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Influence of Moisture Degradation on Fibre-Epoxy Interface in Pre-Preg Laminates

ABSTRACT
The effect of moisture absorption on the mechanical behaviour and on the fibre/matrix interface of HTA/ 6376 composite material was investigated. In order to determine the effect of stacking sequence on the moisture absorption, two different laminate configurations, [08]s and [06 902]s, were considered. The specimens were immersed in deionized water at room temperature (19C 2). The absorption characteristics of carbon fibre epoxy laminates were investigated by the measurement and analysis of the weight change and hygrothermal induced expansion. The specimens exhibited Fickian Diffusion behaviour and absorbed on average 0.8% moisture by weight over the complete exposure period. It was found that the specimen lay-up sequence affected the overall moisture absorbed, with a higher moisture content in the [06 902]s specimens. The interlaminar shear strength (ILSS) of both dry and wet specimens was determined using a double-notched test method (ASTM D3846-08). A statistical analysis of the results determined that the absorbed moisture caused an increase in ILSS values by up to 18.7%. The increase in ILSS is dependent on the exposure time, with the four month immersed specimens having increased by a substantial amount.The results obtained have been found to be in line with data reported in literature. The predominant reason for the increase in ILSS is due to the increase in the flexibility of the resin due to an increase in moisture content. Digital Image Correlation (DIC) was used in order to determine the strain and displacement in the x- and y-directions. Fractography analyses were conducted to detect the type of accumulated damage and to investigate the effect of moisture on the fibre/matrix interface. This was investigated by Scanning Electron Microscopy (SEM).

Keywords:

Moisture

absorption,

Hygrothermal,

Moisture

Diffusion,

Diffusivity,

Interlaminar Shear Strength

DEDICATION

To my dad, who taught me to climb as high as I can dream and that the best kind of knowledge to have is that which is learned for its own sake.

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ACKNOWLEDGEMENTS
From the formative stages of this thesis, to the final draft, I owe an immense debt of gratitude to my supervisor, Dr. Trevor Young, who has been the ideal supervisor. His sage advice, insightful criticisms, and patient encouragement aided the writing of this thesis in innumerable ways.

I would also like to thank Dr. Kali-Babu Katnam whose steadfast support and tireless help for this thesis was greatly needed and deeply appreciated.

For their efforts and assistance, a special thanks as well to Mr. Adrian McEvoy and Mr. Robert Telford.

Finally, I would be remiss without mentioning Dr. Walter Stanley, whose important contribution of talent and time given unselfishly in proceeding with this work.

To each of the above, I extend my deepest appreciation.

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TABLE OF CONTENTS
ABSTRACT ........................................................................................................................i DEDICATION .................................................................................................................. ii ACKNOWLEDGEMENTS ............................................................................................. iii LIST OF FIGURES ..........................................................................................................vi LIST OF TABLES ......................................................................................................... viii NOMENCLATURE ..........................................................................................................ix 1 INTRODUCTION ...................................................................................................... 1 1.1 1.2 1.3 2 Background ......................................................................................................... 1 Outline of Thesis ................................................................................................. 3 Objectives ............................................................................................................ 3

LITERATURE REVIEW ........................................................................................... 4 2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 2.11 Introduction ......................................................................................................... 4 Variables affecting Moisture Absorption ............................................................ 4 Effect of Water Temperature and Relative Humidity Variations ........................ 5 Effects on Mechanical Properties ........................................................................ 6 Mass-Gain Ratio and Alternative Measuring Techniques ................................ 12 Effect of Seawater in Preference to Conventional Methods ............................. 13 Mechanical Adhesion ........................................................................................ 14 Natural Fibres .................................................................................................... 15 Thermoplastic versus Thermoset polymers ....................................................... 16 Digital Image Correlation (DIC).................................................................... 16 Fractography studies ...................................................................................... 17 Diffusion and Ficks second law ....................................................................... 19 Interlaminar Shear Strength (ILSS) ................................................................... 22 Equation for calculating the ILSS .................................................................. 22

THEORETICAL ANALYSIS .................................................................................. 19 3.1 3.2 3.2.1

EXPERIMENTAL .................................................................................................... 23 4.1 4.1.1 4.1.2 4.1.3 Material ............................................................................................................. 23 Test specimens ............................................................................................... 23 Conditioning and Specimen Exposure ........................................................... 23 Measurements ................................................................................................ 24 iv

4.2 4.2.1 4.3 4.4 5

Interlaminar Shear Strength (ILSS) Test ........................................................... 25 Experimental Apparatus and Procedure ........................................................ 26 Digital Image Correlation (DIC) ....................................................................... 27 Fractography Studies ......................................................................................... 30

RESULTS AND DISCUSSION ............................................................................... 31 5.1 5.2 5.3 5.3.1 5.3.2 5.3.3 5.3.4 5.4 5.5 Fickian Diffusion and Specimen Weight Gain .................................................. 31 Volumetric Expansion ....................................................................................... 35 Interlaminar Shear Strength (ILSS) ................................................................... 36 ILSS Results .................................................................................................. 36 Stress State ..................................................................................................... 38 Flexibility of Resin ........................................................................................ 39 Limitations and constraints during ILSS testing............................................ 43 Digital Image Correlation (DIC) ....................................................................... 46 Fractography Analysis ....................................................................................... 51

6. CONCLUSIONS AND FUTURE RESEARCH .......................................................... 61 6. 1 Conclusions ............................................................................................................... 61 6.2 Recommendations for Future Research ..................................................................... 63 6.2.1 Raman Spectroscopy ........................................................................................... 63 6.2.2 Thermoplastics versus Thermosets ..................................................................... 63 6.2.3 Relative Humidity Chamber ............................................................................... 63 6.2.4 Reversible/Irreversible Effects ............................................................................ 64 6.2.5 Epoxy Resin Toughness ...................................................................................... 64 REFERENCES................................................................................................................. 65 Appendix A: Turnitin originality report.A1 Appendix B: Specimen Dimensions...B1 Appendix C: Drawing of clamp adapted from ASTM Standard D3846-08...........C1 Appendix D: Specimen Weight Gain Values.....D1 Appendix E: Experimental data from ILSS Test....E1 Appendix F: SEM Micrographs..F1

LIST OF FIGURES
Figure 3-1. Fickian Diffusion Curve (Shen and Springer, 1975; Greene, 2007) ............. 21 Figure 3-2. Specimen dimensions .................................................................................... 22 Figure 4-1. Explorer Analytical Balance ......................................................................... 24 Figure 4-2. Shadowgraph Projector ................................................................................. 25 Figure 4-3. Clamp used in ILSS Testing .......................................................................... 26 Figure 4-4. Tinius Olsen H25KS Model .......................................................................... 27 Figure 4-5. Speckled Specimen........................................................................................ 28 Figure 4-6. Strain Master experimental setup (adapted from La Vision, 2010) .............. 29 Figure 4-7. JEOL JCM 5700 (www.jeolusa.com) ........................................................... 30 Figure 5-1. Moisture content (w/w %) - [08]s configuration ........................................... 32 Figure 5-2. Moisture content (w/w %) - [06 902]s configuration .................................... 32 Figure 5-3. Force against Extension [08]s ........................................................................ 40 Figure 5-4. Force against Extension [06 902]s .................................................................. 40 Figure 5-5. Stress against Strain [08]s specimens ............................................................. 42 Figure 5-6. Stress against Strain [06 902]s specimens ....................................................... 42 Figure 5-7. Wet I [06 902]s x-displacement (a) At failure (b) After failure ...................... 46 Figure 5-8. Dry [08]s specimen y-displacement (a). Before failure (b) At failure ............ 47 Figure 5-9. Dry [06 902]s specimen y-displacement (a). Before failure (b) At failure ..... 47 Figure 5-10. Dry [08]s specimen - Strain Exx (a) At start of load (b) At failure........... 48 Figure 5-11. [06 902]s Specimen - Strain in the x-direction (a) Dry specimen (b) Wet specimen ........................................................................................................................... 49 Figure 5-12. Fracture surface of a dry [08]s specimen - magnification x10 .................... 52 Figure 5-13. Fracture surface of a dry [08]s specimen - magnification x1000 ................ 53 Figure 5-14. Fracture surface of a wet [08]s specimen 2month withdrawal - magnification x10 .................................................................................................................................... 53 Figure 5-15. Fracture surface of a wet [08]s specimen 2month withdrawal magnification x1000 ................................................................................................................................ 54 Figure 5-16. Fracture surface of a wet [08]s specimen 4 month withdrawal - magnification x10 .................................................................................................................................... 55 Figure 5-18. Fracture surface of a dry [06 902]s specimen - magnification x10 .............. 56

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Figure 5-17. Fracture surface of a wet [08]s specimen 4 month withdrawal - magnification x1000 ................................................................................................................................ 56 Figure 5-19. Fracture surface of a dry [06 902]s specimen - magnification x1000.......... 57 Figure 5-20. Fracture surface of a wet [06 902]s specimen 2month withdrawal magnification x10............................................................................................................. 58 Figure 5-21. Fracture surface of a [06 902] specimen - 2month withdrawal - magnification x1000 ................................................................................................................................ 58 Figure 5-22. Fracture surface of a wet [06 902] specimen 4 month withdrawal magnification x10............................................................................................................. 59 Figure 5-23. Fracture surface of a wet [06 902]s specimen - 4month withdrawal magnification x1000......................................................................................................... 60

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LIST OF TABLES
Table 2-1. Aspects of property deterioration in polymer-based composite materials (Hull, 1981). ............................................................................................................................... 10 Table 5-1. Moisture content (w/w %) .............................................................................. 34 Table 5-2. Volume Change (%) ....................................................................................... 35 Table 5-3. ILSS values ..................................................................................................... 37 Table 5-4. ILSS percentage increase values .................................................................... 37 Table 5-5. [08]s Specimen - Load and extension values ................................................... 41 Table 5-6. [06 902]s Specimen - Load and extension values............................................ 41

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NOMENCLATURE
Symbol Description Units mm2/s mm2/s N/m2 MPa MPa % % N K % mm mm g g

D Dz E F GIIC M0 M P Tg Vf Vx Vy

Diffusion Coefficient Diffusion Coefficient in the z-direction Elastic Modulus Interlaminar Shear Strength Mode II Fracture Toughness Initial moisture content Maximum moisture content Load at failure Glass Transition Temperature Volume Fraction Displacement in the x-direction Displacement in the y-direction Mass of dry specimen Mass of wet specimen

c0 c w l

Initial moisture absorption state

Fully saturated moisture absorption state Width of specimen Distance between notches mm mm

Strain Strain in the x-direction Strain in the y-direction Stress Stress in the z-direction

N/m2 N/m2

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Abbreviations ANOVA CCD CFRP DIC GFRP RH RPL SEM UV Analysis of Variance Charge Coupled Device Carbon-Fibre Reinforced Plastic Digital Image Correlation Glass-Fibre Reinforced Plastic Relative Humidity Repeated Progressive Loading Scanning Electron Microscopy Ultraviolet

Chapter 1

Introduction

1 INTRODUCTION
1.1 Background
In the last two decades, advanced polymer-matrix composite materials have been widely used as a substitute for traditional structural materials. As high specific strength and stiffness ratios are required for aeronautical structural components, advanced polymermatrix composite materials provide several opportunities for lower structural weight than conventional metallic components. Initially, composites were only used in secondary structures, like the interior details and floor, and in less critical-load bearing components with such examples as hatch doors of landing gear. At present they are being introduced into primary structures of aircraft such as the wing, fuselage and control surfaces. Composites also find an increasing use in non-aerospace structures. Marine applications provide a sizeable growth potential, from sailboats to kayaks. Automobile and construction applications are also profiting from their low specific mass and very high static strength. Composites generally have long fatigue lives and are easily maintained and repaired. However, cost and confidence remain obstacles towards the increased use of composite materials in all industries. In this regard, for reliable structural design, a detailed understanding is required related to: fastening methods, damage tolerance, hygrothermal effects, lightning-strike protection and material compatibility. This thesis investigates the influence of hygrothermal effects on shear strength of polymer-matrix composites.

The comprehensive understanding of hygrothermal effects is important in order to predict service-life, maintainability and durability. It will also allow future designers to tailor for specific applications by selecting the suitable physical and mechanical properties needed and by choosing from a variety of fibres and resin available. In-service composites are exposed to harsh environments for long periods of time and thus have a tendency to suffer from hygrothermal effects. These are mainly due to environmental attacks such as temperature, humidity, radiation and chemical exposure. In addition, the effect of moisture should also be taken into account. Moisture is absorbed from the humidity in the atmosphere. This causes degradation in the material properties and is therefore of much concern especially in aeronautical applications. Consequently, moisture absorption in composites has received a growing interest and a great deal of evidence has been collected 1

to demonstrate that both physical and mechanical properties can be strongly affected; thereby affecting the overall performance of the composite. These effects can be examined from a microscopic point of view, on the scale of fibre diameter, or from the macroscopic point of view; where the fibre/matrix interface is examined and the overall effects on the lamina considered. A macroscopic point of view is approached here and the material is assumed to be homogenous.

Moisture induced degradation in mechanical properties can be due to a number of reasons. Fibres are insensitive to environmental changes; the susceptibility of the laminates is mainly due to the matrix. Moisture diffuses through the matrix and fibre/matrix interface. The absorbed moisture causes physical and/or chemical changes in the matrix, loss of adhesion of fibre/resin interface, and/or loss of fibre strength and stiffness. The absorbed water also softens the matrix resin and thus reduces the overall stiffness of the laminate. A considerable reduction of tensile strength, fracture toughness and lowering of the glass transition temperature (Tg) with increased moisture concentration has been reported (Selzer and Friedrich, 1997; Choi et al., 2001; Akbar and Zhang, 2008). Compression strength also decreases and this leads to a larger damage area.

To investigate the influence of moisture ingress on shear strength of polymer-matrix composites, an existing test method (double-notched test method) was employed in the current thesis work to characterize the inter-laminar shear properties of both dry and wet composite specimens. Testing was conducted after two time periods - two and four months. The manner in which composite materials absorb moisture is dependent on a number of factors some of which include: temperature, fibre orientation, density, diffusivity and fibre volume fraction etc. While not exhausted, several of these factors have been investigated (Whitcomb and Tang, 2001; Bao and Yee, 2002; Vaddadi et al., 2003; Baker et al., 2004). Two lay-up configurations were examined in order to determine the effects of different stacking sequence on the diffusion parameters. The specimens were exposed to a 100% RH environment, by fully immersing them in water. To utilize the full potential of the carbon/epoxy laminates, their fracture mechanical behaviour under these conditions also had to be determined. All specimens tested were examined visually and with the aid of optical microscopes. In order to thoroughly detect the type of accumulated damage, 2

fractography studies were conducted. The effects of moisture on the fracture surfaces of the specimens were examined using Scanning Electron Microscopy (SEM).

1.2 Outline of Thesis


The thesis follows a course, from a review of existing work, through to the presentation of the results of the investigation. The purpose of this section is to provide a brief overview of the chapters. Chapter 2 describes the concept of moisture diffusion, its variables and its implication on in-service applications. It is written with the presumption that the reader has a solid grasp of composites but is not familiar with the physical affects due to moisture absorption. Chapter 3 investigates Fickians Law of diffusion and the application in relation to composite materials. Chapter 4 discusses the experimental work undertaken, its methods and procedures. Implications of the assumptions made in Chapter 3 are discussed in Chapter 5 where the results of Chapter 4 are also presented. In Chapter 6, overall conclusions are drawn, limitations are discussed, and further research is proposed. Appendix A-F contains the data compiled during the experiments, detailed drawings of specimens, parts manufactured to aid in the testing procedures and SEM micrographs.

1.3 Objectives
The objectives of this project were:

1. To predict and analyse the maximum weight gain of carbon/fibre laminates as a function of exposure time. 2. To determine the diffusion coefficient of the laminates. 3. To investigate the effect of moisture absorption on the fibre/matrix interface and evaluate the overall effects on the laminate by performing interlaminar shear strength tests. 4. To utilise Digital Image Correlation (DIC) to determine the stress and strain fields on composite material subjected to hygrothermal effects. 5. To examine the difference of the fracture profiles of dry and wet specimens by using Scanning Electron Microscopy (SEM).

Chapter 2

Literature Review

2 LITERATURE REVIEW
2.1 Introduction
The study of composite materials involves many topics, of which include manufacturing processes, strength of anisotropic materials and micromechanics. Consequently, no single individual can claim a complete understanding of all these areas. Therefore, in order to establish a complete and comprehensive understanding of moisture absorption in composite materials, it is necessary to evaluate and address critical points of the current knowledge of researchers in this area. This also provides the gaps and limitations towards a more specific topical area.

This literature review has three main themes, (1) the variables affecting moisture absorption including; immersion temperature and the effect of seawater. More importantly, (2) its effects on mechanical properties of composite materials, including, polymeric composites most susceptible to moisture absorption. In order to fully establish the effect on the specimens, (3) the use of Digital Image Correlation (DIC) and Scanning Electron Microscopy (SEM) was investigated and the limitations of these methods established.

2.2 Variables affecting Moisture Absorption


Perreux and Suri (1997) highlighted that the degradation of the material is mainly influenced by two things: mechanical and environmental stresses. These factors are interrelated; if damage has occurred in the structure, this leads to an increase in the moisture absorbed by the composite material. Equally, if the material has undergone hygrothermal ageing it would be more easily susceptible to damage. Akbar and Zhang (2008) reported that there exist critical factors which influences the way in which composite materials absorb moisture. These factors include; temperature, reinforcement orientation, fibre volume fraction, and the density, polarity and permeability in regard to the fibre nature. The surface protection, diffusivity and area of the exposed surface are also key points. Choi et al. (2001) investigated the effect of void content on the hygrothermal behaviour of composite laminates. By observing the diffusion rate coefficient and water absorption behaviour of unidirectional laminates containing different amounts of

void fraction, it was evident that laminates containing a higher number of voids, follows non-Fickian diffusion characteristics at the initial stages of water absorption.

Bao and Yee (2002) highlighted that in theory, diffusion can be predicted solely from the fibre volume fraction and the neat resin of a composite but that in reality the situation is much more complicated. In advanced composites a large amount of interface is present, as the fibre diameter and inter-fibre distance are both extremely small. Bao and Yee explained the influence of inadequate wetting of the fibre/matrix interface; this is reviewed in Section 2.7. Similarly, Whitcomb and Tang (2001) studied how the effective diffusion varies with fibre volume fraction (Vf). The effective diffusion for low to moderate fibre fractions (Vf < 40%) are essentially the same, following Fickians Law, however a big difference exists for higher fibre fractions (Vf >40%). The effect of fibre orientation and variation in thickness of the specimens on the absorption of water has been investigated by a number of experimentalists (Selzer and Friedrich, 1997; Choi et al., 2001; Akbar and Zhang, 2008), all obtaining similar results. The diffusion rate and the equilibrium water uptake are not influenced by the stacking sequence because the penetration length of water molecules and the resin content are not changed. Judd and Wright (1978) determined that irrespective of fibre and fibre surface treatment, or resin type, the interlaminar shear strength of composite material decreases by about 7% for each 1% of voids up to a total void content of about 4%. It is important to characterize the void content of composite materials as numerous properties are affected by this.

2.3 Effect of Water Temperature and Relative Humidity Variations


According to Akbar and Zhang (2008), the amount of moisture absorbed is found to be independent of the exposure temperature, but directly proportional to the relative humidity of the environment. Similar to the findings of Asp (1998), Selzer and Friedrich (1997) experimentally examined the effect of moisture absorption on the fracture toughness of carbon fibre-reinforced polymers by immersing specimens into three baths of different temperatures: 23, 70 and 100C. They found that the decrease in fracture toughness when tested in mode I and mode II were independent of the temperature of the baths, but solely related to the moisture content. Selzer and Friedrich (1997) noted a decrease of 8% in the 5

half saturated specimens in mode I and a decrease in the fully saturated specimens of around 15% in the mode II fracture toughness ( values, when compared to the dry

specimens. However, the results are not consistent with the work obtained by Russel and Street (1985) who observed a greater decrease in fracture toughness with an increase in temperature. They found that the values obtained were significantly different at 100C than at lower temperatures, with the effect of moisture causing a decrease of up to 22% in the fracture toughness at a 100C. Later in the research work of Selzer and Friedrich (1998), they confirmed their results obtained previously (1997) and also verified that an increase in the water temperature only results in an increase in the absorbed moisture, leading to a reduced time in saturation of the specimens. Similarly, Baker et al. (2004) anticipated an increase in temperature of 10C would cause the diffusion rate to double. The diffusion of moisture into a composite matrix over time varies exponentially with temperature. Vaddadi et al. (2003) varied the relative humidity from 50% to 85% in their chamber but kept it at a constant temperature of 85C. When plotting the relative weight gain (%) against time, they noted that both curves were nearly equal at the diffusivity of the initial stage of exposure.

Choi et al. (2001) noted that the diffusion coefficient of a specimen immersed in a water bath (100% RH) at 70C is bigger than the one in a 95% RH chamber held at the same temperature. They found that the equilibrium water uptake obtained in the humidity chamber had a larger amount of saturated water uptake than that in the bath. These conclusions are not consistent with the work completed by Hao et al. (1992), who observed higher moisture content for carbon/PPS laminates when exposed to higher relative humidity environments. For specimens exposed to a fixed relative humidity environment at high temperatures, the moisture content is low. It can thus be concluded that a laminate exposed to a low temperature/high relative humidity environment will have higher moisture content, than when exposed to a high temperature/low relative humidity environment.

2.4 Effects on Mechanical Properties


Akbar and Zhang (2008) experimentally investigated the presence of moisture in a polymer composite. Polymers undergo both dimensional and property changes when exposed to a hygrothermal environment. When examining composites which utilize polymers as matrices, the sensitivity to environmental changes was found to come from the matrix; 6

since fibres are insensitive to these changes. As a result, if a quasi-isotropic composite is exposed to such an environment it affects the transverse, shear and longitudinal properties.

According to Choi et al. (2001) longitudinal properties dominated by fibre properties in unidirectional composites may not drop so noticeably but such properties as compression strength and interlaminar shear strength are significantly affected by the moisture absorbed, especially at high temperatures. This is due to the fact that the influence of moisture and temperature affects the matrix and interfacial performance. Longitudinal tensile strength is a fibre dominated property and thus moisture and temperature will not cause adverse effects. However, the longitudinal compressive strength and interlaminar shear strength are dominated by the matrix of the composite and is therefore greatly affected.

At room temperature the reduction of interlaminar shear strength may not be significant but when operating at temperatures between 100C and 130C these reductions can be up to 50-60%. Akbar and Zhang (2008) found a 13% decrease in the interlaminar shear strength (ILSS) for carbon/epoxy laminates subjected 60C/100% RH (immersion). They found that the water absorbed by the epoxy laminates, causes reversible plasticization of the matrix and combined with temperature effects, these factors cause significant changes in the matrix toughness thereby affecting the laminate strength. When exposed to different immersion time periods, the ILSS is seen to weaken over time. The epoxy matrix absorbs a significant amount of moisture, where the fibres absorb little or no moisture. This leads to a significant mismatch in moisture-induced volumetric expansion between matrix and fibres, causing the evolution of localized stress and strain fields in the composite at the interfacial region (Akbar and Zhang, 2008). According to Hull (1981) these stress and strain fields have different gradients in the material; due to non-uniform water content and concentration under non-equilibrium conditions. The build-up of internal stresses can also occur even when the moisture content in the material is uniform due to different swelling characteristics of adjacent laminae in a laminate.

Matthews and Rawling (1994) tested multidirectional laminates and observed the effects on the dominant 0 load bearing layers. When tested in tension, temperature and moisture have little effect on the failure of the dominant 0 load bearing layers. When tested in a resin 7

dominated situation, such as applied tension or where the resin is required to support the fibres against buckling in compression, the effects due to temperature and moisture are significant. For example, a 45 CFRP laminate, tested in tension at 130C and 1.5% moisture, shows a 40% drop in strength at room temperature. Selzer and Friedrich (1997) observed the same effect; however they also found that the more the specimens absorbed moisture, the bigger the reduction. The reduction in strength was up to 66% and they concluded that the moisture effects were more predominant in tensile tests that were dependent upon the strength of the matrix and interface.

It was found by Akay et al. (1997) that moisture has no influence on the elastic modulus but causes a severe decrease on the flexural strength of Kevlar/epoxy resin laminates. This was also confirmed by Perreux and Suri (1997). This is contrary to the predictions of Hull (1981), who explained that moisture affects the flexibility of the epoxy resin, thus reducing the elastic modulus. Changes in elastic modulus have no effect on longitudinal tensile strength but the longitudinal compressive strength and the interlaminar shear strength are greatly affected. Baker et al. (2004) predicted for a carbon/epoxy composite, cured at 180C, moisture absorption causes a reduction of up to 10% in compressive strength for subsonic aircraft and up to 25% for supersonic aircraft. These figures were surpassed by Selzer and Friedrich (1997) who found that the compressive strength reduced by up to 35% for carbon/epoxy 0 laminates and up to 37% for 90 laminates.

Matthews and Rawling (1994) reported that the absorbed moisture causes the resin to soften, and therefore composites whose properties are resin dominated, will experience severe reductions at elevated temperatures. This is particularly evident as the glass transition temperature of the resin is approached. Other effects include; micro-cracking of the resin or fibre-matrix interface, blistering or delamination.

Thermosetting resins cover a broad class of chemicals and a corresponding range of physical and mechanical properties can be obtained. The curing agent plays a role in determining the kinetics of water uptake and the degradation in mechanical properties. However, in order to effectively explain the reduction in the glass transition temperature (Tg), an epoxy matrix is considered. The water molecules attach by hydrogen bonding, the 8

water then acts as a plasticizer, thus reducing the Tg. However, when the environmental conditions change and the moisture diffuses out, these effects are reversible, and some properties such as the elastic modulus will return to its original value. Moisture absorption also leads to irreversible effects on material properties, as listed in Table 2.1.

Table 2-1. Aspects of property deterioration in polymer-based composite materials (Hull, 1981)

Reversible changes Resin Water swelling

Irreversible changes (1) Chemical break-down by hydrolysis

Temperature flexibilising Physical ordering of local regions

(2) Chemical break-down by UV radiation (3) Chemical break-down by molecular thermal activation (4) Chemical break-down by stress induced effects associated with swelling and applied stress (5) Physical ordering molecular regions of local

(6) Chemical composition changes by leaching (7) Precipitation and swelling phenomena to produce voiding and cracks (8) Non-uniform de-swelling produce surface cracks and crazes to

(9) Chemical effect of thermoplastic polymer content on long term stability Interface Flexibilising interface (1) Chemical break-down as above 1,2,3,4 (2) Debonding due to internally generated stresses associated with shrinkage and swelling and the applied stress (3) Leaching of interface Fibre (1) Loss of strength due to corrosion (2) Leaching of fibre (3) Chemical break-down by UV radiation

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De S (2007) conducted a study on the Influence of Moisture Absorption on QuasiStatic and Long-Term Failure of a GFRP Pipe. De S saturated pipes in a water bath at 50C and evaluated the effect of moisture absorption on numerous mechanical properties. Decreases of 30% of flexural modulus in the longitudinal direction were observed. Creep tests were also conducted on the GFRP pipes to determine the long-term circumferential modulus. There was a strong influence on the initial stiffness and on the viscoelastic behaviour of the GFRP pipes. Lateral deflections were similar in both dry and wet GFRP pipes. It is however interesting to note that moisture had no influence on the failure of the GFRP pipes. Rupture energy and strain at failure of the GFRP pipes under several loading conditions were determined. This was also concluded by Faria (2005) who examined more exclusively the failure behaviour of GRP pipes under compressive ring loads.

Perreux and Suri (1997) observed a decrease in viscous properties and glass transition temperature (Tg). The rate of damage that occurs during fatigue also increases during repeated progressive loading (RPL) tests. Contradicting these statements Jones et al. (1984) showed that the rate of damage during fatigue tests of hygrothermally aged composites can even be smaller than that of unaged composites. A decrease in the strength of the composite was reported but the effect on fatigue was unchanged. This was also confirmed later by Selzer and Friedrich (1997) who performed fatigue tests on carbon/epoxy laminates. Their explanation was simple, carbon fibres generally exhibit good resistance to fatigue and therefore the effects of moisture on polymers with high fibre content should be insignificant.

Hao et al. (1992) found that during mode II interlaminar fracture toughness tests, the critical load and displacement became larger with an increase in the absorbed moisture. They effectively explained that moisture infuses into polymers; thereby causing the polymer molecules to separate. The molecules can then easily move past the critical strain levels, due to the reduction in their secondary bond attraction. This causes plasticization. Except for the effect on the fibre/matrix interface, Perpelkin (2006) proposed that there is another mechanism of action due to the exposure of composites to a liquid medium, this is known as the Rehbinder effect. This effect is visible in the presence of even minute amounts of surface-active impurities. Surface-active molecules that enter into the region of 11

a growing crack reduce the surface energy of the newly formed surfaces in fracture and thus decreases the mechanical stress required for crack growth (Perpelkin, 2006). In brittle bodies, such as composites that are based on thermosets, the Rehbinder effect is particularly evident but it is also known to effect highly crystalline polyolefins.

The effect on electrical conductivity and resistivity are examined in a subsequent section 2.5.

2.5 Mass-Gain Ratio and Alternative Measuring Techniques


Majority of the studies conducted, estimate the rate of absorbed moisture by periodically monitoring the weights of the specimens on exposure to different hygrothermal environments. Tsai et al. (2006) noted that measuring the mass-gain ratio of thin specimens completely immersed in water is not reliable. The data found from the process of extracting a wet specimen from water is easily influenced and manipulated by the surroundings. Firstly, after extraction the surface of the specimen must be wiped off in order to remove any excess water and laid in the ambient air in order to ensure the remaining surface moisture had evaporated before being weighed. Once the surface of the wet specimen becomes dry, it can start to dewater and thereby changing its inner moisture distribution. If a specimen is thick, the change happens locally and is therefore negligible but this is not the case for thin specimens.

Other authors have also experienced some difficulty in experimentally determining the specimen mass gain and have therefore found an alternative. By measuring the dielectric properties of the ageing material, the mass of the absorbed water can be determined (Bunsell, 1984). Stone (1969) effectively determined the presence of water at the interface by measuring the electrical conductivity changes of glass fibres embedded in a polymeric matrix. The conductivity increases as a result of a conductive layer forming due to the presence of water. Belani and Broutman (1978) measured the resistivity changes of carbon/epoxy specimens exposed to environments containing different levels of moisture. To effectively ensure the elimination of any fluctuations caused by varying pressures of the connector clamps, the ends of the specimens were coated with a conductive silver paint. It was observed that the resistance increased with an increase in moisture and the square root 12

of the resistance varies linearly with moisture content. Desorption tests were also conducted and it was apparent that the change in electrical resistance is reversible and that the material regained its original properties.

Belani and Broutman (1978) suggested that in the presence of moisture the laminates swell in the direction transverse to the fibre direction. The contact pressures between the fibres are affected by the swelling, leading to a change in the length of the conducting path and thereby increasing the resistivity. Banks et al. (2000) evaluated the influence of moisture absorption on the permittivity of CFRP at high frequency range (300 kHz to 3GHz) and also found an increase with increasing moisture content. In the longitudinal direction an increase of 5% in electrical impedance for every 0.1% of moisture content was noted. However, in the transverse direction there is a change of only 0.4% for 0.1% of moisture content. During the initial stage of absorption the change is almost zero and only starts to increase when voids in the matrix become filled with water.

Similarly to Belani and Broutman (1978), Banks et al. (2002) suggested that the increase in electrical impedance is due to an increase in mutual inductance between the fibres and matrix. Abram and Bowler (2005) studied the influence of water vapour during the curing process on the electromagnetic properties of polyurea/polyurethane-based composites. There was a substantial increase in the real relative permittivity of samples cured in different RH environments. The difference is caused primarily by water uptake into the polymer matrix which alters the dielectric properties of the composite material due to its strong polar nature and high value of real relative permittivity (Abram and Bowler, 2005). More detailed research is necessary in this area but thus far it can be concluded that electrical impedance of composite materials are sensitive to moisture absorption.

2.6 Effect of Seawater in Preference to Conventional Methods


Kootsookos and Mouritz (2004) investigated the effect of seawater on the durability of GRP. The effect of seawater had no superior effect when compared to distilled or deionised water. Seawater still caused the same effects, debonding of the fibre/matrix interface as a result of swelling and plasticisation of the matrix. Glass/polyester and carbon/polyester composites were immersed in seawater at 30C. Gellert and Turley (1999) 13

reported that glass fibres chemically react with water, which causes alkali elements to leak out. Carbon fibres do not absorb moisture and are therefore resistant to any corrosive effects of water. If this holds true, then the mass gain curves of these two composites should be significantly different; with the carbon/polyester curve much higher than the glass/polyester. However, Kootsookos and Mouritz found that this was not the case, speculating that the fibres were not solely responsible for the difference in the mass gain curves. The emulsion sizing agent on the fibre reinforcement appeared to influence the absorption behaviour. On glass fibres the emulsion size facilitated greater amounts of water absorption at the fibre/matrix interface. The carbon/polyester interphase absorbed less moisture and was due to the silane sizing agent. Mode I interlaminar fracture toughness testing was performed and showed no variation on the property. A decrease of up to 40% in flexural strength and a considerable decrease in flexural stiffness were found, similar to the findings of Gellert and Turley (1999). The effects on mechanical properties are thus equivalent to the ones obtained by the use of distilled or de-ionised water. To the authors knowledge, this thesis is the first study on the influence of moisture on carbon fibre/epoxy laminates using de-ionised water for exposure to a 100% RH at room temperature.

2.7 Mechanical Adhesion


Perepelkin (2006) effectively explains that the weak spot of fibre composites is found in the surface of the adhesive contact between the fibres and matrix. The degree of adhesion is an important aspect as the fracture properties of a composite is determined by fracture of the matrix and/or destruction of the adhesive contact. It also determines their response to aqueous and corrosive environments. A composite with a weak interface exhibit high resistance to fracture but moderately low strength and stiffness. Similarly, composites with a strong interface have high strength and stiffness but are very brittle. The relationship between properties and interface characteristics are naturally complex, as other properties, such as fatigue and creep, are also affected by the interface.

In advanced composites a large amount of interface is present, as the fibre diameter and inter-fibre distance are both extremely small. Bao and Yee (2002) explained that an open space at the interface may exist due to inadequate wetting of the fibre by the matrix, causing fast diffusion in the fibre direction due to the capillary effect. The normalized 14

composite weight gain will be higher than that of the neat resin due to the filling of voids at the interface. To improve adhesion and wetting, coupling agents and surface treatments have been used. The rigidity of reinforcing fibres where strong adhesion is present leads to the restriction on the matrix segmental motions near the interface. This has been verified by research of supported polymer thin films on silicon substrate (DeMaggio et al., 1997; Lin et al., 1999). Tsengolou et al. (2006) confirmed the theory presented by Bao and Yee (2002) that water diffuses rapidly into composites along the fibre-matrix interface if wetting of the fibres by the matrix is incomplete. They also supported the fact that by improving adhesion and wetting, this will inhibit the environmental agents to penetrate and destroy the interface, thereby suppressing subsequent hygrothermal degradation in composites.

2.8 Natural Fibres


The use of natural fibres as an effective alternative for glass fibres in engineering composites is becoming increasingly important. Although, in this body of work more conventional fibres1 are looked at, it is necessary to evaluate the knowledge accumulated through research of moisture absorption of natural fibres. Natural fibres generally have more disadvantages than conventional fibres including lower impact strength and higher moisture absorption rates. The latter is of great importance in this study. Natural fibres also suffer from dimensional changes, thermal instability and micro-cracking (Athijaymani et al., 2009). A study conducted in order to assess the effect of different fibre loadings on the absorption of moisture, found that with an increase in fibre content and length there is an increase in moisture absorption (Bunsell, 1984). The transport of water via micro-cracks, flow of water molecules through the fibre-matrix interface and diffusion through the bulk matrix are almost identical in all fibres, and thus the capillarity mechanism is almost indistinguishable. Decreases in tensile strength of natural fibres are also similar to those of conventional fibres reported in literature. In dry conditions, an increase of tensile strength with increasing fibre content is evident, however it is important to note that the decrease in tensile strength of wet specimens are the same, irrespective of fibre content.

Carbon Fibre, Glass Fibre and Boron Fibres.

15

2.9 Thermoplastic versus Thermoset polymers


Epoxies are the most widely used matrix system in advanced composites, however epoxy resin is most susceptible to moisture absorption (Daniel and Ishai, 1994). Epoxy resins typically absorb over 4% moisture by weight, where thermoplastic resins absorb less than 1% by weight (Baker et al., 2004). As discussed in section 2.5, thermoset composites can experience a decrease of up to 40% in a number of their mechanical properties. Conversely, when exposing thermoplastic composites to similar environments their properties are not adversely affected. Chen-Chi and Shih-Wen (1991), found that thermoplastic composites, such as carbon fibre reinforced polyetheretherketone (PEEK/CF, trade name APC-2) showed excellent retention of mechanical properties even at 80C, 85% RH. Polyphenylenesulfide composites (PPS/CF) showed a small decrease at the same temperature and relative humidity; however this degradation was mainly due to thermal effects. Similar findings were reported by Matthews and Rawling (1994) and Ma and Yur (1991), who experimentally confirmed that PEEK, like many thermoplastic matrices, does not absorb a significant amount of moisture. Even when used in wet conditions at elevated temperatures as high as 120C, PEEK still retains its mechanical properties.

2.10 Digital Image Correlation (DIC)


Digital image correlation (DIC) is a computer-based image analysis technique that enables the measurement of strain and displacement over a virtual grid on a materials surface (Haddadi and Belhabib, 2007). It is a non-contact method as it allows the strain to be measured without any disturbance to the mechanical response of the material. It is low cost and the experimental setup is relatively easy.

The technique is based on the comparison of images taken with a digital charge coupled device (CCD) camera at different increments of the load applied (Dempsey, 2010). Before testing the specimen must be coated with a random speckle pattern. This is done by applying a white coat; a point airbrush can then be used to obtain a random speckle. The quality of the applied speckle pattern has a great influence on the accuracy of the results. Lecompte et al., (2005) completed extensive research on the quality of speckle patterns for digital image correlation. The suggestions were used in section 4 of this thesis and therefore a detailed analysis will not be included here. Other errors that influence the correlation 16

results include: size of the subset, distortion and systematic errors caused by gray-value interpolation (Haddadi and Belhabib, 2007).

2D DIC utilizes one camera to take images of this pattern on the surface of the specimen. These images and data are then post processed in order to determine the strains and displacements (Yaofeng et al., 2007). During the post processing contour plots are

generated. These are useful to determine the areas of interest as any stress concentrations would be visible.

2.11 Fractography studies


The use of scanning electron microscopy (SEM) as a method of analyzing the fracture surfaces of composites has become increasingly important. Fractography studies can reveal the mode of deformation for comparison and the exact mechanical deformation; it is thus ideal for use in-service to determine the fracture of a real product. SEM is one of the most versatile instruments available for the examination and analysis of the microstructural characteristics of solid objects (Goldstein et al., 1981). SEM has a large depth of field; this allows more of a specimen to be in focus at one time (Schweitzer, 2010). The degree of magnification is also more controllable, as SEM utilizes electromagnets rather than lenses. By using SEM, a better understanding of structure-property relations can be obtained. Analysis on the microstructure characteristics such as fibre shape, diameter and structure (e.g. crystal size, voids) can help determine the expected mechanical properties of the material. Fibre dispersion or misalignment in the laminate during manufacture can also be determined. Misaligned fibres can cause micro-buckling of fibres and is therefore important (Nakanishi et al., 1997). The fibre-resin system, the mechanisms of the crack nucleation and propagation and the temperature at which fracture occurred also affects the fracture surface. Room temperature fracture causes deformation of soft or rubbery phases, while fracture at colder temperatures causes less deformation. Fracture at colder temperatures however tends to be less reproducible.

SEM conducted to observe the effect of moisture absorption on the fracture surfaces of carbon-fibre/epoxy specimens showed that the fibre-matrix interface becomes poor with increasing moisture content (Selzer and Friedrich, 1995). The effect was observed by 17

comparing micrographs of dry and wet specimens. Fracture surfaces of dry specimens showed large scale hackling. Failure of the interface is evident at the wet specimens, which show less hackling, with more bare fibres visible. Pantelakis et al., (2010) observed a swelling at the fracture surface for wet specimens loaded in tension. This could indicate extensive delamination and intralaminar cracking. An irregular fracture pattern was observed in wet specimens loaded in fatigue; specifying a more gradual and less brittle fracture mode occurred. Another observation that is particularly important is the degree of fibre pull-out. Fibre ends will be present in the fracture surface depending on the degree of fibre pull-out. Gilchrist and Svensson, (1995) have established a relationship between the loading mode and the number of fibre ends found on the fracture surface, and thus will not be further discussed herein. The degree of fibre pull-out also has a direct relationship to the strength of the adhesion of the fibres to the matrix. The better the adhesion the more fibre pull-out and vice versa.

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Chapter 3

Theoretical Analysis

3 THEORETICAL ANALYSIS
This chapter describes the relevant theory associated with the evaluation of moisture absorption on composite materials, when exposed to either a humid environment or fully immersed in water. Section 3.1 outlines Fickians Law of diffusion and derives the equations necessary to determine the diffusion coefficient. Section 3.2 reviews the interlaminar shear strength characteristics and the equation required in order to determine the interlaminar shear strength of the material.

3.1 Diffusion and Ficks second law


Polymer composites can exhibit both Fickian and Non- Fickian moisture absorption characteristics with the diffusion process. The former being discussed here. Diffusion in polymer composites is influenced by a variety of variables such as; loading, fibre arrangement and interface characteristics. These variables have been thoroughly examined by Bao and Yee (2002) and therefore will not be repeated here. Using Ficks second law, which is applicable to homogenous and isotropic materials, the experimental data can be rationalized. This method has been verified as being valid for carbon fibre-reinforced epoxy resin composites (Shen and Springer, 1975).

Cranks (1987) theory of plate diffusion is followed here. It holds for a relatively large and thin plate of composite material. In the z direction being the thickness of the material, the water concentration can be accumulated by the one-dimensional diffusion equation. (3.1)

Where D is the diffusion coefficient and is considered to be constant in the direction of diffusion z so that equation (3.1) can be rewritten as:

(0 z L, t > 0)

(3.2)

The boundary conditions are: c = c0 c = c (0 < z < L, t < 0) (z = 0, L, t > 0)

19

Where t is time; L, thickness of the specimen; z, distance measured from the bottom surface; subscripts 0 and represent initial and fully saturated states, respectively; and Dz is the moisture diffusion coefficient in the z-direction. Equation (3.2) can then be solved and equation (3.3) is established. { } { } (3.3)

The percentage of water absorbed in the composite is defined as follows: (3.4) This can be abbreviated as: (3.5) Using equations (3.3) and (3.4) and estimating at a specified time t, this can be reduced to ( ) (3.6)

At the initial time t0, the absorbed water is then given by: ( ) (3.7)

By plotting the percentage moisture content, M against the square root of time, the resulting figure would be:

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Figure 3-1. Fickian Diffusion Curve (Shen and Springer, 1975; Greene, 2007)

The following equation can then be used to determine the diffusion coefficient from the experimental data plot (obtained from the slope) and the diffusion mechanism identified. ( ) (

(3.8)

Where Mm on the graph represents the moisture content at saturation or M in equation (3.8).

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3.2 Interlaminar Shear Strength (ILSS)


The interlaminar shear strength (ILSS) is dominated by the matrix and fibre/matrix interface (Khan et al., 2010). Hull (1981) experimentally confirmed this by observing that crack propagation can occur entirely by shear of the matrix without disturbing or fracturing any of the surrounding fibres. It is thus a measure of the in situ shear strength of the matrix layer between plies (Daniel and Ishai, 1994).

3.2.1 Equation for calculating the ILSS


The following equation was obtained from Daniel and Ishai (1994) in order to calculate the interlaminar shear strength of the test specimens. The dimensions needed, can be seen in Figure 3-2 below.

(3.9)

l
Figure 3-2. Specimen dimensions

The load at failure initiation (P) is divided by the product of the width of the specimen (w) and the distance between the notches (l). Units of Pascals (Pa) or Newton per metres squared (N/m2).

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Chapter 4

Experimental

4 EXPERIMENTAL
This section contains an in-depth explanation of the test methods used to obtain the data discussed in Chapter 5. This section was imperative in the project, in order to verify assumptions made and substantiate the results obtained by other researchers. This section follows a sequence, or an order, in which the experimental studies were carried out. Section 4.1 outlines the material, manufacturing and the relative humidity environment the specimens were immersed in. Section 4.2 describes the experimental procedure and apparatus used in order to carry out the ILSS test. Section 4.3 outlines the DIC process and analysis and finally section 4.4 describes the equipment and sample preparation needed in order to carry out SEM on the fracture surfaces.

4.1 Material 4.1.1 Test specimens


Two symmetric laminates, with [08]s and [06 902]s configuration using HTA/6376, were laid up and cured in an autoclave at 180C for two hours, in accordance with Hexcel recommended curing cycle. Using a diamond blade saw, the laminates were then grooved and cut to manufacture single lap joints, with overall dimensions of 12.5mm x 179mm x 2mm. The notch depth of 1mm, width of 2mm and an overlap area of 5mm, are shown in Appendix B. Actual dimensions of each specimen were measured using a Baty R400XL shadowgraph projector with a Metronics Quadra Check 2000 monitor (Figure 4-2). For each specimen the average of three measurements per dimension was used. A total of twenty one specimens of each lay-up were manufactured and tested. Information on the fibre treatment for improved fibre-matrix adhesion was not available. The average fibre volume fraction (Vf) was 59.2%.

4.1.2 Conditioning and Specimen Exposure


The cut surfaces were carefully polished in order to remove possible edge damage effects; due to the cutting operation. The specimens were then dried in an oven at 120C for 60 minutes. The dry specimens were stored in a dessicator to control the relative humidity and the wet samples immersed in a bath of de-ionized water and kept at room temperature (19 2C) in a sealed plastic container. Exposing the specimens to a 100% RH environment, by fully immersing them in water, is the worst possible moisture attack (Selzer and Friedrich, 23

1995). All samples were orientated in a vertical direction to permit water diffusion to occur from both sides of the samples during the process of water absorption. After two time periods - two and four months, the specimens were subjected to interlaminar shear strength tests.

4.1.3 Measurements
The specimens underwent weekly measurements where the specimens were quickly removed from the container, wiped down with a microfibre cloth, in order to remove any excess water or surface condensation, and weighed on an Explorer Analytical Balance (Figure 4-1) with a resolution of 1 x 10-4g. For each measurement a minimum of three replicates were used. To ensure minimization of any discontinuity in the moisture absorption process, the weighing process was completed in a relatively short time frame and the effect of this removal on weight gain determination was negligible.

Figure 4-1. Explorer Analytical Balance

The thickness and notch width of the specimens were measured using a Baty R400XL shadowgraph projector (1) with a Metronics Quadra Check 2000 monitor (2) (Figure 42). This process was repeated for the entire immersion period. All specimen weight gain values can be found in the corresponding tables in Appendix D, where the mass gain due to moisture absorption is measured in terms of the percentage of the dry mass of the material. 24

Figure 4-2. Shadowgraph Projector

4.2 Interlaminar Shear Strength (ILSS) Test


A standard test method (double-notch) for interlaminar shear strength of the material was carried out. To avoid out-of-plane bending a clamp (Figure 4-3) for the interlaminar shear test was manufactured, adapted from ASTM Standard D3846-08. A detailed drawing of the clamp is illustrated in Appendix C. This test method only requires a small amount of material and this allowed for several specimens to be tested which provided a reliable statistical description of the data. Testing was performed under three conditions: Dry, withdrawal I (2 months) and withdrawal II (4 months). Seven specimens of each condition and lay-up configuration were tested. The tests were performed at room temperature in a laboratory air environment. When testing the wet specimens care had to be taken in order to ensure the environment did not affect the specimens. The specimens were removed 30 minutes prior to testing and stored in a plastic bag to minimize interference in the moisture content and were then immediately tested. During the testing procedure, a distinct difference between the dry and wet specimens was observed.

25

Figure 4-3. Clamp used in ILSS Testing

4.2.1 Experimental Apparatus and Procedure


The experimental tests were performed using a Tinius Olsen H25KS mechanical testing machine. The experiment was set up as shown in Figure 4-4 using a 25kN Load Cell (1). The specimen (2) was placed in the clamp (3) so that it is flush with the base and centred. The screws were torque finger tight. Using the control panel (4) the load and extension was zeroed. The specimen assembly was gripped at both ends using serrated wedges (5). The specimen was then tested in increments of 1mm/min at the cross head. Upon failure, the maximum load carried by the specimen during the test was recorded. A force against extension graph was plotted. After failure occurred the specimens were unloaded at a constant cross head rate of 25mm/min. The interlaminar shear strength was determined using equation (3.9) and compared with published values for the material.

26

1 Lo 5 ad Lo Cel 3 ad l Lo Cel 2 ad l 4 Cel Cel l l

Figure 4-4. Tinius Olsen H25KS Model

4.3 Digital Image Correlation (DIC)


The three main steps in the correct usage of DIC include; (1) Acquisition, which involves the surface preparation of specimens and correct illumination. (2) Interrogation, relating to the correlation and estimation process. (3) The validation or the analysis of the results.

Preparation of Specimens The area of interest on the specimens was sprayed using a coat of acrylic white paint. Using a Badger Airbrush model 200-3, a finely dispersed, non-uniform pattern coat of black was then applied. A fully prepared specimen can be seen in Figure 4-5.

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Figure 4-5. Speckled Specimen

Equipment A high magnification camera (1) was attached to a horizontal rail (2) using mounts (3) (Figure 4-6). The tripod (4) setup was positioned in front of the Tinius Olsen. Two LEDs (5) were connected and used as gated light sources. The procedure in section 4.2.1 was then followed to prepare the test. The 2D DIC was started simultaneously with the Tinius Olsen. The loading was continued until failure occurred. The DIC was then stopped and the test specimen was unloaded. Before each test, the focus of the camera was adjusted in order to ensure a sharp, focused view of the speckle pattern. In the Da Vis 7.4.0.99 software, the number of images to capture was set to 2500 and the frequency of the image acquisition was set to 3Hz. This procedure was carried out on 3 specimens of each lay-up configuration for dry and withdrawal I time periods.

28

Figure 4-6. Strain Master experimental setup (adapted from La Vision, 2010)

Validation and Analysis Using the strain master DIC system, the movement of the surface pattern applied to the specimen under stress was traced. This was used to determine the strain and displacement in the x- and y-direction, xx, Vx, yy and Vy respectively.

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4.4 Fractography Studies


All specimens tested were examined visually and with the aid of a TRAVELER Universal Serial Bus (USB) Microscope (1.3 Megapixel). Any cracks or delamination which occurred during the handling or testing of the specimens were also recorded. Thorough investigations on the effects of moisture on the fracture surfaces of the specimens were examined by Scanning Electron Microscopy (SEM). The specimens had to be prepared with a conductive coating prior to imaging. Using Argon gas, the specimens were sputter coated with gold in a vacuum chamber. Using a Deposition Rate against Deposition Current graph, suitable values were selected for the specimens. The specimens were then mounted on an aluminium stub for analysis. A JEOL JCM 5700 (Figure 4-7) was used at magnifications ranging from x100 to x3000.

Figure 4-7. JEOL JCM 5700 (www.jeolusa.com)

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Chapter 5

Results and Discussion

5 RESULTS AND DISCUSSION


This section analyses the results from the present work. The analysis begins with Fickian diffusion and specimen weight gain and its subsequent effects on the volumetric expansion of the laminates. The effect of moisture on the ILSS is discussed in section 5.2. Displacement and strain contour plots obtained using Digital Image Correlation (DIC) is examined in section 5.3. The findings of the investigation into the fibre/matrix interface using Scanning Electron Microscopy (SEM) are discussed in section 5.4.

5.1 Fickian Diffusion and Specimen Weight Gain


In order to ensure that saturation of the specimens occurred, the key factors affecting diffusion were optimized. Selzer and Friedrich (1995) and Hao et al. (1992) demonstrated that specimens absorbed more moisture at low temperature/high relative humidity than at high temperature/low relative humidity conditions. This was taken into account and due to the time constraint and the inability to control the water temperature; the specimens were immersed for a maximum of four months in a 100% RH environment. The specimen dimensions and laminate configurations were also optimized in order to guarantee saturation. The thickness was reduced by using the smallest number of plies, however still maintaining a sufficient thickness in order to ensure good ILSS test results (section 5.3.4). By following the weekly weigh-in procedure outlined in section 4.1.3 and by using equation (3.4) and (3.5), the moisture gain percentage was plotted against the square root of time (Figures 5-1 and 5-2).

The results shown in the subsequent graphs were averaged from the measurements of 7 specimens. The curves have not been fitted and no points have been excluded. Some scatter of the data points were observed during the accumulation of the moisture absorption data. This can be due to a number of reasons; the variation of voids on the different specimens, as they were cut from different parts of the panel. The fibre dispersion was also assumed to be the same within each specimen; however from the SEM (section 5.4) it was evident that this was not the case.

31

0.9 0.8 Moisture gain percentage (Wgain %) 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 2 4 6 8 10 12 Sq. root time(t1/2) days
Figure 5-1. Moisture content (w/w %) - [08]s configuration

Withdrawal I Withdrawal II

1 0.9 Moisture gain percentage (Wgain %) 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 0 0 2 4 6
Sq. root time(t1/2) days Figure 5-2. Moisture content (w/w %) - [06 902]s configuration

Withdrawal I Withdrawal II

10

12

32

As mentioned earlier, due to the time constraint on the immersion time, the specimens were only immersed for a maximum of 4 months. As evident from Figures 5-1 and 5-2, this only allowed for the first diffusion stage to be documented. The second stage, which is dominated by the deterioration and relaxation processes, could not be assessed. During the initial stage of immersion the weight of the specimens increased rapidly. The rate of weight gain decreased with time; however the average slope remained constant. This verified Shen and Springer (1975) findings that carbon fibre-reinforced epoxy composites follow Fickian diffusion behaviour. This also indicates that at 4 months (withdrawal II) the specimens, although closer to saturation than at 2months (withdrawal I), had not reached a state of full saturation upon withdrawal. On average the room temperature varied from 19C 2, while the water temperature varied from 19C 3. One week both temperatures fell significantly below the average, with the room temperature being 14C and the water temperature as low as 11C. This affected the rate of diffusion of the specimens; a direct relationship between the temperature and moisture uptake was established, with a decrease in temperature causing a lower weekly absorption rate. This is illustrated in Appendix D, where the specimen weight gain values, room and water temperature data is presented as well as additional notes.

The maximum mass content varied slightly depending on the lay-up configuration. The maximum mass content was higher for the [06 902]s specimens (Table 5-1). This could be explained by the residual stress that developed in the laminates during the cool down period of the material after curing. The residual stress is a function of a number of properties including stacking sequence and ply orientation (Hull, 1989). Subsequently, the residual stress is higher if the thermally anisotropic plies are oriented along different directions. The residual stress in the [06 902]s specimens was thus higher than that in the [08]s specimens. According to Perlevliet et al. (1996), the higher the residual stress, the higher the moisture uptake. The effect of residual stress in the laminates is discussed further in section 5.2.

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Table 5-1. Moisture content (w/w %)

Exposure Time Moisture Gain [08]s 0.626%

2 months [06 902]s 0.762% [08]s 0.784%

4 months [06 902]s 0.906%

The moisture level obtained compared well with those reported in literature. Matthews and Rawlings (1994) predicted that epoxy resins absorb between 1% and 10% by weight of moisture, so a typical composite with 60% fibre volume fraction (Vf) will absorb around 0.3 to 3% moisture. The average Vf for HTA/ 6376 was 59.2% and therefore the moisture level obtained compared well with those obtained from other authors using similar Vf ratios. As previously stated, this thesis has studied moisture absorption from a macroscopic point of view. Whereby the fibre/matrix interface is examined and the overall effects on the lamina are considered. The work obtained here is a good starting point for the design and manufacturing considerations necessary when selecting composite material for certain applications. To effectively consider these results for industry applications the differences are important to note. It is important to note that both faces of the specimens were exposed to de-ionized water, where in-service conditions only expose one face to the atmospheric environment. In addition, the specimens did not have a protective coat and thus different paint schemes on aircraft could have an effect. The specimens were exposed to a constant 100% RH environment for the specified time period. In-service, the level of moisture in the material is known to fluctuate as the material may dry during flight where the humidity is low. Due to this, the time to reach saturation or equilibrium will be longer. Materials that are fully exposed or shaded can lose mass due to erosion and ultraviolet (UV) degradation of surface matrix or paint layers. There are thus a number of variables that have to be considered, including different exposure conditions with the respect to where the aircraft is operating. Therefore, the results illustrated in this thesis represent an usually severe condition. Typical equilibrium moisture contents for epoxy-based composites were found to range from 0.7% to approximately 0.9% after long-term outdoor exposure (Hull, 1981; Vodicka et al., 1999; Zagainov and Lozino-Lozinski, 1996). The percentage achieved in this short-term constant exposure study fell within this region with [08]s specimens having values of 0.78% in specimen weight gain and the [06 902]s specimens having values of 0.9%. Another key parameter is the specimen thickness. The specimen thickness was optimized in this study in order to maximise the rate of diffusion. 34 In-service panel

thicknesses and lay-up configuration may differ considerably. Although, the zero dominated lay-up configurations used in this study is representative of lay-ups suitable for composite aircraft wing skins (OHiggins et al., 2004).

5.2 Volumetric Expansion


As well as the weekly weigh-in, the specimen dimensions were closely monitored with the distance between the notches, thickness and width of each specimen noted (Appendix D). In the initial stage of the immersion, it was found that even with an increase in the total mass there was no overall volume change, this is due to the fact that water may occupy preexisting space in the material first, therefore resulting in no overall volume change during the initial stage of diffusion. On the other hand, water may force its way into the material by opening pre- existing cracks and structural imperfections thereby leading to an increase in the total mass and an increase in the overall volume. The overall volume change for both configurations can be seen in Table 5-2.

Table 5-2. Volume Change (%)

Volume Change (%) Specimen Configuration [08]s [06 902]s Withdrawal I 8.7% 7.2% Withdrawal II 10.2% 8.7%

It is important to note that the volume change in all directions was not equal. The greatest dimensional change occurred in the laminate thickness, at the region between the notches. The main reason for this is that in the area between the notches, diffusion not only occurs through the surface of the specimen but also diffuses into the region in between the notches, thereby causing the rate of diffusion in that area to be the highest. The fibres absorb little or no moisture and it is mostly only the resin matrix that absorbs moisture (Matthews and Rawlings, 1997; Daniel and Ishai, 1994; Cervenka et al., 1989). The absorbed water softens the epoxy resin, causing it to swell, therefore increasing the laminate thickness. The volume change was found to be in line with Belani and Broutman (1978), who suggested that, due to the presence of moisture the laminates swell in the direction transverse to the fibre direction.

35

Some deviation between the moisture and volume change between specimens were also found (Appendix D). This could be due to a number of different types of manufacturing defects such as voids, delaminations, resin starvation, resin-rich pockets, damaged fibres or fibre-matrix debonding (Hyer, 1998). The specimen weight gain and volume change also fluctuated from week to week. This could be due to the weight measurement process, as the data found from extracting a wet specimen from water is easily influenced and manipulated by the surroundings (Bunsell, 1984; Stone, 1969). Great care was taken to ensure minimal interference, by using a weighing scale with a resolution of 1 x 10-4g and using a minimum of three replicates of each measurement. During the process, the specimens were quickly removed from the container, wiped down with a microfibre cloth, in order to remove any excess water from the surface. However, once the surface of the wet specimen becomes dry, it can start to dewater and thereby changing its inner moisture distribution. If a specimen is thick, the change happens locally and is therefore negligible however this is not the case for the thin specimens used in this study (Tsai et al., 2006).

5.3 Interlaminar Shear Strength (ILSS)


The main objective of this thesis was to investigate the effect of moisture on the fibre/matrix interface of carbon fibre/epoxy laminates and consequently its effect on the mechanical properties. It is well known that the fibres do not absorb moisture but only the resin. Therefore it is the strength of the fibre/matrix interface which needs to be tested. A simple tensile test would not suffice, as it measures the strength of the fibres. The ILSS test was therefore chosen. The ILSS is a matrix dominated property and is dependent on factors such as moisture and temperature and is ideal for the analysis (Daniel and Ishai, 1994; Khan et al., 2010). The visible changes in the fibre/matrix interface will be discussed in section 5.5.

5.3.1 ILSS Results


Table 5-3 shows a comparison between the ILSS values for dry, two month (Wet I) and four month (Wet II) withdrawal specimens. The ILSS values are seen to increase over time when exposed to moisture. In literature it has mostly been reported that moisture causes degradation in mechanical properties; however, when examining these reports closely it is evident that this only occurs when laminates are exposed to moisture at elevated 36

temperatures. Matthews and Rawlings (1994), Choi et al. (2001) and Akbar and Zhang (2008) also validated this with their research and found a decrease in ILSS only occurs at elevated temperatures.

Table 5-3. ILSS values

Lay- up Configuration
[08]s [06 902]s

Interlaminar Shear Strength (MPa) Dry


36.1 2.9 19.8 0.9

Wet I
37.5 2.6 23.0 1.8

Wet II
40.2 3.30 23.2 1.19

Table 5-4 shows the percentage increase in ILSS values as a function of exposure time. The influence of moisture is predominant in the [06 902]s laminates, with increases of up to 18.73% after four month immersion. The [08]s laminates obtained increases of almost half the percentage of the [06 902]s laminates, with a maximum value of 11.3% after four month immersion. The effects of moisture on the mechanical properties of composite materials have been well documented in previous literature, however the magnitude of the effect is not agreed upon. The results found in this thesis compared well to published values by Vodicka et al. (1999), who confirmed that at temperatures below the Tg, the presence of moisture increases the ILSS by about 15%.

Table 5-4. ILSS percentage increase values

Lay-up Configuration

Withdrawal 2 months

Withdrawal 4 months

Percentage Increase (%) [08]s [06 902]s 3.76 17.65 11.30 18.73

From the results it is evident that the interlaminar shear strength of a material is a function of the laminate stacking sequence (Daniel and Ishai, 1994). The [08]s laminates have higher ILSS values than the [06 902]s laminates. However, the [06 902]s laminates obtained a higher increase in ILSS due to the absorbed moisture. The design criteria for certain applications can thus be fulfilled by controlling the stacking sequence of the laminates.

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5.3.2 Stress State


The interlaminar shear strength of a resin matrix is dependent on the stress concentration effects associated with the presence of fibres and voids and on the strength of the interfacial bond (Hull 1981). Therefore, in order to effectively explain the phenomena of the ILSS increase over time due to moisture absorption, two factors have to be considered. (1) The stress state in the material before immersion and (2) the stress state in the material after immersion in de-ionized water.

Before immersion A laminate is considered to be stress free at a certain temperature during the curing process. This temperature is normally taken as the glass transition (Tg) temperature of a polymer matrix. When the laminate cools down to room temperature after being cured at an elevated temperature, residual stress develops in the laminate (Lubin, 1998). Similar to hygrothermal effects, residual stresses are a function of certain parameters including ply orientation, stacking sequence and fibre volume ratio (Daniel and Ishai, 1994). Subsequently, the residual stress is higher if the thermally anisotropic plies are oriented along different directions (e.g. [06 902]s configuration laminates). This can also be verified by looking at the [06 902]s moisture gain results. According to Perlevliet et al. (1996), the higher the residual stress, the higher the moisture uptake. This was verified in section 5.1 with the [06 902]s laminates absorbing more moisture than the [08]s laminates. The effect of curing cycle on the development of residual stresses has been studied by a number of researchers and will thus not be included herein (Kawata and Akasaka, 1981; Parlevliet et al., 2006). The residual stress in the laminate is non uniform and this leads to stress concentrations developing in the laminate. The cut notches also caused some stress concentrations at the notch root vicinity (Zagainov and Lozino-Lozinski, 1996).

After immersion The matrix expands or swells during moisture absorption and this leads to a change in the stress state in the material. The swelling of the matrix has caused the stress (residual stress and stress concentrations due to the notches) to distribute over a bigger volume of the material, subsequently causing the laminate to fail at a higher load. The stress and strain fields within the material also changed due to the mismatch in moisture-induced volumetric expansion between matrix and fibres, as the epoxy matrix absorbs a significant amount of 38

moisture, where the fibres absorb little or no moisture (Akbar and Zhang, 2008; Selzer and Friedrich, 1995).

The effect of the redistribution of the stress (residual stress and stress concentrations due to the notches) is only a possible explanation and a more precise analysis of the effect on the residual stress is necessary.

5.3.3 Flexibility of Resin


An important observation was that when the specimens were tested, the extension (or elongation) of the specimens were higher with an increase in immersion time. This can clearly be seen on the Force against Extension graphs (Figure 5-3 and 5-4). With an increase in exposure time, the increase in the attainable load is coupled with higher extension values. The higher extension values are mainly due to the softening of the resin with an increase in moisture content (Selzer and Friedrich, 1997; Matthews and Rawlings, 1994). This was also observed by Hull (1981) and Hamerton (1996) who explained that moisture affects the flexibility of the epoxy resin, reducing the basic hardness and rigidity, thereby also decreasing the brittleness and increasing the ductility. This would also mean that the more the specimens absorbed water, the more the stiffness decreased and the toughness increased. Plasticization of the matrix is also a contributing factor to the increase in ILSS values. Moisture infuses into the polymer; thereby causing the polymer molecules to separate. The molecules can then easily move past the critical strain levels, due to the reduction in their secondary bond attraction. This causes plasticization of the matrix and would result in a lower glass transition temperature Tg (Hao et al., 1992; Huang and Sun, 2007).

39

3500

3000

2500

Force (N)

2000 Dry 1500 Wet I Wet II 1000

500

0 0 0.5 1 Extension (mm)


Figure 5-3. Force against Extension [08]s

1.5

1600 1400 1200 1000 Force (N) 800 600 400 200 0 0 0.2 0.4 0.6 Extension (mm)
Figure 5-4. Force against Extension [06 902]s

Dry Wet I Wet II

0.8

1.2

40

Table 5-5 and 5-6 illustrate more exact values including the standard deviation between the load and extension values for both laminate configurations. It is evident that the increase in ILSS is directly coupled with the increase in elongation. The increase in elongation is higher for the [06 902]s specimens with an increase of 4%, compared to an increase of 2.7% for the [08]s specimens.
Table 5-5. [08]s Specimen - Load and extension values

[08]s specimen Dry Wet I Wet II

Load (N) 2336 195 2553 193 2687 224

Extension (mm) 1.402 0.19 1.442 0.22 1.445 0.15

Table 5-6. [06 902]s Specimen - Load and extension values

[06 902]s specimen Dry Wet I Wet II

Load (N) 1311 121 1477 104 1484 74

Extension (mm) 0.94 0.20 0.98 0.05 0.98 0.24

The increase in extension values does not mean a subsequent increase in the elastic modulus (E). The elastic modulus can either be reduced or could even remain unaffected (Akay et al., 1997). A decrease in E can clearly be seen in Figures 5-5 and 5-6, where the Stress against Strain was plotted. The elastic modulus is determined by the slope of the graph. With an increase in immersion time, an increase in elongation values is found with a subsequent decrease in elastic modulus. As discussed previous, moisture has the effect of flexibilising the epoxy resin, reducing the elastic moduli (Hull, 1989). It is therefore important to note, that while an apparent increase in ILSS values are found other mechanical properties degrade due to the absorbed moisture.

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50000000 45000000 40000000 35000000 Stress (N/m^2) 30000000 25000000 20000000 15000000 10000000 5000000 0 0 0.5 1 Strain
Figure 5-5. Stress against Strain [08]s specimens

Dry Wet I Wet II

1.5

25000000

20000000

Stress (N/m^2)

15000000 Dry 10000000 Wet I Wet II

5000000

0 0 0.2 0.4 0.6 Strain


Figure 5-6. Stress against Strain [06 902]s specimens

0.8

1.2

42

Reversibility/Irreversibility The reversibility/irreversibility of the effects on the mechanical properties has not been experimentally investigated in this thesis, however it is worth mentioning. The most deleterious effects on stiffness and strength are produced by a combination of elevated temperatures and high moisture concentration. It is known that only at high temperatures, the effects on the mechanical properties would be irreversible (Selzer and Friedrich, 1997). Akbar and Zhang (2008) found that the water absorbed by the epoxy laminates at low immersion temperatures ( 20C), causes reversible plasticization of the matrix. However, when combined with temperature effects, these factors cause significant changes in the matrix toughness which would be irreversible. Similarly, Matthews and Rawlings (1994) and Khan et al. (2010) proposed that the flexibility of the resin and the decrease in the elastic modulus values will return to its original value, when the environmental conditions change and the moisture diffuses out. Recommendations for future research in this area are discussed in more detail in section 6.2.

5.3.4 Limitations and constraints during ILSS testing


The ILSS test had some limitations; however, the non-expensive method and the reproducibility of the results proved to be an accurate measure of the integrity of the fibre/matrix interface. The principal criticism of the test is that severe stress concentrations are induced in the specimen at the notch root vicinity, making the determination of the shear strength questionable. Another limitation is that the shear modulus is not obtained.

Tinius Olsen
The Tinius Olsen was used to carry out the ILSS tests. Some slippage of the wedge grips occurred particularly at the start of the test. This can be seen in the obtained Force against Extension graphs (Appendix E). Perfect vertical alignment between the grips was also found to be difficult during the testing procedure. Misalignment of the specimens in the grips could also have occurred. This caused some scatter in the results obtained; however this is not likely to be the governing factor, as the misalignment would not be repeatable. Deviation from linearity on the graphs could also be due to the properties of the resin (Hull, 1989).

43

During testing of the [06 902]s laminates, there was a difficulty in determining the exact strength, as the complete failure of the laminate was preceded by fracture of individual laminae. This was evident at around 800-900 Newtons, where a cracking noise was heard. It is therefore important to note, that while the laminate can sustain an increasing load, incipient failure has already occurred.

Effect of Notch depth


During experimentation it was evident that the double notch shear test is very sensitive to the accuracy of the depth of the notches. According to Shokrieh and Lessard (1998), bending stresses will occur in the gauge area if the depth of the notch is overcut or more than half the specimen. Similarly, compressive stresses will occur in the gauge area, if the depth is undercut or less than half the specimen. During manufacture it was very difficult to control the notch depth and consequently, some scatter in the results was found. It was necessary to find a suitable method in order to eliminate any points that were out of scope and a statistical analysis was used in order to eliminate this. The lay-up configuration also needed to be considered due to the limitations of the double-notched shear test. As a tensile load applied to a double-notch specimen with a 90 lay-up would result in a tensile matrix failure prior to failure in interlaminar shear (Shokrieh and Lessard, 1998). A [06 902]s configuration was used and the experiments showed that the failure for this configuration occurred between the 0 and 90 lay-up.

Thickness of Specimen
Shokrieh and Lessard (1998) also suggested that in order to complete a better shear test, the number of plies should be as high as possible. However, due to the difficulty in manufacturing the specimens, as a thicker lay-up is more prone to human error in the alignment of the plies and the constraint in exposure time, more than 32 plies would not have been feasible. Less than 16 plies would also be undesirable due to the sensitivity of external effects including out-of-plane deformation.

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Statistical Analysis
Three approaches were used in order to eliminate any results that fell outside of the range of data. Initially, an Analysis of Variance (ANOVA) approach was used in order to determine whether the means of the groups were all equal. However, after closer examination, too many variables were present such as the effect of notch depth, length between the notches and the width of the specimen. An analysis of the variables affecting the ILSS results was thus conducted on the seven specimens for each lay-up configuration and for each immersion period. The ILSS results were examined and the outliers identified. As the specimens were clearly marked, each outlier and corresponding specimen was then looked at collectively.

Carbon-fibre reinforced epoxy laminates, or composite laminates in general, comprise of mechanically dissimilar phases. Therefore, depending on the type of mechanical test, different failure modes will occur. When the matrix or fibre/matrix interface is tested, such as the tests conducted in this thesis, failure normally occurs by matrix cracking or shearing of the fibre/matrix interface. Fibres are normally stiff and brittle and this results in fibres rupturing in tension or buckling in compression (Hull, 1981; Hart-Smith, 2004). The fracture surfaces of the specimens therefore had to be examined for specimens with severe fibre pull out or breakage. This would indicate that during the ILSS test, the fibres might have taken the load and therefore the values would be higher. This would signify that pure shear did not occur and the values will therefore be invalid and could not be included in the analysis. A direct relationship was established with the [08]s specimen outliers and the degree of fibre rupture or breakage. Specimens that had significantly higher values were correlated to a higher degree of fibre breakage. As mentioned previous, the double-notch shear test is very sensitive to the accuracy of cutting the notches (Chiao et al., 1977). Specimens with notches overcut or undercut were also identified and there corresponding values examined. Specimens with notches undercut had lower values. Shokrieh and
zz

Lessard (1998) explained this by illustrating that undercutting causes higher positive

inside the notch location leading to premature failure. Failure did not occur at the interface between the two layers and therefore the ILSS test was invalid. After eliminating the outliers, a standard statistical analysis was used whereby the standard deviation and mean average between the groups were determined (Appendix E).

45

5.4 Digital Image Correlation (DIC)


The evaluation of the displacement and strain in the region in between the notches were of focus during the analysis. This data was collected and analysed using various tools from the Da Vis 7.4.0.99 software (Section 4.3). It was assumed that the best approach was to start the analysis at the specimen displacement in the x- and y-direction, as certain criterion was expected. Minimal to zero displacement in the x-direction (Vx) was detected this is due to the clamp and the Tinius Olsen wedge grips (Figure 5-7).

(a)

(b)

Figure 5-7. Wet I [06 902]s x-displacement (a) At failure (b) After failure

Figure 5-8 (a) and (b) present the maximum and minimum displacement in the y-direction (Vy) during loading and at failure. The plots indicate that the area of maximum positive Vy occurred at the right hand edge of the specimen. This was as expected; as the specimen was gripped in serrated wedges with the left hand side of the specimen underneath the notch held stationary as the right hand side moved up as shear occurred. The left hand side should therefore show minimal displacement (0.325mm) with the maximum value at the right hand side of the specimen (0.6mm). 46

(a)

(b)

Figure 5-8. Dry [08]s specimen y-displacement (a). Before failure (b) At failure

The dry [06 902]s specimens obtained displacement values similar to that of the dry [08]s specimens (Figure 5-9). (a) (b)

Figure 5-9. Dry [06 902]s specimen y-displacement (a). Before failure (b) At failure

47

Figure 5-9 verified the problems predicted by Shokrieh and Lessard (1998) discussed in Section 5.3.4. The double notch shear test is very sensitive to the accuracy of the depth of the notches. The notch was overcut at one side of the specimen; this caused the laminates to shear but this did not occur in the mid plane of the specimen as intended. This also verified the prediction that for a specimen with a [06 902]s configuration, failure occurs between the 0 and 90 plies.

Strain in the y-direction (yy) Contour plots of the strain fields were plotted. The contour plots are useful to determine the areas of interest (i.e. stress concentrations). The size of the specimen (Section 4) only allows for a small load to be taken and therefore a relatively small strain value to occur. These values could thus easily go undetected. The yy plots give a good indication of the strain pattern but they are mainly for visualisation and approximation purposes (Figure 510). They are not suitable for detailed analysis. (a) (b)

Figure 5-10. Dry [08]s specimen - Strain Exx (a) At start of load (b) At failure

48

At the start of the load, some strain in the y-direction can be seen. The yy contour plots exhibits a reasonable uniform distribution. There are some inconsistencies present but the overall distribution of the strain values are small, between 0.006 and 0.011, and was therefore assumed to be negligible.

Strain in the x-direction (xx) The dry [06 902]s specimen showed a slightly higher value of xx at the start of the load, when compared to a wet specimen of the same lay-up configuration. The strain values for both specimens in the x-direction were small (< 0.025).

(a)

(b)

Figure 5-11. [06 902]s Specimen - Strain in the x-direction (a) Dry specimen (b) Wet specimen

As discussed in section 5.2, when testing the [06 902]s specimens, failure of individual laminae occurred before failure of the laminate. 2D DIC was consulted in order to establish if this was evident during the analysis, however this could not be detected. There were numerous reasons for not detecting the failure of the individual laminae. Foremost, DIC only detects strains and displacement of the surface of the specimen and incipient laminate failure was likely to have occurred at the middle laminae of the specimens. Another 49

limitation of using the 2D DIC system was that it cannot account for any out of plane displacement and hence zz could not be assessed. Errors relating to DIC The DIC system is extremely sensitive to effects of the surrounding environment. Some precautions were taken in order to eliminate this: The system was regularly calibrated in order to ensure that the best results were obtained. Extreme care had to be taken in order to ensure that during the specimen rotation the camera and tripod set-up had not moved slightly. Dust particles were evident on the lens; it was therefore removed and cleaned during testing however some particles still remained. This caused some features in the obtained images. Care was taken in preparing the specimens, in order to ensure a suitable level of contrast and to ensure good quality of the speckle pattern. This could have also had an influence on the results. A high resolution of 64x64 megapixels was used, which gave a precision of up to 0.01 per pixel for any 2D vectors calculated. An extra light source was added to ensure uniform and sufficient lighting covered the whole zone of interest on the specimen. As discussed earlier, there was some misalignment in the grips. Assuming this was negligible may have also affected the results.

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5.5 Fractography Analysis


Nakanishi et al. (1997) and Perepelkin (2006) effectively explained that the microscopic interfacial properties of a laminate determine its macroscopic mechanical properties. This section was therefore imperative in order to understand the effect of moisture on the interface of carbon-fibre reinforced epoxy laminates and subsequently the increase in ILSS values. This was completed by the use of optical microscopy and scanning electron microscopy (SEM).

Optical Microscopy Some delamination of the surface of the laminates was noted during the weekly weigh-ins. This is as a result of swelling stresses in the matrix due to the absorbed moisture (Pantelakis, 2010). The specimens that experienced delamination were noted and the ILSS values were examined after testing. The delamination was minor and had no effect on the ILSS of the specimens. The lower magnification (x10) micrographs were taken using an optical microscope.

Scanning Electron Microscopy Various magnifications were used ranging from x100 to x3000. At the lower value magnifications there were no visible differences (Appendix F). Magnifications at x1000 and x2000 at 10m showed the best distinction between wet and dry specimens and consequently these micrographs are the focus of analysis here. The main conclusions that can be drawn from the analysis are outlined. The degree of alignment was assumed to be the same in each specimen; however from the SEM this was clearly not the case. It was evident that the fracture surfaces were greatly influenced by the amount of exposure, as this determined the amount of failure present at the matrix. For the dry specimens, where the bonding between the fibre and resin was good, the surface was fairly smooth. The texture of the fracture surfaces varied depending on the exposure period. The difference from a brittle matrix and a ductile matrix is clearly evident. These observations are discussed in greater detail below.

51

Figure 5-12 depicts the fracture surface of a dry specimen of a [08]s laminate. The [08]s laminate showed excellent fibre dispersion. The fibre distribution was uniform and the matrix-fibre bonding good. The dry specimen exhibited brittle fracture (Figure 5-13). There are no porosity cracks visible, indicating essentially a void free laminate (Botelho, 2006). Fibre-pull out was observed at the dry specimens (Figures 5-12 and 5-13); this is due to good bonding between the fibres and the resin. This effect was less, but better than what was anticipated, at the wet specimens (Figure 5-15). This means that even in a wet state the specimens still maintained good adhesion between the fibre and matrix. This minor decrease was due to the moisture causing slight degradation at the interface and the adhesive bond to be affected. It is also important to note that even the brittle matrix is relatively smooth with only a small amount of debonding. This is a characteristic of a strongly bonded carbon fibre-epoxy resin laminate. The amount of failure at the interface determines the overall fracture surface morphology.

Area of analysis conducted by SEM

Fibre Pull-out

Figure 5-12. Fracture surface of a dry [08]s specimen - magnification x10

52

Figure 5-13. Fracture surface of a dry [08]s specimen - magnification x1000

Minor delamination of the top surface of the specimens occurred during the cutting of the notches. This however is confined to the notch root vicinity and therefore was assumed to have no effect on the ILSS results. This is evident in most of the lower magnification (x10) figures but is clearly indicated in Figure 5-14.

Delamination

Figure 5-14. Fracture surface of a wet [08]s specimen 2month withdrawal - magnification x10

53

Micro-cracking of the matrix is evident at the 2month withdrawal specimens (Figure 5-15). The crack propagated along the fibre axis. In the wet specimens, the fracture surface is characterized by the presence of numerous bare fibres. This is due to the moisture penetration through the fibre/matrix interface causing debonding of the fibre and matrix, exposing the fibres. However, areas of fibres still covered by matrix are still evident. This indicates that some degree of adhesion was retained in wet state. The difference from a brittle matrix and a ductile matrix is clearly evident (Figures 5-13 and 5-15).
Bare Fibres

Micro-cracking

Figure 5-15. Fracture surface of a wet [08]s specimen 2month withdrawal magnification x1000

It was not entirely clear if the micro-cracking occurred at the bre/matrix interface or if it occurred solely at the matrix. Huang and Sun (2006) effectively explained that the water absorbed can cause swelling and plasticisation of the polymer matrix and debonding at the bre/matrix interface. However, this debonding was not evident at all specimens. This draws the conclusion that water molecules may have come into free space or macro voids in the laminate, formed by cavities and cracks that developed due to the residual stresses after curing. This could have induced more cavities and cracks, subsequently leading to micro cracking occurring along the fibre direction. Previously, no major differences were evident between the dry and two month withdrawal specimens at low magnifications (Figures 5-12 and 5-14). However, at the four month withdrawal specimens, a noticeable line was evident. This could be due to the fact that when the laminates were pulled, the mismatch of ply properties caused a higher interlaminar shear stress to develop in the ply interface near the free edge. This is often

54

referred to as the Boundary Layer Effect or free edge effect (Hayashi, 1967). These visible lines were evident at all [08]s specimens tested after 4months but were not present at the [06 902]s specimens. This is due to the fact that the fracture surface plies were orientated differently in the [06 902]s specimens. Therefore, by alternating the laminate stacking sequence and the fibre orientation of the plies, both interlaminar shear and normal stresses could be reduced at the free edges. The diffusion characteristics discussed in section 5.1 showed that at the four month withdrawal the specimens were not fully saturated with water. Delasi and Whiteside (1978) explained that epoxy resins absorb moisture, apparently by instantaneous surface absorption and subsequent diffusion through the interior. This means that at the point of half saturation the core of the specimen is nearly dry (Selzer and Friedrich, 1995). This could be a possible explanation for why the line was only evident at the four month withdrawal specimens, as the line occurs at the mid plane of the specimen. However, due to the lack of previous reported knowledge this is merely an assumption.

Visible line

Figure 5-16. Fracture surface of a wet [08]s specimen 4 month withdrawal - magnification x10

The area was closely examined during SEM (Figure 5-17); however no noticeable difference of the matrix or fibres could be concluded. A ductile matrix is even more evident in the 4 month withdrawal specimens and no micro-cracking was visible (Figure 5-17).

55

Figure 5-17. Fracture surface of a wet [08]s specimen 4 month withdrawal - magnification x1000

Analysis of the [06 902]s specimens, showed a less severe change of the fracture surface with an increase in moisture content. Similarly to the [08]s specimens, no change at lower magnification (x10) were evident. Figure 5-18 presents a fracture surface of a dry [06 902]s specimen.

Figure 5-18. Fracture surface of a dry [06 902]s specimen - magnification x10

56

Some problems arose during the coating of the specimen. Smooth, even surfaces are easily coated while rough, uneven surfaces caused reflection problems. This is particularly evident in Figure 5-19.

Reflections

Figure 5-19. Fracture surface of a dry [06 902]s specimen - magnification x1000

The distribution of the fibres was non-uniform in the [06 902]s laminates. Fibres range from being closed packed to being more loosely packed with larger areas of resin between them. This can be compared to a [06 902]s wet specimen micrograph taken after 2months immersion (Figure 5-20 and 5-21). Both dry and wet specimens show hackling and many bare fibres. Hackling is less at the wet specimens which draws the conclusion that shear failure of the resin occurred and fracture close to the fibre matrix interface (Selzer and Friedrich, 1998).

57

Figure 5-20. Fracture surface of a wet [06 902]s specimen 2month withdrawal - magnification x10

A softening of the resin was observed (Figure 5-21) this is due to the increase in moisture content. The fibre ends are also ill defined.

Fibre end

Figure 5-21. Fracture surface of a [06 902]s specimen - 2month withdrawal - magnification x1000

58

A particular thing to note was that no micro-cracking occurred at the [06 902]s specimens. This could be due to the fact that the micro-cracking in the [08]s specimens occurred along the fibre axis and occurred in the vertical direction, in other words, along the thickness of the specimen. In the [06 902]s specimens, some 0 fibres from the adjacent plies are evident at the fracture surface (Figure 5-21 and 5-22). The 0 fibres would thus have inhibited micro-cracking in the through-the-thickness direction.

Figure 5-22. Fracture surface of a wet [06 902]s specimen 4 month withdrawal - magnification x10

No major differences were found between the two month and four month withdrawal SEM micrographs. This was expected, as the difference in percentage moisture content was minimal. The percentage increase in ILSS values from two months to four months

immersion was also small (Section 5.2). However, more bare fibres and hackling are visible at the four month withdrawal specimens (Figure 5-23).

Cohesive failure was evident at all interfaces. The occurrence of either cohesive or adhesive failure will depend on the relative strengths of the interface and the fibre or matrix. Cohesive failure involves fracture of either the fibre or the matrix, where true adhesive failure occurs by separation at the interface (Gersappe and Robbins, 1996). The specimens

59

therefore seem to have maintained structural integrity, and there was no evidence of complete breakdown of the matrix away from the fibre.

Figure 5-23. Fracture surface of a wet [06 902]s specimen - 4month withdrawal - magnification x1000

Although not as evident in these micrographs, a large amount of debris can be seen in micrographs at lower magnifications (x100), these are illustrated in Appendix F. The delamination visible by using optical microscopy and SEM may not necessarily be due to the diffusion of water through the matrix. Interlaminar separation or delamination present at the fracture surface could be due to the fact that during the interlaminar shear test, one laminate tends to slide one lamina over adjacent ones, subsequently causing interlaminar separation or delamination (Daniel and Ishai, 1994). These interlaminar stresses are a function of the laminate stacking sequence, and thus can be controlled by proper design of the stacking sequence (Daniel and Ishai, 1994).

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Chapter 6

Conclusions and Future Research

6. CONCLUSIONS AND FUTURE RESEARCH


This chapter summarizes the essential results, conclusions and deductions obtained from this thesis. It also proposes future research topics and possible techniques that could be used.

6. 1 Conclusions
A study on the effect of moisture absorption on the mechanical behaviour and on the fibre/matrix interface of HTA/6376 composite material was conducted. This was effectively examined by the investigation of the absorption characteristics of carbon fibre epoxy laminates, the measurement and analysis of the weight gain and hygrothermal induced expansion.

The major conclusions can be summarized as follows: 1. During the initial stages of absorption, the specimens exhibited Fickian Diffusion behaviour. The second stage, the deterioration and relaxation stage, was not documented due to the limitation on the immersion time. 2. Due to the time constraint the diffusion coefficient of the laminates could not be calculated. 3. The specimen lay-up sequence affected the overall moisture absorbed, with a higher moisture content of 0.9% for [06 902]s specimens, in comparison to 0.78% for the [08]s specimens. 4. Hygrothermal induced volumetric expansion of up to 10.2 % for [08]s specimens and 8.7% for [06 902]s specimens were found. 5. The interlaminar shear strength values showed an increase of 11.3% and 18.7% for [08]s and [06 902]s specimens respectively, when compared to the dry specimens. 6. The predominant reason for the increase in ILSS is due to the increase in flexibility of the epoxy resin due to the absorbed moisture. This lead to higher elongation values consequently increasing the attainable load. 7. The increase in ILSS is a function of exposure time, with the four month immersed specimens having increased by a substantial amount. 8. The overall behaviour of composite material exposed to a 100% relative humidity environment depends on the amount of moisture content present in the material. 61

9. No difference between the dry, two month and four month withdrawal strain fields of the specimens were evident. This was mainly due to the limitation of the DIC, as it is unable to detect such small values of strain. 10. SEM images showed a change from a brittle to a ductile fracture mode due to an increase in moisture content. All SEM images showed resin adhering to fibres, which indicated that good fibre/matrix adhesion was retained even in a wet state.

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6.2 Recommendations for Future Research


There is no known publication which discusses the influence of moisture on carbon fibrereinforced polymer composites, which is immersed in de-ionized water at room temperature in a very detailed way. Therefore the data generated in this thesis could be used as a guideline for the design of components from this material under the influence of moisture. However, after reflecting on the research questions addressed, several interesting future research topics were noted. The author has tried to qualitatively purpose possible research areas and techniques which could be used.

6.2.1 Raman Spectroscopy


Investigate the possibility of using Raman Spectroscopy in order to predict and follow the effect of moisture absorption (Cervenka et al., 1989). This technique allows for a more detailed analysis of the interfacial region and thereby will provide a greater insight into the long-term effects due to moisture absorption.

6.2.2 Thermoplastics versus Thermosets


According to previous researchers (Daniel and Ishai, 1994; Baker et al., 2004; Chen-Chi and Shih-Wen, 1991) thermoplastic matrices are less susceptible to moisture effects than thermosets. Thermoplastics are also more easily amenable to mass production and repair and therefore may become more favourable to use than thermosets. It may prove to be beneficial to exclusively assess the difference in the diffusion coefficients and degradation of the mechanical properties of these polymers.

6.2.3 Relative Humidity Chamber


Investigate the possibility of testing in a chamber where the temperature and humidity are controlled. This would involve purchasing expensive equipment perhaps exceeding the budget of a final year project; however the use of this method would greatly increase the accuracy of the results as almost no interference would occur with the environment.

A limitation of this thesis was the time constraint on the immersion period. Through purchase of a relative humidity chamber, this limitation would be eliminated as the temperature could be controlled. Baker et al. (2007) predicted that an increase of 10% in 63

temperature would cause the diffusion rate to double. Therefore the level of saturation would be reached quicker and an accurate determination of the diffusion coefficient could be attained.

6.2.4 Reversible/Irreversible Effects


Literature has reported a great deal on the reversibility of the effects of moisture absorption on composite materials (Matthews and Rawlings, 1994; Khan et al., 2010). It has been reported that at low temperature, high relative humidity, the decrease in mechanical properties is reversible once the material has dried. However, at high temperature, high relative humidity the influence of moisture absorption causes irreversible effects (Selzer and Friedrich, 1998). Therefore, in order to accurately predict the performance of a composite structure, the reversibility or irreversibility of the effects due to moisture should be investigated.

6.2.5 Epoxy Resin Toughness


Following the findings of this thesis, a clear relationship is evident between the increase in moisture absorption and the change in toughness of the epoxy resin. Consequently, by investigating the possibility to determine the toughness of the epoxy resin with an increase in moisture content, a greater understanding of the degradation mechanism of the laminates could be achieved. This can be determined by a simple tensile test, as this would allow for a documented change in tensile strength, elongation and hence the elastic modulus, with an increase in moisture content (Perreux and Suri, 1997).

64

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Appendices

Appendix A: Turnitin Originality Report


Turnitin Originality Report

Processed on 03-18-11 11:30 AM GMT ID: 176864416 Word Count: 16212

Similarity Index 24% Similarity by Source Internet Sources: 6% Publications: 20% Student Papers: 7%

sources: 1
1% match (student papers from 03/18/10) Submitted to University of Limerick on 2010-03-18

2
1% match (publications) Sohaib Akbar. "Moisture Diffusion in Carbon/Epoxy Composite and the Effect of Cyclic Hygrothermal Fluctuations: Characterization by Dynamic Mechanical Analysis (DMA) and Interlaminar Shear Strength (ILSS)", The Journal of Adhesion, 07/2008

3
1% match (publications) Selzer, R.. "Mechanical properties and failure behaviour of carbon fibre-reinforced polymer composites under the influence of moisture", Composites Part A, 1997

4
1% match (publications) Choi, H.. "Hygroscopic aspects of epoxy/carbon fiber composite laminates in aircraft environments", Composites Part A, 20010501

5
1% match (publications) Kootsookos, A.. "Seawater durability of glass- and carbon-polymer composites", Composites Science and Technology, 200408

6
1% match (publications) Belani, J.G.. "Moisture induced resistivity changes in graphite-reinforced plastics", Composites, 197810

7
< 1% match (publications) Karbhari, V.M.. "Hygrothermal effects on high V"F pultruded unidirectional carbon/epoxy composites: Moisture uptake", Composites Part B, 200901

8
< 1% match (publications)

A1

Tsai, C.L.. "Characterization of principal diffusivities of composites by suspension method", Composites Science and Technology, 20061201

9
< 1% match (publications) R. Selzer. "Inluence of water up-take on interlaminar fracture properties of carbon fibrereinforced polymer composites", Journal of Materials Science, 1995

10
< 1% match (publications) M. L. Costa. "Strength of Hygrothermally Conditioned Polymer Composites with Voids", Journal of Composite Materials, 06/14/2005

11
< 1% match (publications) Bao, L.-R.. "Moisture diffusion and hygrothermal aging in bismaleimide matrix carbon fiber composites-part I: uni-weave composites", Composites Science and Technology, 200212

12
< 1% match (Internet from 10/28/10) http://districts.asme.org/districte/ECTCPapers/2010Papers/ECTCPaper-OKSamuelKucera.pdf

13
< 1% match (publications) Chen Zou. "The effect of water absorption on the dielectric properties of epoxy nanocomposites", IEEE Transactions on Dielectrics and Electrical Insulation, 2/2008

14
< 1% match (publications) Guedes, R.M.. "Influence of moisture absorption on creep of GRP composite pipes", Polymer Testing, 200708

15
< 1% match (Internet from 5/21/10) http://www.public.iastate.edu/~nbowler/pdf%20final%20versions/conferences/AbramBowler CEIDP2005.pdf

16
< 1% match (publications) X. F. Wan. "Moisture Absorption Behavior of Carbon Fiber-Reinforced Monomer Casting Nylon Composites", Journal of Reinforced Plastics and Composites, 07/01/2004

17
< 1% match (publications) R. Zenasni. "Moisture Effect on the Interlaminar Resistance of Woven Fabric Thermoplastic Composite", Journal of Thermoplastic Composite Materials, 11/01/2006

18
< 1% match (student papers from 03/28/08) Submitted to University of Limerick on 2008-03-28

19
< 1% match (publications) Asp, L.E.. "The effects of moisture and temperature on the interlaminar delamination toughness of a carbon/epoxy composite", Composites Science and Technology, 1998

20
< 1% match (publications) B. R. K. Blackman. "The Effects of Pre-Bond Moisture on the Fracture Behaviour of Adhesively-Bonded Composite Joints", The Journal of Adhesion, 3/2008

A2

21
< 1% match (student papers from 03/11/09) Submitted to University of Limerick on 2009-03-11

22
< 1% match (Internet) http://www.ndt.aeat.co.uk/noticeboards/mms15/documents/MMS13Task5defectassessment methodsDRAFT.pdf

23
< 1% match (Internet) http://www.mcs.vuw.ac.nz/~kris/thesis/node6.html

24
< 1% match (publications) Zleyha Aslan. "Characterization of interlaminar shear strength of laminated woven Eglass/epoxy composites by four point bend shear test", Polymer Composites, 2009

25
< 1% match (publications) F O'Dowd. "Analysis of fibre orientation effects on injection moulded components", Proceedings of the Institution of Mechanical Engineers Part B Journal of Engineering Manufacture, 01/01/2006

26
< 1% match (student papers from 07/06/10) Submitted to Universiti Sains Malaysia on 2010-07-06

27
< 1% match (publications) Perreux, D.. "A study of the coupling between the phenomena of water absorption and damage in glass/epoxy composite pipes", Composites Science and Technology, 1997

28
< 1% match (publications) V. Alvarez. "Cyclic Water Absorption Behavior of Glass--Vinylester and Glass--Epoxy Composites", Journal of Composite Materials, 05/01/2007

29
< 1% match (publications) Mirmohammadi, Mirtaghi Ibrahim, M. Saraj. "Modeling of hexamethylene diisocyanate and psychrometric parameters and other effective factors in t", Indian Journal of Occupational and Envir, Sept-Dec 2010 Issue

30
< 1% match (publications) Haddadi, H.. "Use of rigid-body motion for the investigation and estimation of the measurement errors related to digital image correlation technique", Optics and Lasers in Engineering, 200802

31
< 1% match (student papers from 03/19/10) Submitted to University of Limerick on 2010-03-19

32
< 1% match (publications) A.K. Shrivastava. "Effect of Low Temperature on Mechanical Properties of Bidirectional Glass Fiber Composites", Journal of Composite Materials, 08/07/2008

33
A3

< 1% match (Internet from 11/21/06) http://mech.iust.ac.ir/staff.asp?Code=34&type=Faculty

34
< 1% match (publications) X. J. Fan. "Fundamental Characteristics of Moisture Transport, Diffusion, and the MoistureInduced Damages in Polymeric Materials in Electronic Packaging", Moisture Sensitivity of Plastic Packages of IC Devices, 2010

35
< 1% match (publications) G. Czel. "A Study of Water Absorption and Mechanical Properties of Glass Fiber/Polyester Composite Pipes -- Effects of Specimen Geometry and Preparation", Journal of Composite Materials, 12/01/2008

36
< 1% match (publications) S. Egusa. "Anisotropy of radiation-induced degradation in mechanical properties of fabricreinforced polymer-matrix composites", Journal of Materials Science, 03/1990

37
< 1% match (Internet from 9/21/03) http://mil-17.udel.edu/Pdf/v1ch6e.pdf

38
< 1% match (publications) ZHU, H.y.. "Influence of voids on interlaminar shear strength of carbon/epoxy fabric laminates", Transactions of Nonferrous Metals Society of China, 200909

39
< 1% match (publications) Thompson, M.S.. "Digital image correlation: A technique for determining local mechanical conditions within early bone callus", Medical Engineering and Physics, 200709

40
< 1% match (Internet from 10/12/08) http://www.coe.montana.edu/composites/documents/Mei%20Li%20thesis.pdf

41
< 1% match (publications) Arun, K.V.. "Damage characterisation of glass/textile fabric polymer hybrid composites in sea water environment", Materials and Design, 201002

42
< 1% match (publications) Leman, Z.. "Moisture absorption behavior of sugar palm fiber reinforced epoxy composites", Materials and Design, 2008

43
< 1% match (Internet from 7/3/09) http://etd.gatech.edu/theses/available/etd-03292008011522/unrestricted/anbarasu_arungalai_200804_mast.pdf

44
< 1% match (publications) R. Zenasni. "Effect of Hygrothermomechanical Aging on the Interlaminar Fracture Behavior of Woven Fabric Fiber/PEI Composite Materials", Journal of Thermoplastic Composite Materials, 07/01/2006

45
< 1% match (publications)

A4

Tsenoglou, C.J.. "Evaluation of interfacial relaxation due to water absorption in fiberpolymer composites", Composites Science and Technology, 20061201

46
< 1% match (publications) N. Sharma. "Study of the Effect of Hygrothermal Ageing on Glass/Epoxy Micro-Composites by FTIR-Imaging and Alternating DSC Techniques", Journal of Reinforced Plastics and Composites, 06/04/2008

47
< 1% match (Internet from 12/3/10) http://scholar.lib.vt.edu/theses/available/etd-11192003134415/unrestricted/Dissertation2etdb.pdf

48
< 1% match (publications) Xiaoya Shang. "Structure and Water Absorption of Starch and Polyethylene-Octene Elastomer Composites", Journal of Reinforced Plastics and Composites, 01/14/2008

49
< 1% match (publications) D. Gueribiz. "Homogenization of Moisture Diffusing Behavior of Composite Materials with Impermeable or Permeable Fibers -- Application to Porous Composite Materials", Journal of Composite Materials, 06/01/2009

50
< 1% match (publications) Rubin, A.M.. "Evaluation of porosity in composite aircraft structures", Composites Engineering, 1993

51
< 1% match (publications) Weinberg, M.. "Shear testing of neat thermoplastic resins and their unidirectional graphite composites", Composites, 198711

52
< 1% match (publications) A. Kesavan. "Strain-based Structural Health Monitoring of Complex Composite Structures", Structural Health Monitoring, 07/21/2008

53
< 1% match (publications) Theodore R. Tauchert. "PUBLICATIONS ON THERMAL STRESSES", Journal of Thermal Stresses, 7/1/1992

54
< 1% match (student papers from 12/07/06) Submitted to Ohio University on 2006-12-07

55
< 1% match (Internet from 10/12/10) http://www.tech.plym.ac.uk/sme/mats324/ReviewPapers.htm

56
< 1% match (Internet from 8/15/09) http://answers.yahoo.com/question/index?qid=20081006131312AAHEpYU

57
< 1% match (publications) N. M. Barkoula. "Environmental degradation of carbon nanotube-modified composite laminates: a study of electrical resistivity", Mechanics of Composite Materials, 01/2009

A5

58
< 1% match (publications) P. Vaddadi. "Inverse Analysis to Determine Hygrothermal Properties in Fiber Reinforced Composites", Journal of Composite Materials, 05/04/2006

59
< 1% match (publications) M. KENANE. "Fracture and fatigue study of unidirectional glass/epoxy laminate under different mode of loading", Fatigue & Fracture of Engineering Materials & Structures, 02/2010

60
< 1% match (publications) Nakamura, T.. "Determination of nonlinear properties of thermal sprayed ceramic coatings via inverse analysis", International Journal of Solids and Structures, 20070315

61
< 1% match (student papers from 08/24/10) Submitted to Institute of Graduate Studies, UiTM on 2010-08-24

62
< 1% match (publications) Costa, M.L.. "The influence of porosity on the interlaminar shear strength of carbon/epoxy and carbon/bismaleimide fabric laminates", Composites Science and Technology, 200111

63
< 1% match (publications) Khan, L.A.. "Hygrothermal degradation of 977-2A carbon/epoxy composite laminates cured in autoclave and Quickstep", Composites Part A, 201008

64
< 1% match (publications) Amit Chatterjee. "Thermal degradation analysis of thermoset resins", Journal of Applied Polymer Science, 11/01/2009

65
< 1% match (publications) L. T. Drzal. "Fibre-matrix adhesion and its relationship to composite mechanical properties", Journal of Materials Science, 1993

66
< 1% match (publications) J.R. Xiao. "A Phenomenological Mohr--Coulomb Failure Criterion for Composite Laminates under Interlaminar Shear and Compression", Journal of Composite Materials, 08/18/2006

67
< 1% match (publications) Garland, B.D.. "The development of compression damage zones in fibrous composites", Composites Science and Technology, 200112

68
< 1% match (publications) M. A. McCarthy. "An Experimental Study of Bolt-Hole Clearance Effects in Single-lap, Multibolt Composite Joints", Journal of Composite Materials, 05/01/2005

69
< 1% match (publications) Vaddadi, P.. "Inverse analysis for transient moisture diffusion through fiber-reinforced composites", Acta Materialia, 20030108

70 A6

< 1% match (publications) Y. Yu. "Hygrothermal Aging on Pultruded Carbon Fiber/Vinyl Ester Resin Composite for Sucker Rod Application", Journal of Reinforced Plastics and Composites, 08/16/2005

71
< 1% match (publications) Ellyin, F.. "Environmental effects on the mechanical properties of glass-fiber epoxy composite tubular specimens", Composites Science and Technology, 200409

72
< 1% match (publications) Parlevliet, P.P.. "Residual stresses in thermoplastic composites - a study of the literature. Part III: Effects of thermal residual stresses", Composites Part A, 200706

73
< 1% match (publications) Philip Eyckens. "Strain evolution in the single point incremental forming process: digital image correlation measurement and finite element prediction", International Journal of Material Forming, 08/18/2010

74
< 1% match (publications) Gu, H.. "Delamination behaviour of glass/polyester composites after water absorption", Materials and Design, 2008

75
< 1% match (publications) Kawai, M.. "Fatigue strengths of cross-ply CFRP laminates at room and high temperatures and its phenomenological modeling", International Journal of Fatigue, 200610

76
< 1% match (student papers from 03/18/10) Submitted to University of Limerick on 2010-03-18

77
< 1% match (student papers from 05/01/06) Submitted to Texas A&M University, College Station on 2006-05-01

78
< 1% match (student papers from 10/30/09) Submitted to University of Adelaide on 2009-10-30

79
< 1% match (Internet) http://www.maths.strath.ac.uk/~aas99101/grants/adhesive.pdf

80
< 1% match (Internet from 2/28/11) http://paginas.fe.up.pt/~iccs15/iccs15listabstracts.pdf

81
< 1% match (publications) N. Svensson. "MIXED-MODE DELAMINATION OF MULTIDIRECTIONAL CARBON FIBER/EPOXY LAMINATES", Mechanics of Advanced Materials and Structures, 7/1/1998

82
< 1% match (student papers from 10/28/09) Submitted to University of Adelaide on 2009-10-28

83
< 1% match (student papers from 02/07/10)

A7

Submitted to Central Queensland University on 2010-02-07

84
< 1% match (Internet from 11/14/08) http://www.civil.uminho.pt/masonry/Publications/Historical%20constructions/page%2010471056%20_152_.pdf

85
< 1% match (publications) M. Blikstad. "Three-Dimensional Moisture Diffusion in Graphite/Epoxy Laminates", Journal of Reinforced Plastics and Composites, 01/01/1986

86
< 1% match (student papers from 03/18/10) Submitted to University of Limerick on 2010-03-18

87
< 1% match (publications) D. A. Bond. "Moisture Diffusion in a Fiber-reinforced Composite: Part I - Non-Fickian Transport and the Effect of Fiber Spatial Distribution", Journal of Composite Materials, 06/14/2005

88
< 1% match (publications) Doan, T.T.L.. "Jute/polypropylene composites I. Effect of matrix modification", Composites Science and Technology, 200606

89
< 1% match (publications) Guedes, R.M.. "An experimental and numerical assessment of DCB tests on glass/polyester curved beams cut out from pipes", Polymer Testing, 200812

90
< 1% match (publications) Baskaran Natesan. "Molecular relaxation of isotactic polystyrene: Real-time dielectric spectroscopy and X-ray scattering studies", Journal of Polymer Science Part B Polymer Physics, 03/01/2004

91
< 1% match (publications) Getinet, H.. "The effect of cultivar, maturity stage and storage environment on quality of tomatoes", Journal of Food Engineering, 200808

92
< 1% match (Internet from 4/24/08) http://www.ing.unitn.it/~pegorett/articoli-Alex/ref59.pdf

93
< 1% match (Internet from 10/12/08) http://www.me.berkeley.edu/~lwlin/papers/JMM-2005-nickel.pdf

94
< 1% match (publications) E. GUGLIELMINO. "Influence of Quick Ageing on the Fatigue Behaviour of SMC Composite Materials", Journal of Reinforced Plastics and Composites, 01/01/2001

95
< 1% match (publications) Geraldo Cndido. "Hygrothermal and Stacking Sequence Effects on Carbon Epoxy Composites with Molded Edges", Polymer-Plastics Technology and Engineering, 10/1/2006

96 A8

< 1% match (publications) Dano, M.L.. "Analysis of bolted joints in composite laminates: Strains and bearing stiffness predictions", Composite Structures, 200708

97
< 1% match (publications) Aktas, A.. "Sea water effect on pinned-joint glass fibre composite materials", Composite Structures, 200809

98
< 1% match (publications) ANTONIO DE LUCAS. "Removal of Acetic Acid by Adsorption from an Ethylene Recycle Stream in the EthyleneVinyl Acetate Copolymerization Process", Separation Science and Technology, 1999

99
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100
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103
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134
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135
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paper text:

A15

Appendix B: Specimen Dimensions


This appendix contains the specimen configuration and dimensions details. The data was used during the manufacturing of the specimens.

Number of plies: 16 Thickness: 2mm Notch width: 2mm Notch depth: 1mm All dimensions on diagram in millimetres.

Specimen A: [06 902]s


179 85 5

Figure B-1. Specimen A - Configuration and dimensions

Specimen B: [08]s
179 85 5

Figure B-2. Specimen B - Configuration and dimensions

B1

Appendix C: Drawing of clamp


This appendix contains the drawing of the clamp adapted from ASTM Standard D3846-08. All dimensions on drawing in millimetres (mm).

C1

Appendix D: Mass gain and change in dimensions of specimens


This appendix contains the data obtained by the weekly weigh in procedure outlined in section 4.1.3.

Appendix D1. Dry specimen dimensions


Table D1. Dry specimen dimensions [08]s

[08]s Dry 1 Dry 2 Dry 3 Dry 4 Dry 5 Dry 6 Dry 7

Section thickness Width (mm) Width (mm) Thickness(mm) Weight (g) 12.52 4.94 2.00 7.4821 12.65 5.39 2.02 7.5627 12.65 5.21 2.00 7.4821 12.71 12.67 12.64 12.52 5.21 5.00 5.22 5.14 2.01 2.01 2.00 2.00 7.5393 7.8369 7.7696 7.4388

Table D2. Dry specimens dimensions [06 902]s

[06 902]s Dry 1 Dry 2 Dry 3 Dry 4 Dry 5 Dry 6 Dry 7

Section thickness Width (mm) Width (mm) Thickness(mm) Weight (g) 12.65 5.63 2.00 7.593 12.42 5.27 2.01 7.5929 12.67 5.00 2.00 7.6847 12.62 5.27 2.00 7.5375 12.50 5.14 2.00 7.4965 12.53 5.01 2.00 7.5304 12.58 5.00 2.00 7.4807

D1

Appendix D2. Immersed [08]s specimen dimensions


Table D3. Before immersion dimensions [08]s

[08]s Withdrawal I I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Section thickness (mm) 12.33 12.67 12.68 12.49 12.63 12.64

Before Immersion Width Thickness (mm) (mm) 5.17 5.36 5.17 5.50 5.08 5.26 2.00 2.00 2.00 2.01 2.00 2.00

Weight (g) 7.3817 7.5258 7.5321 7.3638 7.5499 7.5384

Volume (mm3) 127.4922 135.8224 131.1112 138.0769 128.3208 132.9728

12.63 5.21 Section thickness Width (mm) (mm) 12.32 12.63 12.74 12.59 12.67 12.71 12.55 5.15 4.93 5.23 5.48 5.53 5.28 5.54

2.01 7.8069 132.2626 Thickness Weight Volume (mm) (g) (mm3) 2.00 2.02 2.00 2.00 2.01 1.99 2.00 7.4158 7.5998 7.5940 7.5252 7.7774 7.5268 7.4723 126.89600 125.77711 133.26040 138.13748 140.83085 133.54651 139.05400

Room Temperature: 19C Water Temperature: 19C Notes: -------

D2

Table D4. Specimen Dimensions [08]s Week 1

[08]s Section thickness (mm) 12.40 12.59 12.78 12.59 12.75 12.64 12.88 Section thickness (mm) 12.36 12.85 12.74 12.80 12.60 12.56 12.58

Week 1 % Width Thickness Weight Weight (mm) (mm) (g) gain 5.12 2.07 7.3968 0.2045 5.39 2.06 7.5424 0.2205 5.37 2.06 7.5476 0.2057 5.44 2.08 7.3802 0.2227 4.93 2.06 7.5675 0.2331 5.30 2.07 7.5548 0.2175 5.20 2.05 7.8245 0.2254 % Width Thickness Weight Weight (mm) (mm) (g) gain 5.19 2.07 7.4309 0.2036 5.09 2.06 7.6153 0.2039 5.24 2.07 7.6110 0.2238 5.31 2.08 7.5431 0.2378 5.33 2.05 7.7933 0.2044 5.57 2.04 7.5412 0.1913 5.56 2.06 7.4896 0.2315 Volume (mm3) % V 131.42 3.0809 139.79 2.9224 141.37 7.8282 142.66 3.3248 129.48 0.9083 138.67 4.2870 137.30 3.8092 Volume (mm3) % V 132.78 4.6425 134.73 7.1239 138.18 3.6978 141.37 2.3425 137.67 2.2416 142.71 6.8667 144.08 3.6189

Withdrawal I I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Room Temperature: 19C Water Temperature: 19C Notes: --------

D3

Table D5. Specimen Dimensions [08]s Week 2

[08]s Withdrawal I I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness (mm) 12.40 12.59 12.78 12.59 12.75 12.64 12.88 Section thickness (mm) 12.40 12.85 12.80 12.67 12.63 12.56 12.58

Week 2 Width Thickness Weight % Weight Volume (mm) (mm) (g) gain (mm3) % V 5.14 2.07 7.4020 0.2750 135.40 6.2069 5.44 2.12 7.5460 0.2684 146.21 7.6541 5.31 2.12 7.5520 0.2642 142.49 8.6841 5.50 2.10 7.3860 0.3014 144.34 4.5437 5.08 2.08 7.5710 0.2794 136.12 6.0830 5.31 2.07 7.5590 0.2732 140.83 5.9067 5.12 2.06 7.8300 0.2950 146.37 10.670 Width Thickness Weight % Weight Volume (mm) (mm) (g) gain (mm3) % V 5.37 2.14 7.4360 0.2723 142.47 10.295 5.09 2.13 7.6200 0.2657 134.90 7.1239 5.29 2.17 7.6160 0.2899 146.93 10.261 5.31 2.16 7.5480 0.3029 143.41 10.281 5.33 2.16 7.7980 0.2648 161.22 14.486 5.57 2.14 7.5460 0.2550 149.39 11.868 5.56 2.21 7.4940 0.2904 154.02 10.764

Room Temperature: 19C Water Temperature: 18C Notes: -------

D4

Table D6. Specimen Dimensions [08]s Week 3

[08]s Withdrawal I I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness (mm) 12.40 12.59 12.78 12.59 12.75 12.64 12.88 Section thickness (mm) 12.40 12.85 12.80 12.67 12.63 12.56 12.58

Week 3 Width Thickness Weight % Weight Volume (mm) (mm) (g) gain (mm3) % V 5.14 2.07 7.4073 0.3468 135.50 6.3109 5.44 2.12 7.5525 0.3547 146.21 5.6110 5.31 2.12 7.5600 0.3704 142.49 7.5194 5.50 2.10 7.3898 0.3530 144.34 4.5612 5.08 2.08 7.5759 0.3443 138.51 6.0830 5.31 2.09 7.5645 0.3462 140.90 5.9067 5.12 2.25 7.8352 0.3624 146.37 10.670 Width Thickness Weight % Weight Volume (mm) (mm) (g) gain (mm3) % V 5.37 2.18 7.4421 0.3546 142.47 10.295 5.09 2.15 7.6260 0.3447 134.90 7.1239 5.29 2.15 7.6201 0.2899 146.93 10.261 5.31 2.17 7.5529 0.3029 143.41 10.281 5.33 2.18 7.8034 0.2648 161.22 14.486 5.57 2.09 7.5496 0.2550 149.39 11.868 5.56 2.23 7.4974 0.2904 154.02 10.764

Room Temperature: 19C Water Temperature: 18C Notes: -------

D5

Table D7. Specimen Dimensions [08]s Week 4

[08]s Withdrawal I I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 4 Section thickness (mm) 12.41 12.49 12.67 12.55 12.85 12.86 12.80 Section thickness (mm) 12.64 12.88 12.90 12.84 12.85 12.73 12.72 Width Thickness Weight (mm) (mm) (g) 5.04 2.1 7.4094 5.42 2.17 7.5562 5.34 2.15 7.5622 5.49 2.13 7.395 5.05 2.11 7.5801 5.36 2.15 7.5722 5.17 2.29 7.837 Width Thickness Weight (mm) (mm) (g) 5.17 2.14 7.4474 5.05 2.12 7.6325 5.23 2.15 7.6283 5.24 2.08 7.5592 5.37 2.05 7.8091 5.44 2.18 7.5555 5.54 2.18 7.5044 % Weight gain 0.375252 0.403944 0.399623 0.423694 0.400005 0.448371 0.385556 % Weight gain 0.426117 0.430274 0.451672 0.451815 0.407591 0.381304 0.429587 Volume (mm3) 131.3474 146.8999 145.4643 146.7559 136.9881 148.1986 151.543 Volume (mm3) 139.8464 137.8933 145.0541 139.9457 141.4592 150.9676 153.622

% V 3.023903 8.155861 10.94725 6.285615 6.754375 11.45034 14.57737

% V 10.20555 9.633042 8.850078 1.309021 0.446191 13.04497 10.47649

Room Temperature: 19C Water Temperature: 17C Notes: -------

D6

Table D8. Specimen Dimensions [08]s Week 5

[08]s Withdrawal I I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 5 Section thickness (mm) 12.44 12.65 12.69 12.57 12.87 12.86 12.84 Section thickness (mm) 12.64 12.92 12.96 12.84 12.81 12.71 12.72 Width Thickness Weight (mm) (mm) (g) 5.04 2.10 7.4138 5.34 2.12 7.5638 5.38 2.10 7.5626 5.54 2.12 7.3989 5.07 2.12 7.5826 5.36 2.16 7.5723 5.17 2.13 7.8424 Width Thickness Weight (mm) (mm) (g) 5.09 2.17 7.4476 5.05 2.12 7.6348 5.22 2.14 7.6275 5.28 2.12 7.5575 5.59 2.10 7.8098 5.44 2.18 7.556 5.54 2.20 7.5047 % Weight gain 0.434859 0.50493 0.404934 0.476656 0.433118 0.449698 0.454726 % Weight gain 0.428814 0.460538 0.441138 0.429224 0.416592 0.387947 0.433601 Volume (mm3) 131.665 143.2081 143.3716 147.6321 138.3319 148.8879 141.3954 Volume (mm3) 139.6126 138.3215 144.7736 143.7258 150.3766 150.7304 155.0314

% V 3.272953 5.437778 9.351161 6.920189 7.801625 11.96872 6.905005

% V 10.02127 9.973517 8.639602 4.045494 6.778159 12.86737 11.49004

Room Temperature: 19C Water Temperature: 19C Notes: -------

D7

Table D9. Specimen Dimensions [08]s Week 6

[08]s Withdrawal I I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 6 Section thickness (mm) 12.47 12.66 12.70 12.61 12.86 12.83 12.90 Section thickness (mm) 12.58 12.92 12.93 12.91 12.84 12.77 12.73 Width Thickness Weight (mm) (mm) (g) 5.03 2.11 7.4152 5.31 2.15 7.5601 5.37 2.14 7.5661 5.52 2.12 7.3989 5.09 2.11 7.5854 5.29 2.14 7.5753 5.19 2.23 7.8452 Width Thickness Weight (mm) (mm) (g) 5.12 2.13 7.4511 5.01 2.12 7.6343 5.23 2.13 7.631 5.23 2.11 7.5624 5.62 2.12 7.8186 5.45 2.18 7.5588 5.56 2.16 7.5084 % Weight gain 0.453825 0.455766 0.451401 0.476656 0.470205 0.489494 0.490592 % Weight gain 0.476011 0.453959 0.487227 0.494339 0.52974 0.425147 0.483118 Volume (mm3) 132.3479 144.5329 145.9459 147.5673 138.1151 145.2433 149.3007 Volume (mm3) 137.1924 137.2259 144.0389 142.4657 152.9809 151.7204 152.8822

% V 3.808587 6.413147 11.31456 6.873207 7.632678 9.227826 12.88203

% V 8.114084 9.102439 8.088305 3.133286 8.627403 13.60864 9.944488

Room Temperature: 19C Water Temperature: 19C Notes: -------

D8

Table D10. Specimen Dimensions [08]s Week 7

[08]s Withdrawal I I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 7 Section thickness (mm) 12.55 12.77 12.78 12.55 12.88 12.81 12.85 Section thickness (mm) 12.62 12.90 12.94 12.88 12.84 12.75 12.72 Width Thickness Weight (mm) (mm) (g) 5.13 2.15 7.4237 5.43 2.10 7.5723 5.36 2.12 7.5738 5.49 2.11 7.4086 5.02 2.12 7.5978 5.31 2.12 7.5831 5.13 2.11 7.8555 Width Thickness Weight (mm) (mm) (g) 5.1 2.07 7.4636 5.03 2.10 7.6389 5.19 2.11 7.6388 5.21 2.07 7.5676 5.57 2.10 7.8227 5.47 2.11 7.569 5.56 2.19 7.5149 % Weight gain 0.568975 0.617875 0.55363 0.608382 0.634445 0.592964 0.622526 % Weight gain 0.64457 0.514487 0.589939 0.56344 0.582457 0.560663 0.570106 Volume (mm3) 138.4202 145.6163 145.2217 145.3779 137.0741 144.2047 139.0923 Volume (mm3) 133.2293 136.2627 141.7046 138.9069 150.1895 147.1567 154.8838

% V 8.571524 7.210821 10.76224 5.287628 6.821429 8.446789 5.16369

% V 4.990969 8.336637 6.336651 0.557022 6.645297 10.19133 11.38393

Room Temperature: 19C Water Temperature: 19C Notes: -------

D9

Table D11. Specimen Dimensions [08]s Week 8

[08]s Withdrawal I I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 8 Section thickness (mm) 12.57 12.77 12.81 12.56 12.88 12.83 12.87 Section thickness (mm) 12.62 12.90 12.92 12.88 12.82 12.79 12.71 Width Thickness Weight (mm) (mm) (g) 5.13 2.15 7.4267 5.43 2.15 7.5743 5.37 2.14 7.5768 5.51 2.11 7.4124 5.05 2.14 7.5988 5.31 2.13 7.5841 5.18 2.12 7.8555 Width Thickness Weight (mm) (mm) (g) 5.10 2.09 7.4572 5.03 2.12 7.6417 5.22 2.14 7.6374 5.27 2.10 7.5688 5.56 2.10 7.8181 5.57 2.11 7.5701 5.56 2.20 7.5151 % Weight gain 0.609616 0.64445 0.59346 0.659985 0.647691 0.606229 0.622526 % Weight gain 0.558267 0.55133 0.571504 0.579387 0.523311 0.575278 0.572782 Volume (mm3) 138.6408 149.0834 147.21 146.0238 139.1942 145.1111 141.3332 Volume (mm3) 134.5166 137.5604 144.3267 142.543 149.6863 150.317 155.4687

% V 8.744547 9.763459 12.27871 5.755389 8.473576 9.128445 6.857999

% V 6.005374 9.368415 8.304294 3.189200 6.288018 12.55781 11.80457

Room Temperature: 17C Water Temperature: 16C Notes:

Week 9 Unable to take moisture gain and specimen dimensions due to Christmas holidays.

D10

Table D12. Specimen Dimensions [08]s Week 10

[08]s Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 10 Section thickness Width Thickness Weight (mm) (mm) (mm) (g) 12.59 5.14 2.13 7.4625 12.91 5.01 2.13 7.6535 12.98 5.22 2.14 7.6452 12.88 5.27 2.11 7.5772 12.83 5.61 2.10 7.8236 12.76 5.47 2.13 7.5710 12.71 5.56 2.20 7.5181 % Weight gain 0.629737 0.706598 0.674216 0.691012 0.594029 0.587235 0.61293 Volume (mm3) 137.8378 137.7665 144.997 143.2217 151.1502 148.6680 155.4687

% V 8.622682 9.532231 8.807256 3.680577 7.327499 11.32304 11.80457

Room Temperature: 18C Water Temperature: 16C Notes: -------

Table D13. Specimen Dimensions [08]s Week 11

[08]s Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 11 Section thickness Width Thickness Weight (mm) (mm) (mm) (g) 12.52 5.14 2.14 7.4656 12.95 5.04 2.09 7.6593 12.96 5.22 2.15 7.6477 12.88 5.27 2.11 7.5772 12.85 5.61 2.13 7.8237 12.77 5.47 2.15 7.5727 12.71 5.57 2.20 7.5199

% Weight gain 0.671539 0.782915 0.707137 0.691012 0.595315 0.609821 0.637019

Volume (mm3) 137.715 136.4101 145.4501 143.2217 153.5485 150.1816 155.7483

% V 8.525873 8.453845 9.147264 3.680577 9.030446 12.45639 12.00565

Room Temperature: 19C Water Temperature: 18C Notes: -------

D11

Table D14. Specimen Dimensions [08]s Week 12

[08]s Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 12 Section % thickness Width Thickness Weight Weight Volume (mm) (mm) (mm) (g) gain (mm3) % V 12.55 5.14 2.14 7.4656 0.671539 138.045 8.785919 12.95 5.04 2.13 7.6593 0.782915 139.0208 10.52952 12.96 5.22 2.15 7.6485 0.717672 145.4501 9.147264 12.88 5.27 2.11 7.5772 0.691012 143.2217 3.680577 12.89 5.61 2.13 7.8255 0.618459 154.0265 9.36984 12.77 5.47 2.15 7.5738 0.624435 150.1816 12.45639 12.71 5.57 2.2 7.5219 0.663785 155.7483 12.00565

Room Temperature: 19C Water Temperature: 17C Notes: -------

Table D15. Specimen Dimensions [08]s Week 13

[08]s Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 13 Section thickness Width Thickness Weight (mm) (mm) (mm) (g) 12.57 5.14 2.14 7.4710 12.95 5.04 2.10 7.6593 12.99 5.23 2.15 7.6506 12.88 5.28 2.12 7.6000 12.89 5.61 2.14 7.8286 12.78 5.47 2.16 7.5765 12.71 5.57 2.19 7.5240

% Weight gain 0.744357 0.782915 0.745325 0.993994 0.658318 0.660307 0.691889

Volume (mm3) 138.265 137.0628 146.0661 144.1736 154.7496 150.9983 155.0404

% V 8.959283 8.972762 9.609498 4.369624 9.883314 13.06791 11.49654

Room Temperature: 14C Water Temperature: 11C Notes: Decrease in the rate of percentage moisture gain, could be due to the severe drop in temperature. Room temperature 1C drop when compared to standard room temperature. Water temperature 3C colder than usual.

D12

Table D 16. Specimen Dimensions [08]s - Week 14

[08]s Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 14 Section % thickness Width Thickness Weight Weight Volume (mm) (mm) (mm) (g) gain (mm3) % V 12.61 5.12 2.14 7.4717 0.753796 138.1652 8.880696 12.96 5.04 2.13 7.6525 0.693439 139.1282 10.61487 12.99 5.23 2.16 7.651 0.750593 146.7454 10.11931 12.93 5.28 2.09 7.5812 0.744166 142.6851 3.292123 12.92 5.61 2.12 7.833 0.714892 153.6601 9.109718 12.78 5.47 2.12 7.5769 0.665622 148.202 10.97406 12.75 5.55 2.19 7.525 0.705271 154.9699 11.44582

Room Temperature: 15C Water Temperature: 11C Notes: Severe drop in temperature from original immersion temperature.

Table D 17. Specimen Dimensions [08]s - Week 15

[08]s Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 15 Section % thickness Width Thickness Weight Weight Volume (mm) (mm) (mm) (g) gain (mm3) 12.61 5.10 2.16 7.4725 0.764584 138.9118 12.97 4.99 2.11 7.6547 0.722387 136.5598 12.99 5.26 2.16 7.6534 0.782196 147.5872 12.96 5.28 2.15 7.5824 0.760113 147.1219 12.91 5.57 2.12 7.833 0.714892 152.4464 12.79 5.48 2.16 7.5788 0.690865 151.3927 12.77 5.55 2.24 7.5271 0.733375 158.7566

% V 9.468982 8.572875 10.75097 6.503984 8.247904 13.36325 14.16906

Room Temperature: 19C Water Temperature: 17C Notes:

D13

Table D18. Specimen Dimensions [08]s - Week 16

[08]s Withdrawal II II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 16 Section % thickness Width Thickness Weight Weight Volume (mm) (mm) (mm) (g) gain (mm3) % V 12.59 5.13 2.17 7.475 0.798296 140.1531 10.44725 12.97 5.04 2.13 7.656 0.739493 139.2355 10.70022 12.99 5.23 2.17 7.651 0.750593 147.4248 10.62912 12.93 5.26 2.15 7.60 0.993994 146.2254 5.854957 12.92 5.61 2.12 7.8338 0.725178 153.6601 9.109718 12.78 5.47 2.14 7.5808 0.717436 149.6001 12.02099 12.78 5.58 2.21 7.5294 0.764156 157.6004 13.33756

Room Temperature: 19C Water Temperature: 18C Notes:

D14

Appendix D3. Immersed [06 902]s specimen dimensions


Table D19. Specimen Dimensions [06 902]s - Before immersion

[06 902]s Withdrawal 1 I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness (mm) 12.69 12.39 12.71 12.54 12.44 12.57 12.56 Section thickness (mm) 12.58 12.71 12.57 12.61 12.66 12.58 12.52 Width (mm) Width (mm)

Before Immersion Thickness Weight (mm) (g) 2.00 7.6918 2.01 7.387 2.02 7.581 2.00 7.5139 2.01 7.412 2.00 7.5261 2.02 7.4927 Volume (mm3) 135.2754 126.01373 129.14123 125.4000 125.022 130.2252 130.40797

5.33 5.06 5.03 5.0 5.0 5.18 5.14

5.00 4.99 5.00 5.02 4.95 5.12 5.07

Thickness Weight Volume (mm) (g) (mm3) 2.00 7.5822 125.8000 2.00 7.591 126.8458 2.00 7.5178 125.7000 2.02 7.5143 127.87044 2.00 7.603 125.3340 2.01 7.4864 129.4633 2.00 7.5324 126.9528

Room Temperature: 19C Water Temperature: 19C Notes: -------

D15

Table D20. Specimen Dimensions [06 902]s Week 1

[06 902]s Withdrawal 1 I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness (mm) 12.69 12.47 12.71 12.63 12.49 12.58 12.58 Section thickness (mm) 12.64 12.72 12.61 12.57 12.68 12.61 12.51

Week 1 Width Thickness Weight % Weight Volume (mm) (mm) (g) gain (mm3) % V 5.27 2.10 7.710 0.23661561 140.44023 3.81801125 5.04 2.12 7.406 0.25720861 133.239456 5.73407498 5.06 2.13 7.601 0.26381743 137.072060 6.14121039 5.07 2.06 7.558 0.58691225 131.910246 5.19158373 5.06 2.08 7.433 0.28332433 131.454752 5.14529602 5.28 2.07 7.545 0.25112601 137.494368 5.58199795 5.18 2.05 7.512 0.25758404 133.58702 2.43777435 Width Thickness Weight % Weight Volume (mm) (mm) (g) gain (mm3) % V 4.96 2.11 7.602 0.26113792 132.285184 5.15515421 5.03 2.00 7.612 0.27664339 127.96320 0.8809121 4.94 2.10 7.536 0.2420921 130.81614 4.07011933 5.08 2.08 7.533 0.2488588 132.819648 3.87048315 4.96 2.06 7.622 0.2499013 129.559168 3.37112674 5.1 2.05 7.506 0.2618080 131.83755 1.83392055 5.26 2.01 7.555 0.3040199 132.263226 4.18299241

Room Temperature: 19C Water Temperature: 19C Notes: -------

D16

Table D21. Specimen Dimensions [06 902]s Week 2

[06 902]s Withdrawal 1 I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness (mm) 12.68 12.35 12.67 12.68 12.59 12.58 12.65 Section thickness (mm) 12.63 12.68 12.60 12.60 12.66 12.67 12.51 Width (mm) 5.26 5.03 4.94 5.04 5.01 5.21 5.15 Width (mm) 4.96 4.52 5.02 5.00 5.00 5.07 5.07

Week 2 Thickness Weight % Weight (mm) (g) gain 2.23 7.716 0.314620765 2.20 7.412 0.338432381 2.22 7.608 0.356153542 2.16 7.567 0.706690267 2.17 7.44 0.377765785 2.17 7.551 0.330848647 2.18 7.519 0.351008315 Thickness Weight % Weight (mm) (g) gain 2.21 7.608 0.340270634 1.90 7.619 0.368857858 2.21 7.551 0.441618559 2.20 7.54 0.342014559 2.19 7.629 0.341970275 2.18 7.513 0.355310964 2.22 7.559 0.353141097 Volume (mm3) % V 148.733864 9.94893676 136.66510 8.45254375 138.949356 7.59488685 138.039552 10.0793875 136.874703 9.48049383 142.225706 9.21519490 142.02155 8.90557699 Volume (mm3) % V 138.445008 10.0516756 108.89584 14.1510085 139.78692 11.2067780 138.60000 8.39095858 138.62700 10.6060606 140.036442 8.1669062 140.805054 10.9113418

Room Temperature: 19C Water Temperature: 19C Notes: -------

D17

Table D22. Specimen Dimensions [06 902]s Week 3

[06 902]s Withdrawal 1 I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness (mm) 12.62 12.31 12.66 12.55 12.42 12.53 12.58 Section thickness (mm) 12.47 12.64 12.56 12.50 12.65 12.53 12.40

Week 3 Width Thickness Weight (mm) (mm) (g) 5.26 2.19 7.7250 5.05 2.09 7.4174 5.13 2.04 7.6134 4.96 2.12 7.5708 5 2.14 7.4440 5 2.10 7.5571 5.1 2.14 7.524 Width Thickness Weight (mm) (mm) (g) 5.03 2.05 7.6416 4.96 2.17 7.6234 5.04 2.18 7.5480 5.01 2.11 7.5447 4.93 2.13 7.6354 5.19 2.14 7.5186 5.02 2.13 7.5654 % Weight Volume gain (mm3) 0.44943820 145.374828 0.40100250 129.925895 0.43120084 132.489432 0.76767404 131.965760 0.42518701 132.894000 0.41373603 131.565000 0.41773993 137.298120 % Weight Volume gain (mm3) 0.78250559 128.646274 0.43097714 136.046848 0.40190037 137.999232 0.39984216 132.201375 0.43278478 132.836385 0.42748659 139.6859436 0.43810737 132.588240

% V 7.4658274 3.10455128 2.59267013 5.2358532 6.29649181 1.02883312 5.28353604

% V 2.26253895 7.25372696 9.78459188 3.38696798 5.98591363 7.89617437 4.43900410

Room Temperature: 19C Water Temperature: 18C Notes: -------

D18

Table D23. Specimen Dimensions [06 902]s - Week 4

[06 902]s Withdrawal 1 I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness (mm) 12.78 12.84 12.92 12.78 12.60 12.78 12.87 Section thickness (mm) 12.79 12.88 12.76 12.70 12.91 12.78 12.68

Week 4 % Width Thickness Weight Weight (mm) (mm) (g) gain 5.07 2.14 7.7327 0.51223 4.92 2.18 7.4220 0.47380 5.01 2.16 7.6194 0.50652 4.98 2.10 7.5787 0.86240 4.98 2.08 7.4523 0.54371 5.10 2.10 7.5652 0.51952 5.07 2.15 7.5299 0.49648 % Width Thickness Weight Weight (mm) (mm) (g) gain 4.91 2.13 7.6192 0.48798 4.94 2.09 7.6277 0.48346 4.97 2.10 7.5486 0.40969 5.01 2.13 7.5547 0.53764 4.95 2.12 7.6442 0.54189 5.01 2.12 7.5254 0.52094 5.01 2.10 7.5731 0.54033 Volume (mm3) 138.660 137.716 139.815 133.653 130.515 136.873 140.289 Volume (mm3) 133.761 132.980 133.176 135.525 135.477 135.738 133.406

% V 2.502335236 9.287059139 8.265250633 6.581531100 4.394298603 5.105463459 7.577349108

% V 6.328821145 4.83661895 5.947589499 5.986579667 8.093206951 4.847427954 5.083369567

Room Temperature: 19C Water Temperature: 17C Notes: -------

D19

Table D24. Specimen Dimensions [06 902]s - Week 5

[06 902]s Withdrawal 1 I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness (mm) 12.92 12.86 12.92 12.79 12.61 12.8 12.77 Section thickness (mm) 12.71 12.89 12.75 12.72 12.89 12.78 12.70

Week 5 Width Thickness Weight % Weight Volume (mm) (mm) (g) gain (mm3) % V 5.17 2.12 7.7312 0.512234 141.6084 4.681537 4.92 2.19 7.7712 5.201029 138.5639 9.959386 4.95 2.12 7.6206 0.522359 135.5825 4.98776 4.98 2.13 7.5795 0.873049 135.6686 8.188713 4.94 2.09 7.4523 0.543713 130.1932 4.136237 5.11 2.08 7.5648 0.514211 136.0486 4.471823 5.07 2.15 7.5324 0.529849 139.1994 6.741472 Width Thickness Weight % Weight Volume (mm) (mm) (g) gain (mm3) % V 4.91 2.13 7.6218 0.522276 132.925 5.663746 4.94 2.11 7.6324 0.545383 134.3576 5.922014 5.01 2.09 7.5579 0.533401 133.504 6.208413 5.01 2.08 7.5553 0.545626 132.5526 3.661622 4.96 2.10 7.6443 0.543207 134.2622 7.123558 4.96 2.10 7.5264 0.534302 133.1165 2.821791 5.02 2.14 7.5751 0.566884 136.4336 7.467941

Room Temperature: 19C Water Temperature: 19C Notes: -------

D20

Table D25. Specimen Dimensions [06 902]s - Week 6

[06 902]s Withdrawal 1 I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness (mm) 12.84 12.86 12.78 12.82 12.62 12.72 12.74 Section thickness (mm) 12.73 12.93 12.76 12.68 12.90 12.78 12.66

Week 6 Width Thickness Weight (mm) (mm) (g) 5.17 2.17 7.7373 4.92 2.13 7.7764 4.95 2.17 7.6274 4.98 2.05 7.5889 4.94 2.12 7.4564 5.15 2.08 7.5689 5.09 2.14 7.5369 Width Thickness Weight (mm) (mm) (g) 4.91 2.12 7.6266 4.93 2.12 7.6367 5.03 2.10 7.5613 4.95 2.11 7.5585 4.96 2.12 7.6467 4.98 2.11 7.5298 5.03 2.12 7.5796 % Weight gain 0.591539 5.271423 0.612056 0.99815 0.599029 0.568688 0.589908 % Weight gain 0.585582 0.602029 0.578627 0.588212 0.574773 0.579718 0.626626 Volume (mm3) 144.0507 134.7677 137.2764 130.8794 132.1667 136.2566 138.7717 Volume (mm3) 132.5091 135.1392 134.7839 132.4363 135.6461 134.2897 135.0012

% V 6.486971 6.9468 6.299417 4.369522 5.714783 4.631546 6.413531

% V 5.333161 6.538165 7.226635 3.570658 8.22768 3.727997 6.33966

Room Temperature: 19C Water Temperature: 19C Notes: -------

D21

Table D26. Specimen Dimensions [06 902]s - Week 7

[06 902]s Withdrawal 1 I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness (mm) 12.90 12.87 12.93 12.81 12.64 12.78 12.75 Section thickness (mm) 12.77 12.89 12.74 12.75 12.81 12.79 12.71

Week 7 Width Thickness Weight (mm) (mm) (g) 5.20 2.17 7.7427 4.93 2.17 7.7828 4.98 2.11 7.6320 5.02 2.07 7.5897 4.97 2.10 7.4637 5.13 2.10 7.5748 5.09 2.10 7.5421 Width Thickness Weight (mm) (mm) (g) 4.91 2.15 7.6351 4.91 2.11 7.6434 5.08 2.11 7.568 4.97 2.09 7.5658 4.97 2.13 7.6528 4.99 2.12 7.5365 5.02 2.09 7.5821 % Weight gain 0.661744 5.358061 0.672734 1.008797 0.697518 0.647081 0.659308 % Weight gain 0.697687 0.690291 0.667749 0.68536 0.655005 0.669214 0.659816 Volume (mm3) 145.5636 137.6845 135.8659 133.1138 131.9237 137.6789 136.2848 Volume (mm3) 134.8065 133.5417 136.5575 132.4381 135.6079 135.3029 133.3508

% V 7.605374 9.26154 5.207189 6.151383 5.520372 5.723731 4.506459

% V 7.159384 5.278763 8.637639 3.572077 8.19725 4.510588 5.039651

Room Temperature: 19C Water Temperature: 19C Notes: -------

D22

Table D27. Specimen Dimensions [06 902]s - Week 8

[06 902]s Withdrawal 1 I-1 I-2 I-3 I-4 I-5 I-6 I-7 Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness (mm) 12.95 12.91 12.93 12.83 12.67 12.80 12.76 Section thickness (mm) 12.81 12.94 12.77 12.76 12.77 12.80 12.69

Week 8 Width Thickness Weight (mm) (mm) (g) 5.2 2.17 7.7457 4.93 2.17 7.7843 4.98 2.11 7.6358 5.02 2.06 7.5932 4.99 2.12 7.4645 5.13 2.14 7.5761 5.1 2.13 7.5467 Width Thickness Weight (mm) (mm) (g) 4.9 2.13 7.6351 4.95 2.11 7.6462 5.06 2.11 7.5687 4.97 2.09 7.5684 5.44 2.13 7.6554 4.99 2.12 7.5391 5.02 2.15 7.5829 % Weight gain 0.700746 5.378367 0.72286 1.055377 0.708311 0.664355 0.720701 % Weight gain 0.697687 0.727177 0.67706 0.719961 0.689202 0.703943 0.670437 Volume (mm3) 146.1278 138.1125 135.8659 132.6776 134.0334 140.521 138.6119 Volume (mm3) 133.698 135.1518 136.3402 132.5419 147.9685 135.4086 136.9632

% V 8.022449 9.601126 5.207189 5.803506 7.207848 7.90612 6.290959

% V 6.278196 6.548132 8.464743 3.65331 18.05938 4.592301 7.885112

Room Temperature: 17C Water Temperature: 16C Notes: -------

Week 9 Unable to take moisture gain and specimen dimensions due to Christmas holidays.

D23

Table D28. Specimen Dimensions [06 902]s - Week 10

[06 902]s Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 10 Section thickness Width Thickness Weight (mm) (mm) (mm) (g) 12.82 4.90 2.13 7.6421 12.94 4.97 2.17 7.6503 12.77 5.06 2.11 7.5788 12.76 4.97 2.12 7.5707 12.90 5.44 2.09 7.6592 12.83 5.03 2.12 7.5470 12.71 5.03 2.15 7.5891 % Weight gain 0.790008 0.781188 0.811408 0.750569 0.739182 0.809468 0.752748 Volume (mm3) 133.8023 139.5566 136.3402 134.4445 146.6678 136.814 137.4523

% V 6.361161 10.02068 8.464743 5.141157 17.02159 5.677819 8.270393

Room Temperature: 18C Water Temperature: 16C Notes: -------

Table D29. Specimen Dimensions [06 902]s - Week 11

[06 902]s Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 11 Section thickness Width Thickness Weight (mm) (mm) (mm) (g) 12.85 4.90 2.13 7.6422 12.94 4.97 2.15 7.6518 12.77 5.06 2.14 7.5788 12.76 4.97 2.13 7.5736 12.90 5.44 2.09 7.6655 12.83 5.03 2.12 7.5472 12.71 5.03 2.15 7.5897

% Weight gain 0.791327 0.800948 0.811408 0.789162 0.822044 0.812139 0.760714

Volume (mm3) 134.1155 138.2704 138.2787 135.0786 146.6678 136.814 137.4523

% V 6.610056 9.00666 10.0069 5.637106 17.02159 5.677819 8.270393

Room Temperature: 19C Water Temperature: 18C Notes: -------

D24

Table D30. Specimen Dimensions [06 902]s - Week 12

[06 902]s Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 12 Section thickness Width Thickness Weight (mm) (mm) (mm) (g) 12.85 4.91 2.14 7.6422 12.94 4.97 2.15 7.6519 12.89 5.06 2.14 7.5788 12.76 5.01 2.14 7.5745 12.90 5.44 2.13 7.6655 12.83 5.03 2.14 7.5493 12.76 5.01 2.15 7.5922 % Weight gain 0.791327 0.802266 0.811408 0.801139 0.822044 0.84019 0.793904 Volume (mm3) 135.0201 138.2704 139.5781 136.8051 149.4749 138.1047 137.4443

% V 7.329165 9.00666 11.04063 6.987244 19.26124 6.67478 8.264127

Room Temperature: 19C Water Temperature: 17C Notes: ------Table D31. Specimen Dimensions [06 902]s - Week 13

[06 902]s

Week 13

Section % Withdrawal thickness Width Thickness Weight Weight Volume 2 (mm) (mm) (mm) (g) gain (mm3) % V II-1 12.85 4.93 2.16 7.645 0.828256 136.8371 8.773514 II-2 12.89 4.97 2.15 7.6546 0.837834 137.7361 8.58546 II-3 12.89 5.06 2.12 7.5825 0.860624 138.2736 10.00287 II-4 12.78 5.01 2.16 7.5767 0.830417 138.3000 8.156384 II-5 12.85 4.92 2.15 7.6670 0.841773 135.9273 8.452056 II-6 12.81 5.03 2.14 7.5503 0.853548 137.8894 6.50849 II-7 12.76 5.04 2.18 7.5938 0.815145 140.1967 10.43212

Room Temperature: 14C Water Temperature: 11C Notes: Decrease in the rate of percentage moisture gain, could be due to the drop in temperature. Room temperature 1C drop when compared to standard room temperature. Water temperature 3C colder than usual.

D25

Table D32. Specimen Dimensions [06 902]s - Week 14

[06 902]s Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7

Week 14 Section thickness Width Thickness Weight (mm) (mm) (mm) (g) 12.86 4.93 2.16 7.6453 12.87 4.93 2.14 7.6563 12.81 5.06 2.16 7.5825 12.78 5.01 2.13 7.5777 12.83 4.92 2.15 7.6678 12.81 5.03 2.14 7.5505 12.73 5.00 2.18 7.5949 % Weight gain 0.832212 0.860229 0.860624 0.843725 0.852295 0.856219 0.829749 Volume (mm3) 136.9436 135.7811 140.0082 136.3792 135.7157 137.8894 138.757

% V 8.858162 7.044202 11.3828 6.654212 8.283259 6.50849 9.298101

Room Temperature: 15C Water Temperature: 11C Notes: ------Table D33. Specimen Dimensions [06 902]s - Week 15

[06 902]s

Week 15 % Weight gain 0.886286 0.893163 0.892548 0.891633 0.874655 0.888277 0.849663 Volume (mm3) 136.6001 136.6908 136.9722 136.5143 134.8725 137.997 138.4331

Section Withdrawal thickness Width Thickness Weight 2 (mm) (mm) (mm) (g) II-1 12.88 4.91 2.16 7.6494 II-2 12.93 4.94 2.14 7.6588 II-3 12.81 5.02 2.13 7.5849 II-4 12.75 4.98 2.15 7.5813 II-5 12.87 4.92 2.13 7.6695 II-6 12.82 5.03 2.14 7.5529 II-7 12.75 5.05 2.15 7.5964

% V 8.585157 7.761383 8.967547 6.759815 7.610427 6.591635 9.042987

Room Temperature: 19C Water Temperature: 17C Notes: -------

D26

Table D34. Specimen Dimensions [06 902]s - Week 16

[06 902]s Withdrawal 2 II-1 II-2 II-3 II-4 II-5 II-6 II-7 Section thickness Width Thickness (mm) (mm) (mm) 12.87 4.93 2.14 12.93 4.93 2.15 12.80 5.06 2.13 12.78 5.01 2.16 12.90 4.93 2.17 12.81 5.03 2.14 12.76 5.03 2.18

Week 16 % Weight Weight (g) gain Volume (mm3) 7.6507 0.903432 135.7811 7.6602 0.911606 137.0515 7.586 0.90718 137.9558 7.5841 0.928896 138.3000 7.6715 0.90096 138.0055 7.555 0.916328 137.8894 7.5986 0.87887 139.9185

% V 7.934081 8.045781 9.750072 8.156384 10.11018 6.50849 10.21301

Room Temperature: 19C Water Temperature: 18C Notes: -------

D27

Appendix E: Experimental Data from ILSS Tests


This appendix contains the ILSS values obtained. The data was obtained using the procedure outlined in section 4.2.1.

E1. ILSS Test Values


Table E-1. Interlaminar Shear Strength [08]s configuration Withdrawal 2months

[08]s Dry 1 Dry 2 Dry 3 Dry 4 Dry 5 Dry 6 Dry 7

Shear Strength (N/m2) 39.1 x 106 46.8 x 106 38.0 x 106 35.7 x 106 31.5 x 106 36.2 x 106 48.0 x 106

[08]s Wet 1 Wet 2 Wet 3 Wet 4 Wet 5 Wet 6 Wet 7

Shear Strength (N/m2) 52.2 x 106 41.4 x 106 34.4 x 106 35.7 x 106 38.3 x 106 37.7 x 106 28.7 x 106

Table E-2. Interlaminar Shear Strength [08]s configuration Withdrawal 4months

[08]s Dry 1 Dry 2 Dry 3 Dry 4 Dry 5 Dry 6 Dry 7

Shear Strength (N/m2) 39.1 x 106 46.8 x 106 38.0 x 106 35.7 x 106 31.5 x 106 36.2 x 106 48.0 x 106

[08]s Wet 1 Wet 2 Wet 3 Wet 4 Wet 5 Wet 6 Wet 7

Shear Strength (N/m2) 47.0 x 106 45.3 x 106 44.9 x 106 36.5 x 106 26.7 x 106 35.8 x 106 31.2 x 106

Average Dry [08]s Shear Strength = 36.14 x 106 N/m2 Average Wet II [08]s Shear Strength = 37.5 x 106 N/m2 Average Wet I [08]s Shear Strength = 40.23 x 106 N/m2 Increase of 3.76% in Interlaminar Shear Strength of [0 8]s Increase of 11.3 % in Interlaminar Shear Strength of [08]s

E1

Table E-3. Interlaminar Shear Strength[06 902]s configuration Withdrawal 2months

[06 902]s Dry 1 Dry 2 Dry 3 Dry 4 Dry 5 Dry 6 Dry 7

Shear Strength (N/m2) 18.4 x 106 19.3 x 106 19.1 x 106 23.4 x 106 21.1 x 106 20.2 x 106 19.3 x 106

[06 902]s Wet 1 Wet 2 Wet 3 Wet 4 Wet 5 Wet 6 Wet 7

Shear Strength (N/m2) 28.9 x 106 23.8 x 106 21.6 x 106 21.7 x 106 25.9 x 106 21.9 x 106 30.9 x 106

Table E-4. Interlaminar Shear Strength [06 902]s configuration Withdrawal 4months

[06 902]s Dry 1 Dry 2 Dry 3 Dry 4 Dry 5 Dry 6 Dry 7

Shear Strength (N/m2) 18.4 x 106 19.3 x 106 19.1 x 106 23.4 x 106 18.8 x 106 20.2 x 106 21.6 x 106

[06 902]s Wet 1 Wet 2 Wet 3 Wet 4 Wet 5 Wet 6 Wet 7

Shear Strength (N/m2) 22.7 x 106 29.2 x 106 17.7 x 106 21.7 x 106 25.0 x 106 23.3 x 106 23.3 x 106

Average Dry [06 902]s Shear Strength = 19.5 x 106 N/m2 Average Wet I [06 902]s Shear Strength = 23 x 106 N/m2 Average Wet II [06 902]s Shear Strength = 23.22 x 106 N/m2 Increase of 17.65% in Interlaminar Shear Strength of [06 902]s to Wet I Increase of 18.73% in Interlaminar Shear Strength of [06 902]s to Wet II

E2

E2. Force versus Extension graphs [08]s

3000 2500 2000 Force (N) 1500 1000 500 0 0 0.054 0.108 0.162 0.216 0.27 0.324 0.378 0.432 0.486 0.54 0.594 0.648 0.702 0.756 0.81 0.864 0.918 0.972 1.026 1.08 1.134 1.188 1.242 1.296 1.35 1.404 Extension (mm)
Figure E-0-1. Force versus Extension graph [08]s configuration - Dry

3000 2500 2000 Force (N) 1500 1000 500 0 0 0.056 0.112 0.168 0.224 0.28 0.336 0.392 0.448 0.504 0.56 0.616 0.672 0.728 0.784 0.84 0.896 0.952 1.008 1.064 1.12 1.176 1.232 1.288 1.344 1.4 1.456 Extension (mm)
Figure E-0-2. Force versus Extension graph [08]s configuration Wet I withdrawal 2 months

E3

3500

3000
2500 Force (N) 2000 1500 1000 500 0 0 0.056 0.112 0.168 0.224 0.28 0.336 0.392 0.448 0.504 0.56 0.616 0.672 0.728 0.784 0.84 0.896 0.952 1.008 1.064 1.12 1.176 1.232 1.288 1.344 1.4 1.456 Extension (mm)
Figure E-0-3. Force versus Extension graph [08]s configuration Wet II withdrawal 4 months

E4

E3. Force versus Extension graphs [06 902]s

1400 1200 1000 Force (N) 800 600 400 200

0
0 0.048 0.096 0.144 0.192 0.24 0.288 0.336 0.384 0.432 0.48 0.528 0.576 0.624 0.672 0.72 0.768 0.816 0.864 0.912 0.96 1.008 1.056 1.104 1.152 1.2 1.248 1.296 Extension (mm)
Figure E-0-4. Force versus Extension graph [06 902]s configuration Dry

1600 1400 1200 1000 Force (N) 800 600 400 200 0 0 0.036 0.073 0.109 0.145 0.181 0.218 0.254 0.29 0.326 0.363 0.399 0.435 0.471 0.508 0.544 0.58 0.616 0.653 0.689 0.725 0.761 0.798 0.834 0.87 0.906 0.943 0.979 Extension (mm)
Figure E-0-5. Force versus Extension graph [06 902]s configuration Wet I withdrawal 2 months

E5

1800 1600 1400 1200 Force (N) 1000 800 600 400

200
0 0 0.04 0.08 0.12 0.16 0.2 0.24 0.28 0.32 0.36 0.4 0.44 0.48 0.52 0.56 0.6 0.64 0.68 0.72 0.76 0.8 0.84 0.88 0.92 0.96 1 1.04 1.08 Extension (mm)
Figure E-0-6. Force versus Extension graph [06 902]s configuration Wet II withdrawal 4 months

E6

E3: Statistical Analysis


This appendix contains the results included for analysis after a preliminary examination of the fracture surfaces to exclude any outliers based on a number of variables such as depth of the notches. E.3.1. Standard deviation and mean values for [08]s specimens
45000000 40000000 35000000 30000000 25000000 20000000 15000000 10000000 5000000 0 1 2 3 4 5 Actual

Mean

Figure E-0-7. ILSS Values for [0] specimens - Dry

Standard Deviation: 2.9 x 106 N/m2 Mean: 36.14 x 106 N/m2

E7

41000000 40000000 39000000 38000000 37000000 36000000 35000000 34000000 33000000 32000000 31000000 1 2 3 4 5 Actual Mean

Figure E-0-8. ILSS Values for [0] specimens Wet I - withdrawal 2 months

Standard Deviation: 2.6 x 106 N/m2 Mean: 37.5 x 106 N/m2


50000000 45000000 40000000 35000000 30000000 25000000 20000000 15000000 10000000 5000000 0 1 2 3 4 5 Actual Mean

FigureE-0-9. ILSS Values for [0] specimens Wet II - withdrawal 4 months

Standard Deviation: 5.3 x 106 N/m2 Mean: 41.95 x 106 N/m


E8

E.3.2. Standard deviation and mean values for [06 902]s specimens
21500000 21000000 20500000 20000000 19500000 Actual 19000000 18500000 18000000 17500000 17000000 1 2 3 4 5 6 Mean

Figure E-0-10. ILSS Values for [06 906]s specimens Dry

Standard Deviation: 0.9 x 106 N/m2 Mean: 19.55 x 106 N/m2

E9

30000000

25000000
20000000 15000000 10000000 5000000 0 1 2 3 4 5

Actual Mean

Figure 0-11. ILSS Values for [06 906]s specimens Wet I - withdrawal 2 months

Standard Deviation: 1.8 x 106 N/m2 Mean: 23 x 106 N/m2


26000000

25000000

24000000

23000000

Actual Mean

22000000

21000000

20000000 1 2 3 4 5

Figure 0-12. ILSS Values for [06 906]s specimens Wet II - withdrawal 4 months

Standard Deviation: 1.2 x 106 N/m2 Mean: 23.22 x 106 N/m2


E10

Appendix F: SEM Micrographs


This appendix contains the micrographs obtained using Scanning Electron Microscopy. The procedure outlined in section 4.4 was used to obtain the images.

Appendix F1. Fracture surface of dry [08]s specimens at magnification x100

Figure F-1. Fracture surface of a dry [08]s specimen - magnification x100

F1

Figure F-2. Fracture surface of a wet I [08]s specimen - magnification x100

Figure F-3. Fracture surface of a wet II [08]s specimen - magnification x100

F2

Appendix F2. Fracture surface [06 902]s specimens at magnification x100

Figure F-4. Fracture surface of a dry [06 902]s specimen - magnification x100

Figure F-5. Fracture surface of a wet I [06 902]s specimen - magnification x100

F3

Figure F-6. Fracture surface of a wet II [06 902]s specimen - magnification x100

F4

Appendix F3. Fracture surface of dry [08]s specimens at magnification x500

Figure F-7. Fracture surface of a dry [08]s specimen - magnification x500

Figure F-8. Fracture surface of a wet I [08]s specimen - magnification x500

F5

Figure F-9. Fracture surface of a wet II [08]s specimen - magnification x500

F6

Appendix F4. Fracture surface [06 902]s specimens at magnification x500

Figure F-10. Fracture surface of a dry [06 902]s specimen - magnification x500

Figure F-11. Fracture surface of a wet I [06 902]s specimen - magnification x500

F7

Figure F-12. Fracture surface of a wet II [06 902]s specimen - magnification x500

F8

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