The University of New South Wales

Faculty of Applied Science

School of Materials Science and Engineering

Application of Single-part Adhesives

as Healing Agent in Self-Healing Composites

A thesis
By

Xufeng Wang

Submitted in Partial Fulfilment

of the Requirement for the Degree of

Master of Engineering

August 2007
 Table of Contents

Table of Contents……………………………………………………………………..…i
Original statement…………………………………………………………………..…iv
Acknowledgement………………………………………………………………………v
Abstract………………………………………………………………………………...vi
List of figures……………………………………………………………………….…vii
List of tables……………………………………………………………………...….…ix
1. Introduction .................................................................................................................1
2. Literature review.........................................................................................................5
2.1 Introduction ..........................................................................................................5
2.2 Fibre Reinforced Composites...............................................................................6
2.2.1 Composites.................................................................................................6
2.2.2 Matrix.........................................................................................................6
2.2.2.1 Epoxy resins .....................................................................................7
2.2.2.2 Polyester resins ................................................................................7
2.2.2.3 Vinyl ester resins ..............................................................................8
2.2.3 Reinforcement ..........................................................................................10
2.2.3.1 Glass fibre reinforcement...............................................................10
2.3 Mechanical properties of composites................................................................. 11
2.3.1 Tension ..................................................................................................... 11
2.3.2 Compression.............................................................................................12
2.3.3 Interlaminar fracture toughness................................................................13
2.4 Self-Healing .......................................................................................................14
2.4.1 Introduction ..............................................................................................14
2.4.2 Self-healing Mechanisms .........................................................................18
2.4.2.1 Hollow fibres self-healing mechanism...........................................19
2.4.2.2 Microcapsule self healing mechanism ...........................................22
2.4.3 Self-healing system ..................................................................................23

i
 2.4.3.1. Moisture catalyzed adhesives........................................................24
2.4.3.2. Solvent evaporation adhesives ......................................................28
2.4.3.3 Anaerobic adhesives.......................................................................30
2.5 Test methods.......................................................................................................30
2.5.1 Determination of density..........................................................................30
2.5.2 Determination of fibre and resin content .................................................31
2.5.3 Determination of void content .................................................................32
2.5.4 Tension ...................................................................................................33
2.5.5 Compression.............................................................................................33
2.5.6 Interlaminar fracture toughness................................................................34
2.5.6.1 Mode I interlaminar fracture toughness .........................................35
2.5.6.2 Mode II interlaminar fracture toughness........................................36
2.5.7 Flexure testing..........................................................................................37
3. Experimental Procedure...........................................................................................41
3.1 Introduction ........................................................................................................41
3.2 Adhesive Storage Stability .................................................................................42
3.2.1 Materials...................................................................................................42
3.2.2 Experimental procedure ...........................................................................43
3.3 Bonding efficiency .............................................................................................44
3.3.1 Introduction ..............................................................................................44
3.3.2 Materials and Manufacturing ..........................................................................45
3.3.2.1 Laminate manufacturing ................................................................45
3.3.2.2 Cutting and Conditioning...............................................................47
3.3.3 Properties .................................................................................................48
3.3.3.1 Determination of density................................................................48
3.3.3.2 Determination of fibre and resin content .......................................49
3.3.3.3 Determination of void content .......................................................50
3.3.4 Mode I interlaminar fracture toughness testing .......................................51
3.3.5 Mode II interlaminar fracture toughness test ...........................................54

ii
 3.3.6 Three-point flexure testing.......................................................................55
3.3.7 Fractographic examination.......................................................................57
4. Investigation of storage stability ..............................................................................58
4.1 Results ................................................................................................................58
4.2 Discussion ..........................................................................................................59
5. Investigation of bonding efficiency ..........................................................................62
5.1 Laminate properties............................................................................................62
5.2 Mode I interlaminar fracture toughness .............................................................64
5.3 Mode II End Notched Flexure testing................................................................67
5.4 Three-point flexure testing .................................................................................70
5.5 Fractography ......................................................................................................72
5.6 Discussion ..........................................................................................................75
6. Conclusions ................................................................................................................78
6.1 General conclusions ...........................................................................................78
6.2 Future work ........................................................................................................79

iii
 Originality Statement

I hereby declare that this submission is my own work and to the best of my knowledge
it contains no materials previously published or written by another person, or substantial
proportions of material which have been accepted for the award of any other degree or
diploma at UNSW or any other educational institution, except where due
acknowledgement is made in the thesis. Any contribution made to the research by
others, with whom I have worked at UNSW or elsewhere, is explicitly acknowledged in
the thesis. I also declare that the intellectual content of this thesis is the product of my
own work, except to the extent that assistance from others in the project’s design and
conception or in style, presentation and linguistic expression is acknowledged.

Signature ...........................................................

Date ...................................................................

iv
 Acknowledgements

I would like to express my thanks and appreciation to my supervisors, Professor Alan

Crosky, for his support, patient and guidance throughout entire project.

Thanks to Cooperative Research Center for Advanced Composite Structure (CRC-ACS).

Thanks for them sponsor me to study in Australia. I would like to sincerely thank Drs.
Andrew Beehag and Drs. Ben Qi for their valuable advices and support.

I am also grateful to Drs. David Ruys for his positive suggestions and criticisms on my
thesis writing. Thanks to Mr. Karl Toppler and Mr. Nam Huong for the assistance on
experiment work.

Finally I want to thank my friends and other person I did not mention, for their
encouragement and support.

v
 Abstract

The aim of this study was to develop a new single-part healing system for self-healing

composites. The self-healing approach to composite repair has been developed in the

last two decades and means that a damaged area can be repaired by material already

housed within the structure. The background and development of self-healing has been

reviewed. The two main self-healing mechanisms are discussed.

To date only two part self healing systems have been examined. These require diffusion

of the separate constituents to a single location in order to effect cure and restore

strength. Single part adhesives do not have this disadvantage and are therefore very

attractive. Several candidate single-part adhesive or resin systems were considered and

discussed according to the critical requirements of a self-healing system. A series of

experiments was undertaken to evaluate the possibility of candidate adhesive systems

being effective for self-healing by focusing on the determination of storage stability and

bonding efficiency.

The results of storage stability testing showed that the stability of the cyanoacrylate or

polyurethane adhesives was poor. However silane and polystyrene cements showed

good storage stability. Very low bonding efficiency was achieved with polystyrene

cement but a 22% strength recovery was obtained with the silane

3-[tris(trimethylsiloxy)silyl]-propylamine. Suggestions for further research into

single-part healing systems are also given.

vi
 List of Figures

Figure 1.1 Technical considerations for development of self-healing............................3

Figure 2.1 Composite materials classified by matrix and reinforcement geometry. ......6
Figure 2.2 Molecular structures of polyester and vinyl ester resins [12]. ......................9
Figure 2.3 Major forms of woven fabrics.....................................................................10
Figure 2.4 Schematic diagram of the vacuum assisted capillary action filling technique.
.....................................................................................................................17
Figure 2.5 Self-healing concept with microcapsule in polymer matrix composite......18
Figure 2.6 Schematic of hollow fibre self healing mechanism. (a) hollow fibre
self-healing mechanism; (b) the design which shows the release of healing
agent into damaged area..............................................................................20
Figure 2.7 Possible hollow fibre layers location [29]...................................................21
Figure 2.8 Cyanoacrylates anionic polymerization [32]. .............................................25
Figure 2.9 The reaction of polyurethane adhesives......................................................26
Figure 2.10 Silane bonding to inorganic substrates. .......................................................28
Figure 2.11 Formulation of PVA glues............................................................................29
Figure 2.12 Diagram of Mode I, II and III interlaminar fracture test. ............................35
Figure 2.13 Geometry of double cantilever beam specimen for Mode I. .......................35
Figure 2.14 Geometry of DCB specimens for Mode II ENF test. ..................................37
Figure 2.15 Geometry of three-point flexure testing specimen. .....................................38
Figure 2.16 Stress distributions in (a) a Mode II ENF specimen and (b) a three-point
flexure specimen [48]..................................................................................39
Figure 3.1 Hollow glass tubes and adhesive stability test specimens. .........................44
Figure 3.2 Vacuum bagging assembly to cleanse air bubbles in laminates..................47
Figure 3.3 Density determination set-up ......................................................................48
Figure 3.4 Set-up of Mode I interlaminar fracture toughness testing...........................52
Figure 3.5 Adhesive-bonded Mode I interlaminar fracture toughness specimen
geometry......................................................................................................53

vii
Figure 3.6 Adhesive-bonded Mode II ENF test specimen. ..........................................54
Figure 3.7 Adhesive-bonded three-point flexure testing specimen..............................56
Figure 5.1 Load-displacement curves for Mode I interlaminar fracture toughness testing
for a solid laminate, a silane-bonded specimen and a polystyrene-bonded
specimen......................................................................................................65
Figure 5.2 Load-displacement curve in Mode II ENF test for a solid laminate, a
silane-bonded specimen and a non-bonded post-failed Mode I specimen..68
Figure 5.3 Photograph of a) delaminated Mode II specimen, and b) silane-bonded
specimen......................................................................................................68
Figure 5.4 Stress-strain curves of a solid laminate, a silane bonding laminate and a
non-bonded post-failed Mode I specimens in three-point flexure test........70
Figure 5.5 Stress-strain curve of a solid specimen and a silane bonded specimen in
three-point flexure test ................................................................................71
Figure 5.6 SEM images of Mode I fracture surfaces of glass/vinyl ester composite
specimen: a) surface with exposed fibres, and b) matrix dominated surface
.....................................................................................................................73
Figure 5.7 SEM images of Mode II (ENF) fracture surfaces of glass/vinyl ester
composite laminates: a) surface with exposed fibres, and b) matrix
dominated surface. ......................................................................................74
Figure 5.8 SEM images of Silane-bonded fracture surfaces of glass/vinyl ester
composite laminate after interlaminar fracture toughness testing: a) surface
with exposed fibres, and b) matrix dominated surface. ..............................75

viii
 List of Tables

Table 3.1 Healing agent candidates for self healing composite ......................................43
Table 4.1 Results of stability examination ......................................................................59
Table 5.1 Measured values of density and thickness for glass/vinyl ester laminates .....63
Table 5.2 Measured values of fibre content, resin content and void content for glass/vinyl
ester laminates.................................................................................................64
Table 5.3 Adhesive-bonded fracture toughness results ...................................................66
Table 5.4 Results of Mode II ENF test............................................................................69
Table 5.5 Results of three-point flexure testing ..............................................................72

ix
 -Chapter 1

Introduction

Composite materials, due to their characteristics of lightweight, high strength,

high specific modulus, and designed and tailored performance, are now widely

used in structural applications. From civil infrastructure to high-performance

vehicles, the field of composite materials, especially fibre reinforced composites,

has grown rapidly such that over 20 million tonnes are now produced each year in

the world [1]. However, there are still concerns about the structural integrity of

composite materials regarding impact damage. Impact damage can lead to

matrix-cracking and delamination in the material structure, and reduce the

structural capability of the composite. If the damage is not detected and repaired,

premature failure can occur in the material. The cracks or delaminations also

provide sites for ingress of contaminants, such as micro-organisms and moisture.

Therefore, the detection and repair of damage at an early stage is important, as is

the recovery of structural strength and stiffness in a composite after damage has

occurred. For a damaged area on or near the surface, it is not difficult to find and

repair the damage. However, if the damage occurs on a microscopic level inside

1
the material such as matrix micro-cracking and fibre-matrix debonding, the

cracks are difficult to detect and repair by conventional methods. Some

techniques involve removal of the whole possible damage region and

re-manufacture of a new composite structure. However detection of the damaged

area is still a challenge and the consumption of time and labor for these

technologies is also a problem

Consequently, a new and alternative approach, known as ‘self-healing’, has been

developed. “Self-healing” means that the damaged structure is repaired by

materials already contained within it, just like the biological healing in human

organisms. It was first demonstrated by Dry [2] and has subsequently been

developed by several researchers [1, 3-7]. The key advantage is that no external

work is required, the composite system would sense and repair damage by itself,

restoring the material’s strength and performance. The properties of the whole

system would be minimally affected.

For the development of self-healing for composite structure, several key aspects

have been considered and researched. Figure 1.1 shows the general technical

considerations for the development of self-healing composites. The application of

self-healing to composites has been discussed and demonstrated by several

workers by focusing on different considerations. Dry [2, 3] first developed a

hollow-fibre self-healing mechanism in a composite by embedding single hollow

fibres in a polymer matrix composite. Motuku [4] developed the concept by

considering different parameters, such as storage method and healing agent.

Bleay[8] developed new vacuum-assisted hollow fibre filling methods for healing

agent infusion and improved the damage detection method by using X-ray opaque
2
dye. Recently, White and Kessler [5, 9] have introduced a new self-healing

mechanism - embedding microcapsules of healing agent monomer throughout

composite materials.

Healing agent
selection
Certain Storage
environment method
definition decision

Threats to
Evaluation and
material Test and
Consideration
structure verification

Recommended
self-healing approach
for industry

Figure 1.1 Technical considerations for development of self-healing

The aim of this project was to find a new single-part healing agent for

self-healing of composites. To be a healing system, the adhesives or resins must

fulfill several requirements, such as healing efficiency, stability, applicability and

relevant processing requirements. Currently, two-part healing systems have been

accepted and researched by most workers because of their better stability and

3
range of viscosity compared to single-part systems. However, the curing of

two-part healing systems only happens when the hollow fibres storing the healing

agent and catalyst break together and the two parts can successfully ‘mix’ at the

contact point. Single-part healing systems can harden on exposure to atmosphere

(moisture or solvent evaporation) or the absence of an inhibitor. Long-term

stability and repair efficiency of single-part healing systems would be critical

factors for consideration and selection.

In light of the aim of this project, a relevant literature survey and series of

experiments have been conducted. Several adhesive and resin systems have been

considered and evaluated based on the required curing mechanism. The hollow

fibre self-healing mechanism has been selected due to its storage function and the

structural reinforcement effect of hollow fibres. The present study is expected to

further develop this young research area.

4
 Chapter 2

Literature review

2.1 Introduction

With the objective of extending the existing concept of self-healing to the

application of single-part adhesives, the background and introduction to

self-healing mechanism, several potential single-part adhesives, and the screening

test methods are discussed in this chapter.

Firstly, basic information regarding fibre reinforced composites is presented;

followed by a discussion of the self-healing concept, in which the history and

development of self-healing, existing self-healing mechanisms, and investigation

of self-healing agents will be covered. In addition, several potential single-part

adhesives with their physical and mechanical properties are presented. Finally,

test methods are discussed with relevance to the investigation of single-part

adhesives to be used as healing agents.

5
2.2 Fibre Reinforced Composites

2.2.1 Composites

Composite materials are multi-phase materials obtained by artificial combination

of different materials. They exhibit superior properties and have been widely used

in numerous industries throughout the world. A composite material typically

consists of one or more reinforcements (fibrous or particulate) embedded in a

matrix. Figure 2.1 shows the classification of composite materials according to

matrix and reinforcement geometry [10].

Figure 2.1 Composite materials classified by matrix and reinforcement geometry.

2.2.2 Matrix

The matrix is the continuous component in a composite structure, which usually

represents the majority in terms of volume. It is usually a polymer, a metal, a

6
carbon, a ceramic, or a combination of different materials. The role of the matrix

is to hold the dispersed components together, aligning them in the load directions

and transferring the stress when the load is applied to the material. For polymer

matrix composites, thermosetting resins (e.g. epoxy and unsaturated polyester

resin) are the most widely used resin systems.

2.2.2.1 Epoxy resins

Epoxies are thermosetting resins which have low molecular weight, the ability to

cure partially, and present low shrinkage during cure [10]. The resin must be

mixed with catalyzing agent for curing, which is called ‘hardener’ or ‘catalyst’.

The cured resin exhibits good mechanical and thermal properties, high chemical

and corrosion resistance, and good electrical properties.

Epoxies are widely employed throughout the world, especially in the aerospace

industry. The highest demand for epoxies is for use with fibre reinforcement [10].

The ease of manufacturing, superior mechanical properties, low shrinkage during

the curing process, excellent adhesion to most types of substrates, and excellent

chemical and thermal resistance, have made epoxy resin an appropriate choice for

self healing resin systems.

2.2.2.2 Polyester resins

Polyester resins are widely used in construction and industrial applications [10]. These

resins are oligomers with a low degree of polymerization. Depending on the chemical

composition and molecular weight, these oligomers may be viscous liquids or brittle

7
solids.

Polyester resins are one of the cheapest resins available in the engineering industry but

provide only poor adhesion, have the highest water absorption and shrinkage, and have

a high proportion of volatile organic compounds [10]. Polyester resin is only

compatible with glass fibres and is widely used in the construction industry for building

parts that are not weight sensitive. It is also not tough and fractures easily. Polyesters

tend to develop micro-cracks and are difficult to re-bond. They also suffer from osmotic

blistering when not treated with an epoxy resin water barrier [11].

2.2.2.3 Vinyl ester resins

Vinyl ester resins were first commercialized in 1965 by the Shell Chemical Co.

Currently, these resins are commonly used to produce products such as pipes and

chemical storage tanks [10]. They are similar in their molecular structure to polyesters,

but differ primarily in the location of their reactive sites. Figure 2.2 shows the molecular

structure of both polyester resins and vinyl ester resins [12]. In polyester resin, the

recurring ester groups appear in the main body of the chain and, once attacked, the

chain is split and the structure is then susceptible to additional attack. Vinyl ester resins

only have two ester links, which are both terminally located with the reactive ester sites;

they not only have fewer ester group to be attacked, but the main chain will not be

affected once attacked due to the terminal location of the ester groups. As the whole

length of the molecular chain is available to absorb sudden impact loading, this makes

vinyl ester resins tougher and more resilient than polyesters.

8
 (a)

(b)

Figure 2.2 Molecular structures of polyester and vinyl ester resins [12].

The vinyl esters also exhibit better resistance to moisture and many other chemicals

than their polyester counterparts, because the molecules of vinyl esters possesses fewer

ester groups which are susceptible to water degradation. Although the curing schedule

of vinyl ester resin can be tailored to meet specific manufacturing processes, they are

generally cured at ambient temperature. However, they are sensitive to the atmospheric

conditions of moisture and temperature, and in some case will not cure if the

atmospheric conditions are not right. It is difficult to use vinyl esters to bond dissimilar

and already-cured materials [10, 13, 14].

9
2.2.3 Reinforcement

Some major types of reinforcements in composites are continuous unidirectional

fibres, continuous woven fibres and short fibres. Woven or textile fibre reinforced

structures are widely used. The main types of woven fabrics are plain, twill and

satin, as shown in figure 2.3. Compared to other reinforcement forms, woven

fabrics are easy to handle, which can lead to a reduction in the manufacturing cost.

Additionally, woven fabrics have more isotropic properties than unidirectional

forms and provide improved impact damage tolerance.

Plain Twill Satin

Figure 2.3 Major forms of woven fabrics.

The principal fibres in commercial use are various types of carbon and glass, as

well as aramid fibres such as Kevlar. The fibre orientation can be controlled in

each layer of the laminate to generate a wide range of physical and mechanical

properties [13].

2.2.3.1 Glass fibre reinforcement

Glass fibre reinforced plastics (GFRPs) were first developed in the UK during the

10
Second World War and obtained wide acceptance in the 1950s [10]. Currently

they are the largest-volume FRPs employed in the world. The wide range of

properties obtainable from different glass fibre-reinforced composites has enabled

them to be candidate materials in many applications from small electrical

products to large spacecraft.

The properties of GFRPs are determined by the structure of the composite

material, which depends on the types of materials produced using different

processing routes and conditions, together with the choice of constituent format

and weight or volume fraction. Compared to carbon fibre reinforced plastics

(CFRPs), GFRPs show lower specific values, such as modulus to density and

strength to density ratios. However, GFRPs have adequate combinations of

properties at an acceptable manufacturing cost. GFRPs also have a lower level of

anisotropy for the same fibre format than CFRPs, which can make design work

easier.

2.3 Mechanical properties of composites

2.3.1 Tension

Most unidirectional composites have high axial tensile properties, which is one of

the major reasons for their use [15, 16]. The tensile properties are governed by a

number of factors such as the modulus and strength of the fibres, the stress-strain

behavior of the matrix (including viscoelastic behaviour) and the fibre-matrix

interfacial strength. Alif and Carlsson [17] carried out at a series of tension tests

under different loadings and observed cracks using microscopy. They found that

11
the cracks initially occurred in the pure matrix. This was followed by fabric

damage, which occured when the matrix cracks extended to become transverse

cracks. Finally, fibre and matrix debonding, and longitudinal splitting occured.

Based on these results, they proposed that failure occurred as a result of the

development of transverse stress in the narrow region between two cured fabric

layers when they tended to straighten out under the applied uniaxial tension. The

transverse stress was then considered to initiate longitudinal cracks relative to the

tensile axis.

2.3.2 Compression

Most lightweight structures and substructures include compressive members,

which may be loaded in direct compression, or under a combination of flexural

and compressive loads. The usual design process for lightweight structures

attempts to introduce loads as pure compression and pure tension.

The axial stiffness of compressive members can only be controlled by the

cross-sectional area, which is proportional to the weight. The bending stiffness of

axially compressed struts or panels is particularly important, since in-service

buckling must normally be avoided. The stresses in a member of a given

geometry can only be reduced by increasing the effective cross-section under load.

It follows that high specific stiffness and strength in both tension and

compression are desirable features for the ideal lightweight construction material.

The comparatively low compressive strength of some composites, for example

those reinforced with aramid fibres, reduces their potential applications.

12
High modulus, highly anisotropic carbon and organic fibres are relatively weak in

compression compared with intermediate modulus carbon or glass fibres. The

ratio of compressive to tensile strength is low for the highly anisotropic fibres,

but the compressive strength of glass fibres is generally higher than their tensile

strength [15-17].

2.3.3 Interlaminar fracture toughness

One important aspect of material behavior in the mechanical response to loading

is the processes that cause absorption of energy within a composite material as it

is strained. These include the micro-deformation and microcracking processes

that precede final breakage, and thus contribute to the work of fracture.

Interlaminar delamination in composite materials is one of these fracture

processes [15-18]. Usually, interlaminar failure initiates from resin cracks and

proceeds by delaminaiton. The energy absorbed in producing one unit area of

crack surface is defined as the toughness G C (called the critical strain energy

release rate). A tough material is one for which a large amount of energy is

required to cause failure.

Interlaminar cracking (or delamination) is one of the major weaknesses of many

laminated advanced composite structures. The degree and speed of delamination

is affected by the material behavior at the front of the crack tip, which is related

to the effect of local variations in the fibre volume fraction and the manufacturing

conditions.

13
2.4 Self-Healing

2.4.1 Introduction

Since the introduction of fibre reinforced composites, there has been a

progressive increase in their use in structural applications; however, there are still

concerns about the structural integrity of composites following impact loading.

Impact damage may lead to substantial matrix microcracking and delamination

within the bulk of the composite, whilst leaving little visible sign on the outer

surface. As a result, the structural capacity of the composite is reduced, and

premature failure can result if the damage is not detected and repaired. Therefore,

it is important to detect the damage in the early stages. If the damage occurs on or

near the surface or at a macroscopic level, there are several techniques to detect

and repair the crack.

However microscopic level damage such as matrix microcracking, fibre-matrix

debonding and delamination, is not easy to observe or repair [4]. Furthermore,

restoring the structural strength and stiffness after damage occurs is important but

difficult to achieve. Consequently, an alternative approach to repair has been

designed; ‘self-healing’, which means the damaged structure is repaired by

materials already contained within it. It involves a liquid healing system

encapsulated in brittle-walled containers. These containers can be fractured

during impact damage, allowing the liquid resin to flow into the damaged area

where it subsequently cures. The key benefit of this technique is that no external

work is required; the technology would sense and respond to damage, restoring

14
the materials’ strength without affecting the original properties of whole system.

Self healing as a concept was first developed by Dry [19-21], who demonstrated

that hollow glass tubes could be an appropriate container for the repair system.

This approach was initially used for repairing internal cracks in concrete. A

three-part methylmethacrylate adhesive was used inside hollow porous

polypropylene fibres within the concrete, and released from the fibres to reduce

the concrete permeability. A further investigation was undertaken with the

adhesive released from hollow fibres after the samples were tested in flexural

testing. This investigation revealed that the restoration of strength and flexibility

using the self-repair concept worked well in concrete [20].

The application of self-healing in fibre reinforced polymer composites has been

demonstrated by several researchers [1, 4, 8, 9, 22-27]. Healing agent storage

methods have been developed based on the use of hollow tubes and fibres,

particles and microcapsules. The first use of self-healing for a polymer composite

was in 1996 and developed by Dry [22]. He encapsulated a two-part crosslinking

epoxy adhesive and single-part superglue (cyanoacrylate) in hollow glass pipettes

and fibres, and investigated whether this technique could repair the cracks and

prevent the crack reopening, Dry also embedded a filled hollow glass fibre in a

polymer matrix to visually verify the release of the healing agent after impact

loading. After that, Motuku et al [4] developed the concept by considering

different critical parameters, such as the storage methods for the healing agent

(glass, copper and aluminum tubes/fibres) and different healing agents (epoxy and

vinyl ester etc), and found that hollow glass fibres would probably be the most

15
appropriate container for self-healing.

Bleay et al. [8] actually developed a self healing composite system, in which the

hollow glass fibres were filled with a one or two part self repair system mixed

with X-ray opaque dye. The performance of self-repair was successfully assessed

and the damage detection method was also improved by the use of X-ray opaque

dye penetrant. Bleay also successfully conducted a new vacuum assisted capillary

action filling technique, as shown in figure 2.4. It has also been found that

Cyanoacrylate adhesive is difficult to handle in self-healing technology due to its

fast cure, even in a low moisture environment [8]. The visibility of self-healing

performance, and damage detection methods were improved by Pang and Pond

with the application of UV fluorescent dye [1], and the internal structure of a

composite after impact was successfully demonstrated with the ultrasonic C-scan

NDT/NDE technique. Pang and Pond also demonstrated that the effectiveness of

self repair systems deteriorates significantly over time as the healing agent

degrades.

Figure 2.4 Schematic diagram of the vacuum assisted capillary action filling technique.

16
Zako and Takano introduced a method that involves impregnation of small particles (50

μm) of thermoplastic adhesives into glass/epoxy composite laminates [25]. The

thermoplastic particles melted when the damaged composite was subsequently heated.

The results of flexure testing after the curing procedure demonstrated that the strength

and stiffness was actually recovered to some extent.

Figure 2.5 Self-healing concept with microcapsule in polymer matrix composite.

Recently, White et al., Kessler et al., Brown et al. have all taken a different approach by

embedding microcapsules of monomer healing agent throughout a polymer–matrix [9,

26, 27]. Figure 2.5 shows the structure of a microcapsule self-healing mechanism.

These microcapsules fracture and release a healing agent (DCPD – dicyclopentadiene

monomer) upon damage. The healing agent will contact with the particulate catalyst,

17
and ‘ring opening metathesis polymerization’ starts and repairs the damage. Two

catalyst application methods were tested, direct injection of the catalyst into the

damaged area and embedding the catalyst in the matrix during manufacture. The healing

efficiency was significantly better for direct injection being 67% [26], compared with

48% [27] for the embedded catalyst. Subsequently, Kessler et al. and Brown et al.

carried out an investigation into the effect of microcapsule size, and concentration of

catalyst, on fracture toughness [28]. They also optimized the microcapsule surface

morphology, rupture and healing agent release behavior[28].

2.4.2 Self-healing Mechanisms

Currently, there are two main self-healing mechanisms ühollow fibre self-healing

and microcapsule self-healing. Most of the research has been conducted with these two

mechanisms because of the appropriate strength recovery offered and the

non-requirement for external action. The particle adhesive self-healing mechanism [25]

is not widely used because of the extra catalyzing process required.

2.4.2.1 Hollow fibres self-healing mechanism

Hollow fibres can be used as structural reinforcement and they are also able to store

functional components for self-healing composite systems. This mechanism has been

investigated by several researchers [1, 4, 8, 22-24]. Hollow fibres, mostly glass hollow

fibres, are used to store the repair system, which releases into the damaged area upon

fibre fracture. The system allows the following possibilities:

1. Hollow fibres containing single-part adhesives or resins.

18
2. Alternating hollow fibres containing two-part adhesives or resins and a hardener.

3. Hollow fibres containing the resin system with the hardener or catalyst dispersed in

the matrix.

(a)

(b)

Figure 2.6 Schematic of hollow fibre self healing mechanism. (a) hollow fibre

self-healing mechanism; (b) the design which shows the release of healing agent into

damaged area.

Figure 2.6 (a) – (b) illustrates the typical hollow fibre self-healing mechanism in

19
polymer composites.

The key advantages of hollow fibre self healing mechanism are:

1. The hollow fibres can be tailored to match the orientation of the structural reinforcing

fibres, it can minimize the Possion’s ratio effect and the mismatch of properties between

the embedded self-healing system and the host structural fibres.

2. Hollow fibres can be placed in a stacking sequence to address specific failure threats,

as shown in figure 2.7. The hollow fibre layers are located at the likely damage areas,

and can thus repair the damage at an early stage.

Figure 2.7 Possible hollow fibre layers location [29].

3. Different activation methods can be used for curing of the healing agent, according to

the different operating requirements of the structure. For instance, a single-part healing

system which locates near the surface can be catalyzed by UV light, heat, and moisture

etc.

4. Hollow fibres can act as structural reinforcement. Following the development of the

self-healing approach, the dimension of the hollow fibres has been substantially reduced

20
to approach that of the reinforcing fibres. Manufacture of hollow carbon fibres, with

higher stiffness, is under consideration by some workers. These will be used to replace

the hollow glass fibres, which are widely used at present, in order to provide higher

structural properties in the composite [8].

The disadvantages of this mechanism are:

1. Fibre fracture is required for release of the healing system. However the hollow fibres

might not be fractured by microcracks, due to their stiffness. In that case, the repair

agent would not be able to flow out of the hollow fibres to heal the damage.

2. The repair resin must have sufficiently low viscosity to enable it to be encapsulated in

the hollow fibres. The use of hollow fibres with diameters down to 40 m is currently

only possible for healing agents with very low viscosities [8]. An infusion procedure for

the resin system is also required.

2.4.2.2 Microcapsule self healing mechanism

The microcapsule self healing mechanism is illustrated in Figure 2.5. As discussed in

Section 2.3.1, this involves the use of DCPD (dicyclopentadiene) monomer with a

particulate catalyst, Grubb’s catalyst, which can initiate ‘ring opening metathesis

polymerization’. The DCPD monomers are stored inside microcapsules which disperse

in the matrix, the microcapsules rupturing upon damage. DPCD monomers then migrate

through the matrix along the cracks and come into contact with exposed catalyst, which

causes polymerization and filling of the cracks [26-28].

The advantages of this technology are:

21
1. Good repair and strength recovery can be obtained in a resin-only system.

The disadvantages of this mechanism are:

1. Appropriate proximity is required between microcapsules and catalysts to initiate the

reaction.

2. The size of microcapsules affects the fibre profile.

3. Even dispersion of microcapsules and catalysts is required.

4. Limited volume of repair system as the number of microcapsules is not large.

5. The manufacturing of microcapsules is still challenging.

Compared to the microcapsule mechanism, the hollow fibres self healing mechanism

shows high feasibility. Hollow fibres provide a good combination of storage function

and structural reinforcement. They avoid some of detrimental effects on the strength of

virgin materials and act both as reinforcement and a healing agent reservoir.

2.4.3 Self-healing system

A suitable healing resin system for any specific engineering application will require a

careful material selection process based on relevant criteria. The selection of the repair

resin system will have to consider specific environmental requirements; the healing

resin will also need adequate mechanical performance, longevity, and the ability to be

used within hollow filaments. The critical factors are listed as below:

22
1. Repair efficiency, such as modulus, strength, adequate strain to failure, fracture

energy and bonding to fibres and matrix.

2. Long-term efficiency, such as degradation versus storage duration, environmental

resistance and storage life.

3. Applicability, such as cost and compatibility with surrounding materials and

industrial processing.

4. Process requirements, such as viscosity, activation method and curing temperature.

Currently, two-part adhesives or resins, such as epoxy resin and hardener, have

been chosen as the main healing agent by most researchers [1, 8, 9, 26]. The two

parts are respectively infused in adjacent hollow fibres. When damage occurs and

the hollow fibres fracture, the resin and catalyst flow into the damaged area and

cure. Since these two parts do not come into contact with each other unless the

fibres break, the two-part healing system can provide long storage life. The

downside of this is that the simultaneous breakage of the separate fibres storing

the two different parts is required.

Although the long-term stability of a single-part system would be probably worse

than for a two-part healing system, the single-part system is much easier to

activate. It can catalyze on exposure or be hardened by components embedded in

the matrix. For potential single-part healing systems, the key consideration would

be the long-term stability, processing requirements such as viscosity, and

activation of the adhesive. In this research, three activation methods have been

considered: catalyzation by moisture, reaction with a component embedded in the

23
matrix and activation when a certain inhibitor is absent. According to the curing

mechanism required, the selected of potential adhesives is discussed in the

following sections.

2.4.3.1. Moisture catalyzed adhesives

The reaction of this adhesive group depends upon the moisture content in the

environment. The phase change form liquid to solid is brought about by chemical

reaction. Two water catalyzed adhesives have been considered: cyanoacrylates and

polyurethane adhesives.

a. Cyanoacrylates

Cyanoacrylates are solvent-free, one-part adhesives that are available in a wide range of

viscosities. When applied between two surfaces, cyanoacrylates cure rapidly to form

rigid thermoplastics with excellent adhesion to most substrates. Cyanoacrylates

typically obtain fixture within 1 minute and achieve full bond strength in 24 hours [30].

Cyanoacrylate adhesives are based on cyanoacrylate esters, with methyl and ethyl

cyanoacrylates being most commonly used in adhesive formulation. When a

cyanoacrylate adhesive comes into contact with sufficient moisture, anionic

polymerization occurs. The formulation for this is shown in Figure 2.8. This is an

extremely rapid reaction and is commonly completed within seconds. Due to their

ability to bond to a wide variety of materials very rapidly and easily, cyanoacrylates are

commonly known as “super-glues”. However, they have some performance limitations,

such as poor thermal resistance and peel strength, and the bonds are readily disrupted by

24
water and are only stable at temperatures less than 80C [31].

Figure 2.8 Cyanoacrylates anionic polymerization [32].

.bˊPolyurethane adhesives

Single-part moisture-curing polyurethane adhesives are actually based on isocyanate

polymers. These are low molecular weight, linear polymer molecules, with isocyanate

(-NCO) end groups [33]. Unlike the majority of adhesives, polyurethanes are not

produced by a polymerization reaction but by the interaction of the isocyanate with a

hydroxyl-containing organic compound. The reaction is, in principle as described in

Figure 2.9 [34]:

Figure 2.9 The reaction of polyurethane adhesives.

25
The reaction involves a two-stage process. The water and the isocyanate groups first

produce an amine and carbon dioxide. The amine then reacts with other isocyanate

groups to form a urea until all available isocyanate is consumed. Because surface

moisture completes the chemical reaction for moisture-cured polyurethane, these

materials adhere well to visibly damp surfaces. They penetrate into pores and fill gaps

where moisture is usually present to form strong chemical bonds. Polyurethane

adhesives are characterized by a wide range of hardness and flexibility. They have good

environment resistance and good adhesion to various substrates. Low temperature

performance properties are also very good [34].

c. Silane coupling agents

Coupling agents are used to improve the adhesion characteristics in bonding and in

composite materials, especially in the presence of water. They were originally

developed in the 1940s to improve the water resistance of glass fiber reinforced plastics

(GFRPs). Prior to their introduction, water could penetrate along the interface between

the matrix and fiber and destroy the integrity of the bond [35]. The most significant

group of coupling agents is organo-silanes.

The mechanism of bonding for organofunctional silanes involves the formation of stable

links with the organofunctional group (Y) and hydrolysable group (XO) in a silane’s

structure (XO)3SiRY, where R denotes a polymeric group. The organofunctional group

(Y) can react with the polymer matrix. The silane should be matched to the reactivity of

the polymer matrix; for example, a methacrylate silane bonds through styrene

crosslinking to unsaturated polyester resin. At the other end of the molecule, the

26
hydrolysable group (XO) (usually methoxy, ethoxy or acetoxy) can bond well to the

metal hydroxyl groups on most inorganic substrates, especially if the substrate contains

silicon in its structure. The alkoxy groups on silicon hydrolyze to silanols through the

addition of water or from moisture in the air, and then the silanols coordinate with metal

hydroxyl groups on the inorganic surfaces to form an oxane bond, as shown in Figure

2.10. [36].

Silane coupling agents are usually applied in two ways [36]. The most common

application is to apply them in a dilute aqueous solution to the substrate and allow them

to dry before applying the adhesive and making the joint. Alternatively, a small

proportion of the silane may be incorporated in the adhesive as a primer; this method is

more commonly used in the coatings industry. This form of treatment is now used

considerably to enhance the durability of adhesive joints in the presence of water. Since

silane can provide a bonding ‘bridge’ between organic and inorganic substrates, it is

expected that this curing mechanism could be used to re-bond the delaminated surface

of fibre reinforced composites.

27
 Figure 2.10 Silane bonding to inorganic substrates.

2.4.3.2. Solvent evaporation adhesives

This type of adhesive is either based on water or an organic solvent. One group of the

water-based products have been in use for a very long time and are based on natural

products: carbohydrates from plants or protein materials from animal waste. The other

group is based on synthetic materials developed largely to replace some of the

solvent-based adhesives [37]. The two main systems, PVA glue and polystyrene cement,

are discussed below:

a. PVA glue

PVA glues, based on polyvinyl acetate from which the acronym is derived, are probably

the most important range of water-based adhesives [35]. PVA is used as an emulsion

which needs stabilizing. The principle stabilizer is usually about 5% polyvinyl alcohol,

which is specially prepared by hydrolysis of the acetate and retains about 20% of

residual acetate groups in order to provide a low molecular weight. The curing process

starts when the solvent evaporates. It is widely used for woodworking and bonding

paper and plastics. The formula of PVA glue is shown in Figure 2.10:

28
 Figure 2.11 Formulation of PVA glues.

b. Polystyrene cements

Polystyrene cements are low viscosity adhesives used to bond polystyrene and are

widely used in the construction of plastic models. The cement consists of polystyrene

dissolved in a solvent which dissolves a thin layer of the plastic and fuses it to an

adjacent piece. As the solvent evaporates, the strength returns to the polystyrene and the

surfaces are bonded together. It is actually a weld rather than a glued joint. These

cements set in less than 1 minute and fully cure in 8 hours. Polystyrene cement works

best on clean polystyrene surfaces.

2.4.3.3 Anaerobic adhesives

Anaerobic adhesives harden in the absence of air, and the presence of metal will

accelerate their cure [35]. They can be thick or thin, strong or weak, and slow or fast

reacting to fit a variety of engineering applications. Generally, anaerobic adhesives have

an operating temperature range of -50WR150ć, while some of them can operate at up

to 220ć. Typical applications of anaerobic adhesives are threadlocking, threadsealing,

retaining and flange sealing.

Anaerobic adhesives work by filling the interstitial space between the substrates,

thereby it is essential to create a solid thermosetting plastic on both substrates by

undergoing a crosslinking reaction. As is a general principle in adhesion, the surface

toughness of substrates is important in providing a firm basis for bonding, to allow the

adhesives to hold the substrates together.

29
2.5 Test methods

The experimental methods for researching the mechanical properties of composite

materials are much more complex than for other materials and require significant

modification. Because of variations in processing and raw materials, the tests generally

yield variable data. Furthermore, the results can be dependent on the test method, the

specimen design, and the composite manufacturing method.

2.5.1 Determination of density

The density of a polymer matrix composite can be determined by measuring the ratio

between the weight of a specimen in air and it weight in gas-free distilled water at 2ć,

according to the widely accepted test standard ASTM D 792 [38]. This test method

involves measurement of specimen weight in air, then in distilled water while the

specimen is suspended by a wire. A sinker may be attached to the wire if the specific

gravity of the specimen is less than unity. The weight of the completely immersed

sinker and partially immersed wire also needs to be measured for the final density

calculation. The volume of specimens should be at least 1 cm3 and the thickness should

be not less than 1 mm. Specimens should have smooth edges and surfaces. Geometric

irregularities should be avoided because they can entrap air bubbles.

2.5.2 Determination of fibre and resin content

The fibre content of a composite needs to be known in order to analytically determine

the material’s properties (mechanical, physical or electrical). There are several test

methods available to determine the fibre volume content in a composite. One of the

30
most widely used methods involves digestion or ignition of the matrix by one or several

procedures [39], with measurement of the weight of the fibre, in conjunction with the

fibre and matrix density, to calculate the volume content of the fibres and the resin

matrix.

Alternatively, if it can be proved that the composite is free of voids, the fibre volume

fraction can be determined by the measurement of composite density. However, this

method relies heavily on accurate measurement of void content. The other method is

using quantitative metallography; it involves the use of optical microscopy to measure

the fibre area fraction in several polished cross-section areas in the composite. For fibres

of continuous cross-sectional area, the area fraction equates to the volume fraction.

Compared to the previously described method, the fibre content can be determined

quickly using digital image analysis. This method can also be applied to determine resin

and void content.

2.5.3 Determination of void content

The void content of a composite can affect its properties; the higher the void content,

the lower its fatigue and moisture resistance. There are a number of methods that can be

used to determine the void content of a composite. One method to determine the void

content of composite is to determine the density of the fibres, the resin matrix and the

composite. With the measurement of fibre and resin content, a theoretical result of

composite density can be calculated, and then compared to the measured density of the

composite. The void content of the composite is then the difference between the two

results for the composite density [40].

31
Image analysis of polished cross-sections can be used to determine the void content in a

composite, and this method has been widely applied [41]. With a quantitative image

analyzer, the void content can be determined quickly and accurately. Approximately 20

cross-section areas are required for measurement because of the uneven distribution of

voids in fibre reinforced composites. High contrast is required between voids and matrix

and this is usually achieved by filling the voids exposed at the polished surface with

some material, such as filling the void with white powder and inking the surface black

[41].

2.5.4 Tension

Tensile testing of composite materials is much less complex at the present time

than either compression or interlaminar fracture toughness testing [42]. The

uniaxial tension test is the most fundamental test for determination of data for

design of structural components. Tensile tests are carried out to determine the

uniaxial tensile strength, Young’s modulus and Poisson’s ratio. For unidirectional

laminates, longitudinal tension and transverse tension are fibre- and matrix-

dominated properties, respectively.

The American Society for Testing and Materials method ASTM D3039 is widely

accepted for tensile testing of composites [42]. The specimen used in this

standard is straight-sided, and of constant cross-section with beveled end tabs for

load transfer. The purpose of tabbing is to introduce uniform loading into the

specimen as well as to protect the specimen surfaces. The tab materials are

required to have a similar modulus to the laminate material to match the strain,

and a similar coefficient of thermal expansion to the laminate material to avoid

32
bond failure during elevated temperature testing [15]. In order to determine

specimen strain, an extensometer or strain gauge is mounted on the specimen

centre and monitored during the test. Grinding with liquid coolants is

recommended to prevent thermal damage during the machining process.

2.5.5 Compression

The composite axial compressive test is considered to be the most difficult test

because of global buckling of the specimens [18]. A vast variety of test methods

and modification of test pieces has been developed to minimize the buckling.

However, there is still no consensus on the most appropriate test method.

There are three basic methods of introducing a compressive load into the

specimen: 1) end-loading, 2) loading by shear and, 3) combined loading.

Compressive strength for a single material system is different when determined

by different test methods because of differences in the load transfer, fabrication

practices, specimen preparation and geometry, and placement of the test coupons

in the test fixtures [15]. To be successful, a compressive test method must be

reliable, reproducible, and produce minimal scatter in the results.

2.5.6 Interlaminar fracture toughness

Interlaminar fracture toughness can be measured using loading modes I, II, and

III, as shown in Figure 2.11 [15]. Typically, interlaminar fracture toughness is

given as values of G IC or G IIC (Mode I and Mode II, respectively). There has been

considerable research and development into the determination of interlaminar

33
fracture toughness [15]. Standards organization such as American Society for

Testing Materials (ASTM) and Japanese Industrials Standards (JIS) have

evaluated and published several standard methods. All these methods involve

beam-type specimens, and require the measurement of applied load and the

displacement at which a delamination of known length will grow. Regardless of

whether the delamination grows stably or not, the load-displacement curve is used

to determine the interlaminar fracture toughness.

Figure 2.12 Diagram of Mode I, II and III interlaminar fracture test.

2.5.6.1 Mode I interlaminar fracture toughness

The typical double cantilever beam (DCB) specimen, according to the standard

test method ASTM D 5528 [18], is shown in Figure 2.12.

34
 Figure 2.13 Geometry of double cantilever beam specimen for Mode I.

The energy absorbed in making one unit area of crack is defined as the Mode I

toughness G IC (the critical strain energy release rate). Three data reduction

methods for calculating G IC value have been evaluated [43]. These consist of: a) a

modified beam theory (MBT), b) a compliance calibration method (CC) and, c) a

modified compliance calibration method (MCC). MBT is recommended because

it yielded the most conservative value of G IC for 80% of the specimens tested [15].

The MBT expression for GIC is as follow,

3 PG
GI (2.1)
2w(a  ' )

Where P is the load (N) and  is the cross head displacement (mm) at the point of load

P. The term, w, is the specimen width in mm, a is the delamination length (mm),

and ' is a modified parameter which is determined experimentally.

35
2.5.6.2 Mode II interlaminar fracture toughness

There have been many test methods proposed to measure the values of Mode II

interlaminar fracture toughnesṣGIIC [44]. Two of them have received the most

attention; one is three-point loaded the end-notched flexure (ENF) testing, standardized

by JIS; the other one is end-loaded split (ELS) test [15]. There are no international

standards for Mode II testing. The ENF test method is the most widely used to

determine the values of Mode II interlaminar fracture toughness, the only problem with

ENF test being the unstable crack propagation. The test method investigated by

Carlsson and Dharmawan has been widely used [45, 46]. Figure 2.13 shows the

geometry of DCB ENF specimen used in ENF testing.

Figure 2.14 Geometry of DCB specimens for Mode II ENF test.

The following equations are used to evaluate GII from test data:

36
 2 L3  3a 3
C (2.2)
8 E1 f bh 3

9a 2 P 2 C
G II (2.3)
2b(2 L3  3a 3 )

where C denotes compliance, L is the half-span length, a is the crack length, E1f is the

modulus of elasticity in the fibre direction measured in flexure, b is the specimen width,

h is the half specimen thickness, and P is the load.

2.5.7 Flexure testing

In flexure testing, beam specimens are subjected to a combination of non-uniform stress,

viz. maximum tension at the lower surface, maximum compression at the upper surface

and maximum interlaminar shear at the mid-plane [15]. Therefore, the failure can be in

tension, compression, interlaminar shear or a combination of the three. Accordingly,

the results can also be very similar to those from tensile, compressive or interlaminar

shear strength testing. This is the biggest difference between flexure testing and Mode II

(ENF) interlaminar fracture toughness testing. The most widely accepted test standard

for flexure strength testing is ASTM D 790 [47]. The geometry of the specimen is

shown in Figure 2.14.

37
 Figure 2.15 Geometry of three-point flexure testing specimen.

The flexure strength V f , the flexure strain H f and the modulus of elasticity E are

calculated using the following equations:

6 PL
Vf = (2.4)
2bd

6 Dd
Hf = (2.5)
(2 L) 2

V f 2 V f1
Ef = (2.6)
H f 2 H f1

where P is the load at a given point, L is the half-span length, b is the specimen width, d

is the thickness of specimen, D is the flexure deflection at any given point and the

subscripts 1 and 2 refer to predefined points. These points are selected at pre-specified

stress or strain in accordance with the appropriate materials specification or by specific

demand [47].

38
Figure 2.16 Stress distributions in (a) a Mode II ENF specimen and (b) a three-point

flexure specimen [48].

The stress distribution in a three-point flexure un-cracked specimen is different from that

in a Mode II ENF specimen. Figure 2.15 compares the stress distribution in a typical

specimen in a Mode II ENF test and a three-point flexure test using the same three-point

bending set-up [48]. In the Mode II ENF specimen, a shear traction W 0 is applied on the

crack surface with the same magnitude but in opposite directions on the two crack

surfaces. In the three-point un-cracked specimen, there is only the usual shear stress

applied along the mid-plane.

39
 Chapter 3

Experimental Procedure

3.1 Introduction

The aim of the present work was to evaluate the possibility of using a single part liquid

adhesive as a self healing system for composite materials. The focus of the work was on

composites used in non-aerospace applications, such as infrastructure and marine. Glass

fibre vinyl ester composites are commonly used in such applications and were the

composites examined in this study.

As noted in the previous chapter, single part thermosetting adhesives can cure by an

activation process such as catalyzation by moisture, the absence of an inhibitor or

reaction with a component embedded in the matrix. Moisture curing adhesives were

considered particularly attractive since these would be activated for surface connected

cracks in coastal environments and may also be activated in embedded cracks by

diffusion of moisture through the matrix. Accordingly, cyanoacrylate and polyurethane

were selected as candidate adhesives for this study.

40
Single part adhesives can also cure by solvent evaporation which could occur by

diffusion of the solvent into the composite. Polystyrene cement, which cures by

evaporation of an organic solvent, and PVA glue, which cures by moisture evaporation,

were selected as example of this class of adhesive.

A novel concept also examined was the use of an organofunctional silane. These are

used as coupling agents on glass fibres because of their ability to bond glass to an

organic matrix. It was thus considered that they might be effective as a healing agent for

glass fibre composites

Hollow glass fibres were selected to store the healing agent, due to their ability to

provide structural reinforcement in addition to being sufficiently brittle to fracture when

encountered by a crack. Fine glass capillary tubes were used to simulate the hollow

glass fibres.

The stability of the adhesives in the sealed glass capillary tubes was examined first. The

adhesives considered satisfactory were then used to bond fractured Mode 1 samples

back together and the strength recovery measured using Mode 1, Mode 2 and flexural

testing. The glass fibre vinyl ester composite specimens used to evaluate strength

recovery were fabricated by hand lay up and then characterized to determine the density,

fibre and resin fractions and void content.

3.2 Adhesive Storage Stability

3.2.1 Materials

Glass capillary tubes supplied by Drummond Scientific were used to contain the

41
adhesives for the storage stability tests. The capillary tubes had an external diameter of

1 mm and an internal diameter of 0.7 mm giving a 50% hollowness. The tubes were

used in lengths of 75 mm. The adhesives used are given in Table 3.1 which also lists the

manufacturer, product name, curing mechanism and viscosity.

Table 3.1 Healing agent candidates for self healing composite

Curing
Adhesives Manufacturer Product name Viscosity
mechanism
Cyanoacrylate UHU UHU super glue Moisture About 1 cps
Sika
Polyurethane Sikaflex®-298 Moisture 3000 cps
Australia
Model glue Solvent About 50
Humbrol
(Polystyrene based) evaporation cps
Solvent
PVA glue Bostik 3000 cps
evaporation
Silane Coupling 3-[Tris(trimethylsiloxy)silyl] Chemical
Dow corning 1.6 cps
Agent -propylamine reaction
Anaerobic Oxygen
Loctite 1000 cps
adhesives absence

3.2.2 Experimental procedure

Each adhesive was infused into the hollow glass capillary tubes using a vacuum assisted

filling technique. Since most of the adhesives could cure rapidly on exposure to the

ambient environment, the filling procedure was undertaken in a low moisture and low

temperature environment. To reduce the accelerating influence of moisture on the cure,

the hollow tubes were stored in desiccant prior to the filling trials.

Care was taken during the infusion process to avoid leaving any air in the hollow tubes.

The ends of the hollow tubes were sealed immediately with silicone sealant following

the filling procedure. To simulate composite fabrication the glass capillary tubes were

42
placed individually in the middle of a ‘dog-bone’ shaped specimen mold and set in room

temperature curing epoxy resin. Epoxy resin rather than vinyl ester was used since this

provided better transparency.

To evaluate the storage life of the different adhesives, samples for each adhesive were

stored for 7 and 14 days. Each specimen was then loaded in an Instron 1185 causing the

tube to undergo fragmentation. If the adhesives stored inside the hollow tubes was still

liquid it flowed out of the tubes and filled the cracks. Figure 3.1 shows specimens with

embedded hollow glass tubes.

Figure 3.1 Hollow glass tubes and adhesive stability test specimens.

3.3 Bonding efficiency

3.3.1 Introduction

The adhesives providing good storage stability inside the hollow glass tubes were
43
examined for their bonding efficiency in glass fibre reinforced polymer matrix

composites. This was done by carrying out Mode I and Mode II interlaminar fracture

toughness testing, as well as three-point flexure testing, on samples that had been

bonded together using the selected adhesives. The fracture toughness tests were done to

examine the efficacy of the bond under Mode I and Mode II loading while flexure

testing was done to simulate service behaviour.

The specimens were cut from laminates fabricated using the hand lay-up process.

Because of the possible variability from the hand lay up process the specimen density,

fibre content and void content were measured for each laminate.

The specimens were conditioned to 2°C and 50% RH according to ASTM standard D

618 [49] prior to testing, in order to obtain reliable comparisons between each other due

to the influence of temperature and humidity on the properties of materials. After testing,

scanning electron microscopy (SEM) was used to examine and compare the different

fracture surfaces. These methods are discussed in detail in the following sections.

3.3.2 Materials and Manufacturing

3.3.2.1 Laminate manufacturing

The laminates were manufactured from E-glass plain weave woven fabric (aerial weight

323 g/m2) and SPV1265 vinyl ester resin, both supplied by FibreGlass International

(FGI). A 30×300 glass plate, pre-cleaned with acetone then dried, was used as the tool

to manufacture the laminate panels. An FEP release film was placed over the dried

surface of the glass to facilitate removal of the laminates after cure.

44
The glass fibre fabric was cut to the required size. The correct fibre orientation was

produced by using a right-angled template. During the cutting procedure, the fibre

fabrics were kept flat and straight in order to get accurate fibre direction as is required

for composite specimens.

The vinyl ester resin and hardener were mixed according to the manufacturer’s

recommendation (100:1). The mixture was stirred with a spatula until no interphase

between the components could be observed. After mixing, the resin was vacuum

degassed for 5 min to remove entrapped air bubbles. Mixing and degassing were carried

out quickly due to the limited gel time (45 min at 23 ć of the vinyl ester resin system.

Quasi-isotropic laminates were manufactured with two different thicknesses. For Mode

I interlaminar fracture toughness testing, a [(±45°), (0/90°)]3S laminate lay up was

chosen. For Mode II end notched flexure (ENF) testing, a [(±45°), (0/90°)]4S lay up

procedure was chosen. In these two types of laminates, a 12.7 m thick Teflon film was

placed for a length 50 mm along the middle plane, to produce the precrack required for

the double cantilever beam (DCB) specimens, as shown in Figure 2.12 & 2.13. For the

three-point flexure specimens, a [(±45°), (0/90°)]4S lay-up sequence was used without

any Teflon insert. Two separate test panels were fabricated for each of the three tests.

The fabric layers were laid up on the glass, ply by ply. A brush was used to spread the

resin on each layer and a roller was used to squeeze out the air bubbles. After the last

layer was laid up, extra resin was applied on the top surface in order to obtain a flat

surface. The final lay up was placed in a vacuum bagging assembly for approximately

one hour to remove any remaining entrapped air from the laminate. As shown in Figure

3.2, a release film was placed between the laminate and glass plate to facilitate removal

45
of the cured laminate, while the glass plate was used to provide a flat surface for the

laminate. A layer of breather cloth was placed on top of the laminate to absorb the

excess resin and achieve an optimal vacuum level. The arrangement was checked for

leaks at the beginning of vacuum application.

Figure 3.2 Vacuum bagging assembly to cleanse air bubbles in laminates.

3.3.2.2 Cutting and Conditioning

The laminates were postcured at room temperature for 10 days, and then cut into

specimens of the sizes required by the relevant test standards. The cutting was carried

out using a water lubricated diamond saw. The laminates were held tightly during

cutting to ensure that the edges of the test specimens were straight.

According to ASTM test standard D 5528 [43], the specimens for Mode I testing were

cut with dimension of 130 mm by 25 mm, with the un-bonded 50 mm insert in the

longitudinal direction. The specimen dimension for Mode II ENF testing was 160 mm

by 20 mm, with 55 mm pre-crack in the longitudinal direction, followed the method

46
described by Carlson et al. [44, 45]. In addition, the specimens for three point flexure

testing were cut with dimension of 180 mm by 20 mm, according to ASTM test

standard 790 [47].

After cutting, the cut edges of the specimens were ground using 120 grit emery paper.

The specimens were stored in a conditioning chamber for 48 hours prior to testing at a

temperature of 23 ć and a relative humidity of 50% according to ASTM D 618 [49].

This procedure was aimed at bringing the materials into equilibrium with standard

laboratory conditions and obtaining reproducible results.

3.3.3 Properties

3.3.3.1 Determination of density

The density of the laminates was measured according to the method described in section

2.4.1. Three rectangular specimens, 30 mm by 15 mm, were cut from each laminate

using a band saw. The cut edges were polished with P600 emery paper to obtain flat

surfaces, and the specimens then ultrasonically cleaned in ethanol and dried in an oven

at 50 ć for 1 hour. The density determination set-up was designed according to the test

method ASTM D 792 [38], as shown in Figure 3.3.

Figure 3.3 Density determination set-up

47
Each specimen was weighed in air to the nearest 0.0001 g (w1), following which, each

specimen was immersed in distilled water for 12 hours to reach saturation. Once

saturated, the specimens were weighed again (w2). Following this, the specimens were

placed on the pan and completely immersed in water. Any bubbles around the sample

and holder were removed. The apparent mass of the suspended specimen was measured

as w3 (this included the mass of specimen and the wire immersed in the water). Finally,

the wire was immersed in the water to the same depth and then weighed as ww. The

specific gravity was calculated using the following equation:

w1
U1 (3.1)
w2  ww  w3

The density of specimen was calculated using equation 3.2:

U U1 u 997.5 (3.2)

The procedure was repeated for 5 specimens to obtain an average density value.

3.3.3.2 Determination of fibre and resin content

The matrix burn off method (ASTM D 3171 [39]) was used to measure the fibre content

of the laminates. The matrix was burned off in a muffle furnace which was set at a

temperature of 500ć. Each specimen was weighed to the nearest 0.0001g (w1), then

placed in a desiccated crucible and weighed (w2). The crucible was placed in the muffle

furnace which was already preheated to 500ć and the matrix was burned off while the

fibres remained in the crucible. After 3 hours the crucible was taken out of the furnace

48
and allowed to cool in a sealed desiccator before being weighed again (w3). The volume

percent of fibre content was then calculated using equation 3.3:

w1  w3  w2 U c
Vf u u 100% (3.3)
w1 Uf

where U c is the specimen density (measured in section 3.3.1) and U f is fibre density,

both measured in g/ml. The volume percent of matrix content ( Vm ) was calculated

according to:

w2  w3 U c
Vm u u 100% (3.4)
w1 Um

where U m is the matrix density in g/cm3.

3.3.3.3 Determination of void content

The measured specimen density and the fibre and resin densities supplied by the

material supplier were used to determine the void content of the laminates. According to

the test method ASTM D 2734 [40], the theoretical density T can be calculated as

follows:

T 100 ( R / D  r / d ) (3.5)

where R is resin content, D is density of resin, r is fibre content, and d is density of

fibres.

The void content V was then calculated as:

49
 V 100% u (T  M ) T (3.6)

where M is the measured density of the specimen.

3.3.4 Mode I interlaminar fracture toughness testing

The width and thickness of each specimen were measured at five locations and the

average values used. Both edges of the specimen just ahead of the insert were coated

with a thin layer of water-based typewriter correction fluid, to aid in visual detection of

delamination onset. The first 5 mm from the insert on either edge were marked with thin

vertical lines every 1 mm, while the remaining 20 mm was marked with thin vertical

lines every 5 mm. The delamination length was the sum of the initial delamination

length a0 plus the distance of further delamination propagation.

Piano hinges were attached to the specimens as shown in Figure 2.12, and mounted in

the grips of an Instron Model 1185 universal testing machine. An optical microscope

(20 times magnification) was mounted in front of one edge of the specimen to observe

the motion of the delamination as it grew. The Mode I testing set-up is shown in figure

3.4.

The load was applied at a crosshead displacement rate of 0.5 mm/min. As the loading

started, the delamination was observed visually and recorded with an accuracy of± 0.5

mm. As soon as the delamination commenced to grow from the end of insert (growth

past the initial delamination length a0), the location on the delamination curve was

marked as a0. The delamination was continually observed as it progressed along the

edge of specimen, with the position on the delamination curve at each of the five 1mm

50
increments being marked as a1, a2,… an, and then similarly for each of the 5 mm

increments.

The loading was stopped when the delamination extended 30 mm. The specimen was

unloaded at 10 mm/min, and removed from the testing machine. After testing, the

specimens were split open along the remaining length of the delamination plane for use

in the subsequent adhesive bonding tests.

Figure 3.4 Set-up of Mode I interlaminar fracture toughness testing.

A solvent cleaning method was applied to treat the failed specimens’ surfaces. The

specimens were ultrasonically cleaned in ethanol for 5 minutes and air dried. Following

cleaning, the specimens were immediately bonded back together using the using the

candidate adhesive sealing systems which had been found to have good stability when

stored in the glass capillary tubes. The adhesives were applied from the tip of the

51
precrack to the end of the specimen, as shown in Figure 3.5, and the specimens then

stored for 14 days under ambient conditions, with appropriate pressure applied, to allow

full curing. The edges of the specimens were subsequently ground using 400 grit

abrasive paper to remove any excess adhesive. The specimens then underwent Mode I

testing again and the results were recorded.

Figure 3.5 Adhesive-bonded Mode I interlaminar fracture toughness specimen geometry.

There are several methods for calculation of Mode I interlaminar fracture toughness GIc,

according to the ASTM method [43]. The modified beam theory (MBT) method was

used in the present study. To determine the solid laminate and adhesively-bonded

interlaminar fracture toughness, the critical Mode I strain energy release rate for crack

propagation GIc was calculated. According to ASTM standard D 5528, the onset of

crack propagation was determined by the deviation from linearity. The beam theory

expression for the strain energy rate calculation is as follows:

3PcGc
G Ic (3.7)
2b(a  ' )

where Pc is the applied load at the point of deviation in linearity of the

load-displacement curve, Gc is the crosshead displacement at the same point with Pc ,

52
b is the specimen width, a is delamination length, and ' = a modified parameter
(determined experimentally).

3.3.5 Mode II interlaminar fracture toughness test

End notched flexure (ENF) testing was employed to determine Mode II interlaminar

fracture toughness, GIIc, as discussed in section 2.4.6.2. The cutting and conditioning

procedures were the same as previously described in section 3.3.2.2. Three groups of

specimens were prepared for the testing in order to compare the bonding efficiency of

relevant adhesives. As for the Mode I tests, the first group was the original specimens.

The second group was again obtained by splitting open these specimens after testing.

These were then ultrasonically cleaned in ethanol and immediately bonded back

together using the selected adhesives, shown in Figure 3.6, as described in the previous

section. A third group of specimens was also tested. These were again group 1

specimens which had again been subsequently split open. These were tested without

being bonded back together to obtain the baseline load displacement response for

unbonded test pieces.

P
a0 Adhesive layer

2d

L b

Figure 3.6 Adhesive-bonded Mode II ENF test specimen.

53
The specimens were loaded in three-point bending using an Instron Model 1185

universal testing machine at a crosshead rate 0.5 mm/min. This low speed was used with

the aim of obtaining stable crack propagation. Load versus deflection (P G ) curves

were recoded for each specimen, with the deflection of the specimens being recorded as

crosshead displacement.

The Mode II strain energy release rate, GIIc, was calculated for each group using the

formula below:

9P 2 a 2
G IIc (3.8)
16b 2 Ed 3

where P is peak load at failure, a is the initial crack length, b is specimen width,
E is elastic modulus, and d is the specimen half-thickness.

3.3.6 Three-point flexure testing

Three-point flexure testing was performed using a similar set-up to Mode II end notched

flexure testing. A laser extensometer was used to measure the deflection of the

mid-point of the specimens from the loading nose displacement. The crosshead rate was

set at 8.2 mm/min, as determined using the following equation from ASTM D 790 [47].

R ZL2 6d (3.9)

where R denotes the rate of crosshead motion, Z is the rate of straining of the outer fibre

(equal to 0.01), L is the span length, and d is the specimen thickness.

54
 P
Adhesive layer

L b

Figure 3.7 Adhesive-bonded three-point flexure testing specimen.

The total length of the specimens was 160 mm with width b = 20 mm, thickness d =

4.3- 4.5 and span L = 140 mm. As for the Mode II testing three groups of specimens

were again tested: the original laminates, split open laminates, and split open and

re-bonded laminates. The bonded specimens were prepared in a similar manner to that

used for the Mode II ENF test, except that the adhesives were applied without starter

crack inserts, as shown in Figure 3.7. A minimum number of six specimens were

prepared for each group.

Prior to applying the load, care was taken to make sure the loading nose was located at

the mid-point of the span. A load-deflection curve was recorded to determine the flexure

strength and elastic modulus of the specimens. The test was stopped when the

specimens failed at the mid-point. The flexure strength V f and modulus of elasticity

E f was calculated using equations (9) and (10), respectively.

Vf 3PL 2bd 2 (3.10)

E L3 m 4bd 3 (3.11)

55
where P is load at mid-point, L is support span, b is width of specimen, d is depth of
specimen, and m is slope of the tangent to the initial straight-line portion of the
load-deflection curve.

3.3.7 Fractographic examination

The fracture surfaces of the Mode I and Mode II interlaminar fracture toughness

specimens were examined after testing using scanning electron microscopy (SEM). The

specimens were cut to the required size, and then coated with a thin layer of gold to

provide conductivity. A Hitachi S3400 scanning electron microscope was used to

examine the fracture surfaces. This microscope is well suited to investigation of

polymer and biological materials.

56
 Chapter 4

Investigation of storage stability

4.1 Results

The results for storage stability of the self-healing agent candidates inside small

diameter glass tubes after 7 and 14 days are shown in table 4.1. Cyanoacrylates,

polyurethane and PVA glues showed very poor stability inside the glass tubes,

particularly the cyanoacrylates, with the adhesives even beginning to cure during the

sealing procedure. Even under the infusion conditions of low moisture and low

temperature which were used, the cyanoacrylates were totally cured after only 7 days. It

was more difficult to fill the glass tubes with the polyurethane and PVA adhesives, since

their viscosity was higher, table 3.1.

The storage life of the polyurethane and PVA adhesives was longer than that of the

cyanoacrylates, with both adhesives still being fluid after 7 days. However there was

negligible flow after 14 days. The silane coupling agent and polystyrene adhesives

showed much better stability. Both remained totally uncured after storage inside the

capillary tubes for 14 days, and these were therefore selected as candidates for a self

57
healing system.

Table 4.1 Results of stability examination

Storage period
Adhesives
7 days 14 days

Cyanoacrylates Totally cured

Polyurethanes Paste, partly cured Thick paste, negligible

flow
Polystyrenes Liquid phase, fluid Liquid phase, limited
flow
PVA glues Paste, fluid Paste mostly cured

Silane Coupling Agent Liquid phase, fluid Liquid phase, fluid

4.2 Discussion

The long term efficiency and stability is a key consideration in the search for new

healing agents, due to the aim of self-healing, which is the repair of the material

structure without external work. If the healing agent has poor stability, replacement

would be required, defeating the purpose of self-healing. The ideal stable period should

be many (eg, 25) years. Long term stability testing was not possible in the present study

but the results were able to establish which adhesives would not be suitable. The fast

curing of cyanoacrylates, polyurethanes and PVA glues appears to preclude the use of

these adhesive systems as self-healing agents when stored in small-diameter hollow

glass fibres.

Cyanoacrylates were also tested by Bleay [8], to determine whether they could be a

58
healing agent for self-healing composites. A similar result was observed, with

cyanoacrylates even starting to cure during the filling process, blocking the ends of the

hollow fibres, and preventing further filling. Bleay proposed that it was due to the small

internal dimensions of the hollow fibres, which was similar to the size of cracks,

causing a tendency for the adhesives to cure. In the present study, cyanoacrylates were

the first materials considered for testing due to the strong bonding they provide. Filling

of the glass tube fibres in a low moisture and low temperature environment was tried,

but cure still occurred rapidly. This is likely due to the Na+ and Ca2+ ions present in

glass, which are known to catalyze cyanoacrylates.

The filling procedure is impossible to undertake without contact with moisture, and this

is a further reason for the poor storage stability of cyanoacrylates. The adhesive starts to

cure instantly upon contact with moisture, once the container is opened. The same

problem also occurs with polyurethanes. There is almost no method to stop these two

types of adhesives from curing in a normal environment, except by undertaking the

experiments in vacuum, which is not considered to be practically feasible.

In addition, due to the high viscosity of polyurethane and PVA adhesives compared to

the other candidate adhesives, these two types of adhesives have very limited practical

use as healing agents. As noted above the polyurethane and PVA adhesives were

difficult to infuse into the glass capillary tubes and this would be expected to be worse

for the finer hollow tubes which are desirable in a self healing system. In this respect it

is noted that in previous work Trask reported that the viscosity for a self-healing agent

should be below 1000 cps for hollow glass fibres with an external diameter of 60 m

and 50% hollowness [50]. As seen in Table 3.1 the polyurethane adhesive and the PVA

adhesive both have a viscosity of 3000 cps. Additionally, once the materials have been
59
exposed to air, the slow curing that will continue to occur will prevent the adhesives

from flowing easily out of the tubes after fracture of the composite and storage tube.

The silane coupling agent showed good stability over the period examined. It is

probable that some reaction between the silane and the inside of the glass tube would

have occurred but this would be expected to involve only a monolayer leaving the

remainder of the silane unaffected. In view of the absence of any visible change in the

silane, and considering the nature of the silane reaction (as discussed in chapter 2.4.3.1),

it is considered that it has an excellent prospect for long term stability. The polystyrene

cement also exhibited good storage stability. This is considered to be because the

solvent, which inhibits curing of the adhesive, could not disperse and evaporate through

the glass tube or silastic sealing material. Again, the long term stability of this adhesive

would be expected to be good.

In light of the stability examination, the silane coupling agent and the polystyrene

cement were deemed to be the most suitable of the candidate adhesives for further

investigation as self-healing agents.

60
Chapter 5

Investigation of bonding efficiency

5.1 Laminate properties

Prior to testing the bonding efficiency, the density, fibre content, resin content and void

content, of the laminated panels fabricated for each test were determined and are

presented in this section. These properties were measured to assess whether the

specimens from the two different laminates, produced for each type of test, possessed

significantly different properties as a result of any slight differences in the hand lay-up

procedure. Table 5.1 gives the measured values of thickness and density of the two

panels fabricated for each type of test. Due to the 12 layer lay-up used, the Mode I test

specimens were thinner than the other two groups of test specimens, which were

manufactured with 16 layers.

61
 Table 5.1 Measured values of density and thickness for glass/vinyl ester laminates

Testing type Mode I ENF Flexure

Laminate Panel 1 2 1 2 1 2

a 3.19 3.33 4.37 4.47 4.41 4.34

Thickness b 3.29 3.37 4.43 4.45 4.32 4.37
(mm)
c 2.34 3.27 4.30 4.39 4.27 4.40

Ave 3.28 3.33 4.36 4.43 4.33 4.37

Density a 1.53 1.46 1.51 1.57 1.66 1.71

(g/cm3) b 1.51 1.49 1.50 1.60 1.70 1.64

c 1.56 1.51 1.55 1.56 1.66 1. 68

Ave 1.53 1.49 1.53 1.58 1.68 1.68

Table 5.2 gives the results of the fibre content, resin content and void content

measurements. The intended final thickness of the panels was 3mm for the 12-layer

panels, and 5mm for the 16-layer panels. The predicted fibre volume fraction for both

types of panel was 40%, based on the density of E-glass fabric of 2.7 g/cm3 and the

density of vinyl ester resin of 1.35 g/cm3, according to the specification sheets from the

material supplier (Fiberglass International). The results show that the physical properties

of glass/vinyl ester laminates were similar to those predicted. The higher fibre fraction

content of the flexure test specimens is clearly the reason why the density of this group

of specimens is higher than the other two groups of test specimens.

62
Table 5.2 Measured values of fibre content, resin content and void content for

glass/vinyl ester laminates.

Testing type Mode I ENF Flexure

Laminate Panel 1 2 3 4 5 6

Fibre a 47.122 49.028 45.446 47.025 50.200 48.120

Content b 48.232 47.675 46.504 48.384 46.618 47.333
(wt%)
c 46.624 48.852 43.784 47.626 47.214 46.727

Ave 47.326 48.518 45.246 47.678 48.011 47.393

Resin a 52.878 50.972 54.554 52.975 49.800 51.88

Content b 51.768 52.325 53.496 51.616 53.382 52.667
(wt%)
c 53.376 51.142 54.754 52.374 52.786 53.273

Ave 52.674 51.482 54.754 52.322 51.989 52.607

Void a 9.70 8.76 9.96 9.33 10.03 9.75

Content b 8.37 8.94 9.76 9.28 9.65 9.75
(%)
c 9.14 9.14 9.79 9.64 9.34 9.54

Ave 9.07 8.95 9.84 9.42 9.67 9.68

5.2 Mode I interlaminar fracture toughness

Figure 5.1 shows a typical load versus displacement (P- G ) curve at ambient conditions

of temperature and relative humidity recorded from Mode I testing of a solid laminate, a

silane-bonded specimen, and a polystyrene bonded specimen. Both the silane and

polystyrene bonded specimens show similar loading characteristics to the solid laminate

up to a load of approximately 8N but delamination then occurs with no further increase

in load. In contrast, the load continues to increase up to a peak load of approximately 80

N for the solid laminate. While the silane bonded specimen continues to delaminate at

essentially constant load once its peak load is reached the polystyrene bonded specimen

63
delaminates at an ever decreasing load.

Figure 5.1 Load-displacement curves for Mode I interlaminar fracture toughness testing

for a solid laminate, a silane-bonded specimen and a polystyrene-bonded specimen.

It was not possible to measure the propagation interlaminar fracture toughness GIc

accurately in the adhesively-bonded specimens since the fracture propagation was too

rapid. Instead, the interlaminar fracture toughness GIc was determined using the load

and deflection measured at the point of deviation from linearity (NL) in the load –

displacement curve [43]. This is known as the initiation fracture toughness and is

typically lower that the propagation fracture toughness.. The NL GIc is usually used to

generate delamination failure criteria in durability and damage tolerance analyses of

laminated composite structures, according to the corrected beam theory which generates

the following equation:

64
 3PG
G Ic (5.1)
2b(a  ' )

Where P is the critical load at NL point, G is the deflection in the beam corresponding

to load P, a is the initial crack length and b is the specimen width.

Table 5.3 gives the results of the energy release rate GIc determined from the Mode I

interlaminar fracture toughness tests. It should be noted that the average value of GIc of

the polystyrene-bonded specimens of 8.73 J.m-2 is negligible compared to the value of

interlaminar fracture toughness for the original solid laminate, 1157 J/m2. The bonding

efficiency is only 0.75 %. In contrast, for the silane-bonded specimens, the average

value of fracture toughness is 56.2 J/m2, which is significantly better than that of the

polystyrene-bonded specimens and equates to a bonding efficiency of 4.9 %.

Table 5.3 Adhesive-bonded fracture toughness results

Mode I interlaminar fracture toughness

Specimen
Specimen a0 (mm) Pc (N) Gc (mm) b (mm) G Ic (J.m-2)
Mean
Solid
33.5 82.30 7.7319 24.44 1165.8
laminate
33.5 81.43 9.0094 25.61 1282.7
33.4 78.81 7.7188 25.57 1068.4 1157.0
33.4 76.96 7.9188 24.71 1107.6
33.4 74.66 8.7897 25.40 1160.3

Silane-bond 33.5 8.33 3.6819 25.61 53.6

ed laminate 33.4 8.89 3.8569 25.57 60.2 56.2
33.4 9.24 3.3473 25.40 54.7
Polystyrene 33.3 5.71 0.7909 24.47 8.3
-bonded 33.4 5.49 0.7197 25.52 7.0 8.73
laminate 33.3 6.83 1.0619 25.22 10.9

65
5.3 Mode II End Notched Flexure testing

Pure Mode I adhesive joint testing is the most aggressive test for interlaminar fracture

toughness and a composite is unlikely to experience this stress condition in real-world

applications. It was decided therefore that Mode II end notched flexure (ENF) testing

should be carried out to gain a more complete picture of the bonding efficiency by

determining the value of GIIc. This test was only carried out on the silane-bonded

specimens due to their higher bonding strength, as the very poor performance of

polystyrene adhesive indicated that it was an unsuitable self-healing candidate.

Typical load-displacement ( P  G ) curves recorded for the Mode II ENF tests for the

solid laminate specimen, the silane-bonded, and the non-bonded failed post-Mode I

specimen are shown in figure 5.2. The delaminated and the silane-bonded Mode II test

specimens are shown in figure 5.3. It can be seen that the curve for the silane-bonded

specimen follows the same initial path as that of the solid specimen. However, as in the

Mode 1 test, this only occurs for about 10% of the load range with the curve then

dropping suddenly when the shear strength between the two bonded laminates reaches

the bonding strength of silane. Thereafter, the curve is the same as that for the

non-bonded specimen.

66
Figure 5.2 Load-displacement curve in Mode II ENF test for a solid laminate, a

silane-bonded specimen and a non-bonded post-failed Mode I specimen.

Figure 5.3 Photograph of a) delaminated Mode II specimen, and b) silane-bonded

specimen.
67
 Table 5.4 Results of Mode II ENF test

Mode II ENF test

Repair
-2 Mean
Specimen P (N) a0 GIIc (J.m ) Percentage
GIIC
(%)

126.54 45.25 3593

115.36 45.17 2957
Solid
119.73 45.00 3182 3159.5 100
laminate
113.57 44.88 2847
121.34 44.79 3219

24.13 44.77 127.9

Silane 28.52 44.90 179.7
-bonded 29.64 44.83 193.5 150.3 4.7
specimen 22.21 45.16 110.3
25.21 44.83 140.0

The Mode II interlaminar fracture toughness GIIc values obtained are given in Table 5.4.

The test was conducted according to the method described by Wade et al. [51]. In the

test, the compressive force applied by the loading noses pushed the delaminating halves

of the specimens together, obscuring the actual location of the crack front. As a result of

this, the Mode II strain energy release rate, GIIC, was determined in the same way as for

Mode I, i.e, at the point of deviation from linearity in the load – displacement curve

(NL), using the equation given below:

9P 2 a 2
G IIc (4.2)
16b 2 Ed 3

where P is the critical load at the NL point, a is the initial crack length, b is the

specimen width, d is the half-thickness of specimen, and E is the laminate elastic

modulus. The results show that the silane coupling agent provides a bonding efficiency

of 4.7% in Mode II loading which is very similar to that obtained in Mode 1.

68
5.4 Three-point flexure testing

Three point flexure testing was also carried out to simulate the service loading

commonly experienced in a structure. Typical load-displacement curves for the

silane-bonded delaminated specimen and the non-bonded delaminated Mode I specimen

are given in figure 5.4 and compared with the flexural behaviour of the solid laminate.

As in the Mode II ENF test, the flexural stress versus strain curve for the silane-bonded

laminate was initially the same as for the solid specimen but then dropped abruptly at

about 10% of the peak load after which the behaviour was similar to that of the

unbonded specimen.

Figure 5.4 Stress-strain curves of a solid laminate, a silane bonding laminate and a

non-bonded post-failed Mode I specimens in three-point flexure test.

69
In order to ascertain the effect of time on the bonding efficiency of the silane coupling

agent, another set of silane-bonded specimens was stored under standard laboratory

environmental conditions (23oC, 50%RH) for 28 days before being tested in three-point

flexure. Figure 5.5 shows a typical stress-strain ( V  H ) curve obtained from the

experiments. It can be seen that the repair efficiency of the silane coupling agent has

more than doubled with the longer repair time allowed.

Figure 5.5 Stress-strain curve of a solid specimen and a silane bonded specimen in

three-point flexure test.

The results from the flexure testing are given in Table 5.5 The flexure strength ( V f )was

determined as the critical point at failure, according to equation 4.3:

3PcL
Vf (4.3)
2bd 2

where Pc is the critical load at failure, L is the specimen length, b is the width of the

70
specimen, and d is the depth of the specimen.

As seen from the data, the efficiency of bonding increased substantially with the longer

cure time, with the silane-bonded specimens cured for 28 days achieving a 22% repair

efficiency compared with a repair efficiency of only 7% for the specimens cured for 14

days.

Table 5.5 Results of three-point flexure testing.

Three-point flexure testing

Repair
Flexure strength Specimen
Specimen P (N) Percentage
(MPa) Mean
(%)

378.4345 219.9
371.5045 215.8
Solid laminate 379.0047 220.2 219.0 100
382.4329 222.2
372.9534 216.7

23.7906 13.8
Silane-bonded, 29.4473 17.1
16.0 7.3
stored 14 days 27.8657 16.2
29.0997 16.9

Silane-bonded, 81.2027 47.2

47.9 21.9
stored 28 days 83.6674 48.6

5.5 Fractography

The fracture surfaces of the glass/vinyl ester solid laminates after Mode I and Mode II

testing are shown in Figures 5.6 and 5.7. The SEM micrographs clearly reveal that crack

propagation resulted in markedly different fracture surfaces for the Mode I and Mode II

71
tests. The Mode I fracture surface exhibits a very brittle fracture showing bare glass

fibres (fig. 5.7) with very little matrix deformation. In contrast, the Mode II fracture

surface shows extensive matrix deformation, with matrix drawing oriented

predominantly out of the plane (fig. 5.7).

SEM images of Mode I test specimen fracture surfaces

a) Surface with exposed fibres b) Surface with resin matrix

Figure 5.6 SEM images of Mode I fracture surfaces of glass/vinyl ester composite

specimen: a) surface with exposed fibres, and b) matrix dominated surface.

72
 SEM images of Mode II ENF test specimen fracture surfaces
a) Surface with exposed fibres b) Surface with resin matrix

Figure 5.7 SEM images of Mode II (ENF) fracture surfaces of glass/vinyl ester composite

laminates: a) surface with exposed fibres, and b) matrix dominated surface.

Figure 5.8 shows a typical fracture surface of a silane-bonded laminate. It can be seen

that the fracture surface exhibits a rough, complex morphology following crack

propagation in the cured silane coupling agent, indicating significant plastic

deformation. This confirms that the silane coupling agent provides a significant level of

bonding to the glass in the composites.

73
 SEM images of Silane-bonded Mode I test specimen fracture surfaces
a) Surface with exposed fibres b) Surface with resin matrix

Figure 5.8 SEM images of Silane-bonded fracture surfaces of glass/vinyl ester composite

laminate after interlaminar fracture toughness testing: a) surface with exposed fibres, and

b) matrix dominated surface.

5.6 Discussion

The polystyrene adhesive provided only poor bonding efficiency for the glass

fibre/vinyl ester composites, with less than 1 % repair, when tested in Mode I. The

adhesive was able to bond the two surfaces back together, indicating that the solvent had

diffused out of the polystyrene at the bondline, but the results indicate that the bond was

very weak, at least in Mode I loading.

74
Compared to polystyrene adhesives, the bonding efficiency of the silane coupling agent

was much better and improved considerably with increased curing time. When tested in

three-point bending, a bonding efficiency of 22% was obtained after allowing a 28 days

cure. This was three times greater than that observed when the specimens were cured

for 14 days The improvement in bonding efficiency is considered to be attributable to

the longer exposure to moisture in the ambient environment, which would lead to more

silanols from more extensive hydrolysis of the hydrolysable groups (XO) in the silane

coupling agents. The longer the time that a silane coupling agent is in contact with

moisture in the ambient environment, the better is the degree of curing.

In previous work Bleay [1] used a two-part epoxy resin as the healing agent for samples

that had undergone representative impact. Four point bending tests were conducted on

the repaired samples and a healing efficiency of 55% was obtained. White [9] used

dicyclopentadiene (DCPD) monomer and Grubbs’ catalyst as healing agent with a

microcapsule self-healing approach, and gained an average healing efficiency of 60 %.

The present work was undertaken as an initial study into the use of single part adhesives

to avoid the in-situ mixing problems inherent in two part systems. While the bonding

efficiency obtained in the present study was only about 40% of that obtained for the two

part systems mentioned above the results are considered to be very encouraging. The

work has demonstrated that substantial strength recovery can be obtained using silane as

the adhesive and the level achieved may be beneficial in some applications. Moreover,

there may be scope for further improvement by optimizing the silane to the matrix resin

system. The observation that strength recovery increases with time is also encouraging.

Further strength recovery may occur with longer time and this would be worth

examining in a future study.

75
The work also showed that the strength recovery measured in Mode I and Mode II tests

was also reflected in the results obtained from flexural testing. This indicates that the

simpler flexural test can be used reliably as a screening test for candidate self healing

systems.

76
 Chapter 6

Conclusions

6.1 General conclusions

In order to find a new single-part self-healing agent for self-healing composites, several

types of single-part adhesives and resins were considered and tested according to the

critical factors of storage life and bonding efficiency. Focusing specifically on the

examination of storage stability and bonding efficiency to polymer matrix composites, a

range of experimental techniques were used to examine the suitability of the healing

system candidates. The results show that the search for new single-part self-healing

systems is limited by the difficulty of obtaining a suitable combination of appropriate

utility, viscosity and cure schedule. A silane coupling agent was found to be a potential

healing agent, but further research is still necessary to measure longer duration storage

stability and the effect of increased cure time on bonding efficiency. The detailed results

are briefly summarized below:

1. Two-part healing systems harden on reaction of a hardener and a resin, requiring

simultaneous release of separately stored resin and hardener. Compared to these,

single-part systems can catalyze more simply. However, the storage stability inside

77
 small hollow glass fibres is critical and is limited for a number of potential

candidate materials. Moisture catalyzed adhesives — cyanoacrylates and

polyurethanes — showed a very fast cure even in a low moisture and low

temperature environment. This largely precludes these types of adhesives as a

self-healing agent. Solvent based adhesives, such as styrene-based glues, offer

longer storage life and can remain in the liquid phase in hollow glass fibres for more

than 14 days. The silane coupling agent exhibits excellent storage stability within

the periods used in this study, due to its unique curing mechanism.

2. Polystyrene-based glues provide poor bonding efficiency for glass/vinyl ester

composite. This type of adhesives is not a general purpose adhesive and is limited in

effectiveness, failing to effectively bond materials that are not styrene-based.

3. The silane coupling agent examined in the present study provided 22% strength

recovery when loaded in three point bending after curing for 28 days. This was

substantially higher than when cured for shorter time (14 days) suggesting that

further improvement might be possible after longer cure times. Better strength

recovery may also be possible using different silanes.

6.2 Future work

While silane coupling agents are worthy of further study as self-healing agents, another

possible class of adhesives, anaerobic adhesives may also have potential. These are

catalysed by metal ions which could be incorporated into the matrix. On fracture of the

78
storage tubes the anaerobic adhesives would flow into the damaged area so as to come

into contact with the exposed metal ions and cure to fill the crack.

The industrial application of self-healing composites using single-part adhesives could

also be investigated. This would require research into relevant manufacturing methods,

such as hollow fibre preform design and lay-up techniques, and filling processes.

To sum up, future research into the application of a single-part healing agent for
self-healing composites could focus on the two areas listed below:

1. Activation method: Moisture catalyzed and solvent evaporation catalyzed adhesives

show low storage ability, so adhesives with other activation methods, such as
anaerobic adhesives should be considered.

2. Storage technology: Cycanoacrylate adhesives cure rapidly when stored inside

hollow glass fibres, so alternative containers could be considered, such as hollow
carbon or plastic fibres.

79
 REFERENCES

1. Jody, W.C.P., I.P.B., A hollow fibre reinforced polymer composite

encompassing self-healing and enhanced damage visibility. Composites
Science and Technology, 2005. 65: p. 1791-1799.

2. Dry, C., Passive tunable fibres and matrices. International journal of modern
physics B, 1992. 6(15-16): p. 2763-2771.

3. Dry, C., Procedure developed for self-repair of polymer matrix composite

materials. Composite Structures, 1996. 35(3): p. 263-269.

4. Motuku, M.J.G.M., Parametric studies on self-repairing approaches for resin

infused composites subjected to low velocity impact. Smart Materials &
Structure, 1999. 8: p. 623-638.

5. Kessler. M, Scott. N. Self healing of composites using embedded microcapsules:

repair of delamination damage in woven composites. in 10th European
conference on composite materials. 2002. Bruges, Belgium.

6. Brown, E.N.S., N, Microcapsule induced toughening in a self-healing polymer

composite. Journal of Material Science, 2004. 39(1703-1710).

7. Brown, E.N.S., N, Retardation and repair of fatigue cracks in a microcapsule

toughed epoxy composite---Part II in situ self-healing. Composites Science
and Technology, 2005. 65: p. 2474-2480.

8. Bleay, S.M.L., C.B.; Hawyes, V.J., A smart repair system for polymer matrix
composites. Composites: Part A, 2001. 32: p. 1767-1776.

9. White, S.G., N.R., Autonomic healing of polymer composites. Nature, 2001.

409(6822): p. 794-797.

10. Kelly, A., Comprehensive Composite Materials. 2000.

11. Scheirs, J., Compositional and failure analysis of polymers: A practical

approach. 2000. 806.

12. Meyer, R.W., Handbook of polyester molding compounds and molding

technology.

13. Mallick, P., Fibre-Reinforced Composites. Second ed. 1993.

80
14. Cheremisinoff, N.P., Fibreglass Reinforced Plastic. 1995.

15. Hodgkinson, J.M., Mechanical testing of advanced fibre composites. 2000:

Woodhead Publishing Limited.

16. Kaw, A.K., Mechanics of composite materials. 1997.

17. Advanced in composite materials and mechanics, ed. A. Maji. 1999: American
Society of Civil Engineers.

18. Meyers, M.A., Mechanical behavior of materials. 1999, N.J.: Prentice Hall.

19. Dry, C. Alteration of matrix permeability, pore and crack structure by the time
release of internal chemicals. in Proceedings of advanced in cementitious
materials. 1990. Gaithersbury, Maryland: American Ceramic Society.

20. Dry, C., Matrix cracking repair and filling using active and passive modes for
smart timed release of chemicals from fibres into cement matrices. Smart
Materials & Structure, 1994. 3(2): p. 118-123.

21. Dry, C., Three-part methylmethacrylate adhesive system as an internal

delivery system for smart responsive concrete. Smart Materials & Structure,
1996. 5(3): p. 297-300.

22. Dry, C., Procedures developed for self-repair of polymer matrix composite
materials. Composite Structures, 1996. 35(3): p. 263-269.

23. Bleay, M.H.I.B.S., Experimental evaluation of unidirectional hollow glass

fibre/epoxy composites under compressive loading. Composites: Part A, 2003.
34: p. 927-932.

24. Bleay, M.H.I.B.S., Investigation into the behaviour of hollow glass fibre
bundles under compressive loading. Composites: Part A, 2003.
34(1045-1052).

25. Zako, M., Intelligent material system using epoxy particles to repair
microcracks and delamination damage in GFRP. Journal of Intelligent
Material Systems and Structures, 1999. 10(10): p. 836-841.

26. Kessler MR, W.S., Sottos NR. Self healing of composites using embedded
microcapsules: repair of delamination damage in woven composites. in 10th
European conference on composite materials. 2002. Bruges, Belgium.

27. Brown EN, W.S., Sottos N, Retardation and repair of fatigue cracks in a

81
 microcapsule toughed epoxy composite---Part II In situ self-healing.
Composites Science and Technology, 2005. 65: p. 2474-2480.

28. Brown EN, K.M., Sottos N, Microcapsule induced toughening in a

self-healing polymer composite. Journal of Material Science, 2004. 39: p.
1703-1710.

29. Williams, H., Bleeding composite: development in biomimetic self-repair.

2005, Department of Aerospace Engineering, University of Bristol.

30. Cooke, B.A.K., Cyanoacrylates and their values. International Journal of

Adhesion and Adhesives, 1993. 13(2): p. 73-75.

31. Dreifus, O.C., Cyanoacrylates, in Internal technical memorandum. 1986,

Loctite.

32. Verosky, P.J.C.C., Advances in cyanoacrylate technology for device assembly,

in adhesives technology. 1999.

33. Lee, S., The polyurethane book. 2002, New York.

34. Petrie, E.M., Handbook of adhesives and sealants. 2000, New York:
McGraw-Hill.

35. Rich, R., Handbook of adhesive technology. 1994, New York.

36. Plueddemann, E.P., Silane Coupling Agent. 1982: Plenum Press.

37. Allen, K.W., Adhesion and adhesives, Joining Technology Research Center,
Oxford Brookes University.

38. ASTM D 792 - 00, Standard Test Methods for Density and Specific Gravity
(Relative Density) of Plastics by Displacement, in Annual book of ASTM
standards, American Society of Testing Materials.

39. ASTM D 3171, Standard Test Methods for Constituent Content of Composite
Materials, in Annual book of ASTM standards, American Society of Testing
Materials.

40. ASTM D 2734, Standard Test Methods for Void Content of Reinforced Plastics,
in Annual book of ASTM standards, American Society of Testing Materials.

41. Composite failure analysis handbook, ed. U.D.o.T. Wright Lab, Federal
Aviation Administration. 1993.

82
42. ASTM D 3039/D 3039M, Test Method for Tensile Properties of Polymer
Matrix Composite Materials, in Annual book of ASTM standards, American
Society of Testing Materials.

43. ASTM D 5528, Standard Test Method for Mode I Interlaminar Fracture
Toughness of Unidirectional Fiber-Reinforced Polymer Matrix Composites, in
Annual book of ASTM standards, American Society of Testing Materials.

44. Pereira, A.B.d.M., A.B., Mode II interlaminar fracture of glass/epoxy

multidirectional laminates. Composites: Part A, 2004. 35: p. 265-272.

45. Carlsson, L.G.J.T., Mode II interlaminar fracture of graphite/epoxy and

graphite/Peek. Journal of Reinforced Plastics and Composites, 1986. 5: p.
170-187.

46. Dharmawan, F.S.H., I; John, S., Mix mode fracture toughness of GFRP
composites. Composite Structures, 2006. 75: p. 328-338.

47. ASTM D 790 - 03, Standard test methods for flexural properties of
unreinforced and reinforced plastics and electrical insulating materials, in
Annual book of ASTM standards, American Society of Testing Materials.

48. Qiao, J.W.P., Novel beam analysis of end notched flexure specimen for Mode
II flexure. Engineering Fracture Mechanics, 2003. 71: p. 219-231.

49. ASTM D 618, Standard Practice for Conditioning Plastics for Testing, in
Annual book of ASTM standards, American Society of Testing Materials.

50. Wade, G.A.C., W.J., Adhesive bonding and wettability of plasma treated, glass
fibre-reinforced nylon-6,6 composites. Journal of Materials Science Letters,
2000. 19: p. 1829-1832.

83