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A thesis submitted to McGill University in partial fulfillment of the requirements for the degree of Doctor of Philosophy

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I may not have gone where I intended to go, But I think I have ended up where I needed to be Douglas Adams (1952 2001)

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Abstract

This work investigated the factors leading to the generation of process-induced stresses and deformations in woven composites manufactured by Resin Transfer Moulding (RTM). Both intrinsic and extrinsic mechanisms were examined. First, a comprehensive methodology was applied to characterize the thermal, chemorheological and thermomechanical properties of the CYCOM 890RTM epoxy resin. The developed models were essential to establish a clear understanding of the resin behaviour during the processing conditions. Then, the thermomechanical properties of 5-Harness satin woven fabrics were investigated using a micromechanical approach. Different fibre volume fractions between 50% and 62%, corresponding to typical volume fractions used in the RTM process, were examined. These thermomechanical properties were compared to the properties of equivalent unidirectional crossply laminates in order to validate the use of crossply configuration to model the behaviour of woven fabric laminate. The developed resin models and the fibre properties were then implemented in a finite element software, ABAQUS/COMPRO in order to predict the evolution of the laminate properties during the RTM process. Fibre Bragg Grating sensors were then used to characterize experimentally the tool-part interaction occurring during the RTM process. The separation of the composite from the mould during the cool down period was measured by the optical sensors. The maximal shear stress allowed by the laminate before the debonding was estimated to be 140 kPa for a steel mould. The observed tool-part interaction was simulated using frictional contact conditions at the composite/mould interface in a finite element analysis. Finally, using the ABAQUS/COMPRO interface, the manufacturing of a composite structure by RTM was modelled, taking into account simultaneously the intrinsic and extrinsic mechanisms examined. This case study demonstrates the capacity of the process modelling approach to predict the process-induced strains, stresses and deformations of three-dimensional woven composite parts manufactured by the RTM process. The use of such a modelling tool is essential

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for industrial purposes to significantly reduce the design time and manufacturing cost.

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Rsum

Ce travail tudie les facteurs conduisant au dveloppement de contraintes et dformations rsiduelles induites par le procd dinjection sur renforts dans le cas de composites renforts tisss. Les mcanismes intrinsques ainsi quextrinsques ont t pris en considration. Tout dabord, une mthodologie a t utilise pour caractriser les proprits thermo-chimiques et thermomcaniques de la rsine poxy CYCOM 890RTM. Le dveloppement de modles mathmatiques pour dcrire les diffrentes proprits est une tape essentielle pour comprendre clairement lvolution du comportement de la rsine lors du procd de fabrication. Ensuite, les proprits thermo-mcaniques dun tissu satin de 5 ont t examines en utilisant une approche de micromcanique sur un motif lmentaire. Diffrentes fractions volumiques de fibre entre 50% et 62%, correspondant aux fractions volumiques de fibre typiquement utilises pour le procd dinjection sur renfort, ont t tudies. Les proprits ont t compares aux proprits obtenues pour des lamins unidirectionnels croiss quivalents. En gnral, les proprits des deux configurations sont comparables. Ceci justifie lutilisation des proprits de fibre unidirectionnelle dans une configuration croise pour simuler le comportement dun lamin renfort tiss satin de 5. Les modles des proprits de la rsine et des fibres ont t ensuite implments dans un logiciel dlments finis, ABAQUS/COMPRO, afin de prdire lvolution des proprits du lamin pendant le procd dinjection sur renforts. Des fibres optiques rseaux de Bragg ont t galement utilises pour caractriser exprimentalement les interactions entre le composite et le moule gnres pendant le procd. Les fibres optiques saisirent la sparation entre le composite et le moule pendant le refroidissement. La contrainte de cisaillement maximale que le composite peut endurer avant le dcollement a t estime 140 kPa. Cette interaction entre le composite et le moule a t ensuite simule par une analyse dlments finis en utilisant une condition de contact par friction linterface composite/moule. Finalement, la fabrication dune structure composite par le procd dinjection sur renfort a t simule en tenant en compte, simultanment, -vi-

les mcanismes intrinsques et extrinsques tudis. Ce cas dtude dmontre la capacit dutiliser le principe de la modlisation de procd pour prdire les dformations et contraintes rsiduelles gnres par le procd de fabrication pour des pices composite tisses tridimensionnelles. Lutilisation dun tel outil numrique est essentielle pour des applications industrielles afin de diminuer les temps de conception ainsi que les cots de fabrication.

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Acknowledgements

Je tiens tout dabord adresser mes remerciements les plus sincres mon superviseur, Prof. Pascal Hubert. Ses prcieux conseils, son support et ses encouragements tout au long du projet ont t la cl dune exprience de recherche enrichissante et mmorable. I would like to deeply acknowledge Timotei Centea for his precious help for the resin characterization. I would like also to sincerely thank Tadayoshi Yamanaka and Dr. Krishna Challagulla for their valuable help and advice on the unit cell analysis. Je remercie sincrement Jonathan Lalibert pour son aide prcieuse pour les montages exprimentaux ainsi que ses conseils tout au long du projet et son infinie patience. Jaimerai galement remercier le Dr. Vronique Michaud et le Dr. Rui de Oliveira pour leur accueil chaleureux au Laboratoire de technologie des composites et polymres de lEPFL, ainsi que de mavoir permis denrichir mon exprience dans le domaine des fibres optiques. I am grateful to Anthony Floyd and Robert Courdji from Convergent Manufacturing Technologies Inc. for their endless help and invaluable advice with the process modelling simulations. Je remercie galement de tout mon cur ma famille qui ma toujours encourage aller de lavant et poursuivre mes ambitions. Je naurais pas pu arriver l o jen suis sans leurs constants encouragements et conseils. I would like to gratefully thank all the members of the Composite Materials and Structures Laboratory for their invaluable friendship and their support throughout my studies.

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Finally, I would like to acknowledge the financial support from the Consortium for Research and Innovation in Aerospace in Quebec (CRIAQ) and the Natural Sciences and Engineering Research Council of Canada (NSERC). I would like also to acknowledge the industrial and academic partner of this project: Bell Helicopter Textron, Delastek, the Aerospace Manufacturing Technology Centre of the National Research Council of Canada (NRC-AMTC) and cole Polytechnique.

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Table of contents

Abstract............. .................................................................................................... iv Rsum. ..................................................................................................... vi Acknowledgements ............................................................................................ viii Table of contents ................................................................................................... x List of Figures .....................................................................................................xiv List of Tables.... ................................................................................................ xxiv List of Symbols ................................................................................................. xxvi CHAPTER 1 1.1 1.2 1.3 CHAPTER 2 2.1 2.1.1 2.1.2 2.1.3 2.2 2.2.1 2.2.2 2.2.3 2.2.4 Introduction ................................................................................... 1 Introduction ................................................................................... 1 Motivations.................................................................................... 5 Project objectives and thesis outline ............................................. 6 Literature Review and Objectives ................................................. 8 Material behaviour during the cure ............................................... 8 Resin behaviour ............................................................................. 8 Composite thermomechanical properties .................................... 22 Fibre architecture behaviour........................................................ 27 Sources of residual stresses and deformations ............................ 31 Thermal strains ............................................................................ 32 Resin volumetric cure shrinkage ................................................. 34 Tool-part interaction .................................................................... 36 Property gradients: temperature, degree-of-cure and fibre volume fraction ........................................................................................ 38 2.2.5 Secondary effects ........................................................................ 39 -x-

2.3 2.3.1 2.3.2 2.3.3 2.3.4 2.4 CHAPTER 3 3.1 3.2 3.2.1 3.2.2 3.3 3.4 3.5 3.5.1 3.5.2 3.6 3.7 CHAPTER 4 4.1 4.1.1 4.1.2 4.1.3 4.2 4.2.1

Process modelling ....................................................................... 40 Heat transfer and cure kinetics .................................................... 42 Flow and compaction .................................................................. 43 Stresses development .................................................................. 44 COMPRO Component Architecture (CCA) ............................... 47 Literature review summary and objectives ................................. 48 Characterization of the Resin Thermomechanical Properties ..... 52 Characterization methodology .................................................... 52 Thermal stability and cure kinetics (step 1 and 2) ...................... 53 Thermal stability (step 1) ............................................................ 53 Cure kinetics (step 2)................................................................... 55 Rheological behaviour (step 3a) .................................................. 60 Glass transition temperature (step 3b) ......................................... 64 Volumetric changes during cure (step 4a and 4b) ....................... 66 Cure shrinkage (step 4a) .............................................................. 66 Coefficient of thermal expansion (step 4b) ................................. 80 Elastic modulus (step 4c) ............................................................ 84 Summary and discussion ............................................................. 88 Thermomechanical properties of fabric composites ................... 91 Unit cell models .......................................................................... 93 Unidirectional unit cell ................................................................ 93 Crossply unit cell ......................................................................... 94 5-harness satin unit cell ............................................................... 95 Boundary conditions ................................................................... 99 Periodic constraints ..................................................................... 99 -xi-

Loading cases ............................................................................ 101 Thermomechanical properties ................................................... 103 Determination of the thermomechanical properties .................. 103 Unidirectional unit cell thermomechanical properties .............. 104 Crossply and 5-harness satin unit cells thermomechanical properties ................................................................................... 107

Evolution of the 5-HS unit cell stresses during the cure cycle.. 115 Summary and discussion ........................................................... 119 Investigation of the tool-part interaction by fibre Bragg grating sensors ....................................................................................... 121

5.1 5.2 5.2.1 5.2.2 5.3 5.3.1 5.3.2 5.3.3 5.3.4 5.4 5.4.1 5.4.2 5.4.3 5.4.4 5.5

Fibre Bragg grating sensor principle ......................................... 122 Experimental procedure ............................................................ 125 RTM process ............................................................................. 125 FBG sensors .............................................................................. 128 Experimental results .................................................................. 129 Measured in-plane strains: cure cycle 1 .................................... 129 Measured in-plane strains: cure cycle 2 .................................... 133 Laminate coefficient of thermal expansion ............................... 137 Maximum shear stress determination ........................................ 138 Tool-part interaction modelling ................................................ 140 Geometry and finite element mesh............................................ 141 Material model .......................................................................... 142 Boundary conditions ................................................................. 143 Numerical results....................................................................... 146 Summary and discussion ........................................................... 166

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CHAPTER 6

Numerical case study: dimensional stability of carbon epoxy cylinders ................................................................................... 167

6.1 6.1.1 6.1.2 6.1.3 6.2 6.2.1 6.2.2 6.2.3 6.3 CHAPTER 7

Numerical model ....................................................................... 167 Geometry and finite element mesh............................................ 168 Material models ......................................................................... 169 Boundary conditions ................................................................. 170 Results and discussion ............................................................... 171 Temperature and degree-of-cure ............................................... 172 Strains and stresses results ........................................................ 174 Spring-in variation..................................................................... 186 Summary and discussion ........................................................... 193 Conclusions and Future Work ................................................... 195

References......... ................................................................................................. 200 Appendix A A.1. A.2. A.3. Complements on Material Characterization .............................. 211 DSC measurements .................................................................... 211 Rheological measurements......................................................... 212 Solid samples preparation for the rheometer in torsion mode ... 217

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List of Figures

Figure 1-1: Composite manufacturing processes as a function of production rate and part complexity [2].................................................................................. 1 Figure 1-2: RTM process ........................................................................................ 3 Figure 1-3 RTM phenomena interactions ............................................................... 3 Figure 2-1: State transition and property evolution of the CYCOM 890RTM epoxy resin during a typical cure cycle. a) Degree-of-cure, viscosity and glass transition temperature, b) Relative volume variation and elastic modulus ....................................................................................................... 10 Figure 2-2: Volumetric change of the CYCOM 890RTM epoxy resin during a typical cure cycle ......................................................................................... 11 Figure 2-3: Example of construction of the compliance master curve using the principle of time-temperature superposition [62] ........................................ 21 Figure 2-4: Loading on the representative volume element to determine the elastic constants: a) longitudinal load, b) transverse load, c) in-plane shear load .. 22 Figure 2-5: Comparison of experimental values of the transverse Youngs modulus with the predicted values using the strength of materials approach, the semi-empirical approach and the elastic approach as a function of the fibre volume fraction: a) 0 <Vf <1, b) 0.45< Vf <0.75 [67] ......................... 25 Figure 2-6: Comparison of experimental values of the in-plane shear modulus with the predicted values using the strength of materials approach, the semiempirical approach and the elastic approach as a function of the fibre volume fraction: a) 0< Vf <1, b) 0.45< Vf <0.75 [67].................................. 26 Figure 2-7: Main weave configurations. a) Plain weave, b) Twill weave and ..... 28 Figure 2-8: Schematic view of the three analytical models for an 8-harness satin. a) Mosaic model, b) Crimp model, c) Bridging model (adapted from [73]) 29 Figure 2-9 Shape variations due to process-induced stresses: a) spring-in deformation, b) warpage deformation ......................................................... 32 Figure 2-10: Schematic explanation of the spring-in variation as a function of the resin state, below or above Tg (adapted from [99]) .................................. 34 -xiv-

Figure 2-11: Process-induced warpage mechanism due to tool-part interaction [107] ............................................................................................................ 36 Figure 2-12: Process-induced warpage mechanism due to fibre volume fraction gradient ........................................................................................................ 39 Figure 2-13: Process modelling modular approach .............................................. 41 Figure 2-14: Schematic representation of the coordinate systems in ply and the global orientation ......................................................................................... 45 Figure 2-15: ABAQUS/COMPRO structure ........................................................ 47 Figure 2-16: Summary of the investigations on process-induced stresses and deformations ................................................................................................ 48 Figure 3-1: Characterization procedure for the thermoset resin ........................... 53 Figure 3-2: Resin weight variation with temperature from a TGA dynamic test at 20C/min...................................................................................................... 54 Figure 3-3: Resin weight variation for three hour at 180C .................................. 55 Figure 3-4: Typical heat flow of a Dynamic Scanning Calorimetry dynamic test at 2C/min ........................................................................................................ 56 Figure 3-5: Comparison of experimental data and predicted cure kinetics model for isothermal tests: a) degree-of-cure with the time, b) cure rate as a function of the degree-of-cure ..................................................................... 57 Figure 3-6: Cure rate as a function of inverse absolute temperature at low degreeof-cure ( = 0.1) under isothermal conditions ............................................. 58 Figure 3-7: Ultimate degree-of-cure under isothermal conditions as a function of the glass transition temperature ................................................................... 59 Figure 3-8: Comparison of experimental data and predicted cure kinetics model for dynamic tests .......................................................................................... 60 Figure 3-9: Evolution of the measured and predicted viscosity with temperature for rheological dynamic tests at three temperature rates ............................. 61 Figure 3-10: Evolution of the measured and predicted viscosity with time for rheological isothermal tests ......................................................................... 62 Figure 3-11: Determination of the gel point at 180C .......................................... 62

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Figure 3-12: Comparison of glass transition temperatures measured with Modulated Differential Scanning Calorimeter, Thermo Mechanical Analyzer and rheometer in torsion mode and the predicted values obtained with the DiBenedetto model ........................................................................ 66 Figure 3-13: Shrinkage measurement methods set-up: a) modified rheology, b) gravimetric. .................................................................................................. 70 Figure 3-14: Gap and normal force variation for a typical modified rheology test for an isothermal cure at 180C ................................................................... 71 Figure 3-15: Evolution of the measured resin shrinkage by the modified rheology method and predicted values with time under isothermal conditions ......... 72 Figure 3-16: Evolution of the measured resin shrinkage by the modified rheology method and the predicted values as a function of the degree-of-cure under isothermal conditions................................................................................... 73 Figure 3-17: Resin weight and temperature variation for a typical gravimetric test for an isothermal cure at 160C ................................................................... 74 Figure 3-18: Resin weight and temperature variation for a typical gravimetric test for an isothermal cure at 170C ................................................................... 74 Figure 3-19: Resin weight and temperature variation for a typical gravimetric test for an isothermal cure at 180C ................................................................... 75 Figure 3-20: Evolution of the measured resin shrinkage by gravimetric method and predicted values with time under isothermal conditions ...................... 76 Figure 3-21: Measured and predicted cure shrinkage for isothermal tests with the gravimetric method ...................................................................................... 76 Figure 3-22: Comparison of the two shrinkage measurement methods with degree-of-cure at 160C ............................................................................... 78 Figure 3-23: Comparison of the two shrinkage measurement methods with degree-of-cure at 170C ............................................................................... 79 Figure 3-24: Comparison of the two shrinkage measurement methods with degree-of-cure at 180C ............................................................................... 79 Figure 3-25: Resin relative dimensional change with temperature of a neat resin sample with an initial degree-of-cure -xvi1

of 0.883 ....................................... 81

Figure 3-26: Resin relative dimensional change during the heating part of cycle 3 at 3C/min .................................................................................................... 82 Figure 3-27: Variation of the coefficient of thermal expansion with the degree-ofcure before and after the glass transition ..................................................... 83 Figure 3-28: Evolution of the measured and predicted CTE as a function of T*, for 3C/min heating rate up to different temperatures ................................. 84 Figure 3-29: Evolution of the elastic modulus with temperature and time for a resin sample with an initial degree-of-cure

1

of 0.846 .............................. 86

Figure 3-30: Resin modulus model as a function of difference between instantaneous and glass transition temperature (T*=T-Tg) ......................... 87 Figure 3-31: Measured and predicted elastic modulus with time under two curing temperatures, 160C and 180C ................................................................... 88 Figure 4-1: Applied methodology to determine the thermomechanical properties of the unidirectional crossply and 5-harness woven fabric unit cells .......... 92 Figure 4-2: Unidirectional unit cell finite element model..................................... 94 Figure 4-3: Crossply unit cell finite element model ............................................. 95 Figure 4-4: a) Cross-section of a 4 plies laminate, G30-500 6k carbon fibre/CYCOM 890RTM epoxy resin, observed by optical microscope (x50), b) detail of a yarn ......................................................................................... 96 Figure 4-5: 5-harness satin unit cell: a) unit cell finite element model and dimensions, b) yarn dimensions, c) schematic representation of the fibre orientation along a yarn ............................................................................... 99 Figure 4-6: Unit cell faces, edges and corners notations .................................... 100 Figure 4-7: Boundary conditions: a) for an axial loading, b) for a shear loading, c) for a thermal loading.................................................................................. 102 Figure 4-8: Axial and shear stress distributions of the unidirectional unit cell at 70% fibre volume fibre .............................................................................. 106 Figure 4-9: Axial and shear stress distributions of the crossply unit cell at 70% fibre volume fraction ................................................................................. 109 Figure 4-10: Axial and shear stress distributions of the 5-HS unit cell at 70% fibre volume fraction .......................................................................................... 110 -xvii-

Figure 4-11: Elastic modulus comparison for the crossply unit cell and the 5harness satin unit cell ................................................................................. 111 Figure 4-12: Shear modulus comparison for the crossply unit cell and the 5harness satin unit cell ................................................................................. 112 Figure 4-13: Poissons ratios comparison for the crossply unit cell and the 5harness satin unit cell ................................................................................. 112 Figure 4-14: In-plane coefficients of thermal expansion comparison for the crossply unit cell and the 5-harness satin unit cell .................................... 113 Figure 4-15: Through-thickness coefficients of thermal expansion comparison for the crossply unit cell and the 5-harness satin unit cell .............................. 113 Figure 4-16: Stresses in the three directions of a half 5-HS unit cell (Vf = 50%) at the gel point (t = 70 minutes) .................................................................... 116 Figure 4-17: Stresses in the three directions of a half 5-HS unit cell (Vf = 50%) at the end of the isotherm (t = 120 minutes).................................................. 117 Figure 4-18: Stresses in the three directions of a half 5-HS unit cell (Vf = 50%) at the end of the cool down (t = 275 minutes) ............................................... 118 Figure 5-1: Schematic representation of the open and closed mould processes, a) before the cure, b) at the end of the cure ................................................... 121 Figure 5-2: Phase mask grating technique (adapted from [150])....................... 124 Figure 5-3: RTM steel mould: a) mould opened, b) perform inside the mould .. 126 Figure 5-4: RTM experimental set-up ................................................................ 127 Figure 5-5: Applied cure cycle to the RTM process ........................................... 127 Figure 5-6: Preconditioned fibre Bragg grating sensor ....................................... 128 Figure 5-7: FBG sensors position in the laminate .............................................. 129 Figure 5-8: FBG sensor relative wavelength variation and temperature during cure cycle 1 ........................................................................................................ 130 Figure 5-9: In-situ strain variation during cure cycle 1 ...................................... 131 Figure 5-10: In-situ strain variation from the injection to the end of cure cycle 1 ................................................................................................................... 131 Figure 5-11: In-situ strain variation with the temperature for cure cycle 1 ........ 133 Figure 5-12: FBG sensor relative wavelength variation during cure cycle 2 ..... 135 -xviii-

Figure 5-13: In-situ strain variation during cure cycle 2 from the injection to the end of the cool down ................................................................................. 135 Figure 5-14: In-situ strain variation with the temperature for the cool down of cure cycle 2 ........................................................................................................ 136 Figure 5-15: Comparison of the strain variation at the laminate mid-thickness for the two cure cycles. ................................................................................... 136 Figure 5-16: Temperature and strain variation during the post-cure of the laminate ................................................................................................................... 138 Figure 5-17: Shear stress formation due to the mismatch of the thermal expansion between the composite and the mould at the cool down ........................... 139 Figure 5-18: Composite plate and steel mould finite element model: a) finite element mesh of the laminate, b) finite element mesh of the mould and the laminate, c) close-up of the laminate finite element mesh in the mould, d) schematic position of the analyzed element .............................................. 142 Figure 5-19: Schematic representation of the critical shear stress evolution with a stick-slip behaviour ................................................................................... 145 Figure 5-20: Evolution of the temperature and the degree-of-cure at the laminate mid-thickness at the position A for cure cycle 1 ....................................... 147 Figure 5-21: Evolution of the temperature and the degree-of-cure at the laminate mid-thickness at the position A for cure cycle 2 ....................................... 147 Figure 5-22: Temperature and degree-of-cure field at different times: 0 minutes, 60 minutes, 120 minutes, and 917 minutes ............................................... 148 Figure 5-23: In-plane strain evolution at the laminate mid-thickness for cure cycle 1 in the case of no bonding (model A) and perfect bonding (model B) ..... 150 Figure 5-24: In-plane strain evolution at the laminate mid-thickness for cure cycle 1 using contact interactions (model C) ...................................................... 150 Figure 5-25: Through-thickness strain evolution at the laminate mid-thickness for cure cycle 1 in the case of no bonding (model A) and perfect bonding (model B) ............................................................................................................... 151 Figure 5-26: Through-thickness strain evolution at the laminate mid-thickness for cure cycle 1 using contact interactions (model C) ..................................... 151 -xix-

Figure 5-27: In-plane strain evolution with the temperature at the laminate midthickness for cure cycle 1 in the case of no bonding (model A) and perfect bonding (model B) ..................................................................................... 153 Figure 5-28: In-plane strain evolution with the temperature at the laminate midthickness for cure cycle 1 using contact interactions (model C) ............... 153 Figure 5-29: Through-thickness strain evolution with the temperature at the laminate mid-thickness for cure cycle 1 in the case of no bonding (model A) and perfect bonding (model B) .................................................................. 154 Figure 5-30: Through-thickness strain evolution with temperature at the laminate mid-thickness for cure cycle 1 using contact interactions (model C) ........ 154 Figure 5-31: Comparison of the in-plane strain evolution at the laminate midthickness for cure cycle 1 obtained experimentally and numerically in the case of no bonding (model A) and perfect bonding (model B) and frictional contact (model C)....................................................................................... 156 Figure 5-32: Comparison of the in-plane strain evolution with temperature during the cool down at the laminate mid-thickness for cure cycle 1 obtained experimentally and numerically in the case of no bonding (model A), perfect bonding (model B) and frictional contact (model C) ................................. 157 Figure 5-33: In-plane strain evolution at the laminate mid-thickness for cure cycle 2 in the case of no bounding (model A) and perfect bounding (model B) . 158 Figure 5-34: In-plane strain evolution at the laminate mid-thickness for cure cycle 2 using contact interactions (model C) ...................................................... 159 Figure 5-35: Through-thickness strain evolution at the laminate mid-thickness for cure cycle 2 in the case of no bounding (model A) and perfect bounding (model B) ................................................................................................... 159 Figure 5-36: Through-thickness strain evolution at the laminate mid-thickness for cure cycle 2 using contact interactions (model C) ..................................... 160 Figure 5-37: In-plane strain evolution with temperature at the laminate midthickness for cure cycle 2 in the case of no bounding (model A) and perfect bounding (model B) ................................................................................... 161

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Figure 5-38: In-plane strain evolution with the temperature at the laminate midthickness for cure cycle 2 using contact interactions (model C) ............... 161 Figure 5-39: Through-thickness strain evolution with the temperature at the laminate mid-thickness for cure cycle 2 in the case of no bounding (model A) and perfect bounding (model B)............................................................ 162 Figure 5-40: Through-thickness strain evolution with temperature at the laminate mid-thickness for cure cycle 2 using contact interactions (model C) ........ 162 Figure 5-41: Comparison of the in-plane strain evolution at the laminate midthickness for cure cycle 2 obtained experimentally and numerically in the case of no bonding (model A) and perfect bonding (model B) and frictional contact (model C)....................................................................................... 164 Figure 5-42: Comparison of the in-plane strain evolution with temperature during the cool down at the laminate mid-thickness for cure cycle 2 obtained experimentally and numerically in the case of no bonding (model A), perfect bonding (model B) and frictional contact (model C) ................................. 165 Figure 6-1: Finite element models and boundary conditions: a) RTM finite element mesh, b) close-up of the laminate mesh, c) schematic position of the analyzed elements A and B ....................................................................... 169 Figure 6-2: Predicted temperatures at point A at different locations through the composite thickness ................................................................................... 172 Figure 6-3: Predicted degree-of-cure at point A at different locations through the composite thickness ................................................................................... 173 Figure 6-4: Temperature, glass transition temperature and degree-of-cure evolutions for the RTM process at point A at the mid-thickness of the composite ................................................................................................... 173 Figure 6-5: Radial strain evolution of the [0]8 laminate at the interfaces for the RTM process with a steel mandrel at position A....................................... 175 Figure 6-6: Radial strain evolution of the [90]8 laminate at the interfaces for the RTM process with a steel mandrel at position A....................................... 176 Figure 6-7: Radial strain evolution of the [+30/-30/-30/+30]s laminate at the interfaces for the RTM process with a steel mandrel at position A .......... 176 -xxi-

Figure 6-8: Radial strain evolution of the [+45/-45/-45/+45]s laminate at the interfaces for the RTM process with a steel mandrel at position A .......... 177 Figure 6-9: Radial strain evolution of the [+60/-60/-60/+60]s laminate at the interfaces for the RTM process with a steel mandrel at position A .......... 177 Figure 6-10: Radial stress evolution of the [0]8 laminate at the interfaces for the RTM process with a steel mandrel at position A....................................... 178 Figure 6-11: Radial stress evolution of the [90]8 laminate at the interfaces for the RTM process with a steel mandrel at position A....................................... 178 Figure 6-12: Radial stress evolution of the [+30/-30/-30/+30]s laminate at the interfaces for the RTM process with a steel mandrel at position A .......... 179 Figure 6-13: Radial stress evolution of the [+45/-45/-45/+45]s laminate at the interfaces for the RTM process with a steel mandrel at position A .......... 179 Figure 6-14: Radial stress evolution of the [+60/-60/-60/+60]s laminate at the interfaces for the RTM process with a steel mandrel at position A .......... 180 Figure 6-15: Schematic representation of the composite debonding, depending of the material orientation .............................................................................. 182 Figure 6-16: Evolution of the contact pressure at position A and B for the ....... 183 Figure 6-17: Radial stress evolution of the [0]8 laminate at the interfaces for the RTM process with an aluminum mandrel at position A ............................ 184 Figure 6-18: Radial stress evolution of the [90]8 laminate at the interfaces for the RTM process with an aluminum mandrel at position A ............................ 184 Figure 6-19: Radial stress evolution of the [+30/-30/-30/+30]s laminate at the interfaces for the RTM process with an aluminum mandrel at position A 185 Figure 6-20: Radial stress evolution of the [+45/-45/-45/+45]s laminate at the interfaces for the RTM process with an aluminum mandrel at position A 185 Figure 6-21: Radial stress evolution of the [+60/-60/-60/+60]s laminate at the interfaces for the RTM process with an aluminum mandrel at position A 186 Figure 6-22: Schematic representation of the deformations occurring after the stresses released a) spring-in, b) warpage ................................................. 187 Figure 6-23: Effect of the resin shrinkage and the laminate layup on the spring-in value at the end face .................................................................................. 192 -xxii-

Figure 6-24: Effect of the laminate layup and the mandrel material on the springin value at the end face .............................................................................. 193 Figure A-1: Dynamic test reproducibility at 1C/min and 2C/min temperature ramp ........................................................................................................... 211 Figure A-2: Isothermal test reproducibility at 160C, 170C, 180C and 190C 212 Figure A-3: Strain sweep test performed at 1Hz frequency in oscillatory mode 213 Figure A-4: Time sweep performed at 15% strain and 1Hz in oscillatory mode 213 Figure A-5: Viscosity tests at 170C at 15% strain and 1Hz in oscillatory mode ................................................................................................................... 214 Figure A-6: Viscosity tests at 180C at 15% strain and 1Hz in oscillatory mode ................................................................................................................... 214 Figure A-7: Viscosity tests at 190C at 15% strain and 1Hz in oscillatory mode ................................................................................................................... 215 Figure A-8: Dynamic viscosity tests for a temperature ramp of 1C/min at 15% strain and 1Hz in oscillatory mode ............................................................ 215 Figure A-9: Dynamic viscosity tests for a temperature ramp of 2C/min at 15% strain and 1Hz in oscillatory mode ............................................................ 216 Figure A-10: Dynamic viscosity tests for a temperature ramp of 3C/min at 15% strain and 1Hz in oscillatory mode ............................................................ 216 Figure A-11: Glass transition temperature measurement process. The arrows correspond to one of the three glass transition temperature indicators [155] ................................................................................................................... 218

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List of Tables

Table 2-1: Studies on process-induced stresses and deformations for the RTM process ......................................................................................................... 50 Table 3-1: Cure kinetic model constants............................................................... 59 Table 3-2: Viscosity model constants ................................................................... 64 Table 3-3: DiBenedetto model constants .............................................................. 65 Table 3-4: Curve fitting constants for the shrinkage model obtained by the modified rheology method (Eq. 3-10) and R2 values for isothermal experiments.................................................................................................. 73 Table 3-5: Bilinear curve fitting constants for the shrinkage model obtained by the gravimetric method (Eq. 3-11) .................................................................... 77 Table 3-6: Coefficient of thermal expansion model constants ............................. 84 Table 3-7: Parameters values of the elastic modulus model ................................. 88 Table 4-1: Types of reinforcement and their fibre volume fractions .................... 92 Table 4-2: Carbon fibre and epoxy resin thermomechanical properties ............... 93 Table 4-3: Measured dimensions of a 5-harness satin unit cell ............................ 96 Table 4-4: Nominal ply thickness as a function of the fibre volume fraction ...... 97 Table 4-5: Dimensions and characteristics of the preliminary and final 5-harness satin unit cell................................................................................................ 98 Table 4-6: Comparison of the numerical and analytical values obtained for the nine engineering constants and the coefficients of thermal expansion of the unidirectional unit cell ............................................................................... 105 Table 4-7: Engineering constants and coefficients of thermal expansion obtained for the crossply unit cell for different fibre volume fractions ................... 107 Table 4-8: Engineering constants and coefficients of thermal expansion obtained for the 5-harness satin unit cell for different fibre volume fractions ......... 108 Table 4-9: Experimental values of the coefficients of thermal direction obtained by TMA for a 5-Harness satin unit cell with Vf = 59.4%.......................... 115 Table 4-10: Composite shrinkage coefficients for the 5-harness satin unit cell at 62%, 55% and 50% fibre volume fractions ............................................... 119 -xxiv-

Table 5-1: Coefficient of thermal expansion measured at the post cure ............. 138 Table 5-2: Maximum shear stress for the two cure cycle ................................... 140 Table 5-3: Material properties used as input for the FE models ......................... 143 Table 5-4: Numerical curve gradients obtained with the different models for the in-plane and through-thickness strains for the cure cycle 1 ...................... 155 Table 5-5: Comparison of the experimental and predicted curve gradients obtained with the different models for the in-plane strains ....................... 157 Table 5-6: Numerical curve gradients obtained with the different models for the in-plane and through-thickness strains during the cure cycle 2................. 163 Table 5-7: Comparison of the experimental and predicted curve gradients obtained with the different models for the in-plane strains ....................... 165 Table 6-1: Material properties used as input for the FE models ......................... 170 Table 6-2: Coefficients of thermal expansion of the laminates .......................... 182 Table 6-3: Process-induced dimensional changes for the different laminate layups ................................................................................................................... 188 Table 6-4: Composite cure shrinkage coefficients in the longitudinal, hoop and radial directions ......................................................................................... 189 Table 6-5: Analytical spring-in values for the different laminate layups ........... 190 Table A-1: Pre-cured plaque information ........................................................... 217 Table A-2: Degree-of-cure evolution for samples used for the glass transition temperature measurements ........................................................................ 219 Table A-3: Degree-of-cure evolution for samples used for the tensile modulus measurements ............................................................................................ 219

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List of Symbols

Latin Symbols A Area; constant Fibre areal weight a B b C Cp CTE E Ea E Ek F FN G H HT h K KT Shift factor; constant Constant Constant Stiffness; constant Specific heat Coefficient of thermal kij L l m N n P R RF r S T Tg T

*

Thermal conductivity tensor Length Thickness; length Reaction Corner nodes Reaction order; number of Pressure Generated heat Universal gas constant Reaction force Radius Compliance Temperature; transformation Glass transition temperature Difference between the order; mass;

constant

expansion Elastic modulus; edge node; Activation energy Viscous activation energy Kinetic activation energy Face nodes Normal force Shear modulus Heat flow Total heat of reaction Heat Bulk transfer coefficient; FBG constant

matrix; constant

instantaneous cure temperature and the glass transition temperature t u V Vf Time; thickness Displacement Volume Fibre volume fraction Darcy velocity vector Resin velocity vector w YVf Width; warpage Yarn fibre volume fraction

parallel plates gap; height modulus; sensitivity; constant Effective plane strain bulk Preform permeability tensor k kk Arrhenius constants Rheology constant -xxvimodulus

Greek symbols B Period Fibre bed porosity Degree-of-cure Normalized degree-of-cure Strain, shrinkage Viscosity Angle Constant Fitting parameter Bragg wavelength Dynamic Poissons ratio Density Stress Fibre bed effective stress Shear stress Composite coefficient Subscrits: agp app B c crit f fl gel After gel point Applied Grating Composite; cure; critical Critic Fibre; final Fluid Gelation shrinkage viscosity;

glass Glassy state H i j L l M max q RT r ref S s T t th tot ult V 0 Host material i-direction; initial; inflection j-direction Longitudinal; Linear In-plane Mechanical Maximum Quenched room temperature Resin; radial Reference Shrinkage Solid; surface Temperature Transverse Thermal Total Ultimate volumetric Degree-of-cure Strain Hoop direction Initial; at 0K

coefficient of friction

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CHAPTER 1 Introduction

1.1 Introduction

The development of preimpregnated reinforcements (prepregs) and autoclave moulding have opened doors to high performance composite structures. They enable the manufacturing of composite parts with high mechanical properties, high fibre volume fraction (up to 70%) and low void content. However, with the autoclave process, the material and equipment costs remain very high. Over the last decade, the composite industry has aimed to produce high quality parts at low cost and reduced time. Therefore, out-of-autoclave processes (OOAP) have been increasingly considered to manufacture high performance composite structures as an alternative to the well established autoclave process [1]. As shown in Figure 1-1, most of the OOAP allow the production of equally or more complex composite parts than those manufactured by autoclave, with a higher production rate.

Figure 1-1: Composite manufacturing processes as a function of production rate and part complexity [2]

-1-

Among them, the use of Resin Transfer Moulding (RTM) to manufacture composite parts for aerospace applications has significantly increased in recent years. As part of the Liquid Composite Moulding (LCM) process family, RTM was first developed in the 1950s by the US Navy to produce a 28-ft long boat in fibre glass/polyester. After many years dedicated to marine applications, it is now widely used in diverse industries such as automotive, marine, transportation and aerospace [3, 4]. This closed mould process presents many advantages over the autoclave process [5, 6]: The material and equipment costs are low (30-50% of the autoclave process cost). It enables the production of large and complex composite structures with short cure cycles (approximately 50% of the autoclave process time) and high consistency. It allows the use of a wide variety of resin systems and reinforcements. Composite parts manufactured by RTM typically have a good surface finish on all sides while maintaining tight geometrical tolerances. Mechanical properties comparable to autoclave processed parts can be achieved with fibre volume fraction up to 60% As it is a closed mould process, the emission of volatiles remains low. The RTM process consists of five main steps (Figure 1-2). In the first step or preforming (1), dry reinforcements are assembled in a preform whose shape is close to the desired part geometry. Then the preform is placed into the mould and compacted when the mould is closed (2). The mould is afterwards pre-heated to the cure temperature (3). Once the required temperature is reached, the resin is injected into the mould cavity through the injection port, impregnating the preform. The excess resin flows outside the mould through the vent port (4). The heat of the mould activates the polymerization to cure the resin. Once the resin is fully cured, the part is removed from the mould (5). -2-

Four main physical and chemical phenomena are involved during the RTM process: heat transfer, flow and compaction, cure and residual stresses development. As shown in Figure 1-3, these phenomena involve several key material properties and their interaction affects the final properties of the composite structure.

The RTM process produces parts with high consistency which is an advantage for high production rate applications. However, at every step of the process, several phenomena can affect the part quality and dimensions [5]. During the preforming -3-

stage and compaction, the preform manipulation and deformation, when the mould is closed, can cause: fibre displacements, changes in fibre orientation and non-uniform fibre volume fraction distribution. Then fibre motions, porosity and dry spot formation can occur during the injection phase and mould filling. Finally, residual stresses develop during the curing stage leading to shape distortions after demoulding and sometimes leading to the formation of micro-cracks or delaminations. In order to predict such phenomena and defects, many studies on RTM simulations have been carried out. In a recent review on RTM modelling, the RTM simulation approaches were divided into two main categories: the simulation of the mould filling stage and the simulation of the process cycle [7]. Simulations of the mould filling stage have been extensively investigated. These simulations determine the flow front location at any time and the filling time as a function of the part geometry, the resin and preform properties, and the inlet/vent positions. The studies typically investigate the following aspects [8-23]: The prediction of the flow front location, the fibre impregnation and the void content. The prediction of the mould filling time. The prediction of the pressure, temperature and degree-of-cure distribution in the composite during the mould filling. The optimization of the process parameters such as the injection pressure, the resin flow rate, the mould temperature, the inlet and vent positions. The first simulations only considered isothermal conditions [8-15] and were later extended to non-isothermal conditions [16-20] in order to take into account the resin cure kinetics and the heat transfer between the resin and the mould. These simulations can be used as a useful tool for the design and optimization of the RTM mould. On the other hand, fewer studies have been performed on the simulations of the entire RTM process cycle. These simulations allow the prediction of the evolution -4-

of the degree-of-cure and the development of the residual stresses and eventual shape distortions during the cure cycle with [16, 17] and without considering the mould filling stage [24-26]. The different phenomena and interactions occurring during the process (Figure 1-3), as well as the evolution of the order to be realistic and accurate. composite constituent material properties have to be taken into account simultaneously in

1.2 Motivations

For aerospace applications, dimensional stability is one of the major issues as tight tolerances are required. While highly distorted parts are rejected entirely, smaller distortions lead to unwanted stresses as the part is forced to fit the assembly geometry. One decade ago, most of the knowledge in composite manufacturing was based on rule-of-thumb and experience. When a part presented some distortions, the tool geometry was modified so that the composite part met the shape requirements. This approach worked well for simple and similar geometries. However for new and complex parts, such a process took several iterations, increasing production time and cost. Nowadays, both process experience and modelling analysis are employed in industry to predict the strength and failure properties of complex composite parts before the actual part manufacturing, leading to significant reduction in time and cost to produce components. While design and stress analyses are now well established in the aerospace industry, process modelling is proving to be also attractive, especially for well known and extensively employed process, such as autoclave. However, this procedure is not as developed and common for out-of-autoclave processes. In order to predict the final geometry and final properties of a new or complex composite structure, one has to simulate the entire cure cycle and take into account both intrinsic and extrinsic mechanisms that can influence the structure properties. Intrinsic refers to material and part geometry related mechanisms. The property differences between the polymeric matrix and the reinforcement as well -5-

as the property differences in the longitudinal, transverse and through-thickness directions have a significant influence on the development of residual stresses. In addition, the resin change from a liquid to a solid, as the cure progresses, leads to significant variations of its constitutive properties such as the degree-of-cure, the volumetric changes and the elastic modulus. The evolution of these properties affects as well the residual stresses and deformations. On the other hand, extrinsic describes the tool and process related mechanisms, such as the tool-part interaction or the cure cycle (time, temperature, pressure) that can have an effect on the final properties of the composite structure. Hence, it is crucial to clearly understand the different phenomena, involved in composite manufacturing, leading to process-induced stresses and part shape change. Development of accurate material constitutive models, process modelling and a comprehensive understanding of both intrinsic and extrinsic mechanisms are key elements to achieve this purpose.

The main research objective of this thesis is to investigate the different parameters leading to process-induced deformations, including thickness variations and part distortions, of woven composite parts manufactured by RTM. Once the different mechanisms are well understood, process modelling can be applied to predict the process-induced deformations. To achieve this goal, the present research is organized into the following chapters. Chapter 2 presents a detailed literature review on the material behaviour during the cure cycle and the process-induced stresses and dimensional stability in composite manufacturing. Based on this knowledge, the specific objectives of the thesis are formulated.

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Chapter 3 and Chapter 4 are related to the material characterization. Chapter 3 describes the methodological approach developed to characterize the processing properties of thermoset resins. The methodology was applied to define the thermal, chemorheological and thermomechanical properties of a particular RTM one-part epoxy. Chapter 4 analyses the influence of the fibre architecture (unidirectional, crossply, 5-harness satin weave) on the composite thermomechanical properties. Chapter 5 examines the tool-part interaction mechanisms experimentally and numerically for panels manufactured by RTM. Chapter 6 presents a case study on dimensional stability including the diverse factors studied in the previous chapters. Finally, the contributions of this study and recommendations for future studies are presented in Chapter 7.

-7-

This chapter contains a comprehensive literature review on residual stresses and deformation induced during the manufacturing process of composite structures. First an overall description of the evolution of the material behaviour during the cure is presented. The resin properties having an effect on the strain and stress development are described in detail. Some investigations of the influence of the fibre architecture are presented as well. Then the different sources of processinduced stresses and deformations are highlighted. From the literature review, the specific objectives of this thesis are stated.

2.1.1 Resin behaviour

During the processing of composite material, the thermoset resin evolves from a low molecular weight liquid material to a crosslinked macromolecular solid structure. In its liquid state, the thermoset resin consists of monomers. Then as the polymerization is initiated by a catalyst or heat for example, the monomer molecules react, crosslink and grow longer. As the crosslinking process progresses, the long polymer chains join up to form a three-dimensional network. At that moment, the resin evolves in a gel/rubbery state where the polymer chains remain mobile. Finally, when most of the crosslinks have formed and the threedimensional network is fully established, the resin is in a solid/glassy state and the motion of the polymer chains is very restrained. The crosslinking process is quantified by the degree of conversion or degree-of-cure. This variable varies from 0 to 1, 0 corresponding to the uncured state with no crosslink and 1 representing the fully cured state where the three-dimensional network is totally developed.

-8-

Figure 2-1 shows the evolution of the resin properties for a typical cure cycle for the RTM process. As the cure progresses, the degree-of-cure of the resin increases, leading to an increase of the glass transition temperature and the resin viscosity. From Figure 2-1-a, the resin undergoes its liquid-rubbery transformation when the viscosity reaches an infinite value. This gelation occurs after 70 minutes at 180C, at a degree-of cure of 0.7. After that point, as shown in Figure 2-1-b, the resin elastic modulus starts to develop and the resin can sustain strains and stresses without flowing. The resin also begins to shrink, due to the polymer network formation. However, its behaviour remains highly viscoelastic, and the generated strains and stresses can be relaxed to some extent. As the polymerization advances more, the glass transition temperature, Tg, passes the curing temperature and the vitrification happens 50 minutes later at a degree-ofcure of 0.93. A significant increase in the resin elastic modulus can be observed at the vitrification. At that stage, the resin is in its glassy state, and behaves like an elastic solid. The generated stresses cannot be relaxed any more. The gel point and the vitrification time depend of the type of resin and the cure cycle used; the resin may go through the vitrification during the isotherm or at the cool down.

-9-

Figure 2-1: State transition and property evolution of the CYCOM 890RTM epoxy resin during a typical cure cycle. a) Degree-of-cure, viscosity and glass transition temperature, b) Relative volume variation and elastic modulus -10-

Also, as seen in Figure 2-1-b, significant changes in volume take place as the cure progresses. The different mechanisms leading to volumetric change are illustrated in Figure 2-2 for a cube of resin with an initial volume of 1 cm3: Step a-b: as the temperature increases to reach the curing temperature of 180C, the volume of the resin increases due to thermal expansion. Step b-c: at the isothermal curing temperature, the volume of the resin decreases due to the chemical shrinkage resulting from the formation of the chemical network. Step c-e: during the temperature cool-down, the volume of the resin decreases due to the thermal contraction. The dashed line represents the path of a resin passing the vitrification transition during the cool down. The resin coefficient of thermal expansion (CTE) is much higher in its rubbery state (above Tg, step c-d) than in its glassy state (below Tg, step d-e).

Figure 2-2: Volumetric change of the CYCOM 890RTM epoxy resin during a typical cure cycle

Hence, a comprehensive understanding of the resin behaviour during the cure, and an accurate characterization of the evolution of its properties (cure kinetics, -11-

viscosity, glass transition temperature, volumetric changes, elastic modulus) is essential to understand the development of residual stresses and deformations. The next sub-sections present the main models found in the literature to describe these properties. 2.1.1.1 Cure kinetics A variety of cure kinetic models have been proposed to describe the cure behaviour of several types of resin. They can be divided into two categories: mechanistic models and phenomenological models. Mechanistic models are based on the knowledge of how the chemical molecules react with one another during the cure. Due to the complexity of the polymerization reaction, such models can be very difficult to obtain. Also they require the details of the resin chemical formula which is not always available from the manufacturer. Phenomenological models describe the cure reaction ignoring the details of the chemical reaction. Generally, phenomenological models are preferred to describe the curing behaviour of thermoset resins. Phenomenological cure kinetics models are usually determined using a Differential Scanning Calorimeter (DSC) under dynamic and isothermal conditions. The dynamic scans measure the total heat of reaction released during the cure whereas isothermal scans are used to monitor the heat flow during a series of isothermal cures. The measured heat generated by the resin is then converted into cure rate based on the assumption that the rate of reaction, is proportional to the rate of the heat flow, : Eq. 2-1 where HT is the total exothermic heat of reaction. The degree-of-cure of the resin () can be obtained by integrating the area under the curve of cure rate versus time as follows: ,

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Eq. 2-2 Then resin cure kinetics models relate the rate of cure as a function of time, temperature and degree-of-cure. The simplest cure kinetic model is expressed by an n-order equation [27]: Eq. 2-3 where n is the reaction order and k is the rate constant following an Arrhenius temperature dependency: Eq. 2-4 where EA is the activation energy and R is the gas constant. Nevertheless, this model is too simple to realistically describe the various reactions taking place during the cure and the transitions (gelation, vitrification) the material undergoes. Kamal and Sourour [28, 29] developed the following autocatalytic cure kinetic model for the epoxy and unsaturated polyester resin systems: Eq. 2-5 where k1 and k2 are the rate constants following the Arrhenius relationship, and n and m are catalytic constants. When the thermoset resin goes through the glass transition, the reaction slows down rapidly and changes to a diffusion controlled mode. As a consequence, the final degree-of-cure and the rate of cure will be lower than those predicted. In order to take into account the phenomenon of vitrification, Gonzalez-Romero and Castillas [30] introduced a new parameter max in the equation, which corresponds to the maximum degree-of-cure the resin can reach due to the diffusion:

-13-

Eq. 2-6 An alternative way to model the switch from a kinetics-dominated to a diffusiondominated reaction is to add a diffusion factor, f(,T), to the cure kinetics equation: Eq. 2-7 Khanna and Chanda [31] defined a diffusion factor as follows: Eq. 2-8 where c is the critical degree-of-cure when the reaction change to diffusion control, and C is a constant. Cole et al. [32] extended this diffusion factor by expressing the critical degree-ofcure as a function of the temperature: Eq. 2-9 where C0 is the critical degree-of-cure at T=0K and CT is a constant taking into account the increase in critical degree-of-cure with the temperature. Hubert et al. [33] used this diffusion factor with the cure kinetic model from Lee et al. [34]: Eq. 2-10 Using this model, they demonstrated much better prediction of the cure behaviour after the vitrification of epoxy resin than achieved using regular models. 2.1.1.2 Rheological behaviour The resin rheological behaviour describes the evolution of the resin viscosity as a function of many variables such as the temperature, the resin cure, the shear rate or the filler properties. The viscosity is influenced by the thermal effect and the cure effect in opposite way. First, the viscosity decreases as the temperature -14-

increases due to the thermal effect, as shown in Figure 2-1-a. Then the viscosity reaches a minimum value. In liquid injection processes, the resin is usually injected in the mould at this minimum viscosity point in order to allow the resin to flow and better impregnate the reinforcement. As the temperature or time increases, the curing reaction starts and the viscosity increases due to the network formation to finally reach an infinite value at the gel point. The viscosity is usually measured using a rheometer with different types of geometry, such as parallel plate, cone and plate, or rotational cylinder. Similar to the cure kinetic, many models have been developed to capture the cure effect on the viscosity of thermoset resins. A simple empirical isothermal model was first developed by Kamal and Sourour [28] for epoxy resins: Eq. 2-11 where is the viscosity, 0 is the initial viscosity and this model doesnt take into account the gel point. Castro and Macosko developed a model expressing the evolution of the viscosity as a function of the degree-of-cure and the gel point [35]: Eq. 2-12 where is the degree-of-cure, gel is the degree-of-cure at gel point, A and B are constants. Kamal developed also a viscosity model based on the Arrhenius relation for epoxy resins [29]: Eq. 2-13 where n is the reaction order, Ev is the viscous activation energy, kk is a rate constant and Ek is the kinetic activation energy. is a constant. However,

-15-

2.1.1.3 Glass transition temperature The glass transition temperature (Tg) significantly affects the resin mechanical properties as it changes from its rubbery to its glassy state. One of the most common techniques to characterize Tg uses a modulated DSC (MDSC), where Tg is identified by a step change in the specific heat [36, 37]. Thermo Mechanical Analysis (TMA) is another widely used method of measuring the Tg, as a significant change in the coefficient of thermal expansion is noticed when the resin goes through the glass transition (Figure 2-2). The DiBenedetto equation is the most commonly used relationship when modelling the evolution of Tg with the degree-of-cure for thermoset resins [3742]. The relationship is expressed as follows: Eq. 2-14 where Tg is the glass transition temperature, and are the glass transition is the degree-of-cure

researchers fit empirical models to express the variation of Tg with the degree-ofcure [37]. 2.1.1.4 Volumetric changes As described in Figure 2-2, volumetric changes during the cure can be categorized as thermal and chemical contributions. The thermal contribution describes the expansion and contraction due to change in temperature. The chemical contribution represents the contraction due to the cure shrinkage. Coefficient of Thermal Expansion The coefficients of thermal expansion are usually measured by Thermo Mechanical Analyzer (TMA) [43]. This method allows the measurement of the CTE above and below Tg. In order to capture the evolution of the resin thermal

-16-

expansion during the cure, Hill et al. [44] expressed first the volume variation of the resin as a function of the temperature and/or the degree-of-cure: Eq. 2-15 Eq. 2-16 where CTEr,gel and CTEr,cured are the coefficients of thermal expansion of the gelled and fully cured resin respectively, and a0 and b0 are linear fit with temperature. Ruiz and Trochu [43] expressed also the resin coefficient of thermal expansion as a function of the temperature and the degree-of-cure in the following manner: Eq. 2-17 where CTEr,agp is the resin coefficient of thermal expansion after the gel point and is normalized degree-of-cure given by the following equation: Eq. 2-18 where agp is the degree-of-cure after the gel point and ult is the ultimate degreeof-cure. Shrinkage The volumetric cure shrinkage describes the contraction of the resin during the polymerization, due to the network formation. It is the result of the change from Van der Waals links to smaller but stronger covalent links between the molecules as the cure progresses. In the following, volumetric cure shrinkage will be referred as shrinkage for purposes of brevity. Measurement of the shrinkage development along the entire curing process is challenging, as the resin changes from the liquid to the rubbery state and finally the glassy state. The standard ASTM D2566-79 method to measure resin shrinkage is based on the resin volume variation before and after the cure without taking into account the change of resin coefficient of thermal expansion from the -17-

rubbery to the glassy state [45]. This limitation significantly underestimates the magnitude of the shrinkage as shown in Figure 2-2. Water or mercury dilatometers are the most common instruments used to measure shrinkage based on volume dilatometry [44, 46-48]. With a water-based dilatometer, results may be influenced by water absorption of the resin and temperature variation [48]. Pycnometers are also employed to measure the volumetric chemical change in a dry state [49]. However, this method allows only the measurement of the final shrinkage and not its development during the cure. Non-volumetric dilatometry methods usually measure the linear shrinkage and rely on various assumptions to calculate the volumetric shrinkage. The non-volumetric methods regroup various methods, such as the shadow Moire method [50], Dynamic Mechanical Analysis (DMA), Thermo Mechanical Analysis (TMA) [51, 52], online monitoring using LVDT transducers and optical sensors embedded in the resin [53, 54], modified rheology method [55] or gravimetric method [56]. From these experiments, empirical models have been developed in order to predict the amount of shrinkage as a function of the degree-of-cure, the radical concentration or the curing temperature. Linear relationships between the shrinkage and the degree-of-cure were derived for both polyester and epoxy resin systems and the total shrinkage was found to be independent of the curing temperature [44, 55-57]. 2.1.1.5 Resin Elastic modulus Elastic modulus models are important to describe the evolution of the resin mechanical behaviour during the cure, as the material goes through its liquidyrubbery and rubbery-glassy transitions. Dynamic Mechanical Analyzer (DMA) is a common technique to measure the evolution of the elastic modulus with the degree-of-cure. Different loading fixtures such as single or double cantilever and three-point bending can be used on non-cured or pre-cured resin sample [57, 58]. Elastic and viscoelastic models are usually employed to capture this behaviour.

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Elastic models Despite the known viscoelastic behaviour of the resin throughout a majority of the cure process, elastic models can predict, most of the time, the process-induced stresses realistically. According the Svanberg and Holmberg [41], glassy-rubbery transition are well described by elastic models whereas incremental elastic model better captures rubbery-glassy transition. Using an incremental approach, Bogetti and Gillespie [57], Golestanian and El-Gizawy [24], Huang et al. [59] and Johnston et al. [60] used cure-dependent elastic models to compute resin elastic modulus during the entire cure. A linear correlation between the resin modulus and the degree-of-cure was reported in [24, 57, 59]: Eq. 2-19 where and are the uncured and fully cured modulus of the resin

respectively and is the degree-of-cure. In order to capture more accurately the rubbery-glassy transition, Johnston et al. [60] and Curiel and Fernlund [58] relate the resin modulus with the variable T*, equal to the difference between the curing temperature and the instantaneous glass transition temperature, with the following formulation [60]:

Eq. 2-20

where

and

representing the onset and the completion of the glass transition. In that case, the variable T* is expressed as follows: Eq. 2-21 where is the glass transition temperature of the uncured resin, is a

-19-

Similarly, Ruiz and Trochu [43] take into account the resin elastic modulus dependence with the degree-of-cure and glass transition temperature using two functions Fr() and Wr(Tg) as follow: Eq. 2-22 Eq. 2-23 Eq. 2-24 where the subscripts r, c and agp stand for resin, composite and after gel point, is the normalized degree-of-cure defined in Eq. 2-18, c, d, e, h are some constants and is the normalized temperature expressed in the following manner: Eq. 2-25 Where Tg is the glass transition temperature and Tref is a reference temperature. Viscoelastic models Viscoelastic models are more realistic than elastic models, as they take into account the stress relaxation occurring in the resin rubbery state. Wiersma et al. [61] used both elastic and viscoelastic modulus models to predict the spring-in of L-shape composite parts and observed closer agreement with the experimental results using the viscoelastic model. However, the viscoelastic models are more difficult to develop. Extensive material characterization is needed to determine the different model variables. Also, for simulation purpose, they lead to long computational time and heavy computational resources. Generally, the variation of the modulus or compliance versus time or frequency is obtained from a series of experiments at specific temperatures and degree-of-cure. Then each experiment at a specific temperature and degree-of-cure can be shifted from a factor a, to form the master curve. This shift factor accounts for the temperature and/or degree-of-cure dependence of the relaxation time. Figure 2-3 describes this time-temperature principle of superposition to get the compliance master cure. -20-

Figure 2-3: Example of construction of the compliance master curve using the principle of time-temperature superposition [62]

William, Landel and Ferry [63] defined first a temperature shift factor aT , as follows: Eq. 2-26 where C1 and C2 are material dependent constants, and Tref is the reference temperature. This model was used in similar or modified forms in many studies [39, 62, 64-66]. Similarly, Simon et al. [39] developed a conversion shift factor dependency of the relaxation time with the degree-of-cure: Eq. 2-27 to describe the

-21-

where C and

are constants,

Contrary to the resin, the fibres do not react during the cure and their properties remain constant. Knowing the properties of the composite constituents, i.e. resin and fibre, micromechanic analytical relations can be used to determine the elastic moduli and coefficients of thermal expansion of a unidirectional lamina. For the determination of the elastic properties, the simplest approach used is the strength of materials approach or rule of mixtures [67]. For this, the following assumptions are made: Perfect bonding between the fibres and the matrix. The fibres are continuous and parallel. The fibre and the matrix are assumed to be linear elastic materials and follow Hookess law. The fibres have a uniform strength. The composite is free of voids. Considering the representative volume element (RVE) of a fibre surrounded by a matrix presented in Figure 2-4, and subjected to longitudinal, transverse or inplane shear loads, the composite elastic constants can be expressed by the following equations in the ply orientation.

Figure 2-4: Loading on the representative volume element to determine the elastic constants: a) longitudinal load, b) transverse load, c) in-plane shear load

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The longitudinal Youngs modulus: Eq. 2-28 The transverse Youngs modulus: Eq. 2-29 The major Poissons ratio: Eq. 2-30 The in-plane shear modulus: Eq. 2-31 where the subscripts f and r stand for the fibre and resin properties respectively, Vf is the fibre volume fraction, E is the elastic modulus, is the Poissons ratio and G is the shear modulus. With this approach, the predicted values of the longitudinal Youngs modulus E1 and the major Poissons ratio 12 agree well with the experimental data. However, the predicted values of the transverse Youngs modulus E2 and the in-plane shear modulus G12 are generally lower than the experimental data [67]. In order to obtain better prediction in the transverse direction, Halphin and Tsai [68] developed semi-empirical models taking into account the fibre geometry and the packing geometry. Hashin and Rosen [69] and Whitney and Riley [70] developed elastic constant relations based on the elastic approach and defining the effective elastic modulus in terms of the strain energy. Bogettie and Gillespie [57] and Johnston et al. [60] used this micromechanic elastic approach to compute the evolution of the composite elastic constant during the cure cycle. In that case, the elastic constants were expressed as follows: The longitudinal Youngs modulus: Eq. 2-32

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The transverse Youngs modulus: Eq. 2-33 The in-plane shear modulus: Eq. 2-34 The transverse shear modulus: Eq. 2-35 The major Poissons ratio:

Eq. 2-36

The transverse Poissons ratio: Eq. 2-37 The effective plane strain bulk modulus: Eq. 2-38

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Figure 2-5: Comparison of experimental values of the transverse Youngs modulus with the predicted values using the strength of materials approach, the semi-empirical approach and the elastic approach as a function of the fibre volume fraction: a) 0 <Vf <1, b) 0.45< Vf <0.75 [67]

-25-

Figure 2-6: Comparison of experimental values of the in-plane shear modulus with the predicted values using the strength of materials approach, the semiempirical approach and the elastic approach as a function of the fibre volume fraction: a) 0< Vf <1, b) 0.45< Vf <0.75 [67]

Figure 2-5 and Figure 2-6 compared the experimental values of the transverse Youngs modulus and the in-plane shear modulus respectively with the predicted values from the micromechanic approaches. The Halphin-Tsai semi-empirical and the elastic approaches better capture the experimental data whereas, as mentioned previously, the strength of materials approach predicts lower values.

-26-

Using the strength of materials approach, the composite coefficients of thermal expansion can be also expressed as function of the properties of the resin and the fibre in the ply orientation: Eq. 2-39

Eq. 2-40

As the effect of the shrinkage is similar to a contraction, Eq. 2-39 and Eq. 2-40 can be similarly used to determine the longitudinal and transverse effective shrinkage of the composite.

For a composite with unidirectional fibres, the laminate mechanical properties can be predicted using the Classical laminate Theory (CLT). In the case of LCM process, such as RTM, the use of woven textile reinforcements increased significantly in the past decades. Woven reinforcements have higher drapability and better impact resistance than unidirectional fibres that qualify them as good candidates to manufacture complex structures. Woven fabrics are characterized by a recurrent in-plane pattern of the interlaced region. Typically, the three main configurations are plain, twill and satin weaves, as shown in Figure 2-7. In the plain weave pattern, a warp yarn is interlaced over and under the weft yarns (Figure 2-7-a), whereas in the twill weave motif, a warp yarn is woven over two weft yarn and under one weft yarn (Figure 2-7-b). In the satin weave architecture, the warp yarn is intertwined over ng consecutive weft yarn (ng>2) and under one weft yarn (Figure 2-7-c). For the satin weave, the number of consecutive weft yarns ng defined the name of the architecture as (ng + 1)-harness satin weave.

-27-

Figure 2-7: Main weave configurations. a) Plain weave, b) Twill weave and c) 5-harness satin weave

Hence, to predict the thermomechanical properties of woven composites, more parameters have to be taken into account. The fibre architecture geometry, the fibre undulation or the resin distribution throughout the bundles can affect the mechanical and failure properties of the composite. Various analytical and numerical approaches have been carried out to investigate the thermomechanical properties of 2D fabric reinforcements. Analytical models are generally based on the Classical Laminate Theory. Ishikawa and Chou [71-75] developed three analytic models to predict the stiffness and coefficient of thermal expansion of woven fabric composites. The first model, called the mosaic model, described the fabric as an assemblage of asymmetrical crossply laminates, as shown in Figure 2-8-a. In that case, no fibre undulation was taken into account. Therefore, the mosaic model gave good predictions for fabrics with few interlaced regions, such as satin fabric. The second model, called the crimp model, accounted for the fibre undulation and fibre continuity (Figure 2-8-b). It used shape functions to describe the fibre undulation. The crimp model is more suitable for plain weave composite. Finally the bridging model was developed for satin woven fabrics in order to describe the properties difference between the straight threads regions and the interlaced regions (Figure 2-8-c). The straight threads -28-

region A, B, D, and E have higher in-plane stiffness than the interlaced region C, and plays the role of bridge for the load transfer. However these models only considered the undulation in one direction and restrict the two-dimensional (2D) woven structure to one dimension.

Figure 2-8: Schematic view of the three analytical models for an 8-harness satin. a) Mosaic model, b) Crimp model, c) Bridging model (adapted from [73])

Naik and Shembekar [76-78] and Naik and Ganesh [79-81] developed a 2D woven fabric model to predict the elastic properties and the coefficient of thermal expansion of plain weave reinforcements at the ply and laminate level. The fibre architecture geometry in the ply, as well as the position of the different plies in the laminate, with respect to each other, was considered. Their results demonstrated that the elastic moduli were affected by the undulation length, the ply thickness, the gap between two adjacent yarns and the laminate configuration. The elastic -29-

moduli increased with an increase in the undulated length and a decrease in the ply thickness. Shifts of plies in the laminate configuration gave better in-plane elastic properties. Also, depending on the fibre architecture and the material system, an optimum gap could be determined to improve the elastic properties of the woven composite. The results obtained for the CTE of plain weave woven laminates were compared to the properties of unidirectional and crossply laminates. For the same fibre volume fraction, the CTE of the plain-weave composite were higher than the unidirectional one. But it could be lower or higher than the CTE of the crossply laminate depending of the fabric strand crimp. Overall, the authors determined that in the case of plain weave woven fabric, higher fibre volume fraction and lesser crimp gave a lower CTE and Poissons ratio but higher Youngs and shear moduli. Their analytical results were then confirmed experimentally [82]. In addition, Hahn and Pandey [83] used geometry efficiency factors to develop a micromechanics model including the fibre architecture parameters to predict the thermoelastic properties of plain weave woven composite. More recently, finite element analyses (FEA) were used to determine the mechanical properties of woven composites. The advantage of FEA is that it provides information on the internal strains, stresses and displacements generated in the woven fabric. Generally, the analysis is reduced to the behaviour of the smaller representative element or unit cell. Then periodic boundary conditions are applied to the unit cell so that it represents the entire reinforcement. Glaessgen et al. [84] developed a unit cell model to study the internal displacements, strains and stresses in plain weave composite under axial load. To reduce the computational time, the global/local finite element method was used in different studies to model textile composite: a coarse mesh is used on the global structure and a more refined mesh is applied on local region where rapid changes can occur [85-87]. Dasgupta and Bhandarkar [88] investigated the influence of the fibre volume fraction on thermomechanical properties of plain weave composite using a 3D unit cell model. Their results showed that the stiffness increased with the -30-

fibre volume fraction whereas the CTE and the Poissons ratio decreased. This is in agreement with some experimental studies [82]. Lomov et al. also validated the FEA unit cell approach using full-field strain measurement on carbon/epoxy woven composites and glass/polypropylene woven composites [89]. Finally, the unit cell representation of woven composite was also used in the analysis and prediction of process-induced stresses and deformation [24, 25, 59]. For this last purpose, Svanberg et al. used a knock down factor as an alternative method to reduce the fibre longitudinal modulus and compensate for the fibre weave [26]. The design of the fabric unit cell can be facilitated using textile modelling software such as WiseTex [90], developed by the Composite Material Group of the Leuven University, or TexGen [91], developed by Textile Composite Research group at the University of Nottingham. Knowing the yarn properties, the yarn interlacing pattern and the yarn spacing within the unit cell, these softwares determine the unit cell geometry and properties, such as the areal density, the local fibre content and the fibre orientation. The unit cell geometry can also be meshed and exported in traditional finite element software to compute the fabric mechanical properties.

Residual stresses and deformations are one of the major concerns in composite manufacturing. Residual stresses can lead to a reduction of the composite structure performance such as strength and fatigue life, and can initiate cracks in the matrix. As mentioned in CHAPTER 1 section 1.2, the assemblage of composite structures with deformations can be problematic or impossible, leading to the reject of the part. The sources of residual stresses and their effects on composite structures have been widely investigated for over three decades. Overall four main mechanisms have been identified [92]: Thermal strains Resin chemical shrinkage Tool-part interaction -31-

Temperature, degree-of-cure and fibre volume fraction gradient Typically, three common shape variations can occur in a composite part due to process-induced stresses: Spring-in or spring-out (Figure 2-9-a), defined as variation of closed angle, spring-in being a reduction of the initial angle, whereas spring-out is an increase of the initial angle. Warpage (Figure 2-9-b), defined as a bending of a flat laminate. Laminate thickness variations

Figure 2-9 Shape variations due to process-induced stresses: a) spring-in deformation, b) warpage deformation

In the next sections, the mechanisms leading to the shape distortions are discussed in more detail.

Thermal strains were the first studied and probably the most well understood causes of residual stresses [64, 93-96]. Thermal strains describe the strains arising due to the difference in thermal expansion at three scales: firstly, between the matrix and the fibre at the constituent level, second between the longitudinal and transversal direction at the ply level and finally, between the in-plane and out-ofplane direction at the laminate level.

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Polymeric matrices have usually higher thermal expansion than fibres (typical CTE polymer = 50-100 x10-6 C-1, typical CTE fibre = -1-15 x10-6 C-1). This difference in thermal expansion creates stresses at the microscale between the matrix and the fibre with a variation of temperature. This micromechanical stresses can affect the strength and failure of the composite structure, but should not lead to significant distortions, as their effects remain small and local [92]. At the ply level, the CTE difference between the longitudinal and transverse directions generates in-plane stresses and deformations in laminates. These residual stresses and deformations can be predicted and avoided using the Classical Laminate Theory. For example, using symmetric laminates can prevent non-symmetric coupling, whereas balance lay-up or crossply laminates can prevent shear-normal coupling. Finally antisymmetric laminates and crossply laminates can prevent bending-twisting coupling. Finally, at the laminate level, the thermal expansion difference between in-plane direction, dominated by the fibres, and through-thickness direction, dominated by the matrix, results in the change of curvature for angled laminates. This phenomenon is also known as spring-in (Figure 2-9-a). A simple analytical equation, developed by Radford, predicts the angle variation, , as a function of the temperature variation, [97]: Eq. 2-41 From this equation, it can be predicted that the higher the temperature variation ( is, the higher the spring-in value should be. However, it does not take into account the difference of the coefficients of thermal expansion above and below the glass transition temperature, which was shown to be significant in section 2.1.1.4. Svanberg and Holmberg [98] and Ersoy et al. [99] demonstrated that the spring-in could increase or decrease with T, depending when the resin goes through its glass transition. Figure 2-10 describes the paths the resin can take -33, and the in-plane and throughand respectively thickness composite thermal expansion coefficients,

while cooling down from the same curing temperature (Tcure). If the resin goes through its glass transition and reaches its glassy state during the dwell, it will follow the path A-B during the cool-down, with a glassy CTE. On the other hand, if the resin does not go through its glass transition, it will still be in a rubbery state by the end of the isotherm. The resin will then cool-down following the path A-CD. The glass transition happens at C, with a significant decrease in CTE. So, for the same T, the spring-in can be different.

Figure 2-10: Schematic explanation of the spring-in variation as a function of the resin state, below or above Tg (adapted from [99])

As explained previously, shrinkage is a contraction of the resin due to the formation of the 3D crosslinked network. In the composite, its effect will be then more significant in the matrix dominant direction (transverse direction at the ply level and through-thickness direction at the laminate level). Thus, the shrinkage difference between the longitudinal and through-thickness directions acts similar to the thermal contraction (Section 2.2.1) on the residual stresses and deformations and is a source of spring-in. Shrinkage also has a significant effect

-34-

on composite surface finish quality and can lead to surface defects such as ripples, sink marks or fabric print through [100]. In order to take into account the effect of shrinkage in the prediction of the springin angle, Radford [97] modified the previous developed analytic equation (Eq. 2-41) as follows: Eq. 2-42 where l and t are the in-plane and through-thickness composite shrinkage respectively. Recently, Ersoy et al. adjusted Eq. 2-25 to take also into account the difference of resin behaviour before and after the temperature of glass transition [99]:

Eq. 2-43 where and are the in-plane and through-thickness composite and are the

in-plane and through-thickness composite thermal expansion coefficients in the glassy state, Tg is the glass transition temperature, Tq is the quenched temperature and TRT is the room temperature. As previously, l and t are the in-plane and through-thickness composite shrinkage.

The consideration of shrinkage as a significant cause for residual stresses and deformation was not always addressed and has evolved considerably in the past few decades. At first, shrinkage was supposed to have a negligible effect on residual stresses [42, 64, 93, 94, 96]. Researchers assumed that shrinkage occurred while the resin was in its rubbery state, and therefore the arising chemical strains were simply relaxed by the viscoelastic property of the resin in that state. However, Lange.et al. [101] established that this was not true for all -35-

resin systems. Using a bi-layer beam bending technique, they measured the builtup of residual stresses for an epoxy and an acrylate. While the epoxy developed stress only on cooling below Tg, the acrylate system generated stresses during the cure above Tg. Many other researchers [41, 57, 97-99, 102-106] took into account the chemical strains to predict the residual stresses and deformations, even when the viscoelastic behaviour of the resin was taken into consideration [40, 61]. When taken into account, experimental and numerical studies determined that the cure shrinkage increased the spring-in value [61, 99, 106].

Tool-part interaction takes into account the effect of the mould on the laminate. Figure 2-11 presents the tool-part interaction mechanism leading to shape deformation. During the heat-up of the cure cycle, the mould stretches the laminate (a), generating shear stresses at the interface between the mould and the composite and through-thickness stress gradient in the laminate (b). These interfacial stresses and through-thickness stress gradient generally lead to a bending of the laminate away from the mould at the demoulding (c). This particular bending of a flat panel is also known as warpage.

Figure 2-11: Process-induced warpage mechanism due to tool-part interaction [107] -36-

The common tool materials used in composite manufacturing are steel and aluminum and carbon/epoxy. As both steel and aluminum have coefficients of thermal expansion much higher than the composite, warpage is often observed at the demoulding stage with these types of mould. On the contrary, composite moulds create lower shear stresses as they have a low coefficient of thermal expansion and their behaviour is similar to the part itself. However, composite moulds are not as stiff and durable as metallic moulds and the part geometry might not be as reliable. Radford [102] and Svanberg [98] first introduced the notion of tool-part interaction. They observed that in the case of the autoclave and RTM process an increase of the spring-in value that could not be explained by the presence of thermal or chemical strains. Svanberg [41, 103] developed then numerical models to predict the observed values of spring-in. Different boundary conditions were used to simulate the effect of the tool, and frictional contact behaviour appeared to give the closest agreement with the experiments. Twigg et al [107, 108] studied experimentally and numerically the effect of tool-part interaction on induced warpage of unidirectional laminate manufactured by autoclave. An empirical relationship was used to relate the autoclave pressure and the part aspect ratio to the induced warpage. The increase of the autoclave pressure increases the residual stresses or the deformation as it amplifies the contact with the mould, and therefore the effect of the tool-part interaction. Numerically, the tool-part interaction was simulated by introducing a shear layer between the mould and the composite part whose elastic properties could be changed to adjust the property of the interface. Twigg et al. [109] also developed an experimental approach to quantify the interfacial shear stress during the cure of composite by autoclave. They defined the interface condition as a combination of stick-slip behaviour. Potter et al. [110] investigated the presence of residual strains by measuring the curvature of unidirectional laminate cured in autoclave. Tools were specially designed to impose an interaction with the composite part. They found that the high expansion of the mould was the driving factor to induce stress in the -37-

surface layer of the prepreg and then through the thickness of the prepreg. De Oliveira et al. [111] investigated experimentally the influence of the mould material on the development of residual strains using fibre Bragg grating optic sensors in unidirectional and crossply laminates manufactured by autoclave. In both cases, they observed higher strains for moulds with higher thermal expansion. Also, the effect of the autoclave pressure were similar to the one observed by Twigg et al. [107]. Finally, Fernlund et al. [112, 113] studied the effect of the tool surface. They found that the use of a FEP release film in addition to release agent decreased the spring-in and demonstrates the strong influence of the tool even with the use of release agent.

Temperature and degree-of-cure through-thickness gradients in the laminate are generally an issue for thick composite laminates. Usually negligible in thin laminate, significant temperature gradients can arise in thicker parts as a result of exothermic resin reaction and low composite thermal conductivity in the transverse direction. Temperature gradient results in degree-of-cure gradient as well. Gillespie [57], Huang [59] and Ruiz [104] determined that for thick composites, temperature and cure progression path affects the magnitude of the residual stresses and deformation. Actually, high temperature processes produce an outside-to-inside cure progression, as the composite surfaces cure before the core. This leads to high residual stresses in the laminate and potentially resulting in matrix cracking. On the contrary, low temperature process generates an insideto-outside cure progression. This type of cure pattern reduces the residual stresses, but results in long cure progress and low mechanical properties as the part might not be fully cured. Finally, one-side cure progression, using different temperatures at the composite surfaces, reduces the process time and the magnitude of the residual stresses. However, this configuration creates an unsymmetrical residual stresses distribution and warpage might happen at the demoulding. Therefore, cure cycles, different from the traditional one used for thin parts, should be used -38-

to avoid such gradients. Optimized cure strategies based on in-situ temperature measurements and control of the mould temperature have been proposed for the autoclave [114, 115], RTM [104, 116] and filament wound structures [117]. The through-thickness fibre volume fraction variation has also an influence on thin laminates [118]. Such a phenomenon is observed in vacuum bagging processes, such as autoclave, where the bleeder absorbs the excess of resin while increasing the fibre volume fraction of the ply at the composite surface. On the contrary, the ply in contact with the tool is resin rich and has a lower fibre volume fraction. Radford [119] demonstrates that this fibre volume fraction gradient creates some warpage in the case of flat panel, as shown in Figure 2-12. Also it generates an increase in the spring-in angle for convex tooling, but a decrease of the spring-in value for concave tooling. Similar results have been observed by Huang et al. [120] and Darrow [118].

Figure 2-12: Process-induced warpage mechanism due to fibre volume fraction gradient

Other effects such as the part geometry (shape, thickness, length, corner radius), or cure cycle (cooling ramp rate, one hold or two holds) can also have an effect on

-39-

the composite part distortion. However, some disagreements exist on the effect of certain parameters. Concerning the part geometry, some researchers found experimentally [102, 107, 113] and numerically [121-123] that higher value of spring-in and warpage occurred for thinner parts, but others did not see a significant difference [61]. Similarly, the effect of the corner radius seems to be controversial. Dong [121] predicted linear increase of the spring-in with the radius, but others observed only a small contribution [118, 120]. Jain [105] determined that for a radius-tothickness ratio above 1, the spring-in was independent of the radius or the thickness of the laminate. In addition, the part length also tends to increase the overall spring-in [107, 113]. The effect of the cure cycle on spring-in was investigated by Fernlund et al. [112, 113]. A two-hold cure cycle with the gelation occurring and the end of the first hold generated more spring-in than a one-hold cure cycle. However, the cooling rate did not seem to influence the spring-in value [98]. Most of these secondary effects are the result of the interaction of the four primary effects explained above. For example the effect of different cure cycles is related to the state of the resin (rubber or glass) and the coefficient of thermal expansion in that physical state. Or the effect of the corner radius is related to the tool-part interaction and the thermal and chemical strains. Therefore, depending on which primary effects are interacting, the results can be contradictory.

The sources of residual stresses are multiple and caused by different phenomena. Hence, in order to consider all these effects, the entire process has to be examined. Process modelling has been widely used in order to take into account different phenomena leading the residual stresses and deformations for the entire cure cycle. The main approach applied in process modelling is to divide the process in sub-models to study some phenomena independently. An incremental finite element method (FEM) can be then used in each sub-model to solve the governing -40-

equations. Generally, for composite manufacturing, the process can be divided into three independent sub-models: heat transfer and cure kinetics, flow and compaction, and stress development as shown in Figure 2-13. The material property models as well as the process variables are the external inputs of the subanalyses. The coupling of the sub-model is ensured by using the output of one sub-model as input for the following sub-model. First developed by Loos and Springer [96], this approach has been then applied by many other researchers for the autoclave process [42, 57, 59-61, 64, 95, 122, 124, 125] and the RTM process [25, 26, 41, 103, 104].

-41-

The governing equation solved in this analysis is the Fouriers heat conduction equation: Eq. 2-44 where is the composite density, Cp is the composite specific heat, kij are the components of the composite thermal conductivity tensor, T is the temperature and t is the time. is the heat generated during the exothermic chemical reaction and is related to the resin cure kinetic as follows: Eq. 2-45 As presented previously in the paragraph 2.1.1.1, the cure rate can be described by various cure kinetic model. Initial conditions are then applied to the temperature and the degree-of-cure: Eq. 2-46 Different boundary conditions such as convective, adiabatic or prescribed temperature can be applied at the external surface of the system: Eq. 2-47 where Ts and are the temperature and the normal derivative of the

temperature at the external surface, h is the convective heat transfer coefficient and T(t) is the cure cycle applied during the process. An incremental finite element method is then employed to solve the heat transfer equation with the applied initial and boundary conditions. Thus, the heat transfer analysis computes the variation of degree-of-cure in the laminate and the change of temperature in the laminate and the mould using the material properties and the process cure cycle.

-42-

In this analysis, both the behaviour of the composite constituent, the resin and the reinforcement have to be considered. The general approach to model the resin flow through the fibre reinforcement is to consider it as flow through a porous media using Darcys law [126]: Eq. 2-48 where is the Darcy velocity vector, is the resin viscosity, is the preform

2.1.1.2, the resin viscosity is a function of the degree-of-cure and the temperature. The Darcy velocity vector is related to the resin velocity vector

where is the fibre bed porosity. Eq. 2-48 is valid in the permanent flow regime and saturated porous media, such as an autoclave process. Assuming a linear resin flow, it can be also generalized to unsaturated porous media like in the RTM process. In that case, velocity vector at the unsaturated flow front, saturation, and is the Darcy

tensor, which is a function of the fibre volume fraction (Vf) and the fibre is the pressure gradient between the injection points and the unsaturated flow front [127]. As the flow front advances, the reinforcement is compressed by the resin pressure. This causes a change in fibre volume fraction which affects significantly the permeability. The compaction behaviour of the reinforcement is generally represented by the effective stress formulation used in soil mechanics [128] expressed as follows: Eq. 2-50 where (t) is the applied stress, pressure. is the fibre bed effective stress and P is the resin

-43-

In order to solve the coupled equations, initial conditions are applied to the fibre volume fraction, the resin pressure and the fibre bed effective stress: Eq. 2-51 Different boundary conditions can be also applied to specify the pressure and the permeability at the edge of the laminate. An incremental finite element method is then employed to solve the Darcys law and the fibre bed compaction equations with the applied initial and boundary conditions. In this work, the RTM process is modelled after the injection phase, once the preform is fully saturated by the resin. Therefore, the resin flow and the fibre bed compaction were not considered.

The governing equations of the stress analysis are based on the classical laminated plate theory. Considering the laminate as a two-dimensional orthotropic material, the compliance relationship in the ply orientation can be written as follows: Eq. 2-52 where the subscript l and t refer to the longitudinal and transverse directions, [xyz] and [xyz] are the laminate strains and stresses in the material directions. [S] is the compliance matrix expressed as follows:

Eq. 2-53

where El and Et are the longitudinal and transverse moduli, lt and tl are the Poissons ratio and Glt is the shear modulus. If the material coordinate system is different from the global coordinate system, this relation can be transformed to the global coordinate system using the transformation matrix [T]: -44-

Eq. 2-54 where [S] is the compliance matrix in the global coordinate system. The transformation matrix [T] is expressed as a function of which is the angle difference between the ply coordinate (l, t) to the global coordinate (1,2,3) as shown in Figure 2-14: Eq. 2-55

Figure 2-14: Schematic representation of the coordinate systems in ply and the global orientation

Then, the stiffness relationship can be determined by inverting the compliance matrix: Eq. 2-56 where [Cij] is the stiffness matrix in the global coordinate. Therefore, the stiffness matrix is a function of the elastic properties of the ply which can be determined using the micromechanic approaches (Eq. 2-28 to Eq. 2-37) presented in paragraph 2.1.2. As presented in paragraph 2.2, during the process, strains arise due to thermal and chemical effects, and the total strain in the laminate is the summation of the strains caused by these two effects: Eq. 2-57

-45-

i

composite cure shrinkage respectively, computed from the micromechanic model (Eq. 2-39 and Eq. 2-25), T is the temperature variation and shrinkage strain variation. A finite element incremental method is then employed to solve these equations, assuming that the fibre properties are constant or only function of the temperature and the resin behaves as a cure-hardening instantaneous linear elastic (CHILE) material. For a given increment, knowing the field of degree-of-cure and temperature from the heat transfer analysis, the instantaneous composite elastic constants can be computed using the resin elastic modulus model and the micromechanic approach. Similarly, the thermal and chemical strains can be computed for a given increment knowing the resin thermal and shrinkage behaviour with the temperature and the degree-of-cure and using the micromechanic approach. The stresses in the laminate can be then calculated from the classical laminated theory Eq. 2-56. Then the laminate strains and stresses development during the cure cycle are obtained by adding the total strains and stresses of the consecutive increments: Eq. 2-60

Eq. 2-61 In this manner, the evolution of the strains and stresses can be computed for the entire cure cycle, taking into account the thermomechanical properties of the composite constituents.

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In this work, the commercial finite element software ABAQUS and the COMPRO Component Architecture (CCA) were used to model the RTM process based on the approach described above. The CCA, developed by Convergent Manufacturing Technology Inc., is a subroutine allowing the interface between the material properties and the ABAQUS finite element solver as shown in Figure 2-15. Using the material model database, it computes the evolution of the material properties (resin, fibre and composite) at each increment as described above, and transfers them to the ABAQUS finite element solver which computes the strains and stresses using the classical laminated plate theory. Due to the ABAQUS structure, two analyses are required to model the manufacturing process. First, a heat transfer analysis is performed to determine the temperature and degree-ofcure fields of each integration point in the model. Then, a stress analysis is solved, using the temperature and degree-of-cure history computed in the previous analysis, to determine the strains, stresses and displacements caused by the cure cycle.

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As presented from the previous sections, process-induced stresses and deformations have been widely studied experimentally, analytically and numerically. Figure 2-16 presents a brief summary of the different aspects investigated in the past researches on process-induced stresses and deformations.

-48-

The following conclusions can be drawn: 1) The majority of the studies concerned the autoclave process (Figure 2-16a). Only few addressed the issue of residual stresses and dimension change for the RTM process. 2) The different sources of process-induced stresses and deformations are clearly identified in the literature (Figure 2-16-b). The main investigations focussed on the thermal strains, the resin cure shrinkage and the tool-part interaction. However, in a majority of case, these different aspects were not considered simultaneously. 3) Most of them focused on unidirectional carbon reinforcements and epoxy resin (Figure 2-16-c). Despite their increasingly use in the industry, only few researches investigated the woven reinforcements and the effect of the fibre architecture on the development of the residual stresses. 4) Finally, most of these studies considered simple geometries, such as flat or angled structures and few examined more complex structures (Figure 2-16-d). Concerning the RTM process, Table 2-1 details the main studies carried out on the process-induced stresses and deformations. Most of the works were performed on glass fibre reinforcements with epoxy resin and took into account the effect of the thermal strains and the resin shrinkage. However the effect of the tool-part interaction was not very well investigated. The importance of the development of constitutive material models was also addressed in the first section of this literature. Accurate material models are essential in order to capture more realistically the behaviour and evolution of the material during the manufacturing process.

-49-

Numerical Tapered geometry X X epoxy / 5HS Carbon woven fabric Perfect bonding

Experimental / Numerical Geometry Tool-part interaction Material Sources of residual stresses Other

Fibre waviness

L-shaped bracket, C-spar structure Epoxy / Glass woven fabric X X Flat panel X Polyester / Unidirectional glass fibre X

Numerical

process

Table 2-1: Studies on process-induced stresses and deformations for the RTM

-50Numerical Single stiffener structure Epoxy / Unidirectional glass fibre X Flat panel Polyester / glass mat and non crimp glass fabric X

Temperature gradient

In the light of the above, the current thesis investigates the process-induced residual stresses and deformation of 5-harness satin woven composite structures manufactured by RTM. In order to achieve this goal, the following objectives were considered: 1) Resin characterization: implementation of a methodical approach to characterize the processing properties of the RTM one-part epoxy resin and develop the resin constitutive models. A particular emphasis should be set on the volumetric cure shrinkage and the thermal expansion of the resin and the composite, as these parameters have a significant influence on the dimensional stability. 2) Effect of the fibre architecture: Investigation of the influence of the 5harness satin carbon reinforcement architecture on the composite thermomechanical properties. 3) Tool-part interaction: Investigation of the tool-part interaction for the RTM process experimentally using fibre Bragg grating sensors (FBG) and numerically using a finite element modelling. 4) RTM process modelling: Implementation of the constitutive material models into a finite element model to predict the geometrical variations such as spring-in or warpage. The main sources of residual stresses and the different phenomena involved in the RTM process are taken into account simultaneously.

-51-

As presented in CHAPTER 2, accurate material constitutive models are essential in order to realistically capture the behaviour and evolution of the material during the manufacturing process. In this chapter, the characterization steps and the development of the material constitutive models of a commercial epoxy resin are detailed. Supplied by Cytec, the CYCOM 890RTM epoxy [129] is a low viscosity resin developed especially for the RTM process. It is a one part system reacting at high temperature. It can be injected at 80C with a viscosity of 0.390 Pa.s, and its typical cure cycle is two hours at 180C. No complete characterization has previously been performed on the CYCOM 890RTM epoxy, and no constitutive material models were available in the literature.

Figure 3-1 presents the methodical approach developed in order to investigate the processing properties of thermoset resins and applied on the CYCOM 890RTM epoxy resin. First, thermal stability tests are conducted to determine the resin temperature processing window (step 1). The curing behaviour is then investigated in order to obtain the evolution of the degree-of-cure, , as a function of time and temperature (step 2). The resin rheological behaviour (step 3a) and the glass transition temperature Tg (step 3b), are then measured as a function of the degree-of-cure. Next, knowing the resin rheological behaviour, the cure shrinkage, V, is determined as a function of the degree-of-cure (step 4a). The coefficient of thermal expansion (step 4b) and the resin modulus (step 4c) are expressed as a function of the glass transition temperature. Finally, the developed material constitutive models can be implemented in any finite element software (step 5) to predict the final properties of a composite structure as a function of the cure cycle used. -52-

The next sections present in details the characterization steps and the development of the material constitutive models.

3.2

Tests performed Thermal stability tests were carried out on a Thermal Gravimetric Analyzer (TGA) Q500 from TA Instruments. A temperature ramp at 20C/min from 25C to 700C was applied to a 12.24 mg sample. The sample was under nitrogen from

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25C to 550C and air from 550C to 700C. A three-hours isothermal test was also performed at 180C under nitrogen. Results and Analysis The corresponding weight variation, under the dynamic and isothermal conditions, is presented in Figure 3-2 and Figure 3-3 respectively. For RTM processing, the temperature will not exceed 200C. At this temperature, a weight loss of 1.2% caused by the evaporation of volatiles present in the resin was measured under dynamic conditions. The resin thermal stability was confirmed by a weight loss of less than 2.1% after a three hours isothermal experiment at 180C. Therefore, the resin is not subjected to significant degradation during its typical cure cycle.

Figure 3-2: Resin weight variation with temperature from a TGA dynamic test at 20C/min

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Tests performed The resin cure kinetics was measured with a Modulated Differential Scanning Calorimeter (MDSC) Q100 from TA Instruments. The testing conditions were chosen based on typical processing conditions suggested by the manufacturer. Dynamic scans with heating rates of 1C/min and 2C/min, from 25C to 250C, and isothermal scans at 160C, 170C, 180C and 190C, were performed on uncured neat resin sample. Isothermal tests were followed by a dynamic ramp in temperature in order to measure the residual heat of reaction. Each testing condition was carried out up to three times in order to verify the result reproducibility (Appendix A). As mention in the literature review, CHAPTER 2, section 2.1.1.1, the measured heat, generated while the resin reacts, can be related to its cure rate and the degree-of-cure. The cure kinetic model is then the relation that expresses the cure rate as a function of the degree-of-cure.

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Results and analysis Figure 3-4 shows the heat flow profile measured by DSC during a dynamic experiment. The total heat of reaction, HT, was calculated by integrating the area under the curve. For this epoxy resin, the average HT is 430 samples. Each sample weights 5.25 25 J/g for 4

the degree-of-cure and the cure rate for the isothermal tests. The maximum cure rate is obtained for a degree-of-cure of 0.5. At temperatures lower than 180C, the degree-of-cure does not reach 1.0 due to the diffusion effect. Therefore, the autocatalytic cure model with a diffusion factor, developed by Hubert et al. was chosen to describe the evolution of the degree-of-cure with time and temperature [33]. This model, expressed by the following equation, gave a good correlation with the experimental data: Eq. 3-1 where k is a rate constant following an Arrhenius temperature dependency: Eq. 3-2

Figure 3-4: Typical heat flow of a Dynamic Scanning Calorimetry dynamic test at 2C/min -56-

Figure 3-5: Comparison of experimental data and predicted cure kinetics model for isothermal tests: a) degree-of-cure with the time, b) cure rate as a function of the degree-of-cure

From Eq. 3-1 and Eq. 3-2, the activation energy Ea was determined by calculating the slope of versus 1/T at low degree-of-cure ( = 0.1), as shown in Figure 3-6. Using the data under isothermal conditions, as presented in Figure 3-7, -57-

a linear relationship was observed between the ultimate degree-of-cure ( the glass transition temperature Tg.

C0

max)

and

and

CT

parameters from the linear fit. The step change in the specific heat (Cp) measured by modulated DSC was used to identify Tg. The other parameters, A, n, m, and C were calculated using a least squares non-linear regression between the cure rate and the degree-of-cure for all tested temperature conditions. The values are presented in Table 3-1.

Figure 3-6: Cure rate as a function of inverse absolute temperature at low degreeof-cure ( = 0.1) under isothermal conditions

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Figure 3-7: Ultimate degree-of-cure under isothermal conditions as a function of the glass transition temperature

Table 3-1: Cure kinetic model constants Model constants A (s-1) Ea (J/mol) n m C C0 CT (K-1) 58528 68976 0.6 0.63 15.66 -0.90 0.0039

Figure 3-5 compares the experimental data measured by DSC for four isothermal temperatures with the predictions obtained with the kinetics model (Eq. 3-1). The variations of the resin degree-of-cure with time and the rate of cure as a function of the degree-of-cure are presented in Figure 3-5-a and Figure 3-5-b, respectively. The cure kinetics model accurately predicts the resin cure evolution for the different isothermal cases considered. The goodness of fit is reflected by R2 values above 0.965 as shown in Figure 3-5-b. The prediction for the dynamic conditions is presented in Figure 3-8. A good agreement for the cure rate -59-

prediction is obtained up to 190C and 220C at temperature ramp of 1C/min and 2C/min respectively. After those points, the cure kinetic model predicts a faster decrease in cure rate than measured experimentally. Since the processing temperature is below 190C, this discrepancy is not a point of concern.

Figure 3-8: Comparison of experimental data and predicted cure kinetics model for dynamic tests

3.3

Tests performed Rheological measurements were performed with an AR2000 rheometer from TA Instruments. Since this epoxy was not previously characterized, the Linear Viscoelastic Region (LVR) was first determined. A strain sweep test is initially performed, followed by a time sweep test. These two tests are presented in Appendix A. For this particular epoxy, the optimal oscillatory conditions to remain in the LVR were found at 15% strain and 1Hz.

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Dynamic scans at heating rates of 1C/min, 2C/min and 3C/min and isothermal scans at temperatures of 80C, 170C, 180C and 190C were performed on uncured neat resin sample, using a 40 mm parallel plate geometry in oscillatory mode at 15% strain and 1 Hz. Each testing condition was carried out up to five times in order to verify the result reproducibility Appendix A. Results and analysis Figure 3-9 and Figure 3-10 show the evolution of the viscosity under different dynamic and isothermal conditions. First the resin viscosity decreases as the temperature increases, until it reaches a minimum value. After a certain time, the viscosity increases quickly. This sharp increase in viscosity corresponds to the gel transition. The equality between the storage and loss shear moduli, G and G, was used as criterion to determine the gel point [130]. As shown in Figure 3-11, at the curing temperature of 180C, the gel point occurred around 72 minutes in average.

Figure 3-9: Evolution of the measured and predicted viscosity with temperature for rheological dynamic tests at three temperature rates

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Figure 3-10: Evolution of the measured and predicted viscosity with time for rheological isothermal tests

A model taking into account the influence of both the temperature and the degreeof-cure was used to characterize the rheological behaviour of the resin. The -62-

following equation presents the modified gel model used to describe the evolution of the resin viscosity [131]: Eq. 3-3

gel

is the degree-of-cure at the gel point, and Ai, Ei, A, B and C are

constants. From the temperature-time history measured for each rheological test, the degree-of-cure of the resin was calculated using the cure kinetics model (Eq. 3-1) and the gel point was determined as gel = 0.7. Although this value can seem relatively high for an epoxy resin, similar results were obtained by OBrien and White [38]. Furthermore, this resin was developed for the RTM process which requires a long gel time in order to maximize injection time. Eq. 3-4 can be also expressed as a linear relationship between the viscosity and the inverse of the temperature: Eq. 3-5 From Eq. 3-5, a linear regression was then used to calculate the constants A1, E1 and A2, E2, using the dynamic data and the isothermal data respectively before the gel point. The other parameters, A, B and C were calculated using a least squares non-linear regression between the viscosity and the temperature. The values of the different parameters are reported in Table 3-2. Figure 3-9 and Figure 3-10 compare the predicted and measured viscosity evolution with time and temperature. The viscosity model (Eq. 3-3) accurately predicts the onset of resin gelation and the evolution of resin viscosity with temperature and degree-of-cure, with a R2 value superior to 0.80. From Figure 3-10, it is shown that the resin remains liquid even after three hours at the recommended injection temperature of 80C. A typical RTM injection lasts less than 30 minutes, so no gelation will occur during this time. -63-

Table 3-2: Viscosity model constants Model constants A1 (Pa.s) A2 (Pa.s) E1 (J/mol) E2 (J/mol) A B C gel 9.81x10-19 6.41x10-3 115305 12074 -0.5 1 3.5 0.7

3.4

Tests performed Three different methods were used to measure the glass transition temperature: MDSC, TMA and the rheometer in torsion mode. With the MDSC technique, Tg is identified by a step change in the specific heat, during the dynamic ramp following an isothermal test, whereas with the TMA, it is identified by a change in CTE. Using the rheometer in torsion mode, the glass transition temperature can be determined by observing the three modulus based indicators: the onset of a sharp drop in the storage modulus G, the peak in the loss modulus G and the peak in the tan . A succession of dynamic tests was performed at 5C/min to 180C followed by a short isotherm in an oscillatory mode at 0.1% strain and 1Hz on solid samples pre-cured to an initial degree-of-cure

1,

manufactured as explained

in Appendix A. The chosen heating rate of 5C/min was low enough to ensure thermal equilibration between the rheometer and the sample but high enough to avoid large changes in degree-of-cure at higher temperatures. Once the glass transition temperature was measured, the sample was cured to a known degree-ofcure

2

and quickly cooled down to room temperature. The procedure was then

2

repeated from

to a higher

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Results and analysis The evolution of the Tg with the degree-of-cure was modeled with the DiBenedetto equation (Eq. 2-14). , the parameter associated with fully cured , the resin, was determined as the highest recorded glass transition temperature.

glass transition temperature of uncured resin, was determined by MDSC testing, by heating an uncured resin sample from -50C to 25C. The fitting parameter was calculated using a least squares non-linear regression between the values of Tg determined at the peak of tan and the degree-of-cure. The DiBenedetto constants are presented in Table 3-3. This model accurately predicts the evolution of the glass transition temperature, with a R2 value of 0.999. The value of the fitting parameter is close to the expected value found by other researchers for

thermosetting resins ( = 0.4 [132]). Table 3-3: DiBenedetto model constants Model constants (C) (C) -14.23 213.75 0.396

Figure 3-12 compares the predicted and measured glass transition temperatures with the degree-of-cure. The DiBenedetto equation captures the trend of the Tg obtained with different methods well. Differences between the testing methods were expected as the glass transition passage does not affect thermodynamic and mechanical properties at the same point, but rather occurs over a range of temperatures.

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Figure 3-12: Comparison of glass transition temperatures measured with Modulated Differential Scanning Calorimeter, Thermo Mechanical Analyzer and rheometer in torsion mode and the predicted values obtained with the DiBenedetto model

3.5

As explained in CHAPTER 2, the volumetric changes of a thermoset resin are a combination of chemical effects (shrinkage) and thermal effects (coefficient of thermal expansion, CTE). Since volumetric changes are one of the main causes of dimensional variability and residual stress development during the cure of composite materials, a special attention was set on their characterization.

Two different methods, the modified rheology method and the gravimetric method, were applied to measure the shrinkage of the CYCOM 890RTM epoxy resin.

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Principle The modified rheology method [55] is a simple test, easy to setup. It measures the shrinkage after the gel point using a rheometer with parallel plate geometry. A controlled normal force is applied to maintain the contact between the plates and the resin sample while the gap variation between the parallel plates is measured. The linear shrinkage is first determined based on the change in gap between the parallel plates (i.e. sample thickness) with the following equation: Eq. 3-6 where L is the linear shrinkage, is the resin Poissons ratio, h is the value of the

gap at a given time and h0 is the initial value of the gap. Assuming that the inplane strains in the resin are zero and that the resin is incompressible ( = 0.5), the linear shrinkage can be converted to volumetric shrinkage with the following equation: Eq. 3-7 where is the volumetric shrinkage, h0 is the initial value of the gap and h is the

The gravimetric method, more complex, measures the change in buoyancy of a resin in a known fluid at a controlled cure temperature to determine the shrinkage [56]. It is based on the Archimedean principle which links the mass, the volume and the density of solid bodies immersed in liquid as follows: Eq. 3-8 where ms is the mass of the solid, mfl is the mass of the fluid, ms(air) is the mass of the solid in air, ms(fl) is the mass of the solid in the fluid, s is the density of the solid and fl is the density of the fluid.

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During cure under isothermal conditions, resin shrinkage causes an increase in density that can be detected by the change in buoyancy. The buoyancy is monitored by measuring the apparent change in weight of the immersed sample. Therefore, the shrinkage

Eq. 3-9

where

is the apparent resin weight change, fl,Tfl is the density of the fluid

at the actual fluid temperature Tfl and Vr,Tc is the volume of the uncured resin at the curing temperature Tc. Tests performed For the modified rheology method, the shrinkage measurements were performed with an AR2000 rheometer from TA Instruments with 25 mm diameter plates as shown in Figure 3-13-a. The initial sample thickness was 1 mm 0.05 mm. Tests were carried out at three different isothermal cure temperatures, 160C, 170C and 180C, to avoid thermal expansion phenomena, and the normal force was set to 0.1N. Three to four experiments were performed for each temperature for reproducibility purposes. The experimental procedure was divided in two steps. In the first step, the rheometer was set in a gap control mode as the resin was in its liquid state: the value of the gap was controlled and kept constant to his initial value h0 and no normal force was applied. The maximum strain was set at 15% with a frequency of 1Hz in order to be in the Linear Viscoelastic Region (LVR) of this epoxy resin. When the viscosity reached 500 Pa.s, the second step or normal force control mode was initiated. In this step, the resin has gelled and can withstand pressure without flowing. The normal force (FN) was kept constant to 0.1N, a maximum torque of 500 N.m at a frequency of 30 Hz was also applied and the actual gap h was measured. The gravimetric method required pre-experiment preparation and was delicate to operate as sources of error can be easily introduced. According to Schoutens -68-

[133], the main sources of error of common immersion techniques are: air bubbles adhesion to the sample surface causing an artificial increase in buoyancy, effect of surface tension on the wire supporting the specimen and temperature fluctuation. In this study, the experimental procedure developed by Li et al. [56] shown in Figure 3-13-b, was modified as follows. Two resin samples were immersed simultaneously in one litre of Dow Corning 200-100 silicone fluid at constant temperature. The samples had a mass of 2.45 0.1 g to minimize temperature changes due to the exothermal curing reaction. One specimen was linked to an Ohaus precision scale, model AV114C, with a capacity of 110g 0.0001g, used for the weight measurement. The second resin specimen had a type K thermocouple embedded for resin temperature monitoring. A thermocouple was also immersed in the silicone fluid. High temperature Nylon 6 bagging film was used to enclose the resin. In their experimental set-up, Li et al. were moulding thin silicone bags with a silicone mould rubber. These bags had first to be preconditioned before use as they were swelling in silicone oil. They were then sealed using machined aluminum plugs and a binding sleeve. In order to decrease the time of this preparation phase, Nylon 6 bagging film was used and came out to be more user-friendly while meeting the required specifications. The Nylon 6 bagging film appeared to have a better dimensional stability in the silicone fluid with the temperature and to be resilient enough to pick up any volumetric change. Therefore no pre-conditioning was needed before running experiments. Its standard thickness inferior to 0.1 mm allowed a quick heat up of the resin to the curing temperature as well as a quick dissipation of the exothermic heat. It can be used for cure up to 205C. An impulse bag sealer was used to seal it, so that no external material was introduced to close the bags and entrapped air was easily removed. Nylon bags were hanged from the weight below hook with a steel wire and a Kevlar thread. The steel wire was used to avoid surface tension effect and fluid absorption and minimize potential source of error. Kevlar thread was used to link the scale to the steel wire and avoid heat transfer to the scale. A heating blanket regulated by temperature controllers was used to heat up the silicone bath two hours before the experiment in order to have a uniform fluid temperature. -69-

Experiments were carried out at 160C, 170C and 180C for three to four hours. Three to four tests were performed for each temperature for reproducibility purposes. A data acquisition system from National Instruments (NI 9211) was used to record the temperatures and a RS232 cable was used to connect the precision scale to the computer. A Labview interface was used to simultaneously record the temperatures and the apparent weight.

Results and analysis Figure 3-14 shows the parallel plate gap and the normal force variation during a typical modified rheology test at 180C. During the gap control, the normal force increased, implying an expansion of the resin sample. As the rheometer temperature was kept constant, this expansion was caused by the heat released during the exothermic reaction creating locally an increase in temperature. A Ktype thermocouple placed at the center of the plate, in the middle of the sample, measured a 1C increase of the resin temperature and confirmed this phenomenon. Nevertheless, the increase in temperature occurred during the first hour of the experiment when the resin was liquid. As the shrinkage was measured during the normal force control step, for more than four hours, this variation of temperature did not affect the results. In the normal force control step, the normal force was set to 0.1N. The gap started to decrease due to the shrinkage until it reached a -70-

constant value. The shrinkage was then calculated using the gap variation in Eq. 3-7.

Figure 3-14: Gap and normal force variation for a typical modified rheology test for an isothermal cure at 180C

Figure 3-15 shows the measured variation of shrinkage with time for samples at three isothermal temperatures (160C, 170C, 180C). The average total volumetric shrinkage was 3.36% 0.2% which is in the range usually found for epoxy resins (2%-7%) [51, 56]. The curing temperature had not a significant influence on the total volumetric shrinkage which was consistent with the work by Haider et al. [55] and Li et al. [56]. Figure 3-16 presents the shrinkage as a function of the degree-of-cure, obtained from Dynamic Scanning Calorimetry (DSC) experimental data. After the gel point, the variation of the shrinkage is a linear function of the degree-of-cure which is in agreement with previous studies [44, 55, 56]. Thus the resin shrinkage can be modelled as follows:

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Eq. 3-10 where is the resin degree-of-cure, gel is the degree-of-cure at gelation, V is the volumetric shrinkage, and A is a constant. The degree-of-cure at gelation, gel = 0.7, was determined from the cure kinetic model (section 3.2.2). For each temperature, the constant A was calculated using a least squares method for linear regression. The fitting constants and the R 2 values are listed in Table 3-4. As shown in Figure 3-15 and Figure 3-16, this model agreed overall well with the experimental data at 170C and 180C. However, at 160C, the model underestimated the shrinkage where the shrinkage onset occurred before gel = 0.7. The shrinkage occurring before gel is not taking into account by the model, which explains the difference between the measured and predicted values at that temperature.

Figure 3-15: Evolution of the measured resin shrinkage by the modified rheology method and predicted values with time under isothermal conditions

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Figure 3-16: Evolution of the measured resin shrinkage by the modified rheology method and the predicted values as a function of the degree-of-cure under isothermal conditions

Table 3-4: Curve fitting constants for the shrinkage model obtained by the modified rheology method (Eq. 3-10) and R2 values for isothermal experiments Isothermal experiments 160C 170C 180C Average A (%) 12.29 12.68 12.28 12.42 R2 0.993 0.995 0.995

Figure 3-17 to Figure 3-19 show the temperatures and sample apparent weight variation recorded during the gravimetric method. First, the apparent weight decreased as the resin sample expanded and reached the isothermal temperature equilibrium. After 20 to 30 minutes, the apparent weight started to increase due to the shrinkage development until it reached a maximum. At 160C, the exotherm due to the curing reaction was negligible (<1C). At 170C and 180C, an increase of the resin temperature of 3C and 6C respectively was noticeable. The temperature increase caused a thermal expansion of the sample, and therefore -73-

increased the sample buoyancy while decreasing its apparent weight. However, no decrease of the resin apparent weight was visible as the exotherm occurred. Thus, the effect of the thermal expansion was considered negligible compared to the shrinkage and thus was not accounted in the calculation.

Figure 3-17: Resin weight and temperature variation for a typical gravimetric test for an isothermal cure at 160C

Figure 3-18: Resin weight and temperature variation for a typical gravimetric test for an isothermal cure at 170C -74-

Figure 3-19: Resin weight and temperature variation for a typical gravimetric test for an isothermal cure at 180C

The variation of the shrinkage, computed from the weight change (Eq. 3-9), with time and degree-of-cure is presented in Figure 3-20 and Figure 3-21, respectively. As in the previous method, the degree-of-cure was obtained from DSC experimental data (section 3.2.2). The result of Figure 3-21 corroborates the conclusion obtained with the previous method: curing temperature has no influence on the evolution of the shrinkage. The resin shrinkage followed a bilinear relationship with the degree-of-cure expressed as follows: Eq. 3-11 where is de degree-of-cure, i is the degree-of-cure at the inflection point, V is the volumetric shrinkage and A1, B1, C1 and D1 are the model constants. A least squares method for linear regression was used to calculate the constant A1, B1, C1 and D1 reported in Table 3-5.

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Figure 3-20: Evolution of the measured resin shrinkage by gravimetric method and predicted values with time under isothermal conditions

Figure 3-21: Measured and predicted cure shrinkage for isothermal tests with the gravimetric method

-76-

Table 3-5: Bilinear curve fitting constants for the shrinkage model obtained by the gravimetric method (Eq. 3-11) Linear equation 1 A1 (%) B1 (%) 160C 170C 180C Average 7.78 7.86 8.64 8.10 -0.40 -0.54 -0.13 -0.35 R2 0.994 0.992 0.996 Linear equation 2 C1 (%) 13.93 19.38 22.85 18.72 D1 (%) -4.69 -9.58 -11.99 -8.75 R2 0.986 0.990 0.984 Inflection

i

The rate of volumetric shrinkage increased after the inflection point (A=8.10% and C=18.72% before and after the inflection point respectively). The resin reached a volumetric shrinkage of 6% before the transition point and kept increasing up to 10%. Therefore it can be assumed that the change in the volumetric cure shrinkage rate at the inflection point corresponded to the gelation phenomenon. Similar results have been observed in previous studies for a MY750 epoxy resin [56] or nonconductive adhesives with a thermomechanical analyzer [51]. The change in shrinkage rate can be related to the polymer chain movement and molecular rearrangement. Before the gelation, polymer chains are free to move and rearrange and the induced deformation can be accommodated by the resin flow. After the gelation, the resin transforms from liquid to solid and develops a mechanical modulus. Molecular rearrangement remains significant but the mobility of the polymers chains is greatly reduced. At this point, the deformations induced by the molecular rearrangement cannot be dissipated by the resin flow inducing a higher shrinkage rate. Figure 3-22 to Figure 3-24 compare the evolution of the shrinkage obtained with the modified rheology and the gravimetric methods. The modified rheology method measured only the shrinkage after the gel point. From Figure 3-21, it appears that the shrinkage measured with the gravimetric method was actually 5.39% 0.4% at the gel point (gel = 0.7). Therefore, an initial shrinkage of 5.39% was added to the results obtained by the modified rheology method. The -77-

shrinkage after the gel point measured by the two methods was in good agreement especially at 160C and 170C. At 180C, the rate of the shrinkage increase measured with the gravimetric method was slightly higher compared to the modified rheology method. This phenomenon could be explained by the small exotherm taking place at 180C (Figure 3-19). The 6.5C temperature overshoot could lead to an increase of the cure rate and consequently the shrinkage rate. Also, the potential release of the volatiles present in the resin in form of gas was not taken into consideration for the shrinkage characterization using the gravimetric method. The release of the volatiles can indeed affect the sample buoyancy leading to an increase in the apparent weight and therefore an increase in the measured shrinkage. Even if very low void level was observed on the cured sample at the end of test, this issue might explain the shrinkage discrepancy observed between the modified rheology method and the gravimetric method.

Figure 3-22: Comparison of the two shrinkage measurement methods with degree-of-cure at 160C

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Figure 3-23: Comparison of the two shrinkage measurement methods with degree-of-cure at 170C

Figure 3-24: Comparison of the two shrinkage measurement methods with degree-of-cure at 180C

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These results validate the use of a simple method, the modified rheology method, to measure the shrinkage after gelation. However, the gravimetric method demonstrates that the shrinkage occurring before gelation is not negligible and can represent up to one half of the total shrinkage. The arising shrinkage before gelation does not induce residual stresses as the resin is in the liquid state and can flow. However, shrinkage prior to gelation can lead to surface finish defects such as fabric print through in closed-mould process (i.e. Resin Transfer Moulding) where no pressure is applied after the injection to the composite part to compensate the shrinkage effect.

Tests performed Tests were carried on a TMA 2940 from TA Instruments. The influence of the curing temperature and the degree-of-cure was investigated using fully and partially cured resin samples. The samples were prepared with the rheometer with 40mm plates. Release agent was applied on each plate to ensure an easy demolding. The curing temperatures considered were 160C, 170C and 180C, and the influence of the degree-of-cure was observed after the gel point, from = 0.8 to =1. Then the 40mm disk was cut in smaller samples of about 5mm by 5 mm and 1mm thick. Three to four cycles from room temperature up to 250C, then back down to room temperature, at a rate of 3C/min were performed for each sample. A normal force of 0.05N was applied on the probe in order to maintain contact with the sample. Results and analysis Figure 3-25 and Figure 3-26 show a typical experiment applied on one sample and the determination of its CTE. From Figure 3-25, a difference between the first cycle and the two last cycles can be noticed. During the first cycle, both thermal expansion and cure shrinkage occur due to the advancement of the degree-of-cure with temperature. During the last two cycles, the relative dimensional changes, , are similar, only thermal expansion takes place. Thus, the CTEs were -80-

measured using the heating part of the cycles excepting cycle 1. Figure 3-26 represents the heating part of cycle 3. The sample relative dimensional change evolves linearly with the temperature and the slope corresponds to its CTE. The curve inflection corresponds to the glass transition of 197C. As expected, the resin CTE increases as the sample evolves from the glassy to the rubbery state.

Figure 3-25: Resin relative dimensional change with temperature of a neat resin sample with an initial degree-of-cure

1

of 0.883

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Figure 3-26: Resin relative dimensional change during the heating part of cycle 3 at 3C/min

Figure 3-27 presents the variation of the measured coefficient of thermal expansion with the degree-of-cure, after the gel point, from = 0.8 to = 1. It can be noticed that the CTE remains constant with the degree-of-cure below the glass transition temperature, but decreases with the degree-of-cure above the glass transition temperature. Below Tg, the resin is in its glassy stage, the movement of molecules is very limited. The network formation has no influence on the expansion of the resin. The CTE remains low and constant with the increase of the degree-of-cure. However, above Tg, the movement of the molecules increases and is less limited. In this case, the network formation will have a bigger influence on the molecule mobility by reducing it. Due to this higher mobility, the CTE above Tg is higher than the CTE below Tg, and decreases with the increase of the degreeof-cure.

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Figure 3-27: Variation of the coefficient of thermal expansion with the degree-ofcure before and after the glass transition

The glass transition temperature is thus an important parameter for the evolution of the CTE. Taking example from the expression of elastic modulus as a function of T* [58, 60], the evolution of the CTE was plotted as a function of the difference between the instantaneous and glass transition temperature, T*=T-Tg, in Figure 3-28. The same reasoning used for the evolution of the CTE with the degree-ofcure can be employed. Far below Tg, the CTE remains low and constant with the increase of temperature as the movement of the polymer chain is limited. However, as the temperature increases and get closer to the glass transition temperature, the movement of the molecules increases and the CTE starts to increase linearly. The following model was developed to describe this evolution using least squares method for linear regression: Eq. 3-12 where CTEglass is the resin CTE in the glassy state, A0 and T are two constants. The model constants are expressed in Table 3-6.

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Figure 3-28: Evolution of the measured and predicted CTE as a function of T*, for 3C/min heating rate up to different temperatures

Table 3-6: Coefficient of thermal expansion model constants Model constants CTEglass (C-1) A0 (C-2) T (C) 5.97 10-5 7.54 10-6 -20.4

3.6

Tests performed The torsion mode of the rheometer was used to capture the evolution of the elastic modulus with the cure. As described previously in section 3.4, this method enables to follow the change of the shear moduli, G and G with the temperature. Knowing the cure kinetics of the epoxy resin, the shear moduli can be related to the degree-of-cure as well. Then, assuming that the resin is isotropic and that the variation of the Poissons ratio with the temperature and the degree-of-cure has a

-84-

negligible influence on the shear modulus [43, 57], the shear modulus can be related to the tensile modulus with the following equation: Eq. 3-13 where E is the tensile modulus, G is the shear modulus and is the Poissons ratio. The manufacturers data sheet listed a room-temperature tensile modulus E of 3.1 GPa, and the average shear modulus G of the resin at room temperature was measured to be 1.30 GPa. Therefore, using Eq. 3-13, the Poissons ratio was determined to be 0.2, which is in the expected range for cured epoxy resins. Partially cured neat resin samples to a known degree-of-cure with specific cure cycles designed to reach a fully cured state. Results and analysis As expected, and shown in Figure 3-29, the evolution of the modulus was very sensitive the glass transition temperature. A significant decrease in the modulus was observed as soon as the sample reached the glass transition region and changed from glassy to rubbery state (T>Tg). Then the modulus remained low until vitrification. Once the specimen passes the vitrification (T<Tg), its elastic modulus started to increase as it evolved from the rubbery to the glassy state.

1

(Table A-3),

-85-

Figure 3-29: Evolution of the elastic modulus with temperature and time for a resin sample with an initial degree-of-cure

1

of 0.846

As the glass transition temperature is an important factor in the evolution of the modulus, a resin modulus model was developed as a function of the difference between the instantaneous cure and glass transition temperature, T*=T-Tg [58, 60] and can be represented as shown in Figure 3-30. This model can be expressed as follows:

Eq. 3-14

with

using Eq.2-14.

-86-

Table 3-7 presents the values of the fitting parameters obtained with the least squares non linear regression method which give the best agreement with the experimental data. Figure 3-31 compares the experimental and predicted resin modulus obtained at 160C and 180C. Overall, the model captured both the onset of the modulus decrease due to the glass transition and the vitrification at different curing temperatures, with R2 values above 0.78. This model neglects the viscoelastic characteristic of the resin. This can be justified due to the slow curing process of the studied resin, which enables the relaxation of the internal stresses generated before the vitrification. On the contrary, in the case of a fast curing material system, the generated internal stresses dont have time to be relaxed and a modulus viscoelastic model have to be considered.

Figure 3-30: Resin modulus model as a function of difference between instantaneous and glass transition temperature (T*=T-Tg)

-87-

gel

Values 0.700 -150C -15.18C -7C 5C 3.20 109 Pa 1.50 109 Pa 1.11 109 Pa 1.30 107 Pa 9.0 107 Pa 0.4C

Figure 3-31: Measured and predicted elastic modulus with time under two curing temperatures, 160C and 180C

3.7

In this chapter, a comprehensive methodology was applied to characterize the processing properties of the CYCOM 890RTM epoxy resin. The detailed

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procedure and techniques presented can be applied to intensive characterization purpose of a wide range of thermoset resins. The model parameters obtained from each characterization technique showed close agreement with the experimental data. 1) A cure kinetics model taking into account the diffusion phenomena was found to accurately predict resin cure kinetics behaviour for the Resin Transfer Moulding processing condition range. 2) A chemorheological model was developed to accurately predict the onset of resin gelation and the evolution of resin viscosity with temperature and degree-of-cure. 3) The DiBenedetto equation was found to describe the cure dependence of Tg well. 4) A two-phase linear model was used to predict the cure shrinkage behaviour of the resin before and after the gel point in the same processing condition range. A change in the shrinkage rate was detected due to the liquid-solid transition. 5) Finally, two models taking into account the influence of Tg were determined to describe the coefficient of thermal expansion and the elastic modulus evolution during the cure, respectively. Far below Tg, the CTE remained constant, whereas a linear variation of the CTE was found for temperatures close and above Tg. Two different methods were used to characterize to resin shrinkage. The first method, a modified rheology method, involved a simple procedure to measure the volumetric shrinkage after gelation with a rheometer and parallel plate geometry. The second more complex method used the change in buoyancy of an immersed sample in a fluid at constant temperature to determine the volumetric shrinkage during the entire cure. Both methods measured the same amount of shrinkage after gelation. Depending on the resin system and its manufacturing process, it is possible to define which characterization method is more suitable to perform -89-

1) For low gel or short tgel (gel < 0.2 or tgel < 10 min), the modified rheology method is more appropriate to characterize the shrinkage evolution of the resin. In that case, most of the shrinkage will occur after the gelation, and the modified rheology method will be a simple but accurate way to capture its evolution. As this method does not require sample preparation, even resin with shorter processing window (tgel < 5 min) can be tested. 2) For high gel or long tgel (gel > 0.5 or tgel > 30 min), the gravimetric method, less user friendly, is more appropriate as up to half of the total shrinkage can occur before gelation and need to be measured. Resin systems with long gel time are more suitable as the sample preparation can take up to 10 minutes. 3) For intermediate gel or tgel values, both methods can be used depending on the amount of information desired. This phenomenal approach provides a clear understanding of the resin processing behaviour. In the next chapters, the developed material models will be then implemented in a finite element software, ABAQUS/COMPRO CCA, to solve coupled thermochemical-stress processing problems, to predict the final properties of a composite structure manufactured by RTM.

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After a detailed characterization of the resin properties, this chapter outlines the influence of the fibre architecture on the elastic and thermal properties of composite material. The reinforcement investigated in this study was a 5-harness satin woven reinforcement made of G30-500 6k carbon fibre [134, 135]. The properties of woven fabric composite are usually modelled using the properties of unidirectional crossply laminates. The influence of the fibre waviness is therefore not taking into account. In order to verify the validity of this assumption and determine how the fibre waviness affects the composite properties, the thermomechanical properties of a 5-harness woven fabric and a unidirectional crossply reinforcement were investigated using a micromechanical approach on periodic units or unit cells with the finite element method. Knowing the properties of the composite constituents (fibre and resin), the analysis of the unit cell or smallest representative volume element (RVE) enables the determination of the global properties of the composite structure. Three fibre volume fractions (Vf) typical for the RTM process (between 50% and 62%) were analyzed. For both unit cells, the fibre arrangement in the yarns was assumed to be similar and follow a hexagonal packing. Table 4-1 presents the different types of reinforcement studied and their respective fibre volume fractions. In order to achieve the desired fibre volume fraction for the unit cells, the yarn fibre volume fraction had to be modified as reported in Table 4-1. The following methodology was then used to determine the thermomechanical properties of the crossply and 5-HS woven fabric unit cell as shown in Figure 4-1.

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Table 4-1: Types of reinforcement and their fibre volume fractions Unit cell fibre volume fraction (Vf) 62% 55% 50% 62% 55% 50% Yarn fibre volume fraction (YVf) 86% 77% 70% 86% 77% 70%

Unit cell

Figure 4-1: Applied methodology to determine the thermomechanical properties of the unidirectional crossply and 5-harness woven fabric unit cells

The yarn thermomechanical properties were first determined using the properties of the G30-500 6k carbon fibre and the cured CYCOM 890RTM epoxy listed in Table 4-2 in the hexagonal unidirectional unit cells. The epoxy resin was -92-

considered isotropic and the carbon fibres orthotropic. The yarn fibre volume fraction investigated were 70%, 77% and 86%. Then, these computed yarn properties were used as input to the unidirectional crossply and 5-HS woven unit cells at 50%, 55% and 62% fibre volume fraction. Table 4-2: Carbon fibre and epoxy resin thermomechanical properties Carbon fibre G30-500 6k [134, 135] E1,f = 230 GPa E2,f = E3,f = 22 GPa 12,f = 13,f = 0.3 23,f = 0.35 G12,f = G13,f = 22 GPa G23,f = 8.15 GPa CTE1,f = -0.7x10-6 C-1 CTE2,f = CTE3,f = 8x10-6 C-1 Epoxy resin CYCOM 890RTM [129] Er = 3.1 GPa r = 0.3 Gr = 1.2 GPa CTEr = 55x10-6 C-1

*The subscripts f and r stand for fibre and resin respectively. 1, 2 and 3 correspond to the three principal direction of the material

4.1

An dimensionless unidirectional unit cell was modelled with a hexagonal packing as seen in Figure 4-2. A circular cross section was assumed for the fibres. Keeping a constant size for the unit cell, the fibre radius r was modified in order to obtain the required Vf using the following relation: Eq. 4-1 where L, w and h are the length, width and height of the unit cell. The calculated radius values are presented in Figure 4-2 to obtain the 70%, 77% and 86% fibre volume fraction required.

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The global coordinate system of the unit cell is represented by the axes (1, 2, 3). Two material sections were defined for the resin and the fibre and a local rectangular coordinate system (x, y, z) was created to apply the carbon fibre orthotropic properties. This local system was based on three fixed points of the geometry A, B and C, where A is the origin, B is a point lying on the x-axis and C a point lying on the y-axis. The unit cell was meshed using 28990, 35640 and 30320 three-dimensional solid elements, type C3D8. The C3D8 element is an 8node linear brick element used for stress/displacement problems. Its degrees-offreedom are the displacements in the x-, y- and z- directions.

The dimensionless crossply unit cell model and its dimensions are shown in Figure 4-3. Again a circular cross section was assumed for the fibres. In order to achieve the desired fibre volume fraction, the fibre radius was kept constant and the yarn fibre volume fraction was varied as described in Table 4-1. 68800 threedimensional 8-node solid elements, type C3D8, were used. Two material sections were defined for the resin and the fibre. In order to identify the fibre orientations, -94-

two local rectangular coordinate systems, (x, y, z) and (x, y, z), were created, based on two sets of three fixed points of the geometry. The points A, B and C were used to define the (x, y, z) coordinate system, and A, B and C the (x, y, z) one, where A and A correspond to the origin, B and B are points lying on the x and x-axes respectively, and C and C define the y and y-axes.

The development of the 5-harness satin woven unit cell was done in three steps. First, the dimensions of actual unit cells were observed and measured. Then the measured dimensions were applied to a preliminary unit cell model. From the YVf and Vf obtained with this preliminary model, the dimension of the unit cell were adjusted to the desired Vf. Three unit cells were cut from a four plies laminate, manufactured by RTM with the G30-500 6k 5HS carbon fibre and the CYCOM 890RTM epoxy. The length, -95-

width and thickness were first measured using a digital calliper. The cross section of one unit cell was then observed under an optical microscope with the magnification x50 in order to obtain the yarn dimensions. The cross section is shown in Figure 4-4 wherein ellipsoidal yarn cross sections were observed. The measured unit cell dimensions are reported in Table 4-3.

Figure 4-4: a) Cross-section of a 4 plies laminate, G30-500 6k carbon fibre/CYCOM 890RTM epoxy resin, observed by optical microscope (x50), b) detail of a yarn

Table 4-3: Measured dimensions of a 5-harness satin unit cell Dimensions Length (mm) Width (mm) Thickness (mm) Yarn width (mm) Yarn thickness (m) 11.89 11.21 1.33 2.28 178 0.085 0.151 0.006 0.04 0.128

The laminate fibre volume fraction was determined to 62% using the following equation [136]: Eq. 4-2

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where

is the fabric ply areal weight, f is the fibre density, n is the number of

plies and t is the laminate thickness. A fabric ply areal weight of 370 g/m2 and the fibre density of 1.78 g/cm3 were provided by the manufacturer. Similarly, the nominal ply thickness can be determined for each considered fibre volume fraction using Eq. 4-2, as reported in Table 4-4. Table 4-4: Nominal ply thickness as a function of the fibre volume fraction Fibre volume fraction (Vf) 62% 55% 50% Average Ply thickness (mm) 0.34 0.38 0.42 0.38

From these observations, a preliminary 5-harness satin fibre architecture was developed with the following dimensions 11 mm x 11 mm x 0.38 mm. Because of the 5-harness satin pattern, five yarns with a 170 m thickness were positioned along both the width and the length with a 0.2 mm gap in between the adjacent yarns. This led to a yarn with a 2 mm width. The 5-harness satin architecture was then created using TexGen [91], a software dedicated to the modelling of textile structure in three dimensions. Based on the volumes generated by TexGen, the YVf was estimated for each desired Vf using the following relationship: Eq. 4-3 As shown in Table 4-5, it appeared that the 5-harness unit cell with the dimension cited previously resulted in yarn fibre volume fraction of 95% for a global fibre volume fraction of 62%. This YVf seems too high and not representative of what can happen experimentally. Therefore the dimensions of the unit cell were slightly modified to 12 mm x 12 mm x 0.36 mm. The gap between the adjacent strands was set to 0.05 mm leading to a yarn width of 2.35 mm. With these modifications, the yarn fibre volume fraction decreased to 86% at a fibre volume fraction of 62%, which seems more realistic. -97-

The unit cell volumes were then imported and meshed in a finite element software. The mesh and the dimensions of the final unit cell are presented in Figure 4-5. Once again, two material sections were defined for the resin and the fibres and two local rectangular coordinate systems, (x, y, z) and (x, y, z), were created in order to identify the fibre orientations. To account for the fibre waviness, these local systems were defined using the local numbering of each element, so that the out-of-plane axes remained always normal to the element surface, as shown in Figure 4-5-c. 11872 three-dimensional solid 8-node elements, type C3D8, were used to mesh the geometry. Table 4-5: Dimensions and characteristics of the preliminary and final 5-harness satin unit cell Preliminary 5-HS unit cell Vf (%) Unit cell length (mm) Thickness (mm) Yarn width (mm) Yarn thickness (m) Gap (mm) Yarn volume (mm3) Unit cell volume (mm3) Yarn volume fraction (%) 62 11 0.38 2 170 0.2 29.87 45.98 95 55 11 0.38 2 170 0.2 29.87 45.98 85 50 11 0.38 2 170 0.2 29.87 45.98 77 Final 5-HS unit cell 62 12 0.36 2.35 170 0.05 37.24 51.84 86 55 12 0.36 2.35 170 0.05 37.24 51.84 77 50 12 0.36 2.35 170 0.05 37.24 51.84 70

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Figure 4-5: 5-harness satin unit cell: a) unit cell finite element model and dimensions, b) yarn dimensions, c) schematic representation of the fibre orientation along a yarn

4.2

Boundary conditions

The unit cell is a periodic unit representative of the global composite structure. In other words, the global composite structure can be represented by a succession of in-plane adjacent identical unit cells. Therefore continuity in displacement must be satisfied at the unit cell boundaries to ensure that the adjacent unit cells cannot be separated or superposed [137-140]. This means that the opposite faces of the unit cell should deform identically and remain parallel to each other to maintain the periodicity for any loading conditions. In order to fulfill this condition, periodic constraints were applied on the nodes of the opposite faces. This required -99-

first that the number of nodes on opposite faces and their distribution were identical. Once an identical node distribution was ensured using the same mesh seed on opposite faces, a simple program written in MATLAB was used to pair the nodes having the same in-plane position, on opposite faces and edges. Then, constraint equations were applied in term of displacements on each pair of nodes to ensure the periodicity in the three global directions. In the following, ui represents the displacement in the ith-direction (i=1,2,3), Fj represents the nodes on the face j, excluding the edges and corners nodes, Ekl corresponds to the nodes located on the edge sharing the faces k and l, excluding the corners nodes, and finally, Njkl stands for the corner node sharing the faces j, k and l. The described notations are illustrated in Figure 4-6.

Then, the periodic constraint equations for the opposite faces were defined as follows [137]: Eq. 4-4 Eq. 4-5 Eq. 4-6

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These equations ensure that the opposite faces F1 and F2, F3 and F4, F5 and F6 remain parallel for any loading conditions. The periodic constraints on the opposite edges, to ensure that they remain parallel for any boundary conditions, were expressed in the following manner [137]: Eq. 4-7 Eq. 4-8 Eq. 4-9 Eq. 4-10 Eq. 4-11 Eq. 4-12 Eq. 4-13 Eq. 4-14 Eq. 4-15

Each model was loaded under seven different cases: three axial strains, three shear strains and one temperature change to determine the nine engineering constants and the coefficients of thermal expansion in the three directions. The axial and shear strains were applied through fixed displacements on the corner nodes of the unit cell.

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Figure 4-7: Boundary conditions: a) for an axial loading, b) for a shear loading, c) for a thermal loading

The axial strains simulated material tensile tests in the three global directions 1, 2 and 3. Normal displacements ui were applied to each corner nodes of the faces F2, F4 and F5 while the opposite faces F1, F3 and F6 were fixed in the three directions. For example, in the 1-direction, the corner nodes of F1 are fixed in the three directions, while identical displacements u1 were applied at each nodes of F2 in the 1-direction. The displacement of the corner nodes of F2 was also prevented in the directions 2 and 3 as shown in Figure 4-7-a. These axial loadings enable the determination of the three elastic moduli E1, E2 and E3 and the Poissons ratio 12, 13 and 23. The shear strains were simulated by applying tangential displacements uj to each corner nodes of the faces F2, F4, F5 while the opposite face F1, F3 and F6 were -102-

constrained in the three directions. For example for the shear load in the 1-2 direction, the corner nodes of F1 were fixed in the three directions, and the corner nodes of F2 were subjected to a displacement u2 in the 2-direction. The corner nodes of F2 were also constraint in the directions 1 and 3 as shown in Figure 4-7b. These shear loads allow the determination of the shear moduli G12, G13 and G23. Finally, an increase in temperature from 25C to 150C was applied to the unit cell models in order to determine the coefficients of thermal expansion in the three global directions. Each corner nodes of the faces F1, F3 and F6 were fixed in the direction 1, 2 and 3 respectively as shown in Figure 4-7-c.

4.3

Thermomechanical properties

4.3.1.1 Elastic properties Using the Hookes law, the constant of the stiffness matrix were first determined:

Eq. 4-16

For each loading cases, knowing the applied axial displacement ui or tangential displacement uj, and the dimension of the unit cell li, the applied strain to the unit cell, ij, was determined as follows: Eq. 4-17 The stresses were calculated by dividing the reaction forces obtained at the fixed corner nodes by the area of the face they belong. Eq. 4-18

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Once all the independent constants of the stiffness matrix were calculated, the stiffness matrix was inversed to obtain the compliance matrix. From the compliance matrix, the elastic moduli, shear moduli and Poissons ratio can be extracted using Eq. 4-19.

Eq. 4-19

4.3.1.2 Coefficients of thermal expansion The coefficient of thermal expansion in the ith-direction, CTEi, is the ratio between the strain in the ith-direction, below: Eq. 4-20 Similarly as mentioned previously, the strain was calculated using Eq. 4-17, where the displacement ui,j corresponds to the measured displacement at the corner nodes due to the thermal load. , and the variation in temperature, T, as expressed

Table 4-6 presents the values of the elastic and shear moduli, Poissons ratios and coefficients of thermal expansion, obtained numerically with the method described above, in the case of the unidirectional unit cell. The material properties of the carbon fibre and the epoxy resin, listed in Table 4-2, were used as input for -104-

the finite element model. As expected, the elastic and shear moduli increase with an increase in the fibre volume fraction, whereas the coefficients of the thermal expansion decrease with an increase in fibre volume fraction. Table 4-6: Comparison of the numerical and analytical values obtained for the nine engineering constants and the coefficients of thermal expansion of the unidirectional unit cell Vf = 86%

Numerical results Theoretical values

Vf = 77%

Numerical results Theoretical values

Vf = 70%

Numerical results Theoretical values

E1 (GPa) E2 (GPa) E3 (GPa) 12 13 23 G12 (GPa) G13 (GPa) G23 (GPa) CTE1 (x10-6 C-1) CTE2 (x10-6 C-1) CTE3 (x10-6 C-1)

198.18 14.83 14.82 0.300 0.300 0.354 10.47 10.45 5.49 -0.57 14.32 14.32

198.23 11.87 11.87 0.300 0.300 6.42 6.42 -0.58 16.88 16.88

177.95 11.73 11.73 0.300 0.300 0.356 6.78 6.78 4.33 -0.47 19.44 19.44

177.81 9.16 9.16 0.300 0.300 4.41 4.41 -0.47 22.58 22.58

161.76 9.98 9.98 0.300 0.300 0.362 5.29 5.29 3.66 -0.37 23.50 23.50

161.93 7.78 7.78 0.300 0.300 3.55 3.55 -0.38 27.01 27.01

The numerical property values were compared to the analytical values obtained with the strength material approach presented in CHAPTER 2, section 2.1.2. As expected the analytical values underestimate the material mechanical properties in the transverse direction, and good agreements were found in the longitudinal direction. The stress distributions for the unidirectional unit cell at 70% fibre volume fraction are presented in Figure 4-8 for the axial and shear loadings. Similar stress distributions were observed at 77% and 86% fibre volume fractions. -105-

Figure 4-8: Axial and shear stress distributions of the unidirectional unit cell at 70% fibre volume fibre

These elastic constants and coefficients of thermal expansion, obtained from the unidirectional models, were used as input for the yarn properties at different fibre volume fractions in the crossply and 5-harness satin models.

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The material properties of the epoxy resin listed in Table 4-2 were used as input for the resin properties for the finite element models. In those models, the yarn fibre arrangement was assumed to be hexagonal, and the yarn fibre volume fractions different from 1. Therefore, as explained previously, the material properties of the unidirectional models, listed in Table 4-6, were used as input for the fibre properties in the finite element models. Table 4-7: Engineering constants and coefficients of thermal expansion obtained for the crossply unit cell for different fibre volume fractions Vf = 62% Yarn Vf E1 (GPa) E2 (GPa) E3 (GPa) 12 13 23 G12 (GPa) G13 (GPa) G23 (GPa) CTE1 (x10-6 C-1) CTE2 (x10-6 C-1) CTE3 (x10-6 C-1) 86% 76.78 76.78 9.93 0.037 0.369 0.369 4.96 3.60 3.60 1.75 1.76 35.77 Vf = 55% 77% 68.83 68.83 8.71 0.035 0.374 0.374 3.91 3.09 3.09 2.12 2.14 41.51 Vf = 50% 70% 62.29 62.29 7.94 0.035 0.380 0.380 3.36 2.77 2.77 2.50 2.52 46.09

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Table 4-8: Engineering constants and coefficients of thermal expansion obtained for the 5-harness satin unit cell for different fibre volume fractions Vf = 62% Yarn Vf E1 (GPa) E2 (GPa) E3 (GPa) 12 13 23 G12 (GPa) G13 (GPa) G23 (GPa) CTE1 (x10-6 C-1) CTE2 (x10-6 C-1) CTE3 (x10-6 C-1) 86% 74.24 74.31 9.50 0.059 0.380 0.380 7.32 3.32 3.32 1.62 1.62 37.55 Vf = 55% 77% 65.95 65.95 8.42 0.056 0.384 0.384 4.95 2.91 2.91 2.04 2.03 42.92 Vf = 50% 70% 59.44 59.44 7.72 0.054 0.388 0.388 3.97 2.65 2.65 2.49 2.48 47.31

Table 4-7 and Table 4-8 present the engineering constants and the coefficients of thermal expansion of the crossply unit cell and the 5-harness satin unit cell respectively. As expected, the properties of the crossply and the 5-harness satin are orthotropic with E1=E2, 13=23, G13=G23 and CTE1=CTE2. In both cases, the elastic properties of the unit cells increased with an increase in the fibre volume fraction, whereas the coefficients of thermal expansion decreased with Vf. The stress distributions, in the case of axial and shear loadings, of the crossply and 5HS unit cells at 50% fibre volume fraction are presented in Figure 4-9 and Figure 4-10 respectively. Similar stress distributions were observed at 55% and 62% fibre volume fractions.

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Figure 4-9: Axial and shear stress distributions of the crossply unit cell at 70% fibre volume fraction

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Figure 4-10: Axial and shear stress distributions of the 5-HS unit cell at 70% fibre volume fraction

Figure 4-11 to Figure 4-15 compare the value of the elastic moduli, the shear moduli, Poissons ratios and the coefficients of thermal expansion obtained for the crossply and 5-harness satin unit cells. From Figure 4-11, it can be noticed that the in-plane elastic moduli, E1 and E2, are slightly smaller for the 5-harness satin unit cell than for the equivalent unidirectional crossply unit cell. This is due to the fibre undulation that reduces the fibre strength in the in-plane directions. No difference between the two unit cells was noticed for the through-thickness elastic modulus E3 because of the matrix-dominated behaviour in that direction. On the other hand, the in-plane shear modulus G12 is noticeably higher for the 5harness satin than for the crossply as shown in Figure 4-12. This behaviour is caused by the yarn interlacing in the 5-harness satin woven reinforcement. As for the through-thickness elastic modulus, the out-of-plane shear moduli, G13 and G23, are comparable for the crossply and 5-harness satin composites. An in-plane -110-

modulus of 64 GPa and an in-plane shear modulus of 4.3 GPa were determined experimentally by the manufacturer for a 55% fibre volume fraction carbon epoxy laminate with the CYCOM 890RTM epoxy resin and a 5HS woven fabric with similar properties to the G30-500 6k carbon fibre. These experimental values are similar to the one obtained numerically. As presented in Figure 4-13, the in-plane 5-harness satin Poissons ratio values, 12, are higher than those of the corresponding crossply laminate at the same Vf, again as a result of the fibre undulation. Similarly the out-of-plane Poissons ratio values, 13 and 23, are higher for the 5-harness satin composite than the crossply unit cell. Finally, concerning the thermal properties presented in Figure 4-14 and Figure 4-15, the 5-harness satin laminate gives slightly higher through-thickness CTEs than the crossply laminate, and comparable in-plane CTE were observed.

Figure 4-11: Elastic modulus comparison for the crossply unit cell and the 5harness satin unit cell

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Figure 4-12: Shear modulus comparison for the crossply unit cell and the 5harness satin unit cell

Figure 4-13: Poissons ratios comparison for the crossply unit cell and the 5harness satin unit cell

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Figure 4-14: In-plane coefficients of thermal expansion comparison for the crossply unit cell and the 5-harness satin unit cell

Figure 4-15: Through-thickness coefficients of thermal expansion comparison for the crossply unit cell and the 5-harness satin unit cell

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These results are in agreement with previous experimental and numerical studies on the thermomechanical behaviour of plain weave fabric composites by Naik and Ganesh [79-82]. Their investigation demonstrates that the thermomechanical properties of plain weave laminate are dependent of the architecture strand crimp and the gap between adjacent strands. Lower strand crimp results in lower CTE values for the plain weave laminate compare to the crossply laminate and the Youngs modulus of woven laminate with small gap is slightly smaller than the one the of crossply laminate with the corresponding Vf. The 5-harnes satin model can be considered as a low strand crimp woven laminate, and therefore the results obtained agree well with those conclusions. The coefficients of thermal expansion were also measured experimentally. Four 5-harness satin plies laminate, with the layup [(0/90)(90/0)]s was manufactured by RTM. The fibre volume fraction, Vf, was related to the cured specimen thickness using Eq. 4-2. The sample thickness was measured at three to five different locations with a calliper. A fibre volume fraction of 59.4% was determined. Using a precision diamond saw, the laminate was cut into 12x12 mm unit cells. Then, TMA tests were carried out to measure the coefficients of thermal expansion in the three directions. A force of 0.05N was applied to the probe to ensure a constant contact with the composite sample. Three cycles from room temperature up to 220C, then back down to room temperature, at a rate of 3C/min were performed for each sample. The results are reported in Table 4-9 and Figure 4-14 and Figure 4-15. The experimental values are greater than the numerical values but remain in the same order of magnitude. This difference might be because the fibre volume fraction of the laminate manufactured by RTM is smaller than the one calculated by Eq. 2-25, due to the presence of voids or resin rich areas.

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Table 4-9: Experimental values of the coefficients of thermal direction obtained by TMA for a 5-Harness satin unit cell with Vf = 59.4% CTE Test 1 Heating 2 Cooling 2 Heating 3 Cooling 3 Heating 2 Cooling 2 Heating 3 Cooling 3 CTE1 (x10-6 C-1) 3.337 3.140 3.132 3.110 2.997 3.000 2.975 3.081 3.096 0.1169 CTE2 (x10-6 C-1) 3.669 3.765 3.733 3.730 3.563 3.441 3.503 3.492 3.612 0.1272 CTE3 (x10-6 C-1) T<Tg 52.98 52.12 56.03 54.69 53.95 1.746 CTE3 (x10-6 C-1) T>Tg 178.6 188.4 190.3 191.6 187.2 5.907

Test 2

4.3.4 Evolution of the 5-HS unit cell stresses during the cure cycle

Using the finite element software ABAQUS and the COMPRO Component Architecture (CCA), the evolution of the stresses in the 5-harness satin unit cell during a typical cure cycle of the epoxy resin can be predicted. A heat transfer analysis was first performed, followed by a stress analysis. The stress/displacement elements (C3D8), used for the stress analysis, were replaced by 8-node linear brick heat transfer elements (DC3D8) in the heat transfer analysis. This type of element only has the temperature as degree of freedom. The simulated cure cycle was two hours at 180C followed by a cool down to 25C at 1C/min. The material constitutive models of the one-part epoxy resin, CYCOM 890RTM, developed in CHAPTER 3, were implemented in the COMPRO CCA material database. The properties of the yarn, presented in Table 4-6, were used as the fibre properties in the finite element model. Figure 4-16 to Figure 4-18 show the stresses in the x-, y-, and z-directions at different times for a 5-HS unit cell with a 50% fibre volume fraction and 70% yarn fibre volume fraction. In order to -115-

observe the state of stress inside the unit cell, the model was cut in two along the (yz) plane. Before the gel point, no stresses were present in the unit cell. Small compressive stresses arose after the gel point due to the resin shrinkage at the fibre overlap. The compressive stresses increased during the isotherm with a maximum compressive stress around -20 MPa at the end of the temperature hold in the three directions. At the end of the cure cycle, the fibres remained in compression with stresses around -50 to -100 MPa. The resin is in tension in the in-plane direction and in compression in the through-thickness direction. Similar results were obtained for the 55% and 62% fibre volume fraction 5-HS unit cell.

Figure 4-16: Stresses in the three directions of a half 5-HS unit cell (Vf = 50%) at the gel point (t = 70 minutes) -116-

Figure 4-17: Stresses in the three directions of a half 5-HS unit cell (Vf = 50%) at the end of the isotherm (t = 120 minutes)

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Figure 4-18: Stresses in the three directions of a half 5-HS unit cell (Vf = 50%) at the end of the cool down (t = 275 minutes)

can be as well

estimated using the dimension variations of the unit cell li during the cure as

Eq. 4-21 where l is the unit cell initial dimension, l is the change in dimension between the gel point and the end of the isotherm and the subscript i represent the principal directions x, y and z.

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The composite shrinkage coefficients of the 5-harness satin unit cell, for the three fibre volume fraction investigated, are reported in Table 4-10. Due to the influence of the fibres, the in-plane composite shrinkage coefficients are small. In the direction 3, the behaviour of the composite is dominated by the resin. Therefore, the composite shrinkage coefficient is greater in that direction, and decreases as the fibre volume fraction increases. Table 4-10: Composite shrinkage coefficients for the 5-harness satin unit cell at 62%, 55% and 50% fibre volume fractions Vf = 62% Yarn Vf

c,1 c,2 c,3

4.4

In this chapter, the thermomechanical properties of 5-harness satin woven laminate were investigated and compared to an equivalent unidirectional crossply laminate using a micromechanical approach. Various fibre volume fractions were investigated corresponding to typical volume fraction used in the RTM process. The following trends were observed: 1) Elastic modulus: due to the fibre waviness, the in-plane moduli of the 5-harness satin laminate, E1 and E2, are a slightly smaller than a unidirectional crossply laminate with the same fibre volume fraction, and the through-thickness moduli, E3, are very comparable. 2) Shear modulus: the in-plane shear modulus of the 5-harness satin laminate, G12, is noticeably higher than the crossply one, especially with for high fibre volume fraction because of the yarn interlacing effect. The out-of-plane shear moduli, G13 and G23, remain comparable. -119-

3) Poissons ratio: because of the fibre undulation, the in-plane 5-harness satin Poissons ratio, 12, is higher than the corresponding crossply laminate at the same Vf. The out-of-plane Poissons ratio, 13 and 23 are comparable for the two unit cells. 4) Coefficient of thermal expansion: the 5-harness satin laminate gives a slightly higher through-thickness CTEs than the crossply laminate and a comparable in-plane CTE. These results demonstrate that the properties of the 5-harness satin woven fabric and the equivalent unidirectional crossply laminate are slightly different but overall comparable. This validates the use of the properties of unidirectional fibre to model the behaviour of this type of fabric architecture. Using the ABAQUS/COMPRO CCA platform, the evolution of the stress in the 5-harness satin unit cell was also predicted and the composite shrinkage coefficients were determined. The thermomechanical properties of the unidirectional fibre with a YVf of 70% will be therefore implemented with the detailed properties of the resin in the ABAQUS/COMPRO CCA platform in order to predict the properties of a 5harness satin carbon/epoxy composite structure at 50% fibre volume fraction.

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This chapter focuses on the influence of the tool-part interaction on the processinduced stresses. As explained in CHAPTER 2, section 2.2.3, most of the studies investigating the tool-part interaction focused on open mould process (i.e autoclave or vacuum bag processes) whereas few studies have been conducted on the effect of tool-part interaction for closed mould processes such as RTM. However, the interaction between the mould and the laminate is quite different for these two processes as shown in Figure 5-1.

Figure 5-1: Schematic representation of the open and closed mould processes, a) before the cure, b) at the end of the cure

Autoclave or vacuum bagging processes consist of a flexible membrane and a solid mould whereas the RTM process consist of two solid moulds with a constant -121-

cavity volume. At the beginning of both processes, the laminate and the mould cavity have the same thickness t0. In the case of the autoclave process, an external pressure Pa is applied to the flexible membrane during the entire cure cycle, leading to a compaction of the laminate. The contact between the composite structure and the solid mould is maintained until the end of the cure cycle. For the RTM process, the pressure is applied to the resin through the injection pressure, Pinj, at the beginning of the cure cycle. During the cure, the resin cure shrinkage decreases the laminate thickness to a value t. As the mould cavity remains constant with a thickness t0, this can lead to a loss of contact between the mould and the composite part and poor surface finish [100, 141]. This phenomenon does not happen in the autoclave process due to the autoclave pressure Pa applied continuously to the flexible membrane and compensates for changes in laminate thickness. This difference of the tool-part interaction mechanism might have an influence on the process-induced stresses and laminate deformations. Therefore the tool-part interaction was investigated in the RTM process using fibre Bragg grating optic sensors and then modelled using finite element method. The experiments were carried out at the laboratory of Polymer and Composite Technology from the cole Polytecnique Fdrale de Lausanne (EPFL) in Switzerland.

5.1

Strain gauges are a common method to measure the strain development throughout the cure cycle [92, 109]. However, it is difficult to embed the strain gauges into composite laminates and they are usually mounted on the tool. Alternatively, fibre optic sensors appear to be an interesting method to measure in-situ, the development of the residual strains during composite manufacturing [111, 125, 142-148], as well as the material transition (gel point, glass transition) [143] or the degree-of-cure [149]. Their advantage over strain gauges is that they can be easily integrated in the composite at the performing stage of the manufacturing. Small and non-intrusive, they have also a minimal impact on the -122-

mechanical properties of the composite. Different kind of fibre optic sensors can be used, such as fibre Bragg grating (FBG) sensors [111, 125, 143, 147, 148], extrinsic Fabry-Perot interferometric (EFPI) sensors [142, 144, 146, 149] or FBG/EFPI hybrid sensors [145]. In this work, FBG sensors were used to measure the development of internal strain in a composite laminate manufactured by RTM, as the cure progresses.

A fibre Bragg grating (FBG) sensor is an optical fibre with a periodic modification of the core refractive index along the fibre. A phase mask technique is commonly used to imprint the periodic pattern to the optical fibre. This technique uses the optical fibre photosensitivity property: by exposing an optical fibre under ultraviolet light, its refractive index can be modified permanently. Figure 5-2 details the phase mask technique. A piece of silica glass, transparent to ultraviolet light, with a grating pattern with a period of mask on one side is used as a phase mask. When ultraviolet light passes through the mask, it is diffracted by mask grating pattern. When the UV diffracted beams reach the optical fibre, they photoimprint, i.e. change locally its refractive index, with a grating period B, equal to half of the pattern period ( ). Then, when a source of light is connected to the optical fibre with a FBG, only a narrow-band of the signal is reflected with the Bragg wavelength B, given by [150]: Eq. 5-1 where n is the effective refractive index of the core and B is the grating period.

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Any change in the optical fibre properties which varies the grating period or the refractive index, such as strain or temperature, will then change the Bragg wavelength. In the case of an axial applied strain app and a temperature change T, the Bragg wavelength shift B can be related to both the temperature T and the strain , as follows: Eq. 5-2 where K and KT are the strain and temperature sensitivities of the optic sensor and f is the fibre optic coefficient of thermal expansion. When the FBG optic sensor is embedded in a host structure of a different material, such as a composite laminate, and assuming a perfectly bounded interface between the two, the thermal strain of the host structure can influence the response of the FBG sensor [111]. Eq. 2-25 can be then modified as follows: Eq. 5-3

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where tot is the total strain transferred to the optical fibre and th is the thermal strain experienced by the host material that can be expressed in the following manner: Eq. 5-4 where CTEH is the coefficient of thermal expansion of the host material.

5.2

Experimental procedure

Radial injections were carried out at constant pressure in a rectangular steel mould to manufacture carbon/epoxy laminates with a 50% fibre volume fraction and the following dimensions: 34.5 cm x 24.5 cm x 0.2 cm. Figure 5-3 and Figure 5-4 present the mould and the RTM set-up. Six heating cartridges on each side of the mould (top and bottom) were used to apply the desired cure cycle. The mould surface was treated with release agent (Frekote 770-NC) and flexible silicone joints were used to seal the mould. Five plies of 5-harness satin G30-500 6k carbon fabric [134, 135] were stacked with the following layup [(0/90)(90/0)(0/90)(0/90)(90/0)]. The preform was debulked 30 minutes under vacuum to remove the eventual entrapped air. Once the preform was placed into the mould, the mould was closed and the system was preheated at 180C prior the resin injection. Vacuum was as well applied to the mould cavity in order to facilitate the resin injection. The CYCOM 890RTM one-part epoxy resin [129] was not degassed before the injection but preheated at 80C in the injector to reach its optimal viscosity and injected in the mould with injection pressure of 0.35MPa. The filling time was less than 5 minutes for all injected plates. Two cure cycles were applied as shown in Figure 5-5: Cure cycle 1 : 2 hours isotherm at 180C (CYCOM 890RTM epoxy typical cure cycle) Cure cycle 2: two holds cure cycle, 2 hours at 170C following by 30 minutes at 190C. -125-

The cure cycle 2 was designed so that the resin reaches the gel point during the first temperature hold and to determine the influence of the cure cycle on the development of the internal strain. Two plates were manufactured for each cycle.

Figure 5-3: RTM steel mould: a) mould opened, b) perform inside the mould

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After the cure, the laminates were placed in an oven and subjected to a set of 15 minutes isotherms at 35C, 50C and 70C with 1C/min temperature ramp in -127-

between. Using the FBG already embedded in the laminate, the strain variation was measured during these particular conditions in order to determine the coefficient of thermal expansion of the cured laminate.

The FBG sensors were provided by Technica SA. Their initial wavelength was 1562 0.5 nm with a bandwidth inferior to 0.3 nm, and a diameter of 210 5 m. Their strain and temperature sensitivity (K and KT) were 7.7x10-7 -1 and 6.92x10-6 C-1 respectively. Previous studies reported a decrease in the fibre optic response followed by a stabilisation while ramping up the temperature [151]. In order to assure the thermal stability of the Bragg wavelength with temperature, a preconditioning or pre-annealing is then necessary. It consists of heating the FBG in an oven at elevated temperature to accelerate the decay phenomenon and reach the moment where the Bragg wavelength remains stable with temperature. As the curing temperature of the composite is 180C, the FBG sensors were preconditioned 24 hours at 200C in an oven before use. Figure 5-6 shows a FBG sensor after preconditioning.

After the preconditioning, the initial optical fibre wavelength, B0, was recorded prior embedding the sensor in the laminate. For each laminate, three FBG sensors were positioned at the center of the laminate, through the thickness of the -128-

laminate, at the bottom, middle and top surface, as shown in Figure 5-7. A thermocouple type K was also placed in the mould cavity to monitor the temperature of the composite part inside the mould. An optical sensing interrogator sm125-500 from Micron Optics was used to monitor the variation of the FBG wavelength B during the entire cure.

5.3

Experimental results

For each cure cycle, two plates were manufactured. However, in some cases, the connection between some of the FBG and the optical sensing interrogator failed during the experiment and the wavelength variation was not recorded entirely. Therefore, in the following, only the experiments where the data of the three FBG were completely recorded are presented. Nevertheless, the experiments with the partial data were compared to the one with the full set of data, and showed good agreement.

Figure 5-8 presents the wavelength variation of the three FBG sensors during the entire cure cycle. The wavelength variation was set to zero at the beginning of the recording (t=0 minutes). First, the wavelength increased as the mould heated-up and the sensors expanded with the temperature. Then a decrease in the wavelength was observed at the injection due to the temperature gradient between the mould and the resin. As the resin was colder than the mould, the sensors contracted when -129-

the resin reached them. During the isotherm, the wavelength remained constant and it decreased at the cool down. A wavelength discontinuity was observed at around 250 minutes in the cool down which corresponds to a separation of the composite from the mould, as explained in the following.

Figure 5-8: FBG sensor relative wavelength variation and temperature during cure cycle 1 Using Eq. 5-3, the total strain variations (tot) in the laminate during the cure were calculated and plotted in Figure 5-9. During the mould heat-up stage, before the resin injection, the FBG sensor is not bonded to the dry fibres. As there is not fixed contact points between the sensor and the fabric, the strain occurring in the fabric might not be totally transferred to the FBG, and the measured strain might not be consistent and reliable. For these reasons, the strains were then set to zero at the beginning of the injection as shown in Figure 5-10. Also, once the resin is injected, the strain transfer between the composite and the FBG sensor might not be optimum up to the gel point, as the resin acts as a viscous liquid before that point. Thus the data provided by the FBG sensors before the gel point have to be -130-

used with caution. For this epoxy resin, the gel point occurs around 70 minutes after the injection at 180C.

Figure 5-10: In-situ strain variation from the injection to the end of cure cycle 1

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Overall, the composite remained in compression during the cure. Small compressive strains were introduced in the laminate at the injection (around -50 ). Then the strain remained constant during the two hour isotherm at 180C. Since the FBG sensors captured the in-plane strains, the resin shrinkage was not clearly observable. During the cool down, a strain discontinuity was observed at around 250 minutes or 150C. This behaviour corresponded to the composite plate separation from the mould because of the coefficient of thermal expansion (CTE) mismatch between the composite and the steel tool. Figure 5-11, showing the strains as a function of temperature confirmed this assumption. The evolution of the strain with the temperature was linear with two different slopes before and after the discontinuity. A slope of 15.3x10-6 C-1, corresponding to the CTE of steel, was measured before the discontinuity (150C<T<180C). The slope changed to 4.46x10-6 C-1 after the discontinuity (25C<T<150C). This value is in the order of magnitude of the in-plane coefficient of thermal expansion of the composite with a 50% fibre volume fraction (CTE1 = 2.49x10-6 C-1, CTE2 = 2.48x10-6 C-1), as seen in CHAPTER 4, Table 4-8. Thus, during the cool down, the composite followed the thermal contraction of the steel mould until the shear stress at the interface mould/composite becomes too high and the laminate separated from the mould. A similar phenomenon was as well observed for laminate manufactured by the autoclave [111]. At the end of the cool down, the composite remained in compression with the value of the residual strain around 700 .

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Figure 5-11: In-situ strain variation with the temperature for cure cycle 1

From Figure 5-10, the strain variation at the top and middle of the laminate appeared to be slightly higher than in the bottom of the laminate. However, this observation was not repeatable from one laminate to another. Actually, the FBG response can be also influenced by the FBG position and its local interaction with the woven fabric. For example, the alignment of the FBG with respect to the fibre orientation has an influence on the strain measurement. This parameter is difficult to control in the RTM process as the resin flowing in the preform can modify the FBG initial position. Therefore, in that case, we can assume that the alignment of the middle FBG sensors was slightly different from the top and bottom ones. As the plate is only 2 mm thick, the strain variation at different position through the thickness should be similar.

The same approach was applied to the cure cycle 2. The influence of the cure cycle on the development of the internal strain was then observed. Figure 5-12 presents the relative wavelength variation for the cure cycle 2. Similarly as in cure -133-

cycle 1, the wavelength increased first as the mould temperature increased. Then a small decrease in wavelength is observed when the resin is injected into the mould. The wavelength remained constant during the first isotherm at 170C and increased as the temperature increased to the second isotherm at 190C. During the cool down, the wavelength decreased, and a discontinuity was observed at around 350 minutes. Using Eq. 5-3, the strain variation was then extracted and set to zero at the injection, as shown in Figure 5-13. Small compressive strains around -50 were introduced at the injection. The strain remained constant during the first isotherm, and increased at the second hold due to the part expansion with temperature. During the cool down, a stain variation is noticed at around 350 minutes or 150C that again corresponded to the separation of the composite from the mould. The debonding occurred at the same temperature as for the cure cycle 1. The evolution of the strain with the temperature in Figure 5-14 also confirms this behaviour. From 190C to 150C, the composite behaved similarly as the steel mould with a thermal expansion of 12.6x10-6 C-1. After the discontinuity, from 140C to 25C to thermal expansion changes to 4.34x10-6C-1, which is in the order of magnitude of the in-plane composite CTE as seen previously. At the end of the cool down, the composite remained in compression with the value of the residual strain around -700 . As suggested previously, the difference between the strain measurements through the thickness might be due to a change of the FBG position at the injection or during the cure cycle.

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Figure 5-12: FBG sensor relative wavelength variation during cure cycle 2

Figure 5-13: In-situ strain variation during cure cycle 2 from the injection to the end of the cool down

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Figure 5-14: In-situ strain variation with the temperature for the cool down of cure cycle 2

Figure 5-15: Comparison of the strain variation at the laminate mid-thickness for the two cure cycles.

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Figure 5-15 compares the strain variation obtained for the two cure cycles at the laminate mid-thickness. The change in cure cycle did not seem to affect the laminate properties as well as the interaction between the mould and the composite plate. The debonding occurred at the same temperature and similar inplane strains were obtained at the end of the two cure cycles.

The laminates with the embedded FBG sensors were heated up in an oven and subjected to a succession of isotherms and temperature ramps at 1C/min. The measured strain and the temperature are plotted in Figure 5-16. Then the coefficients of thermal expansion were determined for each ramps as well as the cool down by measuring the slope of the strain with the temperature and were reported in Table 5-1. Overall, the in-plane coefficient of thermal expansion of the laminate (CTEc) was around 2.5x10-6 C-1. This value is in agreement with the inplane coefficients of thermal expansion obtained numerically with the 50% 5harness satin woven unit cell model reported in Table 4-8 (CTE1 = 2.49x10-6 C-1, CTE2 = 2.48 x10-6 C-1) and confirms the validity of the micromechanical approach used in CHAPTER 4. This value is lower than the value in the mould after the separation of the laminate from the mould (Figure 5-11 and Figure 5-14). Thus, it can be assumed that, after the separation, a small interaction between the laminate and the mould still remains as the apparent composite CTE in the mould is higher than the CTE obtained for a free standing laminate.

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Figure 5-16: Temperature and strain variation during the post-cure of the laminate

Table 5-1: Coefficient of thermal expansion measured at the post cure Laminate CTE (cure cycle 1) (C-1) FBG middle* FBG top* Heating ramp 1 Heating ramp 2 Heating ramp 3 Cool down Average

*

Laminate CTE (cure cycle 2) (C-1) FBG bottom* FBG top* 2.05 10-6 2.66 10-6 2.89 10-6 2.77 10-6 2.59 10-6 1.53 10-6 2.06 10-6 1.49 10-6 1.31 10-6 1.60 10-6

1.62 10-6 2.04 10-6 2.46 10-6 2.59 10-6 2.18 10-6

2.14 10-6 2.56 10-6 2.73 10-6 3.30 10-6 2.68 10-6

As the optical sensing interrogator had only four inputs, only two FBG per plate were linked to the device.

From these experiments, the maximum shear stress that the composite can sustain before the separation of the laminate from the mould can be determined. Figure 5-17 describes the development of the shear stress at the mould/composite interface, due to the difference in coefficient of thermal expansion between the mould and the composite. -138-

Figure 5-17: Shear stress formation due to the mismatch of the thermal expansion between the composite and the mould at the cool down

The shear stress is related to the composite in-plane stress C, which is related to the composite mechanical strain C,M by the composite Youngs modulus EC, as follows: Eq. 5-5 where t is the laminate thickness and L0 is the laminate length. The value of the elastic modulus, determined in CHAPTER 4 for the 5-harness satin woven unit cell at 50% fibre volume fraction (Table 4-8, E1 = 59.44GPa), was assumed to be the Youngs modulus of the composite Ec. The mechanical strain is the difference between the total strain C,tot measured by the top and bottom FBG sensors and the free thermal expansion C,TH as expressed below: Eq. 5-6

-139-

where CTEC is the in-plane coefficient of thermal expansion of the composite determined experimentally using the FBG and T is the temperature variation. The total strain corresponds to the maximum strain variation sustained by the laminate at the interface before the separation, and was measured as follows: Eq. 5-7 where tot,i and tot,f are the total strains measured by the top and bottom FBG sensors at the beginning of the cool down and before the strain discontinuity, as shown in Figure 5-10 and Figure 5-13. The different values obtained for the maximum shear stress were reported in Table 5-2. Using Eq.3, the residual stress in the composite were estimated around -20 MPa at the end of the process. Table 5-2: Maximum shear stress for the two cure cycle Maximum shear stress (kPa) Cure cycle 1 134 136 140 Maximum shear stress (kPa) Cure cycle 2 128 170 18

5.4

The RTM process and the tool-part interaction between the composite and the mould was then investigated numerically using the commercial finite element software ABAQUS and the COMPRO Component Architecture (CCA) subroutine. As explained in CHAPTER 2 section 2.3.4, a heat transfer analysis was first performed, followed by a stress analysis. In each analysis, three steps were defined: an isothermal cure, a cool down and the demoulding. The demoulding of the part was simulated by removing all the tooling element and constraints from the composite part.

-140-

A 2 mm thick composite plate and a steel rectangular mould were modelled using the actual dimensions of the RTM mould and the manufactured composite plate. Due to the problem symmetry, only one quarter of the system was analyzed as shown in Figure 5-18-a. A 1 cm gap between the mould and the composite sides was added to allow the composite part to expand and not exceed the tool boundaries (Figure 5-18-b). From Chapter 4, it was noticed that the properties of a 5-Harness fabric ply can approximate fairly well by an equivalent [0/90] noncrimp fabric. Therefore, five plies 5-Harness satin laminate [(0/90)(90/0)(0/90)(0/90)(90/0)] at 50% fibre volume fraction was modelled by ten unidirectional layers with the following layup [0/90/90/0/0/90/0/90/90/0]. At 0, the fibre were oriented in the length of the plate, as shown in Figure 5-18-c. Ten elements were used for each layer through the composite thickness. Threedimensional 8-node solid elements were used: DC3D8 for the heat transfer analysis and C3D8 for the stress analysis. The plate and the mould were meshed with 8160 and 8640 elements respectively.

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Figure 5-18: Composite plate and steel mould finite element model: a) finite element mesh of the laminate, b) finite element mesh of the mould and the laminate, c) close-up of the laminate finite element mesh in the mould, d) schematic position of the analyzed element

The material constitutive models of the one-part epoxy resin, CYCOM 890RTM, developed in CHAPTER 3, were implemented in the COMPRO CCA material data base. The properties of the fibre with yarn fibre volume fraction of 70%, developed in CHAPTER 4 (Table 4-6) were used as input in the finite element model and are presented in Table 5-3. The fibre properties were assumed constant and independent from the cure cycle. As the cure progresses, the thermoset resin evolves from a liquid state to a rubber state and finally a glass state. Therefore, three sets of properties (Liquid, Rubber and Glass) were used for the epoxy resin to account for these transformations for the elastic modulus and the coefficient of thermal expansion. For convergence purpose, the resin elastic modulus was set to -142-

13 MPa in the liquid state. A smaller modulus led to a non convergence of the simulation. As presented in CHAPTER 2, the resin was supposed to behave like a cure hardening instantaneous linear elastic (CHILE) material during the entire simulation. Table 5-3 presents also the properties of steel used for the RTM mould. Table 5-3: Material properties used as input for the FE models G30-500 6k CYCOM 890RTM Epoxy Resin Liquid Density (kg/m3) El (GPa) Et (GPa) Poisson ratio CTE l -6 (10 m/m.C) CTE t (10-6m/m.C) Max. volumetric shrinkage (%) 1220 1.3.10-2 1.3.10-2 0.2 350 350 Rubber 1220 0.2 130 130 Glass 1220 3.2 3.2 0.2 55 55 3.36 1790 162 9.92 0.3 -0.36 22 7833 230 230 0.2 12 12 Carbon Fibre (YFV=70%) Steel

5.4.3.1 Displacements In order to reproduce the model symmetry, the displacements of the nodes located on the symmetric planes (xz) and (yz) were fixed in the directions 2 and 1 respectively. The bottom corner node, located at the intersection of the two symmetric planes, was fixed in the direction 3 as well to prevent the possible rigid body motion. The top and bottom mould surfaces were fixed in the z-direction in order to simulate the press that kept the cavity thickness constant and the two-part mould fixed in the RTM process. The mould top surface constraint in the z-143-

direction was then removed during the cool down to allow the mould contraction. No initial pressure was applied to the mould or the composite part.

5.4.3.2 Temperature The two cure cycles (cure cycle 1 and cure cycle 2) applied in the experiment were used as temperature input for the numerical analysis. The temperature field was applied to the top and bottom element layer of the mould to simulate the heating cartridges. The heat was then transferred to the entire mould and the composite part by conduction. The mould was assumed adiabatic during the isotherm. During the cool down, the natural convection was applied by defining a heat transfer coefficient of 10 W/m2C on the mould external surfaces. The preform was assumed completely saturated with resin at the beginning of the simulation. In the experiment, the resin was injected at 80C in a mould preheated at 180C. Injection simulations using the software PAM-RTM showed that at the end of the injection, once the part was totally impregnated, the average temperature of the composite was around 160C. Therefore, in the process modelling simulation, the initial composite temperature was set at 160C to account for this initial temperature gradient and the initial mould temperature was set to the curing temperature at 180C. Finally, the injection simulation predicted a filling time less than 1 minute, which is too short for the resin to start reacting. Thus, the initial degree-of-cure of the epoxy resin was set to 0.001 in the curing simulation.

5.4.3.3 Contact interactions In the stress analysis, three different types of contact interaction were used to model different behaviours between the laminate and the mould. Model A: no bonding Model A analyzed the behaviour of the composite laminate alone, with no contact constraints. In this analysis, the mould was not modelled as shown in Figure 5-18-

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a, and the cure cycle was applied directly to the laminate. This analysis gives the behaviour of the composite plate in a free standing condition. Model B: perfect bonding Model B investigated the behaviour of a composite laminate perfectly bonded to the mould (Figure 5-18-b). This was ensured by having coincident and equivalent nodes at the interface between the composite part and the mould. Model C: frictional contact Model C examined the effect of contact interaction at the interface of the composite laminate and the mould (Figure 5-18-b). In order to take into account the possible interaction between the mould and the composite part, contact constraints were applied on the composite surfaces in contact with the mould. Contact constraints were defined as follows: hard contact relationships were applied to prevent the transfer of tensile stresses across the interface and minimize the surface interpenetration. A stick-slip behaviour was introduced using the classical isotropic Coulomb friction model, , and a shear stress limit

max. The Coulomb friction model expresses the critical shear stress crit at which

the surfaces in contact start to slide as a function of the pressure of contact P and the coefficient of friction . By introducing max, the sliding then occurs as soon as the magnitude of the equivalent shear stress reaches the minimum between max and P, , as shown in Figure 5-19. The maximum shear stress determined previously was used (Table 5-2) as the shear stress limit. From the literature review, the coefficient of friction was set to 0.3 [109].

Figure 5-19: Schematic representation of the critical shear stress evolution with a stick-slip behaviour -145-

For the different finite element models, the results were reported at the position A, located as shown in Figure 5-18-c. This position corresponded approximately to the experimental position of the FBG sensors and was representative of the strain variations of the composite structure. The temperature and degree-of-cure were analyzed at the centroid of the element located at the laminate mid-thickness. As three FBG sensors were positioned in the experimental set-up at the top, midthickness and bottom of the laminate, the computed total strains were analyzed similarly at the element centroid of the laminate top, middle and bottom layers. However, as the total strains were very similar for the three positions, only the total strain at the laminate mid-thickness was plotted in the graph for clarity purposes. Similarly, the strain in the mould at the top and bottom interface with the laminate were analysed but only the strain of top of the mould was plotted. The total strains included the thermal and mechanical strains.

5.4.4.1 Temperature and degree-of-cure Figure 5-20 and Figure 5-21 show the evolution of the predicted composite temperature and the degree-of-cure for the two cure cycles at the laminate midthickness. Using the DiBenedetto equation (Eq. 2-11) the glass transition temperature was also predicted. In both cases, a negligible cure exotherm was predicted (<1C during the isotherm). The gel point occurred at gel = 0.7 in the isotherm part at 69 minutes for the cure cycle 1 and at 105 minutes for the cure cycle 2. In both case, the vitrification occurs before the cool down, which means that at the end of the isotherms, the resin is in the glassy state. After the isotherm, the part cooled down slowly by natural convection. A maximum degree-of-cure of 0.97 and 0.99 was reached at the end of the cure cycle 1 and cure cycle 2 respectively. Also, as shown in Figure 5-22, the predicted temperatures were uniform over the entire mould and laminate during the cure cycle 1 and no degree-of-cure gradient was present in the laminate. Similar results were observed for cure cycle 2. -146-

Figure 5-20: Evolution of the temperature and the degree-of-cure at the laminate mid-thickness at the position A for cure cycle 1

Figure 5-21: Evolution of the temperature and the degree-of-cure at the laminate mid-thickness at the position A for cure cycle 2

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Figure 5-22: Temperature and degree-of-cure field at different times: 0 minutes, 60 minutes, 120 minutes, and 917 minutes

5.4.4.2 Strain results Cure cycle 1 Figure 5-23 and Figure 5-24 present the evolution of the total in-plane strains for the three different types of tool-part interactions (no bonding, perfect bonding, and frictional contact) for the cure cycle 1, while Figure 5-25 and Figure 5-26 show the total strain evolution in the through-thickness direction. In each case, the laminate expanded first as its temperature increased from 160C to 180C in less than two minutes. As the behaviour of the laminate in the through-thickness direction is dominated by the matrix, the expansion was 10 to -148-

20 times higher in that direction than the in-plane direction. In the in-plane direction, a greater expansion was noticed for the model C, where the frictional contact interactions were used, with a maximum in-plane strain of 190 and 270 in the directions 1 and 2 respectively. When the laminate was perfectly bonded to the mould in model B, the expansion was only 50 and 90 in the two inplane directions. Actually, in the case of the perfect bonding, the nodes at the interface mould/laminate share the material properties of the mould and the laminate. Therefore the mould prevented the composite expansion as its initial temperature was already set to the curing temperature (180C). On the other hand, using frictional contact properties allows the laminate to expand more as the interface is constituted of two nodes with independent properties. In the throughthickness direction, the maximum strain was obtained for the non bonded laminate (model A) with a free expansion of 10888 . For the model B and model C, a through-thickness strain around 4000 was reached, as the mould restrained the free expansion of the laminate. After 60 minutes into the cure, a decrease in the in-plane and through-thickness strains was observed (Figure 5-24 to Figure 5-27) corresponding to the resin shrinkage occurring after the gel point. Then, during the cool down, the temperature decrease led to a decrease in the inplane and through-thickness strains in the composite. From Figure 5-23, it can be noticed that in the case of a perfect bonding (model B), the laminate followed the contraction behaviour of the mould in the in-plane directions with a final total strain of -1760 . The free standing laminate (model A) contracted less with a final strain of -550 . For the model C, Figure 5-24, the evolution of the total strain during the cool down was situated in between the one obtained for model A and model B. No strain discontinuity was observed during the cool down. In the through-thickness direction, the laminate total strain for the perfect bonding and frictional contact models evolved similarly, and reached final total strains of 5200 and -5700 respectively.

-149-

Figure 5-23: In-plane strain evolution at the laminate mid-thickness for cure cycle 1 in the case of no bonding (model A) and perfect bonding (model B)

Figure 5-24: In-plane strain evolution at the laminate mid-thickness for cure cycle 1 using contact interactions (model C)

-150-

Figure 5-25: Through-thickness strain evolution at the laminate mid-thickness for cure cycle 1 in the case of no bonding (model A) and perfect bonding (model B)

Figure 5-26: Through-thickness strain evolution at the laminate mid-thickness for cure cycle 1 using contact interactions (model C)

-151-

Figure 5-27 to Figure 5-30 present the total strain evolution with the temperature in the in-plane and through-thickness directions at the laminate mid-thickness. Overall, the total strain decreased linearly with the temperature. Similar to the experimental section, the laminate thermal contraction was analysed by measuring the slope of the curve. In the in-plane direction, a slope of 3.6x10-6 C-1 was measured in the case of the model A, which is of the order of magnitude of the inplane coefficient of thermal the coefficient of the laminate with a 50% fibre volume fraction as seen previously. For the model B, the measured slope was 12x10-6 C-1 corresponding to the CTE of the steel mould. Therefore, in a case of perfect bonding (model B), the laminate behaved like the mould and followed its thermal contraction. When the frictional contact constraints were applied, a bilinear curve was noticed for the evolution of the composite strain with the temperature. Two slopes, 9.25x10-6 C-1 and 3.40x10-6 C-1 were measured before and after the inflection respectively. The value after the inflection is similar to the slope obtained in the model A and corresponds to the laminate CTE. The value obtained before the inflection is close to the CTE of the mould. Hence, during the cool down, the composite followed the thermal contraction of the steel mould until the shear stress at the interface mould/composite reached the maximum shear stress allowed and the laminate then debonded from the mould. The inflection corresponded to a transition from a bonded to a debonded laminate. In the through-thickness direction, the laminate behaved similarly for the three boundary conditions with a slope around 60x10-6 C-1, which is in the order of magnitude of the through-thickness composite CTE measured numerically in CHAPTER 4, Table 4-8 (CTE3 = 47.31 x10-6 C-1). The slopes obtained for the different models were summarized in Table 5-4.

-152-

Figure 5-27: In-plane strain evolution with the temperature at the laminate midthickness for cure cycle 1 in the case of no bonding (model A) and perfect bonding (model B)

Figure 5-28: In-plane strain evolution with the temperature at the laminate midthickness for cure cycle 1 using contact interactions (model C) -153-

Figure 5-29: Through-thickness strain evolution with the temperature at the laminate mid-thickness for cure cycle 1 in the case of no bonding (model A) and perfect bonding (model B)

Figure 5-30: Through-thickness strain evolution with temperature at the laminate mid-thickness for cure cycle 1 using contact interactions (model C)

-154-

Table 5-4: Numerical curve gradients obtained with the different models for the in-plane and through-thickness strains for the cure cycle 1 Steel mould 1= 2= 3 Slope 1 (x10-6) Slope 2 (x10-6)

Temperature at the discontinuity

Model B 2 12 3 54 1

12 -

9.2 3.4

144 144

(C) The predicted in-plane strains where then compared to the experimental strains obtained with the FBG sensors. Figure 5-31 shows the comparison of the in-plane total strains with time at the laminate mid-thickness. Contrary to the predicted results, small compressive strains around -50 were introduced in the laminate after the injection. In the experiment, the mould and the preform were preheated at 180C, and the resin was then injected at 80C. Thus, when the resin reached the FBG sensors, the resin temperature was lower than the preform and mould temperature, leading to a contraction of the FBG sensors. In the numerical models however, the laminate was assumed fully impregnated at the beginning of the simulation with an initial temperature of 160C. As the initial mould temperature was set to 180C, the composite then expanded due to the positive temperature gradient. Also as mentioned previously, contrary to the measured results, no strain discontinuity was predicted for any of the three models. Nevertheless, during the cool down, the evolution of the strain predicted using frictional contact (model C) is similar to the evolution of the measured strain after the discontinuity. Figure 5-32 compares the in-plane total strain evolution with temperatures during the cool down obtained numerically and experimentally. The obtained experimental and numerical slopes are reported in Table 5-5. It can be observed from Figure 5-32 that model A and model B captured the trend of the strain evolution after and before the experimental discontinuity respectively. This confirms that the -155-

discontinuity corresponds to a separation of the laminate from the mould. Model C does not show a strain discontinuity but presents a transition from the composite behaviour before and after the strain change. The strain inflection occurs almost at the same temperature than the strain discontinuity. From these results, the frictional contact boundary conditions appeared to capture better the evolution of the in-plane composite strain measured by FBG sensors developed during the resin transfer moulding process.

Figure 5-31: Comparison of the in-plane strain evolution at the laminate midthickness for cure cycle 1 obtained experimentally and numerically in the case of no bonding (model A) and perfect bonding (model B) and frictional contact (model C)

-156-

Figure 5-32: Comparison of the in-plane strain evolution with temperature during the cool down at the laminate mid-thickness for cure cycle 1 obtained experimentally and numerically in the case of no bonding (model A), perfect bonding (model B) and frictional contact (model C)

Table 5-5: Comparison of the experimental and predicted curve gradients obtained with the different models for the in-plane strains Slope 1 (x10-6 C-1) Experiment Model A Model B Model C 15.3 3.6 12 9.2 Slope 2 (x10-6 C-1) 4.46 3.4 Temperature at discontinuity (C) 150 144

Cure cycle 2 Similar trends were observed for cure cycle 2. The evolution of the total in-plane and through-thickness strains for the three different types of tool-part interaction are reported in Figure 5-33 to Figure 5-36. In each case, the laminate expanded a -157-

first time as the temperature increased from 160C to 170C followed by a second time from 170C to 190C at 120 minutes. Similarly to cure cycle 1, a greater expansion was observed for model C in the in-plane direction with a maximum inplane strain of 410 and 480 in the directions 1 and 2 respectively at the second hold, compared to 295 and 325 in the two in-plane directions in model B. In the through-thickness direction, the maximum strain of 5444 was obtained for model A, corresponding to its free expansion. Due to the mould restriction, a through-thickness strain around 2000 was reached for the model B and model C. The resin shrinkage occurred then after 110 minutes into the cure as shown in Figure 5-35 and Figure 5-36. In that case, the gelation occurred at the end of the first isotherm. During the cool down period, the composite in-plane and through-thickness total strains decrease with the temperature. The final in-plane total strains were slightly higher than the one obtained with the cure cycle 1, whereas the through-thickness total strain were lower than the one obtained with cure cycle 1. Again no strain discontinuity was observed.

Figure 5-33: In-plane strain evolution at the laminate mid-thickness for cure cycle 2 in the case of no bounding (model A) and perfect bounding (model B) -158-

Figure 5-34: In-plane strain evolution at the laminate mid-thickness for cure cycle 2 using contact interactions (model C)

Figure 5-35: Through-thickness strain evolution at the laminate mid-thickness for cure cycle 2 in the case of no bounding (model A) and perfect bounding (model B)

-159-

Figure 5-36: Through-thickness strain evolution at the laminate mid-thickness for cure cycle 2 using contact interactions (model C)

The total strain evolution with the temperature in the in-plane and throughthickness directions at the laminate mid-thickness are presented in Figure 5-37 to Figure 5-40. Overall, the total strain decreased linearly with the temperature. The measured slopes are reported in Table 5-6. A behaviour similar to the one observed for the cure cycle 1 was found for the cure cycle 2. Model A and Model B correspond to the behaviour of a free laminate and a bonded laminate respectively. Model C shows a transition from a bonded to a debonded laminate as the slope evolves from 8.8x10-6 C-1 to 4.6x10-6 C-1 in the in-plane direction. The transition happened around 175C. In the through-thickness direction, the laminate behaved similarly for the three different conditions with a slope around 60x10-6 C-1, which is in the order of magnitude of the through-thickness composite CTE measured numerically in CHAPTER 4, Table 4-8 (CTE3 = 47.31 x10-6 C-1).

-160-

Figure 5-37: In-plane strain evolution with temperature at the laminate midthickness for cure cycle 2 in the case of no bounding (model A) and perfect bounding (model B)

Figure 5-38: In-plane strain evolution with the temperature at the laminate midthickness for cure cycle 2 using contact interactions (model C)

-161-

Figure 5-39: Through-thickness strain evolution with the temperature at the laminate mid-thickness for cure cycle 2 in the case of no bounding (model A) and perfect bounding (model B)

Figure 5-40: Through-thickness strain evolution with temperature at the laminate mid-thickness for cure cycle 2 using contact interactions (model C)

-162-

Table 5-6: Numerical curve gradients obtained with the different models for the in-plane and through-thickness strains during the cure cycle 2 Steel mould 1= 2= 3 Slope 1 (x10-6) Slope 2 (x10-6)

Temperature at the discontinuity

Model B 2 12 3 34 1

12 -

8.8 4.6

174 179

(C) The comparisons between the experimental and numerical values at the laminate mid-thickness for cure cycle 2, as a function of the time and the temperature variations, are presented in Figure 5-41 and Figure 5-42 respectively. As mentioned previously, no strain discontinuity was predicted for any of the three numerical models. Nevertheless, the model using a perfect bonding (model B) agrees reasonably well with the experiment up to the discontinuity. After the discontinuity, the evolution of the numerical strain using frictional contact (model C) is similar to the evolution of the measured strain. From the evolution of the strain with the temperature (Figure 5-42) and Table 5-7 that present the measured experimental and numerical slopes, it is clear that model A and model B captured again the trend of the strain evolution after and before the experimental discontinuity respectively. Model C shows a transition from the composite behaviour before and after the strain change; however, this transition happened at the higher temperature than in the experiment. This difference might be due to the way the resin is modelled in the simulation. In the numerical analysis, the resin was modelled as an elastic material. However, in reality, the resin behaves like a viscoelastic material, allowing the developed strain to relax before the vitrification. Thus, the mechanical strains generated as the gelled resin is heated up to the second hold of cure cycle 2, are not relaxed in the simulation. This induces an earlier separation of the composite from the mould compare to the -163-

experiment. Nevertheless, from these results, the frictional contact seems to better capture the evolution of the in-plane composite strain developed during the resin transfer moulding process and the eventual debonding measured by FBG sensors.

Figure 5-41: Comparison of the in-plane strain evolution at the laminate midthickness for cure cycle 2 obtained experimentally and numerically in the case of no bonding (model A) and perfect bonding (model B) and frictional contact (model C)

-164-

Figure 5-42: Comparison of the in-plane strain evolution with temperature during the cool down at the laminate mid-thickness for cure cycle 2 obtained experimentally and numerically in the case of no bonding (model A), perfect bonding (model B) and frictional contact (model C)

Table 5-7: Comparison of the experimental and predicted curve gradients obtained with the different models for the in-plane strains Slope 1 (x10-6 C-1) Experiment Model A Model B Model C 15.3 3.6 12 8.8 Slope 2 (x10-6 C-1) 4.46 4.6 Temperature at discontinuity (C) 150 175

-165-

5.5

In this chapter, the tool-part interaction between the laminate and the mould in the RTM process was investigated experimentally and numerically and the following conclusions can be underlined: 1) FBG sensors, embedded in the laminate, were successfully used to measure in-situ the composite in-plane strain evolution during the entire cure. They also captured the debonding of the composite from the mould occurring during the cool down due to the coefficient of thermal expansion mismatch between the laminate and the mould. 2) The maximum shear stress allowed before the debonding of the laminate from the mould was measured and estimated to be 140 kPa. 3) The tool-part interaction was modelled using three different boundary conditions: no bonding, perfect bonding and frictional contact. Only the frictional contact conditions applied at the interface between the laminate and the mould predicted the debonding occurring at the cool down of the cure cycle and described well the strain development in the composite laminate. The predicted separation occurred at the same temperature as the experimental one for cure cycle 1. These results demonstrate the capacity of predicting complex tool-part interactions using frictional contact constraints in finite element analysis.

-166-

In this chapter the different factors leading to process-induced strains and stresses and shape distortions studied previously, such as the resin cure-dependent properties and volumetric shrinkage (CHAPTER 3), the composite thermal strain (CHAPTER 4) and the tool-part interaction (CHAPTER 5) are taken into account simultaneously to compute the process-induced strains, stresses and deformations of a composite part manufactured by RTM. Structural shells parts are common in many fields such as aerospace, automotive or sport industries. Using metallic insert or bladder, such parts can be manufactured by RTM. However, it can be delicate as the internal mandrel can be difficult to extract from the shell composite structure. Hence, a hollow cylinder manufactured by RTM with a metallic insert was used as a case study and a demonstrator of the numerical capabilities. A three-dimensional finite element model based on ABAQUS/COMPRO CCA platform was used to analyze numerically the spring-in and thickness variation of a cylinder manufactured by RTM. The effect of the thermal strains and the volumetric chemical shrinkage was introduced in the analysis through the resin and fibre material constitutive models developed in CHAPTER 3 and CHAPTER 4. Frictional constraints were as well implemented to simulate the tool-part interactions as described in CHAPTER 5. The influence of the laminate layup and the mandrel material on the processinduced deformations was also investigated.

6.1

Numerical model

In order to simulate the RTM process a heat transfer analysis followed by a stress analysis were performed. Each analysis was divided in four steps. First an -167-

isothermal cure took place followed by a cool down. Then the demoulding of the part was simulated by removing the tooling elements (external mould and mandrel) and the constraints and boundary conditions on the mould. Finally, the cylinder residual stresses were released by removing one plane of symmetry to simulate a longitudinal cutting [152]. The cylinder deformation due to the stress release and the final thickness were then examined.

A 2 mm thick cylinder composite on a 10 cm diameter internal mandrel was modelled as shown in Figure 6-1. Only a quarter of the cylinder was analyzed due to the problem symmetry (Figure 6-1-a). The laminate was modelled with 8 plies and 50% fibre volume fraction. Eight elements were used through the composite thickness (Figure 6-1-b). Two unidirectional laminates, [0]8 and [90]8 and three symmetric angle-ply laminates [+/-/-/+]s with equal to 30, 45 and 60 were considered. At 0, the fibres were oriented in the axial direction of the cylinder (Figure 6-1-c). Three-dimensional 8-node solid elements were used: DC3D8 for the heat transfer analysis and C3D8 for the stress analysis. The plate was meshed with 6480 elements and the moulds were meshed with 9922 and 11858 elements for the external mould and the mandrel respectively.

-168-

Figure 6-1: Finite element models and boundary conditions: a) RTM finite element mesh, b) close-up of the laminate mesh, c) schematic position of the analyzed elements A and B

The properties of the composite material G30-500/CYCOM 890RTM, characterized previously in CHAPTER 3 and CHAPTER 4 were used. Similarly as in CHAPTER 5, the carbon fibre properties were taken with 70% yarn fibre volume fraction (Table 4-6). Table 6-1 summarizes the material properties used as input in the finite element models. The properties of steel were used for the external mould. In order to study the effect of the mandrel material on the residual stresses and deformations, steel and aluminum properties were applied to the mandrel. The steel and aluminum properties used in this study are also presented in Table 6-1.

-169-

Table 6-1: Material properties used as input for the FE models CYCOM 890RTM Epoxy Resin Liquid Density (kg/m3) El (GPa) Et (GPa) Poisson ratio CTE l (10-6m/m.C) CTE t (10-6m/m.C) Max. volumetric shrinkage (%) 1220 1.3.10 0.2 350 350 -2

Steel

Aluminum

Glass 1220 3.2 3.2 0.2 55 55 3.36 7833 230 230 0.2 12 12 2700 73 73 0.33 24.3 24.3 -

1.3.10-2

6.1.3.1 Displacements In order to reproduce the model symmetry, the displacements of the nodes located on the symmetric planes (xy), (xz) and (yz) were fixed in the directions 3, 2 and 1 respectively. These nodal constraints prevented as well the possible rigid body motion. During the isothermal step, the top external mould surface was also fixed in three directions in order to simulate the press that kept the cavity thickness constant and the two-part mould fixed. This last constraint was then removed during the cool down to allow the mould contraction. Finally, in the last step, in order to simulate the cylinder longitudinal cutting, the symmetric plane (xz) was removed.

6.1.3.2 Temperature The typical cure cycle for the epoxy system was used: 120 minutes isotherm at 180C followed by a cool down to 25C by natural convection. In a typical RTM process, the resin was injected at 80C in a mould preheated at 180C. Thus, the -170-

initial composite temperature in the finite element analysis was set to 160C in the simulation to account for this initial temperature gradient. The mould was assumed adiabatic during the isotherm. During the cool down, the natural convection was applied by defining a heat transfer coefficient of 10 W/m 2C on the mould external surfaces. The preform was assumed to be completely saturated with resin at the beginning of the simulation and the initial degree-of-cure of the epoxy resin was set to 0.001. Finally, no initial external pressure was applied to the mould.

6.1.3.3 Contact constraints As discussed in CHAPTER 5 section 5.3.4, contact constraints were applied on the composite surfaces in contact with the mould to take the tool-part interactions between the mould and the composite part. Frictional constraints as defined in section 5.4.3.3 were applied with a shear stress limit of 140 kPa and a coefficient of friction of 0.3. It was assumed that these contact conditions were the same for the aluminum mandrel. At the demoulding of the part, all the contact constraints were removed.

6.2

In all the finite element models, the results were observed at the positions A and B, located as shown in Figure 6-1-c. These positions were representative of the strain and stress variations of the composite structure. For both positions, in the thermal analysis, the temperature was analyzed at the nodes and the degree-ofcure was analyzed at the centroid of the element. In the stress analysis, the total strains and stresses were analyzed at the element centroid of the inner and outer layers of the composite part (Figure 6-1-b). The total strains include the thermal and mechanical strains.

-171-

Figure 6-2 and Figure 6-3 show the evolution of the predicted temperature and degree-of-cure at the top, center and bottom center of the composite during the cure cycle at the location A. A negligible cure exotherm was predicted (<1C during the isotherm) for the RTM process. The predicted temperatures were uniform over the entire part during the cure cycle and no degree-of-cure gradient was present. The gel point occurred after 70 minutes at gel = 0.7 in the middle of the isotherm as shown in Figure 6-4. The vitrification also happened in the isotherm, 40 minutes after the gelation, when the glass transition temperature goes over the curing temperature. After the isotherm, the part cooled down slowly by natural convection. A maximum degree-of-cure of 0.97 was reached at the end of the cure.

Figure 6-2: Predicted temperatures at point A at different locations through the composite thickness

-172-

Figure 6-3: Predicted degree-of-cure at point A at different locations through the composite thickness

Figure 6-4: Temperature, glass transition temperature and degree-of-cure evolutions for the RTM process at point A at the mid-thickness of the composite

-173-

Figure 6-5 to Figure 6-9 and Figure 6-10 and Figure 6-14 show the evolution of the total strains and stresses in the radial direction at the position A for the different laminates at the part interfaces: external mould/composite outer surface and mandrel/composite inner surface (Figure 6-1-b). The two angle-ply laminates [+30/-30/-30/+30]s and [+60/-60/-60/+60]s behaved similar to the [+45/-45/45/+45]s laminate and in the following only the significant difference in behaviour will be mentioned. In all cases, the composite expands first as its temperature increases from 160C to 180C from 0 to 2 minutes. A greater expansion for the 0 than the 90 laminate was noticed with a maximum radial strain of 3470 versus 1245 , respectively, as the presence of fibre in the hoop direction for the 90 laminate prevented the radial expansion [153]. The expansion of the 45 angle-ply laminate was situated in between with a radial strain of 3220 . Similar values to the 45 angle-ply laminate were found for the 30 and 60 angle-ply laminates. A decrease in the expansion was noticed as the ply angle became closer to the orientation at 90 due to the effect of the fibre in the hoop direction. This thermal expansion led to the development of compressive stresses in the tools as shown in Figure 6-10 to Figure 6-14. Compressive stresses were built up in the composite as well, as the external mould and the mandrel were preventing the composite expansion. As the radial strains were smaller for the 90 laminate, the resulting radial stresses remained also lower than the one in the 0 unidirectional and angle-ply laminates. The maximum radial stresses were around -22 MPa for the unidirectional laminate at 0 and the angle-ply laminates, and -9 MPa at 90. After 60 minutes of cure, a decrease in strain can be observed in Figure 6-8. This corresponds to the resin shrinkage strain occurring after the gel point. The shrinkage led to the release of the radial compressive stresses in the composite and the tools, but not enough to eliminate the contact between the composite and the moulds except for the [90]8 laminate. In that case, the radial stresses in the

-174-

laminate and the moulds became very low and the radial stress in the mandrel reached almost zero during the isotherm at 90 minutes. During the cool down after 120 minutes, the laminates contracted more than the steel tool as the radial strains in the composites remained lower than the radial strains in the mandrel and the external mould. As the temperature decreases, the radial stresses of the laminates decrease in magnitude, independently of the layup.

Figure 6-5: Radial strain evolution of the [0]8 laminate at the interfaces for the RTM process with a steel mandrel at position A

-175-

Figure 6-6: Radial strain evolution of the [90]8 laminate at the interfaces for the RTM process with a steel mandrel at position A

Figure 6-7: Radial strain evolution of the [+30/-30/-30/+30]s laminate at the interfaces for the RTM process with a steel mandrel at position A

-176-

Figure 6-8: Radial strain evolution of the [+45/-45/-45/+45]s laminate at the interfaces for the RTM process with a steel mandrel at position A

Figure 6-9: Radial strain evolution of the [+60/-60/-60/+60]s laminate at the interfaces for the RTM process with a steel mandrel at position A

-177-

Figure 6-10: Radial stress evolution of the [0]8 laminate at the interfaces for the RTM process with a steel mandrel at position A

Figure 6-11: Radial stress evolution of the [90]8 laminate at the interfaces for the RTM process with a steel mandrel at position A

-178-

Figure 6-12: Radial stress evolution of the [+30/-30/-30/+30]s laminate at the interfaces for the RTM process with a steel mandrel at position A

Figure 6-13: Radial stress evolution of the [+45/-45/-45/+45]s laminate at the interfaces for the RTM process with a steel mandrel at position A

-179-

Figure 6-14: Radial stress evolution of the [+60/-60/-60/+60]s laminate at the interfaces for the RTM process with a steel mandrel at position A

The separation of the composite cylinder from the mould can be noticed when the radial stresses at the interface of the mandrel or the external mould became almost zero. As shown in Figure 6-10 to Figure 6-14 and mentioned previously, the laminate oriented at 90 separated first from the mandrel during the isotherm at around 90 minutes due to the resin shrinkage. The 0 unidirectional laminate and the angle-ply laminates separated from the tool during the cool down. [0]8 debonded at around 302 minutes or 92C. The angle-ply laminates separated at 285 minutes, 352 minutes and 335 minutes for the 60, 45 and 30 ply angles respectively, as reported in Table 6-2. In that case, the separation of the composite from the tool was caused primarily by the difference in their coefficient of thermal expansion. Table 6-2 presents the coefficients of thermal expansion in the radial, hoop and longitudinal direction of the five laminates. The laminate CTEs were determined using the dimension variations li of the laminate generated by the FEA during the cool down as follows: -180-

Eq. 6-1 where the subscripts r, and L stands for the radial, hoop and longitudinal directions respectively, and l is the initial laminate length at the beginning of the cool down. For the composite oriented at 0, the transverse CTEs of the composite, in the hoop (CTEc,) and radial (CTEc,r) directions, are equal and greater than the mould CTE (CTEc, = CTEc,r > CTEsteel). Therefore, during the cool down, the composite contracted more than the mould, leading to a debonding of the composite from the external mould and compressive stresses in the mandrel as shown in Figure 6-10. For the laminate at 90, the composite CTE in the hoop direction is dominated by the behaviour of the fibre, and is then smaller than the CTE of the mould. However, it remains greater than the CTE of the mould in the through-thickness direction (CTEc,r > CTEsteel > CTEc, ). Hence, as the part cooled down, the composite contraction in the hoop direction was smaller than the mould contraction, locking the composite part in the external mould. Then, the composite part debonded from the mandrel as its contraction was greater in the through-thickness direction. This mechanism is schematically represented in Figure 6-15. Depending on the ply angle value, the symmetric angle-ply laminates behaved similarly to the 0 or 90 unidirectional laminate. The [+30/-30/-30/+30]s laminate separated from the external mould as its CTE values followed the same trend as the 0 laminate compared to the CTE of the mould, while the [+45/-45/45/+45]s and [+60/-60/-60/+60]s laminates behaved like the 90 laminate and debonded from the mandrel.

-181-

Layup

Mandrel

Steel Aluminum

Figure 6-15: Schematic representation of the composite debonding, depending of the material orientation The radial strain and stress evolutions obtained for the position B were similar to those observed at position A. However, it was noticed that the separation of the laminate from the mould happened earlier than at position A. This means that the debonding happens from the side of the composite part (position B) towards the centre (position A). By analyzing the evolution of the contact pressure at the -182-

interface, as shown in Figure 6-16 for the 45 angle-ply laminate, it was noticed that the contact pressure at position B became null 30 minutes earlier than at position A, which confirms the previous assumption. A similar phenomenon was observed experimentally by Twigg et al. [109] on plate manufactured by autoclave.

Figure 6-16: Evolution of the contact pressure at position A and B for the [+45/-45/-45/+45]s laminate during the RTM process with a steel mandrel

Figure 6-17 to Figure 6-21 present the evolution of the radial stress of the five laminates for the RTM process with a mandrel in aluminum. The values of the radial stresses in the composite and the mould were similar to the values obtained with a mandrel in steel. The same debonding mechanism occurred for the five laminates. However, as the aluminum CTE is greater than the steel CTE, the aluminum mandrel contracted more than the steel mandrel; and the separation of the composite from the mould occurred earlier as presented in Table 6-2.

-183-

Figure 6-17: Radial stress evolution of the [0]8 laminate at the interfaces for the RTM process with an aluminum mandrel at position A

Figure 6-18: Radial stress evolution of the [90]8 laminate at the interfaces for the RTM process with an aluminum mandrel at position A

-184-

Figure 6-19: Radial stress evolution of the [+30/-30/-30/+30]s laminate at the interfaces for the RTM process with an aluminum mandrel at position A

Figure 6-20: Radial stress evolution of the [+45/-45/-45/+45]s laminate at the interfaces for the RTM process with an aluminum mandrel at position A

-185-

Figure 6-21: Radial stress evolution of the [+60/-60/-60/+60]s laminate at the interfaces for the RTM process with an aluminum mandrel at position A From these simulations, the ease of demoulding can be anticipated by observing the state of stress in the external mould and the mandrel. For example, a difficult demoulding can be expected for the [0]8 and [+30/-30/-30/+30]s laminates as the mandrel remained in compression at the end of the cure with the value in the order of -500 kPa.

The simulation of the cylinder radial cutting by removing a plane of symmetry released the residual stresses and generated some spring-in and warpage in the structure as shown in Figure 6-22. The spring-in was calculated by evaluating the angle variation 1. In an angled composite laminate, such as L-shape bracket, Albert and Fernlund determined that the spring-in was a combination of a corner component and a flange warpage component [113]. Hence, for the cylinder, the measured spring-in would be then equivalent to the spring-in corner component in an angled composite laminate. -186-

The cylinder warpage was caused by the generation of shear stress at the interface between the mould and the composite during the heat-up of the cure cycle, while the mould stretches the laminate [107]. The warpage (w) was determined by evaluating the bending of the cylinder. A positive value means that the cylinder warps away from the mandrel. The spring-in, thickness and warpage variations are presented in Table 6-3. In order to estimate the influence of the resin shrinkage on the deformation, the finite element analyses were also computed with 0% of resin volumetric shrinkage.

Figure 6-22: Schematic representation of the deformations occurring after the stresses released a) spring-in, b) warpage The analytical values of spring-in were calculated using the equations (Eq. 2-41 and Eq. 2-25) developed by Radford [97] taking into account the temperature change, the thermal expansion of the composite in the in-plane and throughthickness directions, as well as the cure shrinkage. It should be noticed that the inplane direction defined by Radford corresponds to the hoop direction defined in this work. Therefore, the CTEc, and CTEc,r determined in Table 6-2 were used as the CTEl and CTEt in Eq. 2-41 and Eq. 2-25.

-187-

Layup

No shrinkage Steel mandrel Aluminum mandrel No shrinkage Steel mandrel Aluminum mandrel No shrinkage Steel mandrel

Face

Spring-in ()

Aluminum mandrel

[0]8 0.02 0.14 0.11 0.23 0.27 0.29 0.41 0.42 0.54 0.66 0.67 0.70 0.70 0.66 0.63 1.9917 1.9922 1.9871 0.60 0.57 1.9954 0.53 0.51 1.9934 1.9870 1.9877 1.9867 1.9842 1.9858 0.52 0.49 1.9972 1.9887 0.26 0.26 1.9950 1.9878 1.9888 1.9895 1.9877 1.9890 1.9873 1.9842 1.9858 0.27 0.27 1.9981 1.9890 1.9901 0.07 0.06 1.9968 1.9907 1.9928

Sym. Face

0.02 -7.7x10-3

0.05

0.04

1.9977

1.9914

1.9937

End face

8.5x10-4

-4.1x10-3

[+30/-30/ -30/+30]s

Sym. Face

End face

-7.1x10-2

-2.6x10-2

-1.6x10-2

Table 6-3: Process-induced dimensional changes for the different laminate layups

-188-

[+45/-45/ -45/+45]s

Sym. Face

End face

1.3x10-2

8.8x10-3

8.0x10-3

[+60/-60/ -60/+60]s

Sym. Face

End face

8.4x10-2

3.9x10-2

3.1x10-2

[90]8

Sym. Face

End face

5.7x10-2

-1.5x10-2

-1.4x10-2

The chemical shrinkages of the composite in the three directions were determined using the dimension variations of the laminate li during the cure as follows: Eq. 6-2 Only the shrinkage occurring after the resin vitrification, when the resin had build up a significant elastic modulus, was assumed to contribute to the residual stresses. Actually, before the vitrification, most of the generated strain can be relaxed due to the resin viscous behaviour. A similar assumption was used in [113] to estimate the shrinkage components. The composite cure shrinkage coefficients are reported in Table 6-4. The hoop and radial chemical shrinkage of the composite were used as

l

and

spring-in values are then summarized in Table 6-5. Table 6-4: Composite cure shrinkage coefficients in the longitudinal, hoop and radial directions

Layup

(10-5 m/m)

c,L

(10-5 m/m)

c,

(10-5 m/m)

c,r

-189-

Table 6-5: Analytical spring-in values for the different laminate layups [+30/-30/ -30/+30]s 20.8 38.6 6.39 10.72 150 0.242 0.004 0.246 [+45/-45/ -45/+45]s 4.1 43.1 0.89 13.71 150 0.531 0.012 0.543 [+60/-60/ -60/+60]s -3.5 38.6 -1.30 10.72 150 0.572 0.011 0.583

c, c,r

T (C) TH () S () ()

Figure 6-23 shows the influence of the layup on the spring-in. The spring-in was negligible for the laminate oriented at 0 and increased as the fibre orientation follows the curvature of the composite part. Nevertheless, the values of the spring-in remain small (< 1). The results demonstrate as well the significant influence of the resin shrinkage on the spring-in, as an increase up to 50% was observed in the numerical spring-in values due to the shrinkage strain. The numerical spring-in values were compared to the analytical values predicted by the Radford equations (Eq. 2-41 and Eq. 2-25). Overall, the analytical and numerical spring-in values followed the same trend. The numerical values of the spring-in, taking into account the effect of the shrinkage, are in reasonable agreement with the analytical values of the total spring-in ((TH + S). Good agreements are observed as well for the unidirectional laminates without the influence of the shrinkage. However, more discrepancy can be observed between the analytical and numerical spring-in of the angle-ply laminates without considering the resin shrinkage. Considering now the values of the spring-in taking into account the effect of the shrinkage, the difference between the analytical and numerical values might be -190-

due to the effect of the mould interaction, which was not considered with the Eq. 2-25. This demonstrates that the tool-part interaction has a possible influence on the process-induced deformations. From Figure 6-23, the effect of the tool-part interaction seems more important for the [+60/-60/-60/+60]s and [90]8 laminates. In those configurations, this laminates present the maximal CTE difference with the mould in the hoop direction. This CTE mismatch can generate a throughthickness stress gradient which is released when the cylinder is cut, leading to an increase in spring-in. Nevertheless, the tool-part interaction does not seem to be a major mechanism leading to the cylinder spring-in variation. Similar conclusions were observed experimentally for autoclaved L-shape composite brackets [113], where the tool-part interaction affected more significantly the flange warpage component than the corner component. From Table 6-3, a difference can be noticed between the spring-in reported at the symmetric face and the end face of the cylinder. This difference was due to a bending of the cylinder in the longitudinal direction. As the stresses are released, the cylinder warps away from the mould leading to a greater spring-in at the free end of the cylinder as shown in Figure 6-22. The values of the warpage are also reported in Table 6-3. Figure 6-24 compares the spring-in values obtained with a steel and an aluminum mandrel. The change of the mandrel material does not affect the spring-in significantly. In the case of open mould processes, such as autoclave or filament winding, previous studies observed higher composite strains and spring-in using moulds with higher thermal expansion [111, 113, 154]. For this type of processes, the mould stretched the laminate during the initial heat-up of the cure cycle, generating shear stresses at the interface between the mould and the composite and high through-thickness stress gradient in the laminate. These interfacial stresses and through-thickness stress gradients were locked in the composite as it cured and led to residual stresses and deformations at the demoulding. For the RTM process, the mould was preheated to the curing temperature before the injection. Hence, there is only a small amount of stress gradients that remains locked in the composite during the cure due to the mould expansion. This explains -191-

that the change of mandrel material from steel to aluminum does not affect the residual stresses and the spring-in for the RTM process. Finally, the thickness variation is negligible (<1%) for all simulations.

Figure 6-23: Effect of the resin shrinkage and the laminate layup on the spring-in value at the end face

-192-

Figure 6-24: Effect of the laminate layup and the mandrel material on the springin value at the end face

6.3

In this chapter, a numerical study was performed to analyse the dimensional stability of representative composite part manufactured by the RTM process. Five different laminate sequences were investigated. The cure-dependent factors, such as thermal strain and volumetric shrinkage, as well as tool-part interactions were taken into account simultaneously to compute the process-induced strains and stresses and deformations. The following conclusions emphasized: 1) The simulations captured the possible debonding of the composite from the mould due to the tool-part interaction and the difference in thermal expansion coefficient and the shrinkage strain. In most cases, this debonding occurred during the cool down of the cure cycle. However, for the [90]8 laminate, the separation happened during the isotherm primarily due to the significant effect of the shrinkage in the radial direction. The ease of demoulding (mandrel extraction) was also estimated by analyzing -193-

the state of stresses in the moulds at the end of the cure and was found to be dependent of the material properties and the laminate layup. 2) The process-induced deformations were predicted for the different layup configurations. As expected, these results showed the significant contribution of the thermal strain and the shrinkage strain on the spring-in variation. However, the tool-part interaction do not seem to be a major mechanism leading to process-induced deformations in the case of the RTM process. 3) For the thermal boundary conditions tested, representative of the RTM process, the change of the mandrel material did not have a notable influence on the process-induced deformations. This process modelling approach can be applied to determine to process-induced deformations of different geometry configurations, such as L-shape or C-shape brackets.

-194-

This work investigated the factors leading to the generation of process-induced stresses and deformations in woven composites manufactured by Resin transfer Moulding. Both intrinsic and extrinsic mechanisms were examined. The contributions of this work are summarized as follows. 1) A comprehensive methodology was developed to characterize the processing properties of thermoset resin systems. As a case study, this phenomenal approach was then applied for the characterization of a specific epoxy resin, CYCOM 890RTM epoxy resin. Empirical models were developed in order to determine the evolution of the resin property (cure kinetics, viscosity, glass transition temperature, cure shrinkage, coefficient of thermal expansion and elastic modulus) for any temperature cycle. These models were essential to establish a clear understanding of the resin behaviour during the processing conditions. Among the different chemo-physical resin properties, a particular effort was involved in the measurement of the resin cure shrinkage. Two measurement methods were improved and validated. It was determined that the total cure shrinkage of CYCOM 890RTM epoxy resin was 10%, of which 3.4% occurred after the gel point. It was then assume that only the resin cure shrinkage happening after the vitrification, when the resin has developed a significant elastic modulus, would induce residual stresses. The developed models were then implemented in finite element software in order to solve coupled thermochemical-stress processing problems and predict the evolution of laminate properties during the manufacturing process. 2) The thermomechanical properties of 5-Harness satin woven fabrics were investigated numerically using a micromechanical approach. -195-

Unit cells or periodic units representative of the global composite structure were developed for the different laminate configurations and periodic boundary conditions were applied to ensure the continuity in displacement at the unit cell boundaries. The elastic constants and coefficient of thermal expansion were determined for different fibre volume fractions corresponding to typical volume fraction used in the RTM process and compared to equivalent unidirectional crossply laminates. Overall, the thermomechanical properties of a 5-HS woven fabric laminate are very comparable to an equivalent unidirectional crossply laminate. The main difference results in the in-plane shear modulus G12 which is higher than the crossply one due to the yarn interlacing effect. This validates the use of the properties of unidirectional fibre in a crossply configuration to model the behaviour of 5-harness satin woven fabric laminate. The properties of the unidirectional fibre were therefore implemented in the finite element software to predict the properties of the 5-harness satin woven laminate during the manufacturing process. 3) Fibre Bragg Grating sensors were used to characterize the tool-part interaction for the RTM process. The optic sensors captured the separation of the composite from the mould due to their difference in coefficient of thermal expansion during the cool down period. The maximum shear stress stand by the laminate before the debonding was estimated to be 140 kPa for a steel mould. Finite element analyses were used to simulate the tool-part interaction. Different boundary conditions were applied at the composite/mould interface. The frictional contact conditions, using the maximum shear stress observed experimentally, successfully predicted the measured composite in-plane strain development as well as the separation of the laminate from the mould for the RTM process. This frictional contact constraint was then used in the process modelling to simulate the tool-part interaction occurring during the RTM process. -196-

4) Finally, taking simultaneously into account the intrinsic and extrinsic mechanisms investigated and mentioned above, the RTM process was then modelled. The developed epoxy resin properties models, the carbon fibre unidirectional properties, as well as the investigated frictional contact conditions were implemented in a numerical case study to compute the process-induced strains, stresses and deformations generated during the RTM process. The effect of the laminate sequences and the mould material were also investigated. The simulations predicted a debonding of the laminate mainly due to the coefficient of thermal expansion mismatch between the composite and the mould. However, depending of the laminate layup, the cure shrinkage can have a significant influence on the separation of the laminate from the mould during the process. The predicted process-induced deformations varied with the laminate sequences. A maximum spring-in was found for the 60 angle-ply laminate and the 90 unidirectional laminate due to the maximal difference between their longitudinal and transversal properties. A significant increase of the spring-in value with the resin shrinkage was observed. Contrary to the autoclave process, the results showed a small influence of the tool-part interaction for the RTM process, and the change of the mandrel material did not affect the value of the spring-in. The numerical total spring-in agreed reasonably well with the corresponding analytical values. This case study also validates the use of an existing process modelling approach, originally developed for the autoclave process, for three-dimensional composite parts manufactured by the RTM process. In conclusion, a predictive tool to simulate the strains, stresses and deformation generated during the RTM process was developed. This process modelling tool accounts for the resin cure-dependent properties developed in CHAPTER 3, the composite properties investigated in CHAPTER 4 and the tool-part interaction -197-

examined in CHAPTER 5. This process modelling approach was then applied to a numerical case study in CHAPTER 6, establishing the efficacy of this tool to predict the process-induced deformations. This approach can be then applied to various 3D geometry configurations and/or manufacturing processes, demonstrating the potential value of this work for industrial purposes. For future work on the investigation of the process-induced deformations in woven composite manufactured by RTM, further studies could be carried out in order to examine different issues that arose during the course of this project: 1) Micromechanics constitutive laws for the thermomechanical properties of woven fabric could be developed. Actually, it was demonstrated in CHAPTER 4 that the properties of the 5-HS woven fabric were similar to an equivalent unidirectional crossply configuration. However, this might not be true for a plain weave or twill woven architecture where the fibre waviness is more dominant. With the increasing use of woven fabric in industry, the implementation of the true woven fabric properties in the COMPRO CCA platform would expend greatly its modelling capabilities and increase the results accuracy. Further experimental validation of the unit cell approach by characterizing the fabric properties at various fibre volume fractions would be also interesting to carry out. 2) The use of FBG sensors for complementary experiments could be carried out to investigate the effect of the parameters that were examined numerically (i.e. laminate layup and the mould material). Also, pressure sensors could be added in the experimental set-up in order to measure the pressure variation during the RTM process. 3) Further validation of the RTM process modelling could be investigated using an extensive experiment approach. As different mechanisms leading to the process-induced stress occurred simultaneously, experimental set-198-

ups should be developed in order to isolate each effect individually. Also, the effect of more extrinsic parameters such as the laminate layup, the tool material, the composite geometry or the cure cycle could be investigated experimentally. 4) This RTM process modelling could be also combined with mould filling simulations in order to take into account the effect of the resin flow, the fibre permeability and the fibre compaction on the process-induced strains, stresses and deformations.

-199-

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Appendix A regroups some extra information on diverse aspect of the material characterization.

Figure A-1 and Figure A-2 show the test reproducibility under dynamic and isothermal conditions.

Figure A-1: Dynamic test reproducibility at 1C/min and 2C/min temperature ramp

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Figure A-2: Isothermal test reproducibility at 160C, 170C, 180C and 190C

Figure A-3 and Figure A-4 present the strain sweep and time sweep tests performed in order to determine the LVR. From these results, the resin LVR was determined at 15% strain and 1Hz frequency.

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Figure A-3: Strain sweep test performed at 1Hz frequency in oscillatory mode

Figure A-4: Time sweep performed at 15% strain and 1Hz in oscillatory mode

Figure A-5 to Figure A-7 show the reproducibility of the rheological tests under isothermal conditions, and Figure A-8 to Figure A-10 show the reproducibility of the rheological tests under dynamic conditions. Overall, for each condition, the -213-

gel point occurred at the same time. The value of the minimal viscosity varied a little but not significantly.

Figure A-5: Viscosity tests at 170C at 15% strain and 1Hz in oscillatory mode

Figure A-6: Viscosity tests at 180C at 15% strain and 1Hz in oscillatory mode

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Figure A-7: Viscosity tests at 190C at 15% strain and 1Hz in oscillatory mode

Figure A-8: Dynamic viscosity tests for a temperature ramp of 1C/min at 15% strain and 1Hz in oscillatory mode

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Figure A-9: Dynamic viscosity tests for a temperature ramp of 2C/min at 15% strain and 1Hz in oscillatory mode

Figure A-10: Dynamic viscosity tests for a temperature ramp of 3C/min at 15% strain and 1Hz in oscillatory mode

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Neat resin plaques were pre-cured in an oven on an aluminum plaque with an embedded K thermocouple. The thermocouple readings, acquired every 30 seconds and automatically fed into the cure kinetics and viscosity models allowed real-time tracking of the degree-of-cure. When the desired post-gelation degreeof-cure

1

was attained, the plaques were removed from the oven and quickly

cooled. Once at room temperature, the plaques were cut using a ceramic saw and polished with sandpaper into samples approximately 45mm long, 13mm wide and 1.5mm thick. The exact dimensions of each specimen were measured before testing. As the resin exhibits a very low fracture toughness close to the gel point, the sample were pre-cured above = 0.8, so that they did not break in the rheometer during the torsion test. Table A-1 presents the details of the pre-cured solid plaque. The three first plaques where used to determine the fully cured behaviour of the resin. Plaques 4 and 5 were used to measure the evolution of Tg and the elastic modulus with the temperature and the degree-of-cure. The final column of Table A-1 provides the total number of specimens cut form each plaque. Note that not all specimens cut were used to obtain final data. Some were used to test different approaches or testing conditions while others were simply invalidated due to inadequate quality or known experimental errors. Table A-1: Pre-cured plaque information Plaque 1 2 3 4 5 Isotherm time (min) 320 320 320 154 150 Isotherm temp (C) 160 170 180 180 180 1 0.95 0.98 1 0.847 0.827 Nb. of samples 5 4 4 4 4

To measure the evolution of the glass transition temperature, the pre-cured samples was heated at 5C/min in the rheometer while its degree of cure was -217-

tracked by means of the cure kinetics model as shown in Figure A-11. .Once the resin passed the glass transition temperature (2), determined by one of the three modulus based indicators, the resin was brought to the manufacturer recommended cure temperature of 180C and allowed to isothermally reach a desired degree of cure 2, as shown at (3). Then, the sample was quickly removed from the rheometer and cooled. The procedure was then repeated from 2 to a higher 3 and so on to measure the Tg for different values of degree-of-cure.

Figure A-11: Glass transition temperature measurement process. The arrows correspond to one of the three glass transition temperature indicators [155] Table A-2 summarizes the degree-of-cure evolution the samples underwent during the experiments. 1 denotes the pre-cure degree of cure right after removal from the oven. Samples from plaques 4 and 5 were eventually cured to high values, so as to confirm the results of plaques 1, 2 and 3.

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Table A-2: Degree-of-cure evolution for samples used for the glass transition temperature measurements Plaque 1 Sample a b 2 a b 3 a b c 4 a b 5 a b 1 0.95 0.95 0.98 0.98 1 1 1 0.847 0.847 0.827 0.827 2 0.95 0.95 0.98 0.98 1 1 1 0.9 0.87 0.883 0.926 0.91 0.931 0.915 0.969 0.961 0.936 0.981 3 4 5

Table A-3 shows the evolution of the degree-of-cure during the tensile modulus experiments. These experiments were carried out under isothermal conditions at 180C and 160C. Table A-3: Degree-of-cure evolution for samples used for the tensile modulus measurements Plaque 4 5 Sample c c 1 0.847 0.827 2 0.991 0.998

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