres has been attempted by many methods, including: shear

[223], electrical [211], ultrasonic [219] and magnetic alignment [131, 134]. In particular,

magnetic alignment has gained considerable interest due a number of advantages compared

to other techniques [207] such as: (1) Magnetic forces being contactless volume forces that

remotely orient magnetically anisotropic materials along field lines into 3D spatial configurations [52], (2) Permanent magnets and electromagnets being readily available and producing strong enough fields to orient the reinforcements [52], (3) Compared to electric fields,

magnetic fields do not produce currents and are not sensitive to surface charge and pH [207].

Reinforcements that are aligned to magnetic field lines, can in turn, offer control of

the material properties. The performance, however, depends critically upon the degree of

orientation; which is in turn dependent not only on the applied magnetic field strength but

also on the size, shape, volume [52] and magnetic properties of reinforcing filler used, as

well as the curing rate and viscosity of the matrix [7].

Therefore, accurate manufacturing requires an understanding of the material system and

its relationship to the experimental set-up. This in turn allows for the prediction of the fibre

dispersion [41] and helps to further understand the limiting factors of the magnetic field in

producing a bespoke material property.

Typically the focus involves the analysis of homogeneous fields [130, 131, 154] as this

results in a homogeneous dispersion of oriented fibres; due to a torque being applied to

rotate the fibres, but no translation of the fibres taking place. However, it is also possible to

expand the design space by considering the use of non-homogeneous fields. Such controlled

motion and transport of fibres would allow similar structures as those demonstrated in, for

example, the non-uniform dispersion of cellulose fibrils in tree structures [172].

In this section, we study the alignment of magnetic nickel-coated carbon fibres suspended in a viscous PDMS pre-cure solution, whose viscosity is increasing with time, under

the action of a homogeneous field. The distribution of fibres is investigated under an electromagnet by varying the magnetic field strength and analysing the fibre distribution in-situ

during the curing process. Comparisons are made to a model developed in Ref. [41], which

considers the effects of a viscosity increase during the cure process and is expected to bet-

127

ter represent the behaviour of real-life materials, in comparison to other models [52, 134],

when the fibres are oriented during the curing process [225].

Furthermore, neodymium permanent magnets are arranged in different configurations

to investigate some of the potential orientational effects that could be produced with such a

method. The configurations include an approximately homogeneous field, through thickness

reinforcement, variable angle reinforcement and a non-homogeneous field. It is anticipated

that an appreciation of the possibilities of magnetic orientation will drive further innovation

into novel engineering materials through self-assembly, which is becoming an increasingly

important area of research as the need for highly optimised structures continues to develop.

4.2.2

PDMS (Sylgard 184) is used, without modification, as the matrix material. The reinforcement is provided by nickel coated carbon fibres of length 250 m and diameter 4.8 m

(aspect ratio 52, Ni/C 40/60 wt% purchased from Marktek Inc. and used as received). The

dimensions of the fibres were chosen for optical observation of the alignment, in-situ and

post-cure, whilst considering the difficulty to orient longer fibres in viscous solutions. The

PDMS fibre reinforced elastomers are made by direct mixing of the two compounds; this

involves the careful addition of a weighed sample of NiC fibres to a petri dish consisting of

a known amount of PDMS resin. Firstly, the mixture is agitated to partially homogenise the

mixture, then sonicated for 1 hour to further separate agglomerated fibres (agglomerations

of fibres can be seen in the fibre compound before processing, Fig. 4.2b). The mixture is

then left to settle for 24 hours to allow larger particles to settle to the bottom; this ensures a homogeneous material upon curing. This supernatant (1) is then separated and the

curing agent is added at a ratio of 1:10; the solution is then added to petri dishes and allowed to cure under the magnetic field. The remaining PDMS residue and NiC sediment is

then cured, burned off at 500 C and weighed to determine the amount of unused NiC fibre

material; this allows the fibre concentration of the PDMS specimens to be determined.

PDMS has been chosen as the matrix material for a number of reasons beyond its wide

use in both industry and research, it has many advantages which make it an attractive material when compared to NR:

It does not undergo crystallisation at large strain (i.e. Strain-induced Crystallisation).

1 The

term supernatant is here used to describe the homogeneous liquid suspended above the sediment.

128

Magnetic Response

It is more viscous in suspension, although the viscosity can be altered by the addition

of solvents.

No evaporation occurs during the cure process, resulting in less shrinkage.

It is transparent in the visible light spectrum, increasing the amount of information

viewable under a microscope.

The rate of cure, network density and stiffness of the material can all be tailored.

In addition, it can undergo isothermal room temperature curing, which will make identification of a magnetic constitutive model easier.

The reinforcements were chosen based on the requirement for a macro-sized magnetically responsive anisotropic filler, allowing it to be easily viewable under an optical microscope; this means the fibre length can easily be calculated, whilst allowing the fibre position

and orientation to be tracked more easily. In turn this allows the effects on the magnetic orientation speed, fibre dispersion and fibre orientation to be assessed in relation to the applied

magnetic field direction, field intensity, field homogeneity and fibre size.

The fibres themselves are not perfect and SEM images of the specimen indicates that

whilst the majority of fibres are in relatively good condition (see Fig. 4.2a), many features

of geometrical irregularities and damage can be observed (Fig. 4.2b - 4.2f). The simple

nature of the process is intended to reduce the damage to the fibres and fibre coating whilst

ensuring the quality of the final specimens. However, some of the fibres are already damaged

before specimen processing (i.e. as received), resulting in a distribution of fibre lengths that

is shown in Fig. 4.3.

Experimental Techniques

All testing was performed on the same batch of pre-cure reinforced PDMS solution at room

temperature. The resulting specimens were analysed by a Carl Zeiss Jenavert optical microscope. The magnetic field was applied by either an electromagnet (Newport Instruments

Electromagnet Type C, 4900 turns on each coil) or a configuration of N52 neodymium

magnets. The approximate concentration of all tested specimens was calculated as 2.1 wt%,

unless otherwise stated.

The initial testing procedure involved analysing the dispersion of fibres under the effect

of the electromagnet: firstly by observing the change of orientation, subject to a 0.08T

magnetic field, and recording the evolution of the fibre distribution at time intervals of,

t = {0, 60, 160, 220, 340, 3600} minutes. Secondly, the fibre distribution after 24 hours was

129

Fig. 4.2 NiC fibre characterisation under SEM. (a) good fibre (b) agglomeration of fibres

(pre-cure) (c) uneven nickel coating (d) Broken fibre (e) broken interface (g) almost fully

broken interface of small fibre.

Fig. 4.3 (a) The fibre length distribution, fitted to Eq. 2.4 (c=23.0, d=1.59). The averaged

values of 6 specimens are c=25.7 4.9 and d=1.61 0.15 (b) Micrograph image of the

aligned fibres, showing the variation in length and orientation (Selected fibres highlighted

in white).

130

Magnetic Response

measured for separate specimens, having been subject to magnetic field strengths of, |B| =

{0.01, 0.03, 0.05, 0.08} T.

A second series involves investigating the potential for curing specimens between magnets for 24 hours. Three configurations are constructed, (1) A homogeneous field between

four neodymium magnets, (2) An out-of-plane reinforcement with fibres reinforcing the

through thickness direction as well as the in-plane direction, (3) A variable angle, in-plane,

configuration to demonstrate the potential to spatially vary the reinforcement direction.

4.2.3

Fig. 4.4a shows the electromagnetic setup used to apply a homogeneous magnetic field to the

specimens, whereby the magnetic field strength is varied by controlling the applied current.

The homogeneity of the magnetic field ensures the fibres orient themselves parallel to the

magnetic field due to the magnetic torque, but do not translate. The magnetic

fieldstrength

between the electromagnet plates can then be calculated by N.I = B

Lcore

iron

Lgap

0

, where

N is the number of coil turns, I is the applied current, Liron is the length of the iron in the

circuit, Lgap is the air gap between the plates, iron is the magnetic permeability of iron and

0 is the magnetic permeability of free space.

The result is a transversely isotropic PDMS specimen; the transverse direction directed

between the electromagnet plates. However, the orientation of the fibres is not an instant

process and is highly dependent upon many factors, primarily the magnetic properties of the

fibres, the viscosity of the solution and the magnetic field. The effect of the magnetic field

strength is shown in Fig. 4.4b, and indicates the fibres are not completely oriented, even at

0.08 Tesla, most likely due to the observed damage on the fibres (See Fig. 4.2).

To characterise the fibre angle distribution and to aid in comparisons, Eq. 2.3 presented

in section 2.3 can be applied; as shown in Fig. 4.4b. Whilst this function is useful in characterising the resultant distribution of fibres, it provides no predictive capabilities. The

prediction of particle alignment in the presence of a magnetic field is a useful tool, as it

allows for a bespoke fibre alignment with optimal manufacturing efficiency. However, this

is not a trivial matter, and the accuracy of any solution depends on a number of parameters

such as: the filler geometry, orientation, aspect ratio, magnetic susceptibility and matrix

viscosity. A number of methods are available in the literature that take into account these

parameters [52, 134], however further discrepancies can occur due to a number of factors,

such as distribution in fibre lengths, varying magnetic responsiveness of fibres, movement

of the matrix, magnetic coupling of fibres, mechanical fibre interaction, matrix evaporation,

131

Fig. 4.4 (a) The curing PDMS specimen during the alignment procedure between the coils of

the Electromagnet (Newport Instruments Electromagnet Type C), (b) The fibre distribution

after 24 hours under various magnetic fields (|B0 | = {0.01, 0.03, 0.05, 0.08} T), fitted to the

fibre distribution function, Eq. 2.3 (b=0.44, 0.92, 1.58, 2.95).

matrix shrinking and viscosity increases during the cure process. These add to the complexity of the solution and mean that predictions are generally unable to satisfactorily capture

the evolution of the fibre alignment (e.g. see the fitting of the fibre angle distribution in

Ref.[134]).

However we introduce a model that considers the increasing viscosity of the solution

and allows the evolution of the fibre distribution, , to be calculated. The model considers

the motion of a magnetic fibre, embedded in a viscous fluid under a homogeneous magnetic

field. The fibre has a geometry given by the aspect ratio, AR, with the direction of the main

fibre axis given by the vector, n, subject to a magnetic field with direction, B. The fibre

has a cylindrical shape which can be approximated as a prolate spheroid with characteristic

half-lengths and r ( > r), aspect ratio AR = /r and volume = 4/3 r2 .

which, assumThe application of an external magnetic field induces a magnetisation M

ing a linear dependence of the magnetisation upon the field and an arbitrary angle of the

fibre with the direction of B, can be defined by,

= m 1B + a 1 (n n)B

M

0

0

(4.1)

magnetic susceptibility, which is positive for a paramagnetic material. The coefficients m

and m denote the magnetic susceptibilities parallel and perpendicular to the main axis of

the fibre.

In addition, the total energy per unit volume of this fibre in a homogeneous field can be

132

Magnetic Response

1

= a 01 (n B)2 .

2

(4.2)

This fibre is acted upon by a magnetic torque, T , when the main axis of the fibre is

not aligned to the magnetic field direction. The resulting rotational hydrodynamic drag is

defined by d , which can be related to the rotational velocity around the secondary axis of

, by the following relationship,

the fibre,

B)

= d1 (I n n)T = d1 (I n n) (M

(4.3)

The scalar hydrodynamic drag quantity, d , can be calculated as quasi-static values of

Stokes flow around a spheroid particle (see for instance [92, 212]), i.e.,

d

8 3

.

3 [ln(2 AR) 1/2]

(4.4)

This shows a clear dependence upon the viscosity of the solution, , which is generally

assumed to be constant. However, if the fibres are aligned during the curing phase of the

composite, then the viscosity, and therefore the drag on the fibres, will be time-dependent.

A common empirical expression for a time-dependent viscosity is,

(t) = 0 et/c

(4.5)

where c is the characteristic time for the initial viscosity, 0 , of the solution to increase e

times, in isothermal conditions [194]. Such an expression has been used previously in the

literature [7, 50] and gives a good approximation of the cure cycle up to the gel-point (2)

[5, 210].

As a result, the time dependent normal vector of the fibre can be described in terms of

the magnetic quantities [258], i.e.,

dn

= o1 et/c (n b) [I n n]b

dt

(4.6)

where b := B/B0 is the magnetic field vector normalised to the reference value B0 , i.e.

the intensity of the homogeneous field. o defines the characteristic time constant, which

2 The

gel-point is the intermediate stage between a liquid and a solid, indicated by a rapid increase in

viscosity.

133

assuming a dilute solution of fibres and no fibre-fibre interaction, can be described by,

o =

0 d0

0

2 AR 0

=

,

2

2

a B0

a B0 ln (2 AR) 1/2

(4.7)

Considering that the fibres and magnetic field lie in the same 2D plane, with a magnetic

field that does not change direction, the governing equation can be described in dimensionless form by,

d

1

= e tr sin(2) ,

dtr

2

(4.8)

which is expressed in terms of , the relative angle between the fibres and the magnetic field.

Here, tr := t/o represents the normalised time, and is the ratio between the orientational

time constant, o , and the characteristic curing time, c , i.e. = o /c .

The solution of Eq. (4.8) in terms of the initial angle 0 is,

tan((tr )) = tan(0 ) e

1+e tr

(4.9)

which is a useful tool to predict the fibre distribution achieved after a time tr . In fact, the

total number of fibres, dN, oriented at time tr within an angle d, can be worked out in

terms of the distribution function (,tr ) as, dN = (,tr )d. Hence one has (,tr ) =

dN/d = (dN/d0 )(d0 /d), which allows the distribution to be obtained from (4.9).

By assuming a random orientation at time tr = 0, then the initial distribution dN/d0 is

constant and equal to 1/. By inverting Eq. (4.9) and taking the derivative with respect to

0 , one obtain the following distribution function,

1 d0

1

(,tr , ) :=

=

d

such that

R /2

/2

e

e

1+e tr

2e tr

sec()2

+e

(4.10)

tan()2

d = 1.

For such a distribution function, if the characteristic orientation time, o , is greater than

the characteristic curing time, c , i.e. < 1, the viscosity increases too quickly for the

fibres to fully align to the magnetic field lines and there is a resultant large spread in fibre

orientation. Alternatively, when c is much greater than o , i.e. 1, the fibres will align

quickly and the effect of the increasing viscosity, , is negligible. This effect, on the fibre

angle distribution, is shown in Fig. 4.5 for two values of .

From Eq. 4.10, it is possible to find the probability, p1 , of having a fibre with an orientation of 1 at time tr ,

134

Magnetic Response

(b)

0.4

Probability Density

Probability Density

(a)

0.3

5

2.5

Time, tr

0 90

45

45

Angle,

0

5

90

2.5

Time, tr

0 90

45

90

45

Angle,

Fig. 4.5 Orientation distribution of the fibre as predicted by the model (4.10) at different

times, tr , for (a) = 5 and (b) = 0.5. A random orientation of the fibres is assumed at

tr = 0.

1e tr

2

p :=

(,tr , ) d = atan tan( )e

(4.11)

tan( p /2)

1

tr = ln 1 ln

tan( )

(4.12)

This gives the time necessary to align a percentage of the fibres, p , to within 1 . It

depends upon the ratio = 0 /c , between the orientation time and the curing time of the

composite, which implies that a large value of means the composite cures too quickly for

orientation to take place.

By using the implications of this relationship for , it is possible to work out the minimum magnetic field that allows the orientation spread of 1 for p of fibres at cure, i.e.,

1/2

tan( p /2)

0 0

2 AR2

B0 min =

ln

.

c a ln(2 AR) 1/2

tan( )

(4.13)

This shows the evident dependence of the magnetic field intensity upon the curing rate

of the composite, i.e., 0 /c , as well as the magnetic and geometric properties of the fibres.

The contour plot of this function, illustrating this dependence, is shown in Fig. 4.6. The red

checked regions of the plots show where the magnetic field is higher than 1 T. Magnetic

fields up to 1 T can be generated in a normal lab environment through the proper assembly

of neodymium magnets [227], without using large and complex electromagnets. Therefore,

135

any configuration which falls within this checked region would likely require fields that

cannot be generated by standard magnets, but requires more complex equipment such as

superconducting magnets [131].

Fig. 4.6 Contour plots of the theoretical minimum magnetic field intensity B0 min (eq. 4.13)

to have 90% of the fibres oriented at 5 deg. B0 min is plotted against (a) the initial curing

rate 0 = 0 /c and the fibre aspect ratio AR (for a = 2.20 103 ), and (b) the initial

curing rate 0 = 0 /c and the fibre magnetic susceptibility a (for ar = 25). The labels

show the magnetic filed intensity in Tesla. The dashed red area represents the region where

B0 is higher than 1 T. Due to the increasing viscosity of the solution, the results are shown

for the steady state (i.e. cured) condition.

To validate the model and improve its predictive capabilities, experimental data has

been collected which records the fibre orientation and fibre length distributions over a 24

hour period subject to a magnetic field of 0.08T. A low wt% (i.e. 2.1 wt%) is used in order

to minimise the effects of magnetic fibre coupling, and similar interactions.

Whilst the model takes into account the effects of geometry, the experimental data indicates a strong dependence of the alignment on the aspect ratio. Smaller fibres are shown

to orient much less than larger fibres; with those fibres with AR greater than 24.1 almost

completely aligned parallel to the direction of the magnetic field (See Fig. 4.7).

This dependence is contrary to the predictions of the model (See Fig. 4.6a), which predicts that given the approximate fibre geometry and magnetic susceptibility, a decrease in

the AR would increase its ability to orient. This is due to the viscous forces on the fibres

decreasing more than any decrease in the magnetic torque on the fibres. However, Fig. 4.6b

suggests a decrease in the magnetic susceptibility of the fibres, which would correlate to

136

Magnetic Response

1.5

0<AR12.7

(a)

0.8

0.6

0.4

0.2

0

100

50

50

Probability Density

Probability Density

12.7<AR24.1

1

0.5

0

100

100

50

Angle, ( )

50

100

Angle, (o )

2.5

Probability Density

(b)

(c)

AR>24.1

2

1.5

1

0.5

0

100

50

50

100

Angle, (o )

Fig. 4.7 The effect of fibre damage and fibre morphology on the magnetic susceptibility.

Orientation of different fibre aspect ratios after 60 minutes under the homogeneous magnetic

field of an electromagnet at a field strength of 0.08T. Fitted to Eq. 2.3 (a) Orientation of fibres

of aspect ratio: {0 < AR 12.7}, b=0.7 (b) {12.7 < AR 24.1}, b=1.4 (c) {24.1 < AR}.

b=37.7.

the damage observed when analysing the nickel-coating of the fibres in Fig. 4.2d-f. These

images indicate that many of the fibres have broken or damaged coatings. Presumably, as

fibres are broken during processing, they also lose some magnetic coating and have a much

lower magnetic susceptibility, a , as a result. This corresponds to a larger value of the

characteristic orientation time, o .

This can be accounted for in the model by assuming a series of characteristic orientation

times, i.e. o1 , o2 & o3 . Each value of o is fitted to a distribution of fibre aspect ratios, and

in this way the variability of the magnetic susceptibility is hoped to be captured. The fitting

of this data can be seen in Fig. 4.8, where observations of the fibre orientations were made

over a 24 hour period.

The orientation of the fibres in-situ, under the influence of a 0.08T field, indicate that

a significant amount of reorientation occurs in the first 60 minutes (31% aligned to within

5 ) and that in 340 minutes the fibres are 56% aligned to within 5 (See Table 4.1). Only a

137

60 mins

160 mins

220 mins

340 mins

24 hours

Model (Eq 4.3)

(a)

0.10

Probability Density

Probability Density

0.15

0.05

0

0

0

0

0

90

60

30

30

60

90

0.10

60 mins

160 mins

220 mins

340 mins

24 hours

Model (Eq 4.3)

01 , 02 , 03

(b)

0.05

0

0

0

0

0

90

60

30

Angle,

30

60

90

Angle,

Fig. 4.8 Fibre distribution measured at intervals over a period of 24 hours, showing the

fitting of Eq. 4.10. (a) One value of is fitted to the interval data, o1 = 15.4. (b) Three

characteristic orientation times improve the fitting of the data, o1 = 20.2, o2 = 15.7, o3 =

12.6

small amount of further orientation occurs after this time due to the increasing viscosity of

the curing solution.

Table 4.1 The percentage of fibres aligned to the magnetic field direction in experimental

testing. The model fittings are shown in square brackets, when considering three characteristic orientation times (o1 = 20.2, o2 = 15.7, o3 = 12.6).

Time (min)

60

160

220

340

3600

1 5 (%)

Experimental, [Model]

31, [17]

40, [39]

34, [47]

56, [55]

57, [59]

1 10 (%)

Experimental, [Model]

43, [31]

60, [59]

55, [66]

67, [73]

66, [76]

1 15 (%)

Experimental, [Model]

48 [43]

66 [70]

64 [76]

71 [81]

70 [83]

The model is able to capture this behaviour, even considering the varying fibre lengths

and the varying magnetic coatings that they are associated with. In particular, the model

is able to give a reasonable approximation of the fibre angle distribution after 24 hours,

whereas conventional models (e.g. See Refs.[52, 134]) would predict a much narrower

distribution due to the increase in viscosity being neglected.

The fitting of the data could be further improved by the use of more characteristic orientation times, i.e. oi . However, around 600 fibres were analysed for each specimen, and so a

distribution of 200 fibres (of approximately equal AR) were used to fit each o value; further

optimisation of Eq. 4.10 would have reduced the significance of the experimental data for

138

Magnetic Response

Neodymium Magnetic Alignment

The design space of reinforced elastomers, wherein the reinforcement is aligned, is potentially huge. However, to achieve such a design space an understanding of the potential

configurations needs to be realised; this can be achieved with an arrangement of permanent

magnets, and this is here demonstrated.

Neodymium Homogeneous Field

An arrangement of four permanent N52 neodymium magnets, positioned around the

curing specimen (Fig. 4.9a), produce a non-homogeneous field, but by careful placement

of the magnets, an approximately homogeneous field can be produced in the region of the

specimen (see Fig. 4.9b). Confirmation of the homogeneity can be seen in the produced

specimens (Here the concentration shown is 6 wt% NiC, as the specimens are used in the experimental tensile testing in section 2.3) which are transversely isotropic and homogeneous

(Fig. 4.9c); the darker area around the specimen is due to the thickness of the specimen

being larger, rather than any accumulation of fibres.

Fig. 4.9 (a) The Neodymium magnetic set-up to create an approximately homogeneous field

for alignment of the reinforcement, (b) The magnetic field strength (0.07-0.08T) approximation calculated using FEMM (ver.4.2), (c) The cured specimen; the arrow indicates the

in-plane direction of the reinforcement

At these increased concentrations (e.g. 6 wt%), the specimens begin to show small

agglomerations such as those shown in Fig. 4.10. Whilst their presence is limited, they are

likely to reduce the mechanical performance of the material and at higher fibre concentrations it is important to develop strategies to reduce their presence [220]. This is often an

issue in fibre reinforced elastomers, however the presence of the agglomerations is likely

139

furthered by the magnetic field; their ferromagnetic nature means they develop a weak magnetisation of their own under the magnetic field, and therefore attract together.

Fig. 4.10 (a) The post-cure fibre distribution from a specimen aligned between the four

Neodymium N52 magnets, fitted to Eq. 2.3 (b=4.3). (b) Manufactured defects and fibre

interaction during the curing process cause some agglomerations to form.

The result is a material with reinforced fibres oriented along the magnetic field lines, the

degree of transverse isotropy indicated by the orientation distribution (Fig. 4.10a).

Neodymium Out-of-Plane Reinforcement

The potential for out-of-plane curing has been explored. In Fig. 4.11 we can observe

the effect of suspending the specimen above the Neodymium magnetic arrangement. Outof-plane reinforcement would be of benefit to applications that require a strong throughthickness reinforcement, and could be considered as an option in through thickness repair

of composites. The angle of the reinforcement through the thickness can be controlled by

consideration of the arrangement of the magnetic field lines.

The variation of the magnetic field is reasonably small throughout the region of the

curing specimen (In respect to its effect upon the magnetic orientation of the fibres, as seen

in Fig. 4.4b), and as a result very little non-homogeneity of fibre distribution is present in

the specimen seen in Fig. 4.11.

Fig. 4.11c shows the in-plane variation of the fibre angle, which indicates the fibre direction is in-plane at the extremities of the specimen mould. There is significant variation

in the fibre angle due to the specimen mould being larger than the magnet. Towards the

magnet centre, indicated by the white dot, the fibres orient themselves increasingly through

the thickness until they are completely vertical. The through-thickness reinforcement can

140

Magnetic Response

Fig. 4.11 (a) The neodymium magnetic set-up to create an out-of-plane reinforcement, (b)

The magnetic field strength approximation calculated using the FEMM software [170], (c)

The cured specimen; the arrow indicates the in-plane direction of the reinforcement. The

centre dot indicates the fibres are oriented orthogonal to the viewed plane.

be viewed in Fig. 4.12.

Fig. 4.12 The out-of-plane cured specimen has a fibre reinforcement angle that varies along

the length of the specimen. The length along the specimen is shown in each image.

Neodymium Variable Angle Reinforcement

When considering complex geometries, or materials undergoing complex loading, it

can be advantageous to consider variable angles throughout the plane of the reinforcement.

Such techniques, which are ubiquitous with natural materials [215], have also been used to

great effect in conventional composite materials [125], and are demonstrated in Fig. 4.13.

Complex variations in the orientation can potentially be produced, and simply depend upon

the configuration of the magnetic field. In this case the in-plane angle of the reinforcement

can be seen to vary along the length and width of the specimen in Fig. 4.13c.

141

Fig. 4.13 (a) The non-homogeneous neodymium magnetic set-up to create an, in-plane,

variable angle reinforcement, (b) The magnetic field strength approximation calculated using FEMM (ver.4.2), (c) The cured specimen; the arrow indicates the in-plane direction of

the reinforcement.

142

4.3

4.3.1

Magnetic Response

Magnetic Actuation

Introduction

is an interesting strategy for material design. However, when the reinforcement is fixed

within the matrix (i.e. post-cure), the magnetic torque is transferred to the overall body of

the material; the result is controlled deformation and locomotion of the specimen.

The exact actuation response of the specimen is determined by the relationship between

the mechanical and field responsiveness, due to the coupled properties that have been tested

in a number of orthogonal configurations [243, 244]. The benefits of oblique arrangements

are predicted by a number of theoretical and numerical models that describe the behaviour

in a magnetic/electric field [22, 70, 213, 214], however there is a lack of experimental investigation of these effects.

This knowledge would allow more complex actuation, as the actuation can be controlled

by both anisotropic mechanical properties and anisotropic magnetic responsiveness. This

magnetic stimulation is contactless and non-invasive, and therefore ideal for bio-medical

applications such as micro-swimmers and micro-actuators [71, 132, 169, 193].

In this section, inspired by the developing interest in nano- and micro-actuating devices

for bio-medical applications such as drug delivery systems, lab-on-chip devices, as well as

new methods for performing micro-surgery and nano/micro fabrication [169], we look at the

creation of a novel magnetically and mechanically anisotropic PDMS elastomer reinforced

composite. The material actuates in a low magnetic field, and shows tailored properties that

depend upon the reinforcing fibre orientation. In particular, the configuration of the actuated

specimen depends critically on the reinforcement orientation, with the intensity of the shape

change dependent on the field intensity. As such, the effect of the magnetic field on the

transversally isotropic mechanical properties is also investigated. It is demonstrated that the

actuation can be controlled in a novel manner, taking advantage of the fibre reinforcement

and the resulting coupled behaviour between the mechanical and magnetic properties.

4.3.2

Experimental Techniques

PDMS (Sylgard 184) is reinforced by nickel-coated carbon fibres (Ni/C 40/60 chopped to

0.25 mm, diameter 4.8m, are purchased from Marktek Inc. and used as received). The fibre reinforced PDMS elastomers are made by direct mixing of the two constituents, and subsequently aligned in the presence of a magnetic field created by four neodymium magnets; a

detailing of the exact sample preparation can be found in section 4.2. The fibres are magnet-

143

Fig. 4.14 Experimental setup of the electromagnet for static actuation of the specimens, with

the magnetic field directed orthogonal to the plane of the fibres. Inset: A sample specimen

of 0 = 90 , actuated in the static magnetic field.

ically responsive, due primarily to the ferromagnetic nickel-functionalisation; the result is

an elastomer that is also responsive to a magnetic field. Rectangular specimens of thickness

0.5 mm are produced with fibre alignments at angles of 0 = {0 , 15 , 30 , 45 , 60 ,

75 , 90 }. The specimens are then cut to dimensions of 30 mm length (gauge length of 27.5

mm in experimental testing) and 7mm width. Burn-off of the solution residue indicated a

concentration of nickel-coated carbon fibres in the PDMS of 6 wt%.

To observe the actuation behaviour, samples are clamped at one end and vertically suspended in between the plates of an electromagnet as shown in Fig. 4.14. The electromagnet

produces a homogeneous field, which is orthogonal to the fibres and has an intensity controlled by varying the absorbed current. At each magnetic field intensity the specimen is

allowed to settle to a stable state. To avoid the effects of gravity and self-weight, in all tests

the samples are vertically oriented.

The presence of magnetically responsive fibres within the elastomer mean that, not only

is the material able to actuate in a magnetic field, but the mechanical performance is also

affected. Therefore, the effect of a uniform magnetic field upon the mechanical properties

was investigated. In order to characterise the effects, the magnetic field is oriented in two

configurations with respect to the material fibre alignment; both of which are orthogonal

to the loading direction and are described as perpendicular and transverse (As described in

Fig. 4.17). The effect of the magnetic field was found to be smaller than the deviation of

the moduli between equivalent specimens (The cyclic testing is shown in Appendix C.1),

therefore individual specimens were conditioned (by cycling to 10% strain 3 times) and

then cyclically tested to 10% strain. The testing involved repeated mechanical loading of

144

Magnetic Response

the specimens in the presence of an increasing magnetic field strength up to 0.09 T. The

mechanical testing of specimens up to 10% strain is justified by consideration that the maximum strain encountered during actuation is no more than 6%.

4.3.3

In the presence of a magnetic field, the elastomer material actuates due to the magnetically

responsive reinforcing fibres. The alignment of these fibres causes two main effects:

Firstly, assuming the fibres are perfectly aligned and orthogonal to the magnetic field,

no torque acts on the sample and it remains undeformed. However a critical magnetic

(crit)

field can be reached, By , at which the configuration becomes unstable, leading to

an equal probability of actuation in a positive or negative direction. This instability

can be visualised experimentally as a sudden increase in the actuation angle when the

magnetic field is slowly increased around this critical value.

Secondly, the actuation type is determined by the fibre alignment angle, 0 , varying

from bending only (0 ) to twisting only (90 ); angles in between show a combination

of bending and twisting actuation. This is caused by the anisotropic magnetic susceptibility of the fibres. The fibres attempt to align themselves parallel to the applied

homogeneous magnetic field, and the resulting torque causes bending/twisting of the

elastomer (See Fig. 4.15).

The results of the actuation in a static homogeneous magnetic field are shown in Fig. 4.16.

In the case of the 0 specimen and the 90 specimen, it is clear to see the bending and twisting behaviour, respectively. At angles between; a combination of bending and twisting

occurs, although one configuration is typically dominant in observations. It is seen that,

in general, the actuation angle increases slowly as the magnetic field intensity increases.

(crit)

However at a certain intensity, By , there is a more rapid increase that is associated with

an instability of the configuration. The gentle increase in the actuation angle before the

instability is most likely caused by the misalignment of fibres within the specimens (See

Fig. 4.16), and means that some fibres are not orthogonal to the magnetic field; as has been

confirmed in Fig. 4.10.

Magneto-Mechanical Testing

The magnetic actuation can be described by considering the magnetic and mechanical strain

energies of the specimen in a magnetic field. However, the mechanical deformation of a

145

90 . Specimens of length 27.5mm, width 7mm and thickness 0.5mm are presented to a

homogeneous magnetic field. A transition from pure bending for 0 , to pure twisting for

90 is observed. For the orientation of the axes see Fig. 4.18.

magnetically responsive material in the presence of a magnetic field can have significant

effects upon the mechanical properties (See, for example, Refs.[242244]) and therefore requires assessment. The results of this can be seen in Fig. 4.17. They show that the magnetic

field has a weak effect on the mechanical properties of the specimen when the magnetic

field is oriented perpendicular to the mechanical load. The largest effect is observed for the

specimen with fibres aligned at 0 degrees, however the magnitude of the modulus increase

for all alignment configurations is smaller than the standard deviation observed in the experimental testing under no external field (Fig. 2.23) and much smaller than the effect of

transverse isotropy, which demonstrates a near magnitude change in modulus between the

stiffest and softest configurations.

In spite of this low magnetic susceptibility, the low bending/twisting stiffness of the

material allows magnetic actuation to be observed in the presence of a magnetic field. Typically, a magneto-mechanical transversely isotropic model would be required to describe this

behaviour, however the minimal effect of the magnetic field on the mechanical properties

suggests the magneto-mechanical behaviour can be adequately estimated by the transversely

isotropic model described in section 2.3.

146

Magnetic Response

20

20

Bend Angle, ( )

Bend Angle, ( )

(a)

15

10

(b)

15

10

5

Bend

Bend

0

0

0.05

0.1

0

0

0.15

20

Bend Angle, ( )

(c)

15

10

5

Bend

0

0

0.02

0.04

0.06

0.08

0.05

0.1

0.15

0.1

Bend/Twist Angle, / ( )

0.12

15

(d)

10

5

Bend

Twist

0

0

0.05

0.1

0.15

20

(e)

Twist Angle, ( )

Twist Angle, ( )

20

15

10

5

(f)

15

10

Twist

0

0

0.05

0.1

0.15

Twist

0

0

0.05

0.1

0.15

Twist Angle, ( )

25

(g)

20

15

10

5

Twist

0

0

0.05

0.1

0.15

Fig. 4.16 Static bending/twisting actuation of specimens with different fibre alignments; (a)

0 = 0 , (b) 0 = 15 , (c) 0 = 30 , (d) 0 = 45 , (e) 0 = 60 , (f) 0 = 75 , (g) 0 = 90 .

The dominant actuation angle (bending or twisting) is recorded in each case.

147

3

(a)

2.5

2

0.00 T

0.03 T

0.06 T

0.09 T

Eq. 2.8

1.5

20

40

60

(b)

2.5

80

0.00 T

0.03 T

0.06 T

0.09 T

Eq. 2.8

1.5

20

Fibre Angle, 0 ( )

40

60

80

Fibre Angle, 0 (o )

a homogeneous magnetic field of maximum strength 0.09 Tesla. (a) The perpendicular arrangement, whereby 0 is orthogonal to the field. (b) The transverse arrangement, whereby

the field lines are in the plane of the reinforcements. At 0 = 90 the field is parallel to the

field lines.

Model Description

To investigate the actuating (i.e. bending/twisting) behaviour, a large rotations beam model

is introduced for which the total energy is the sum of an elastic, e , and a magnetic part,

m , i.e.,

Z L

Etot = ht

(e + m ) ds

(4.14)

where h and t are the beam width and thickness respectively, and s is the abscissa along the

specimen length (0 s L). e and m are given by,

e =

EI 2 GJ 2

(s) + 2 (s) ,

2 L2

2L

m = (n.B)2 .

(4.15)

Here, the elastic energy is expressed in terms of the bending, , and twisting, , angles

which are shown in Fig. 4.18, and accounts for large rotations/displacements. EI and GJ

are the bending and twisting rigidities, respectively. The magnetic energy, m , depends

upon = a f /(20 ), where a represents the magnetic anisotropic susceptibility, 0 the

vacuum permittivity and f is the volume fraction of the fibres [131]. In addition, it depends

upon the relative angle between the magnetic field B = {0, By , 0} (here assumed to be directed along the y-axis in Fig. 4.18) and the fibre orientation in the deformed configuration

n = {nx , ny , nz }, i.e.,

148

Magnetic Response

Fig. 4.18 Schematic representation of the beam model. (a) The undeformed beam showing

the reinforcement angle in the x-z plane, 0 . (b) The twisting angle, . (c) The bending

angle, .

ny = cos(0 ) sin( ) sin(0 ) cos( ) sin()

(4.16)

nz = sin(0 ) cos() ,

To study the equilibrium shape of the beam it is important to define the bending and

twisting angles,

(s) =

m

s,

L

(s) =

m

s,

L

(4.17)

The deformed configuration of the beam can then be identified by looking at the minimum of the total energy, which takes the following form,

EeTotal =

B2y L cos(0 )2

(2m sin(2m ))

8m

B2y L sin(20 )

+

m cos(m ) sin(2m ) 2m cos(2m ) sin(m )

8m

1 2

sin(2(m + m ))

2 sin(2(m m ))

+ By L sin(0 )

+

32

m m

m + m

EIm2 GJm2

1 2

2 sin(m ) sin(2m )

2

By L sin(0 ) 2 +

+

+

16

m

m

2L3

2L3

(4.18)

149

The resulting expression is highly nonlinear, and only numerical solutions can be derived. Never-the-less, it is possible to take a fourth order expansion of the total energy with

respect to the maximum bending and twisting angles; in this way, a closed form approximate

expression of the stable and unstable equilibria configurations of the beam can be obtained.

This approximate expression of the total energy in terms of the maximum bending m and

twisting m angles of the beam is thus given by,

ETotal =

4

1 2 4

By m L cos2 (0 ) B2y m3 Lm sin(0 ) cos(0 )

15

15

1

1

+ B2y m2 Lm2 sin2 (0 ) B2y m2 L cos2 (0 )

5

3

1 2

2

By m Lm3 sin(0 ) cos(0 ) + B2y m Lm sin(0 ) cos(0 )

15

3

1

EIm2 GJm2

1 2 4

By Lm sin2 (0 ) B2y Lm2 sin2 (0 ) +

+

15

3

2L3

2L3

(4.19)

The minimum of this expression describes the stable (undeformed) configuration of the

(crit)

specimen at low magnetic field strengths, however when By By

the configuration becomes unstable (a local maximum of the energy) and two symmetric minima appear. Due

to the equal weight of these minima, the configuration has an equal possibility of a nega(crit)

tive or positive actuation angle. The occurrence of By

can be studied by looking at the

determinant of the Hessian matrix, i.e. the second derivatives of the total energy,

2 Eetot

2

0 ) = m

H(

2 Eetot

m m

2 Eetot

m m

2 Eetot

m2

m =0,m =0

(crit)

is zero,

s

(crit)

By ) =

2 L4

(4.20)

3 EI

.

EI/GJ sin2 (0 ) + cos2 (0 )

(4.21)

In this situation the reinforcing fibres attempt to align to the magnetic field lines, how(crit)

ever the magnitude of By , and the actuation angle at magnetic field strengths above this,

are highly dependent on both the magnetic properties, i.e. , and the mechanical properties,

i.e. E, G. These factors are, in turn, highly dependent upon the alignment of the fibres.

150

4.3.4

Magnetic Response

(crit)

The value of By

the magnetic field up to the point at which a sudden jump in the deformation of the beam is

observed. This effect has been experimentally observed and is shown in Figs. 4.16a-g. For

example, in Fig. 4.16f, a specimen with a 75 reinforcement alignment is shown to have a

sudden increase in the actuation angle at 0.07T, which is captured in the camera samples

on the figure. The slow increase in the actuation angle at field strengths below the critical

value is likely due to the mis-alignment of some fibres in the material. It is also observed

that in each case, a dominant mode of actuation angle is present that suppresses the other,

as shown by the relatively low bending angle, compared to the twisting angle, for 0 = 45 .

(crit)

predicted by the model through Eq. (4.21) are shown in Fig. 4.19

The values of By

against the experimental data. The fitting in Fig. 4.19 was achieved with a value of the

anisotropic susceptibility, a = 2.20 103 ; which is about thirty times larger than the

one reported in the literature for neat carbon fibres [131] and is likely due to the nickel

functionalisation of the fibres, which increase the fibre magnetic response and make the

specimen easier to orient in low magnetic fields. The results show the close agreement of

the model to the experimental results, in particular showing the increased stability of the

bending modes, e.g. 0 , and the subsequent increased value of the critical field strength,

(crit)

By .

The minimisation of (4.19) allows the actuation angles to be determined immediately

(crit)

after the occurrence of the instability (i.e. By = 101%By ), and compared to the prediction of the model in light of the results from Fig. 4.19. Fig. 4.20 shows these actuation

(crit)

angles; this was obtained with parametric values used in calculating By , in addition to

the determined value of a , i.e. 2.20103 . Although a certain degree of dispersion in the

fibre angle is present (See Fig. 4.10), the actuation of the specimens in the magnetic field

confirms the behaviour predicted by the model. Indeed, as seen in Fig. 4.16, a 0 specimen

exhibited only bending, whilst only twisting is observed at 90 . At angles between, either

twisting or bending is observed as the dominant actuation mechanism; although it is still

possible to observe both (See Fig. 4.16d).

151

0.15

By

(crit)

(T)

0.13

0.11

0.09

0.07

0.05

15

30

45

60

75

90

Fibre Angle, ( )

(crit)

at which the undeformed configuration

becomes unstable, assuming the model (4.21). (Parameters: E(0 ) and G(0 ) taken from the

results of the mechanical testing (i.e. = 0.252MPa, = 1.85), I = 1.261013 (m4 ), J =

4.771013 (m4 ), L = 27.5103 (m), a = 2.20103 and f = 6 %). The black dots with

error bars represent the results of the experiment carried out by the authors for specimens

with fibres at 0 = {0 , 15 , 30 , 45 , 60 , 75 , 90 }.

152

Bending/Twisting Angle ( )

Magnetic Response

12

8

Bending

Twisting

Bending - Model

Twisting - Model

0

0

15

30

45

60

75

90

Fibre Angle,

Fig. 4.20 The bending and twisting angles achieved for an imposed orthogonal magnetic

(crit)

field at a field strength just greater than at the occurrence of instability (i.e. 1.01By ),

assuming the model (4.19). (Parameters: E(0 ) and G(0 ) taken from the results of the mechanical testing (i.e. = 0.252MPa, = 1.85), I = 1.261013 (m4 ), J = 4.771013 (m4 ),

L = 27.5103 (m), a = 2.20103 and f = 6 %). The orange dots and purple dots, represent the bending and twisting experimental results, respectively, for specimens with fibre

angles at 0 = {0 , 15 , 30 , 45 , 60 , 75 , 90 }. The solid line represents the model (4.19).

The error bars represent the experimental prediction of the actuation angle, when extrapolated from the magnetic field 1% before and after the occurence of the instability (Given by

the dashed line in Fig. 4.16).

4.4

153

Concluding Remarks

align magnetic nickel-coated carbon fibres in a viscous PDMS solution, whose viscosity

is increasing with time, with a magnetic field. The novel NiC-PDMS composites were

fabricated by dispersing the fibres in the host matrix by sonication and mechanical mixing,

then using low magnetic fields to orientate the fibres. Successful dispersion and alignment

of the fibres was observed, although a small number of agglomerations, misaligned particles

and varying fibre lengths were evident. These features of the fibres are a result of the fibre

manufacture processes, as confirmed by SEM images, and the loss of some of the nickel

coating causes the presence of unaligned and partially aligned fibres.

The distribution of the aligned fibres is analysed, both during the cure process and after, using an optical microscope; this allows the position and orientation of the fibres to be

recorded over time. Investigations of the fibre distributions under various magnetic field

strengths, and at time intervals, are undertaken. The strength of the magnetic field and the

exposure time both define the distribution of fibres, whilst the field direction determines the

mechanical and magnetic properties (i.e. an angle of isotropy). These results are compared

to the introduced model, which models the orientation of an initially homogenous distribution of fibres under a homogeneous magnetic field, and indicates its alignment; subject to

a number of environmental factors. It is possible to extend the model to the application of

non-homogeneous fields, although it is then difficult to derive an analytical solution.

Discrepancies to the model are found. For instance, larger fibres orient more quickly,

even though the inertial forces are greater than any increase in magnetic torque. This is

caused by damage to the fibres during their manufacture, as indicated by SEM images,

which show the magnetic coating has been damaged badly on many of the smaller fibres.

This damage, and defects such as fibre agglomerations and uneven nickel coating, contribute to the mis-alignment of many of the fibres. In addition, at higher fibre concentrations,

chain-like structures and agglomerations are more likely to form due to the magnetic coupling of the ferromagnetic fibres.

It is also demonstrated that spatial alignment is possible, which is a potentially useful

strategy to optimise material performance. To achieve this, four permanent neodymium

magnets are arranged in different configurations to investigate the orientational potential

of through thickness reinforcement, variable angle reinforcement and the use of a nonhomogeneous field.

Transversely isotropic specimens of the material are produced at a number of oblique

angles. Due to the magnetic responsiveness of the fibres in the cured matrix, the magnetic

torque is transferred to the specimen. The result is that the mechanical and magnetic prop-

154

Magnetic Response

erties are controlled by the magnetic field properties, specifically the angle of isotropy is

defined by the direction of the magnetic field lines during the curing phase.

Thus, in the presence of a magnetic field, the material has mechanical and actuation

properties that are both dependent on the field properties. However, the effects of a magnetic

field on the magneto-mechanical properties are minimal for low fibre content, allowing the

introduction of a simple constitutive model to describe the magnetic behaviour.

This novel composite was magnetically actuated to determine its potential for use in

micro-actuator systems. This can be achieved in a low magnetic field (< 0.2 T), due to

the nickel-functionalisation of the fibres. The average anisotropic susceptibility of the fibres

identified from the experiments, by comparison to the model, was a = 2.20 103 , which

is about thirty times larger than the one reported in the literature for neat carbon fibres.

The composite actuator has multi-stable behaviour, induced by the magnetic torque acting

on the fibres: the samples remained undeformed up to a critical magnetic field strength,

after which a sudden increase in the deformation occurs; at which point either a positive or

negative actuation is equally likely. This is predicted by the introduced model, which also

predicts the twisting and bending behaviour that are independently observed for different

initial orientations of the fibre.

Discrepancies between the predicted behaviour and the experimental results can be observed in the observations of the instability. The onset is more difficult to define, given that

a slow increase in the actuation angle is observed in the experimental tests leading up to

the instability. This discrepancy can be attributed to the mis-alignment of the fibre angles,

which are partially aligned away from the plane of isotropy, and changing the relative angle between the magnetic field and fibre orientation, Eq. 4.16. Incidentally, the introduced

model could be adapted to consider misalignment of the fibres, or even variation of the

alignment angle along the length of the beam (i.e. 0 (s)), however this would likely require

the use of numerical solutions to determine the shape of the deformed beam.

It is anticipated that an appreciation of potential orientation configurations, and the associated magnetic manufacturing difficulties, will drive further innovation into novel materials. Particularly in the field of self-assembly, which is becoming an increasingly important

area of research as the need for highly optimised materials continues to develop. However,

it has been demonstrated that the the oblique angle between aligned & embedded fibres and

an applied magnetic field can induce a bespoke actuation behaviour. Similar actuation of

advanced material designs could be utilised to develop complex steering mechanisms for

use in a wide variety of micro-actuator systems such as micro-pumps and micro-valves.

Additional configurations can be envisaged, by consideration of the fibre alignment in other

planes, and spatially aligned. Future work requires the development of a device to test in

155

a low Reynolds number flow, to determine its performance compared to similar, existing,

micro-swimming devices.

Chapter 5

Conclusions

5.1

Original Contributions

In studying the anisotropic effects of nano-inclusions, section 2.2, the mechanical and viscoelastic properties of a graphene oxide reinforced unvulcanised natural rubber are investigated. The report demonstrates that:

Natural rubber nanocomposites, reinforced by graphene oxide, have been successfully

produced by latex-mixing in a simple process that requires no additional heat or

chemical input. The process creates homogeneous specimens containing a regular

size distribution of oxidised nanoparticles of single layer thickness.

A thorough mechanical investigation of the filler network is undertaken. The introduction of the nanoparticles was found to increase the stiffness and strength. The

viscoelastic properties are enhanced by the nano reinforcements and a strong strain

rate dependence is found, which is increased by the addition of the fillers. Cyclic tests

show that an increase in the dissipative energy with filler concentration, caused by

friction between the platelets and the matrix, is greater than the increase in the elastic

energy.

An investigation of the filler network has also been undertaken by retesting the specimen 24 hours after an initial large strain deformation. This test indicated that rotation of the GO is likely to have occurred at large strain, which is permanent to some

degree. This is evidenced by the reduction in strain, for increasing GO concentration,

at which the characteristic upturn in the stress-strain curve occurs.

In response, manufacturing methods of producing anisotropic elastomer composites are explored, section 4.2. The need for optical observation of the fillers in-situ, requires the need

158

Conclusions

It is demonstrated that novel 3-dimensional spatial orientation of the fibre reinforcements can be achieved with the use of a small number of permanent neodymium

magnets. In-plane, through-thickness and variable angle configurations are all developed.

The validation of constitutive models to predict the orientation of the fibres in a solution, for the purposes of spatial orientation in reinforcing materials, is particularly difficult due to the challenges in recording the position and orientation of a large enough

number of fibres over time. Here a parametric study is experimentally achieved in

terms of the effects of magnetic field strength and time, for a large number of fibres

( 600), and is compared to a constitutive model that considers the increasing viscosity of the PDMS solution due to the cure process.

Transversely isotropic manufactured are subsequently experimentally tested to investigate

the anisotropic effect of micro-inclusions, section 2.3.

The produced specimens are shown to have tensile mechanical properties that depend highly upon the reinforcement angle, 0 . This behaviour can be described by

a hyperelastic transversely isotropic constitutive model, for all reinforcement angles,

assuming a plane stress deformation, up to 30%.

The discrepancies between the experimental data at strains above 30% are investigated

and are primarily attributed to the imperfect interface between the fibres and matrix.

Discrepancies can also be attributed to the defined deformation gradient, which is less

effective as the lateral constraint becomes significant (i.e. at reinforcement angles

approaching 90 ).

The rotation of the fibres during mechanical tests is recorded in-situ, up to 60% strain.

The rotation of the fibres helps to validate the constitute model. The rotation of fibres

at large strain is known to cause instabilities, particularly when in compression, and

such a methodology would be useful to a number of investigations.

A large strain numerical model is developed in the FE environment of ABAQUS (ver. 6.12),

section 3, in order to further investigate the effects of the anisotropic inclusion in a controlled environment. To describe the effects of a fibre reinforced composite, a plane stress

numerical model is developed. The multiple fibre representative element (RVE) replicates

the uniaxial tension experiments of the reinforced PDMS specimens of sections 2.2 & 4.2.

159

A platelet-like reinforcement has two reinforcing dimensions, and so the lateral constraint

needs to be accounted for. This is modelled as a 3D multiple platelet RVE, subject to a plane

strain deformation. However, it is advantageous to optimise the computational efficiency of

the model.

It is shown that the 2D multiple fibre RVE can be simplified to a single reinforcement

RVE, when the fibre interaction is negligible (i.e. low wt%).

The effects of the fibre angle distribution on the tangent modulus, strength of the

transverse isotropy and the stress-strain behaviour are investigated. The results quantify the effects of fibre misalignment, and suggest the effect is minimal for moderate

levels of misalignment.

It is shown that the 3D multiple platelet RVE can be simplified to a 2D single platelet

RVE, via a 2D multiple platelet RVE. The simplifications result in a small loss of

accuracy, but a large increase in computational efficiency.

A parametric study is undertaken, and a modified form of the Halpin-Tsai equation

is presented to describe the platelet reinforced RVE. This illustrates the logarithmic

relationship of the parameters that the H-T equation does not predict.

Many features of the single reinforcement RVE numerical models are captured by the

neo-Hookean transversely isotropic constitutive model up to 40-60% strain. Some

discrepancies were found, and are generally ascribed to the compression of the reinforcement, causing instabilities to arise. Never-the-less, the simple model is able to

simultaneously describe 19 angular configurations, in all possible deformation gradients for both the plane stress and plane strain numerical models. This is all done with

only 2 constitutive parameters.

When the magnetically responsive fibres are embedded in the cure elastomer, the magnetic

torque is transferred to the specimen and actuation is possible. This magnetic actuation is

explored in section 4.3.

Previous reports have used a non-uniform magnetic field to actuate spherical particle reinforced elastomers. Here, the use of responsive fibres means that actuation is

possible in a uniform magnetic field, due to the created torque.

Never-the-less, anisotropy with spherical particles is possible due to fibre-fibre interactions that form chain-like structures. This is not desirable, as it can result in

non-homogeneity of the filler distribution and therefore a reduction of the mechanical

160

Conclusions

properties. With fibre reinforcements, this anisotropy is possible without translation

of the fibres, which helps to ensure an even distribution.

The bending and twisting actuation effects depend on the fibre orientation and can

be found, in various forms, in the literature. However, we demonstrate the controlled

combination of bending and twisting, that ranges from bending only, to twisting only,

and depends upon the reinforcement angle.

(crit)

probability of a negative or positive actuation angle. This is caused by the orthogonal

arrangement of the reinforcing fibres, and could not be observed for homogeneously

distributed spherical particles.

A large rotations/displacements beam model has been developed that describes the ac(crit)

tuating bend/twist behaviour, and predicts the existence of the instability point, By .

Magneto-mechanical testing has shown the effects of the magnetic field on the sample

are negligible, and as a result that a simple hyperelastic model can be used to describe

the transversely isotropic model at small strain.

In turn this has allowed the large rotations/displacements beam model to describe the

experimental actuating behaviour, and its dependence on the magnetic field strength

and reinforcement angle, 0 .

5.2

Further Perspectives

The work has demonstrated the effectiveness the anisotropic reinforcements in elastomers

at large strain. However, the subject is vast and a number of key challenges have been identified for the journey ahead.

Experimental techniques for large strain transverse isotropy

The simple tensile testing of anisotropic materials is challenging, as shear and bending

forces are created; due to the oblique angle of the transferred forces [45]. Xiao et al. [256]

discusses many of the difficulties in testing transversely isotropic materials. Oblique test

fixtures can often be used to better transfer the tensile strains, however this more challenging at large strain due to the rotation of the reinforcing direction. As a result, relatively few

experimental procedures have tested the various loading conditions of anisotropic materials, and none comprehensively [24]. The experimental validation of anisotropic constitutive

161

models is essential, and due to the technical challenges, numerical methods are often used

instead. The development of a successful rotating test fixture or similar apparatus, to follow the oblique angle at large strain, would be a big step in the experimental testing of

anisotropic materials.

Efficient modelling of complex effects with dis-continuous reinforcements

A simplified single reinforcement RVE has demonstrated its ability to numerically simulate the behaviour of dis-continuous reinforcements at low concentrations. Its validation

potentially allows its use in the exploration of more complex phenomenon, such as crack

propagation and interfacial properties, in a computationally efficient manner.

Extending the fibre-rotations model

The fibre-rotations model, used to predict the distribution of suspended fibres in a homogeneous field, can be extended to consider the effects of a non-homogeneous field. This

would be vital in the utilisation of non-homogeneous fields to produce bespoke arrangements of spatially aligned and distributed fibres. Similar experimental validation would be

required, especially as locomotion of the fibres occurs in addition to rotation.

In addition, the damage to the magnetic fibre coating requires 3 characteristic time constants to be used, i.e. 01,02,03 . This can be extended to directly consider multiple types of

fibres, simultaneously oriented.

Magneto-mechanical testing of transversely isotropic materials

Magneto-Mechanical testing showed that the magnetic properties of the field and specimen had no significant effect upon the transversely isotropic properties in the presence of a

magnetic field. However, at larger magnetic field strengths and magnetic susceptibility the

effects will increase. Currently, only perpendicular arrangements of the magnetic field, load

and reinforcement angle are experimentally considered in the literature. However oblique

arrangements are of great interest to the scientific community, due to the interesting effects

that can be achieved, such as mixed modes of bending and twisting.

Extending the large displacements/rotations beam model

The large displacement/rotations beam model only considers a uniformly aligned arrangement of magnetic fibres perpendicular to the magnetic field. This model could be extended to consider oblique angles to the magnetic field, or the effects of fibre-misalignment.

In addition, if a higher magnetic field strength or larger filler concentration were used, then

the model would need to consider the magneto-rheological effects of the elastomer in a

162

Conclusions

magnetic field.

Design and test of a micro-swimmer prototype

The bending and twisting effects are envisaged to produce a propulsive force, potentially

for use in a micro-swimmers or actuating device. Future work would require the testing of a

prototype in a low Reynolds number flow, and if successful, development and further testing

of the device to determine the potential propulsive speeds of this system.

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Appendix A

Supplementary Material - Chapter 2

A.1

Natural Rubber shows an S shaped stress-strain curve (Fig. 2.9a). This behaviour is similarly observed in PDMS, although the S shape is weaker due to the limited extensibility of

the elastomer chains. In Section 2.3, the nominal stress-strain behaviour of PDMS is shown

to 60% strain. Here, we display the full stress-strain behaviour.

0.8

0.6

00

15

30

45

60

75

90

0.4

0.2

0

1

1.2

1.4

1.6

1.8

2.2

Stretch,

Fig. A.1 The stress-strain behaviour of 7 selected specimens of NiC fibre reinforced PDMS

samples, shown up to mechanical failure.

Appendix B

Supplementary Material - Chapter 3

B.1

The capabilities of the model are assessed by comparison to the numerical model in Fig. 3.18

(Section 3.4.5). The vs. strain plane, and the stress-strain curves are compared for

the angles 0 = {0 , 45 , 75 }. Here, we supplement the data by including the remaining

angular configurations.

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 5

1

0.5

0

60

20

20

Strain (%)

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

(a)

40

11 , 12 (MPa)

1.5

(b)

60

2

60

40

20

20

40

60

Strain (%)

Fig. B.1 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The plots

represent (a)-(b) 0 = 5 . The other values were (r) = 2 MPa and f = 1000.

186

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 10

1

0.5

0

60

11 , 12 (MPa)

1.5

20

20

40

2

1

0

1

(a)

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

(b)

2

60

60

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 15

1

0.5

0

60

20

20

40

3

2

1

0

2

60

60

40

20

20

40

60

Strain (%)

0.5

11 , 12 (MPa)

Strain Energy,

60

(d)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

0 = 20

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain (%)

1.5

20

(c)

40

Strain (%)

11 , 12 (MPa)

1.5

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

0

60

(f)

(e)

40

20

20

Strain (%)

40

60

2

60

40

20

20

40

60

Strain (%)

Fig. B.2 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 10 , (c)-(d) 0 = 15 , and (e)-(f) 0 = 20 . The other values

were (r) = 2 MPa and f = 1000.

187

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 25

1

0.5

0

60

11 , 12 (MPa)

1.5

20

20

40

2

1

0

1

(a)

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

(b)

2

60

60

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 30

1

0.5

0

60

20

20

40

3

2

1

0

2

60

60

40

20

20

40

60

Strain (%)

0.5

11 , 12 (MPa)

Strain Energy,

60

(d)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

0 = 35

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain (%)

1.5

20

(c)

40

Strain (%)

11 , 12 (MPa)

1.5

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

0

60

(f)

(e)

40

20

20

Strain (%)

40

60

2

60

40

20

20

40

60

Strain (%)

Fig. B.3 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 25 , (c)-(d) 0 = 30 , and (e)-(f) 0 = 35 . The other values

were (r) = 2 MPa and f = 1000.

188

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 40

1

0.5

0

60

11 , 12 (MPa)

1.5

20

20

40

2

1

0

1

(a)

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

(b)

2

60

60

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 50

1

0.5

0

60

20

20

40

3

2

1

0

2

60

60

40

20

20

40

60

Strain (%)

0.5

11 , 12 (MPa)

Strain Energy,

60

(d)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

0 = 55

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain (%)

1.5

20

(c)

40

Strain (%)

11 , 12 (MPa)

1.5

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

0

60

(f)

(e)

40

20

20

Strain (%)

40

60

2

60

40

20

20

40

60

Strain (%)

Fig. B.4 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 40 , (c)-(d) 0 = 50 , and (e)-(f) 0 = 55 . The other values

were (r) = 2 MPa and f = 1000.

189

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 60

1

0.5

0

60

11 , 12 (MPa)

1.5

20

20

40

2

1

0

1

(a)

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

(b)

2

60

60

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 65

1

0.5

0

60

20

20

40

3

2

1

0

2

60

60

40

20

20

40

60

Strain (%)

0.5

11 , 12 (MPa)

Strain Energy,

60

(d)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

0 = 70

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain (%)

1.5

20

(c)

40

Strain (%)

11 , 12 (MPa)

1.5

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

0

60

(f)

(e)

40

20

20

Strain (%)

40

60

2

60

40

20

20

40

60

Strain (%)

Fig. B.5 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 60 , (c)-(d) 0 = 65 , and (e)-(f) 0 = 70 . The other values

were (r) = 2 MPa and f = 1000.

190

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 80

1

0.5

0

60

11 , 12 (MPa)

1.5

20

20

40

2

1

0

1

(a)

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

(b)

2

60

60

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 85

1

0.5

0

60

20

20

40

3

2

1

0

2

60

60

40

20

20

40

60

Strain (%)

0.5

11 , 12 (MPa)

Strain Energy,

60

(d)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

0 = 90

40

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain (%)

1.5

20

(c)

40

Strain (%)

11 , 12 (MPa)

1.5

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

0

60

(f)

(e)

40

20

20

Strain (%)

40

60

2

60

40

20

20

40

60

Strain (%)

Fig. B.6 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 80 , (c)-(d) 0 = 85 , and (e)-(f) 0 = 90 . The other values

were (r) = 2 MPa and f = 1000.

191

B.2

The capabilities of the model are assessed by comparison to the numerical model in Fig. 3.27

(Section 3.5.4). The vs. strain plane, and the stress-strain curves are compared for the

angles 0 = {25 , 45 , 90 }. Here, we supplement the data by including the remaining

angular configurations.

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 0

1

0.5

0

60

(a)

40

20

20

40

11 33 , 12 (MPa)

1.5

3

2

1

0

1

(b)

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 5

1

0.5

0

60

(c)

40

20

20

Strain (%)

20

40

60

Strain (%)

40

60

11 33 , 12 (MPa)

1.5

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

(d)

2

60

40

20

20

40

60

Strain (%)

Fig. B.7 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 0 , and (c)-(d) 0 = 5 . The other values were (r) = 2 MPa

and f = 1000.

192

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 10

1

0.5

0

60

(a)

40

20

20

40

11 33 , 12 (MPa)

1.5

3

2

1

0

1

(b)

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 15

1

0.5

0

60

(c)

40

20

20

40

4

3

1

0

1

(d)

(e)

20

20

Strain (%)

40

60

11 33 , 12 (MPa)

Strain Energy,

0.5

40

60

40

20

20

40

60

Strain (%)

0

60

40

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

0 = 20

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain (%)

1.5

Strain (%)

11 33 , 12 (MPa)

1.5

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

(f)

2

60

40

20

20

40

60

Strain (%)

Fig. B.8 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 10 , (c)-(d) 0 = 15 , and (e)-(f) 0 = 20 . The other values

were (r) = 2 MPa and f = 1000.

193

1.5

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 30

1

0.5

0

60

(a)

40

20

20

40

11 33 , 12 (MPa)

4

3

2

1

0

1

(b)

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 35

1

0.5

0

60

(c)

40

20

20

40

4

3

(e)

20

20

Strain (%)

40

60

11 33 , 12 (MPa)

Strain Energy,

0.5

40

60

1

0

1

(d)

40

20

20

40

60

Strain (%)

0

60

40

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

0 = 40

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain (%)

1.5

Strain (%)

11 33 , 12 (MPa)

1.5

20

4

3

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

(f)

2

60

40

20

20

40

60

Strain (%)

Fig. B.9 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 30 , (c)-(d) 0 = 35 , and (e)-(f) 0 = 40 . The other values

were (r) = 2 MPa and f = 1000.

194

1.5

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 50

1

0.5

(a)

0

60

40

20

20

40

11 33 , 12 (MPa)

4

3

2

1

0

1

(b)

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 55

1

0.5

0

60

(c)

40

20

20

40

4

3

(e)

20

20

Strain (%)

40

60

11 33 , 12 (MPa)

Strain Energy,

0.5

40

60

1

0

1

(d)

40

20

20

40

60

Strain (%)

0

60

40

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

0 = 60

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain (%)

1.5

Strain (%)

11 33 , 12 (MPa)

1.5

20

4

3

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

(f)

2

60

40

20

20

40

60

Strain (%)

Fig. B.10 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 50 , (c)-(d) 0 = 55 , and (e)-(f) 0 = 60 . The other values

were (r) = 2 MPa and f = 1000.

195

1.5

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 65

1

0.5

0

60

(a)

40

20

20

40

11 33 , 12 (MPa)

4

3

2

1

0

1

(b)

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 70

1

0.5

0

60

(c)

40

20

20

40

4

3

(e)

20

20

Strain (%)

40

60

11 33 , 12 (MPa)

Strain Energy,

0.5

40

60

1

0

1

(d)

40

20

20

40

60

Strain (%)

0

60

40

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

0 = 75

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain (%)

1.5

Strain (%)

11 33 , 12 (MPa)

1.5

20

4

3

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

(f)

2

60

40

20

20

40

60

Strain (%)

Fig. B.11 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 65 , (c)-(d) 0 = 70 , and (e)-(f) 0 = 75 . The other values

were (r) = 2 MPa and f = 1000.

196

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 80

1

0.5

0

60

(a)

40

20

20

40

11 33 , 12 (MPa)

1.5

3

2

1

0

1

(b)

2

60

60

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

40

Strain (%)

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

Strain Energy,

0 = 85

1

0.5

0

60

(c)

40

20

20

Strain (%)

20

40

60

Strain (%)

40

60

11 33 , 12 (MPa)

1.5

20

ABAQUS Uniaxial

ABAQUS Shear

Model Uniaxial

Model Shear

2

1

0

1

(d)

2

60

40

20

20

40

60

Strain (%)

Fig. B.12 Comparison between model (3.22) and FE results for different values of the orientation angle in terms of strain energy vs. strain and stress vs. strain curves. The different

plots represent (a)-(b) 0 = 80 , and (c)-(d) 0 = 85 . The other values were (r) = 2 MPa

and f = 1000.

197

B.3

2D-SPRVE Uniaxial

2D-SPRVE Shear

3D-MPRVE Uniaxial

3D-MPRVE Shear

Model Uniaxial

Model Shear

0 = 0

11 33 , 12 (MPa)

11 33 , 12 (MPa)

In Section 3.5.3 the results of simple compression/tension tests for the 3D-MPRVE and

the 2D-SPRVE are shown in Fig. 3.21 for reinforcement angles, 0 = {30 , 45 , 75 , 90 }.

Here, we supplement the data by including the remaining angular configurations.

2

60

(a)

40

20

20

40

60

2D-SPRVE Uniaxial

2D-SPRVE Shear

3D-MPRVE Uniaxial

3D-MPRVE Shear

Model Uniaxial

Model Shear

(b)

60

40

20

11 33 , 12 (MPa)

Strain (%)

4

0 = 15

20

40

60

Strain (%)

2D-SPRVE Uniaxial

2D-SPRVE Shear

3D-MPRVE Uniaxial

3D-MPRVE Shear

Model Uniaxial

Model Shear

0 = 60

2

60

(e)

40

20

20

40

60

Strain (%)

Fig. B.13 Comparisons between the 3D-MPRVE and 2D-SPRVE for the cauchy stress difference (11 33 ) against strain for simple tension and compression, and the cauchy shear

stress (12 ) against the shear strain. Displayed for reinforcement orientations, (a) 0 , (b)

15 , (c) 60 .

Appendix C

Supplementary Material - Chapter 4

C.1

0.4

0.3

E/Einitial

In Section 4.3, the effects of the magnetic field on the magneto-mechanical properties of the

nickel-coated fibre reinforced PDMS are assessed. Initial testing indicated the effect of the

magnetic field to be lower than the variability between equivalent specimens. Therefore,

the same specimen is tested multiple times, so as to more accurately assess the effect of the

magnetic field. The procedure involves conditioning of the specimen, by cycling 3 times to

10% strain. A number of subsequent cycles are then undertaken, with the specimen tested

under different magnetic field strengths. A cyclic test of a sample is shown here, to indicate

the minimal effect on the mechanical properties after the specimen is conditioned.

1

0.5

0

1 2 3 4 5 6 7 8 9 10

Cycle (No.)

0.2

0.1

0

0

10

Strain (%)

Fig. C.1 The cyclic testing of a 0 specimen. The specimen is cycled 10 times, to 10% strain

at a loading rate of 10mm min1 .

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