Professional Documents
Culture Documents
A thesis
By
Xufeng Wang
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 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
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
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
vi
List of Figures
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
high specific modulus, and designed and tailored performance, are now widely
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
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
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
area is still a challenge and the consumption of time and labor for these
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
For the development of self-healing for composite structure, several key aspects
have been considered and researched. Figure 1.1 shows the general technical
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
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
The aim of this project was to find a new single-part healing agent for
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
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
4
Chapter 2
Literature review
2.1 Introduction
adhesives with their physical and mechanical properties are presented. Finally,
5
2.2 Fibre Reinforced Composites
2.2.1 Composites
of different materials. They exhibit superior properties and have been widely used
2.2.2 Matrix
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
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
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 curing process, excellent adhesion to most types of substrates, and excellent
chemical and thermal resistance, have made epoxy resin an appropriate choice for
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
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].
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
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
9
2.2.3 Reinforcement
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
fabrics are easy to handle, which can lead to a reduction in the manufacturing cost.
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].
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
processing routes and conditions, together with the choice of constituent format
(CFRPs), GFRPs show lower specific values, such as modulus to density and
anisotropy for the same fibre format than CFRPs, which can make design work
easier.
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
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
and compressive loads. The usual design process for lightweight structures
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.
12
High modulus, highly anisotropic carbon and organic fibres are relatively weak in
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].
that precede final breakage, and thus contribute to the work of fracture.
processes [15-18]. Usually, interlaminar failure initiates from resin cracks and
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
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
progressive increase in their use in structural applications; however, there are still
within the bulk of the composite, whilst leaving little visible sign on the outer
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
restoring the structural strength and stiffness after damage occurs is important but
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
polypropylene fibres within the concrete, and released from the fibres to reduce
adhesive released from hollow fibres after the samples were tested in flexural
testing. This investigation revealed that the restoration of strength and flexibility
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
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
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
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
thermoplastic particles melted when the damaged composite was subsequently heated.
The results of flexure testing after the curing procedure demonstrated that the strength
Recently, White et al., Kessler et al., Brown et al. have all taken a different approach by
26, 27]. Figure 2.5 shows the structure of a microcapsule self-healing mechanism.
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
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
non-requirement for external action. The particle adhesive self-healing mechanism [25]
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
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.
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
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,
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
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
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
21
1. Good repair and strength recovery can be obtained in a resin-only system.
reaction.
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.
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
industrial processing.
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
than for a two-part healing system, the single-part system is much easier to
the matrix. For potential single-part healing systems, the key consideration would
activation of the adhesive. In this research, three activation methods have been
following sections.
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
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
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
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].
.bˊPolyurethane adhesives
polymers. These are low molecular weight, linear polymer molecules, with isocyanate
(-NCO) end groups [33]. Unlike the majority of adhesives, polyurethanes are not
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
materials adhere well to visibly damp surfaces. They penetrate into pores and fill gaps
adhesives are characterized by a wide range of hardness and flexibility. They have good
Coupling agents are used to improve the adhesion characteristics in bonding and in
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
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
(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
27
Figure 2.10 Silane bonding to inorganic substrates.
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
solvent-based adhesives [37]. The two main systems, PVA glue and polystyrene cement,
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
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
Anaerobic adhesives work by filling the interstitial space between the substrates,
toughness of substrates is important in providing a firm basis for bonding, to allow the
29
2.5 Test methods
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
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
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
method relies heavily on accurate measurement of void content. The other method is
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
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
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
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-
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,
32
bond failure during elevated temperature testing [15]. In order to determine
centre and monitored during the test. Grinding with liquid coolants is
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.
There are three basic methods of introducing a compressive load into the
practices, specimen preparation and geometry, and placement of the test coupons
Interlaminar fracture toughness can be measured using loading modes I, II, and
given as values of G IC or G IIC (Mode I and Mode II, respectively). There has been
33
fracture toughness [15]. Standards organization such as American Society for
evaluated and published several standard methods. All these methods involve
beam-type specimens, and require the measurement of applied load and the
whether the delamination grows stably or not, the load-displacement curve is used
The typical double cantilever beam (DCB) specimen, according to the standard
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
it yielded the most conservative value of G IC for 80% of the specimens tested [15].
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),
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
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,
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
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
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
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
demand [47].
38
Figure 2.16 Stress distributions in (a) a Mode II ENF specimen and (b) a three-point
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
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
fibre vinyl ester composites are commonly used in such applications and were the
As noted in the previous chapter, single part thermosetting adhesives can cure by an
reaction with a component embedded in the matrix. Moisture curing adhesives were
considered particularly attractive since these would be activated for surface connected
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,
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
Hollow glass fibres were selected to store the healing agent, due to their ability to
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,
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
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
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
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
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
Figure 3.1 Hollow glass tubes and adhesive stability test specimens.
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
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.
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
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
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
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
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
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
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
This procedure was aimed at bringing the materials into equilibrium with standard
3.3.3 Properties
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
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
w1
U1 (3.1)
w2 ww w3
U U1 u 997.5 (3.2)
The procedure was repeated for 5 specimens to obtain an average density value.
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
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
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)
49
V 100% u (T M ) T (3.6)
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
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
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
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
3PcGc
G Ic (3.7)
2b(a ' )
52
b is the specimen width, a is delamination length, and ' = a modified parameter
(determined experimentally).
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
P
a0 Adhesive layer
2d
L b
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.
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
54
P
Adhesive layer
L b
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
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 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.
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
56
Chapter 4
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
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.
Storage period
Adhesives
7 days 14 days
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
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
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
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
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
60
Chapter 5
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
61
Table 5.1 Measured values of density and thickness for glass/vinyl ester laminates
Laminate Panel 1 2 1 2 1 2
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
62
Table 5.2 Measured values of fibre content, resin content and void content for
Laminate Panel 1 2 3 4 5 6
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
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
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
laminated composite structures, according to the corrected beam theory which generates
Where P is the critical load at NL point, G is the deflection in the beam corresponding
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
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
65
5.3 Mode II End Notched Flexure testing
Pure Mode I adhesive joint testing is the most aggressive test for interlaminar fracture
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
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.
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Figure 5.2 Load-displacement curve in Mode II ENF test for a solid laminate, a
specimen.
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Table 5.4 Results of Mode II ENF test
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
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
modulus. The results show that the silane coupling agent provides a bonding efficiency
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5.4 Three-point flexure testing
Three point flexure testing was also carried out to simulate the service loading
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
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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
Figure 5.5 Stress-strain curve of a solid specimen and a silane bonded specimen in
The results from the flexure testing are given in Table 5.5 The flexure strength ( V f )was
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
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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.
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
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
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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
Figure 5.6 SEM images of Mode I fracture surfaces of glass/vinyl ester composite
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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
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
deformation. This confirms that the silane coupling agent provides a significant level of
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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
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
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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
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
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
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
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
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
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
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
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
polyurethanes — showed a very fast cure even in a low moisture and low
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.
composite. This type of adhesives is not a general purpose adhesive and is limited in
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
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.
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:
79
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