Sayfa 51

ISTANBUL TECHNICAL UNIVERSITY GRADUATE SCHOOL OF SCIENCE
ENGINEERING AND TECHNOLOGY
PRODUCTION OF FIBER REINFORCED THERMOPLASTIC COMPOSITES
Ph.D. THESIS
Glnur BAER
Department of Polymer Science and Technology
Polymer Science and Technology Programme
OCTOBER 2012
ISTANBUL TECHNICAL UNIVERSITY GRADUATE SCHOOL OF SCIENCE
ENGINEERING AND TECHNOLOGY
Ph.D. THESIS
Glnur BAER
(515062003)
Department of Polymer Science and Technology
Polymer Science and Technology Programme
Thesis Advisor: Prof. Dr. Nurseli UYANIK
OCTOBER 2012
STANBUL TEKNK NVERSTES FEN BLMLER ENSTTS
ELYAF TAKVYEL TERMOPLASTK KOMPOZTLERN RETM
DOKTORA TEZ
Glnur BAER
(515062003)
Polimer Bilim ve Teknolojisi Anabilim Dal
Polimer Bilim ve Teknolojisi Program
Tez Danman: Prof. Dr. Nurseli UYANIK
EKM 2012
Glnur Baer, a Ph.D. student of ITU Graduate School of Science Engineering
and Technology student ID 515062003, successfully defended the thesis entitled
PRODUCTION OF FIBER REINFORCED THERMOPLASTIC COMPOSITES,
which she prepared after fulfilling the requirements specified in the associated
legislations, before the jury whose signatures are below.
Thesis Advisor : Prof. Dr. Nurseli UYANIK ..............................

Istanbul Technical University
Jury Members : Prof. Dr. Hulusi ZKUL ..............................

Prof. Dr. Hseyin YILDIRIM ..............................

Yldz Technical University
Prof. Dr. Ahmet AKAR .............................

Prof. Dr. Ayfer SARA .............................

Yldz Technical University
Date of Submission : 21 June 2012

Date of Defense : 19 October 2012
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FOREWORD
This work is supported by ITU Graduate School of Science Engineering and

Technology.
Firstly, I would like to express my deep appreciation and thanks for my advisor
Prof.Dr. Nurseli Uyank.
I would also like to express my gratitude to Telateks A.. management for giving me
the opportunity to do this project supporting all work and the materials.
Special thanks go to my senior colleagues Emre Batuhan and Handan Deniz who
always support me and share their experiences about life.
Thanks are also expressed to Alparslan Demirural and his team workers from
TBTAK-MAM, Composite Laboratory for giving me the opportunity to use of their
equipments which are very important for this thesis.
I am thankful to Prof.Dr. Melih Papila and M.Sc. Kaan Bilge for giving labour and
their valuable contributes and discussions to my work.
Then I would like to thank to Assist. Prof.Dr. Ali Durmu for helping the thermal
analysis which is important for my thesis.
Finally thanks are also expressed to my family supporting me in my whole life.
October 2012 Glnur BAER

Chemical Engineer
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TABLE OF CONTENTS
Page
FOREWORD...........................................................................................................vii
TABLE OF CONTENTS ..........................................................................................ix
ABBREVIATIONS .............................................................................................. xiiiiii
LIST OF TABLES...................................................................................................xv
LIST OF FIGURES ............................................................................................. xviiii
SUMMARY ............................................................................................................xxi
ZET .................................................................................................................... xxv
1. INTRODUCTION ..................................................................................................1
1.1 Purpose of the Thesis .....................................................................................2
1.2 Hypothesis ..................................................................................................... 3
2. LITERATURE REVIEW ........................................................................................5
2.1 Continuous Fiber Reinforced Polymeric Composites (CFRPCs)..................... 5
2.2 Reinforcement Materials Used in FRPCs ....................................................... 6
2.2.1 Type of fibers ...........................................................................................6
2.2.1.1 Carbon fiber.......................................................................................6
2.2.1.2 Aramid fiber .......................................................................................7
2.2.1.3 Glass fiber .........................................................................................7
2.2.2 Surface treatment of the fibers:Compatibility between fiber and polymer10
2.2.3 Forms of reinforcements.........................................................................10
2.3 Polymer Systems in CFRPCs Production ..................................................... 13
2.3.1 Thermoset polymers...............................................................................14
2.3.2 Thermoplastic polymers .........................................................................15
2.3.3 Advantages & disadvantages of thermoplastic & thermoset matrices.....17
2.4 CFRPCs Manufacturing Methods ................................................................. 19
2.4.1 Manufacturing with thermoset resins ......................................................19
2.4.1.1 Prepregging .....................................................................................19
2.4.1.2 Wet filament winding........................................................................19
2.4.1.3 Hand lay-up of prepreg ....................................................................20
2.4.1.4 Resin transfer molding (RTM) ..........................................................20
2.4.1.5 Infusion process ..............................................................................21
2.4.1.6 Vacuum bagging, autoclave cure .....................................................21
2.4.2 Manufacuring with thermoplastic resins ..................................................22
2.4.2.1 Film stacking....................................................................................24
2.4.2.2 Hybrid yarns and fabrics ..................................................................25
2.4.2.3 Powder impregnation .......................................................................26
2.4.2.4 Melt impregnation ............................................................................27
2.4.2.5 Solvent impregnation .......................................................................27
2.4.2.6 Reactive processing of thermoplastics.............................................28
2.5 Cyclic Butylene Terephtalate ........................................................................ 34
2.5.1 Production of cyclic oligoesters ..............................................................34
2.5.1.1 Direct synthesis ...............................................................................35
2.5.1.2 Poymer-supported method ..............................................................35
2.5.1.3 Cyclo-depolymerisation (ring-chain reaction) ...................................35
2.5.1.4 Production of CBT oligomers ...........................................................35
2.5.2 Polymerisation of cyclic oligoesters ........................................................36
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2.5.3 Properties of CBT and IPCBT.. .............................................................. 39
2.5.3.1 Viscosity .......................................................................................... 39
2.5.3.2 Morphology ..................................................................................... 41
2.5.3.3 Mechanical properties ..................................................................... 44
3. MATERIALS AND METHODS ........................................................................... 45
3.1 Materials ....................................................................................................... 45
3.1.1 Reinforcing materials ............................................................................. 45
3.1.2 Matrix resins .......................................................................................... 48
3.1.2.1 Cyclic butylene teraphthalate .......................................................... 48
3.1.2.2 Polyamide 12 .................................................................................. 48
3.1.2.3 Copolyamide (CoPA) suspension .................................................... 48
3.1.2.4 Unsaturated vinyl ester.................................................................... 49
3.1.3 Other chemicals ..................................................................................... 49
3.1.3.1 Semi permanent mold release agent ............................................... 49
3.1.3.2 Dicumyl hydroperoxide (DCP) ......................................................... 49
3.2 Equipments ................................................................................................... 49
3.2.1 Weighing machine for hand scattering ................................................... 49
3.2.2 Scattering coating machine .................................................................... 49
3.2.3 Fluard machine ...................................................................................... 50
3.2.4 Oven ...................................................................................................... 50
3.2.5 Hot press ............................................................................................... 50
3.2.6 Metal molds ........................................................................................... 51
3.2.7 Infusion system ...................................................................................... 51
3.2.8 Mechanical test device 100 kN............................................................... 51
3.2.9 Mechanical test device 2 kN .................................................................. 51
3.2.10 Impact test equipment.......................................................................... 51
3.2.11 Microscopes......................................................................................... 52
3.2.12 Furnace ............................................................................................... 52
3.2.13 DSC ..................................................................................................... 52
3.3 Production Methods ...................................................................................... 52
3.3.1 Production of IPCBT matrix composites ................................................. 52
3.3.1.1 Preparation of prepregs with CBT powder ...................................... 52
3.3.1.2 Conditioning method of prepregs before composite production ....... 54
3.3.1.3 Production of IPCBT composites in hot press.................................. 55
3.3.1.4 Production of IPCBT composites by vacuum consolidation ............. 57
3.3.2 Production of PBT matrix composites from commingled fabric............... 57
3.3.3 Production of PA matrix composites ...................................................... 58
3.3.4 Production of VE matrix composites ...................................................... 60
3.4 Characterization Methods ............................................................................. 60
3.4.1 Fiber ratio and void content analysis ...................................................... 60
3.4.2 Mechanical characterization................................................................... 60
3.4.2.1 Tensile analysis............................................................................... 61
3.4.2.2 Flexural analysis ............................................................................. 61
3.4.2.3 Compression analysis ..................................................................... 61
3.4.2.4 Impact analysis ............................................................................... 62
3.4.3 Optical analysis...................................................................................... 61
3.4.4 DSC analysis ......................................................................................... 61
4. RESULTS AND DISCUSSION ........................................................................... 63
4.1 Optimisation of Production Conditions of CBT Prepregs ............................... 65
4.1.1 Laboratory scale trials ............................................................................ 66
4.1.2 Scatter coating machine trials ................................................................ 66
4.1.3 Conditioning of prepregs before compression ........................................ 67
4.2 Optimization of IPCBT Composites Production by Compression Molding ..... 69
4.2.1 Compression molding pressure.............................................................. 69
4.2.2 Compression molding temperature ........................................................ 70
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4.2.3 Compression molding time .....................................................................71
4.2.4 Demolding temperature: Rapid and slow cooling ....................................73
4.3 Development of TP Composites: Various Matrices, Reinforcing Materials and
Production Methods ...................................................................................... 75
4.3.1 Production methods ...............................................................................75
4.3.1.1 Production of IPCBT composites with different procesing cycle .......75
4.3.1.2 Production of IPCBT composites by vacuum consolidation..............77
4.3.2 Production of different structures of IPCBT composites..........................79
4.3.2.1 UD IPCBT composites and comparison with UD VE composites ....79
4.3.2.2 IPCBT composites produced with different reinforcements ..............84
4.3.2.3 Production of IPCBT composites with different fiber volume fraction85
4.3.2.4 Production of IPCBT composites with different thicknesses .............85
4.3.3 PA matrix composites.............................................................................86
4.3.4 Composites out of commingled PBT/Glass fabric ...................................88
4.3.5 Production of sandwich structures with CBT and PA prepregs ...............89
5. CONCLUSION AND RECOMMENDATIONS .....................................................93
5.1 Application of The Work ............................................................................... 93
REFERENCES .......................................................................................................97
APPENDICES ......................................................................................................103
CURRICULUM VITAE .......................................................................................... 119
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ABBREVIATIONS
TP :Thermoplastic
CBT :Cylic buthyleneterephtalate
IPCBT :In situ polymerized cyclic buthyleneterephtalate
PBT :Poly buthyleneterephtalate
PA12 :Polyamide 12
CoPA :Copolyamide
RTM :Resin transfer molding
NCGF :Non crimp glass fFabric
CFRPCs :Continuous fiber reinforced polymeric composites
PP :Polypropylene
PA :Polyamide
PET :Poly ethylene terephtalate
FRP :Fiber reinforced plastics
PAN :Polyacrylonitrile
ROP :Ring opening polymerisation
APLC-12 :Anionicly polymerised lactam12
CDP :Cyclo-depolymerisation
MW :Molecular weight
IPCBT :Insitu polymerised CBT
UD :Uni directional
Vf :Fiber volume fraction
DSC :Differential scanning calorimeter
Tc :Crystallization temperature
Xc :Crystallization degree
SEM :Scanning electron microscopy
VE :Vinyl ester
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LIST OF TABLES
Page
Table 2.1 : Glass fiber yield points according to fiber diameter .................................9
Table 2.2 : Reinforcement forms and application areas with advantages ...............11
Table 2.3 : High temperature thermoplastics ..........................................................16
Table 2.4 : Engineering thermoplastics ..................................................................16
Table 2.5 : Comparison of typical thermoset versus thermoplastic .........................17
Table 2.6 : Catalaysts (initiators) used in polymerysation of CBT ...........................38
Table 2.7 : Mechanical properties of PBT and IPCBT.............................................44
Table 2.8 : Properties of reporcessed PBT and polymerised CBT compared to
injection molded polymerised CBT........................................................44
Table 3.1 : Calculated thickness chart according to fiber weights. ..........................56
Table 3.2 : Number of layers for prepregs with 70/30 fiber resin ratio ....................56
Table 4.1 : Prepreg and composite production conditions ......................................63
Table 4.2 : Prepreg production conditions in scatter coating machine ....................67
Table 4.3 : Tensile properties of IPCBT composites conditioned with different
methods................................................................................................68
Table 4.4 : Melting temperature and enthalpies of IPCBT composite .....................70
Table 4.5 : Impact stregths of IPCBT composites at different demolding
temperatures ........................................................................................75
Table 4.6 : Comparison of tensile and flexural properties of IPCBT composites after
different process routes ........................................................................78
Table 4.7 : Tensile and compressive properties of IPCBT and VE composites. ......79
Table 4.8 : Comparison of mechanical properties of IPCBT composites with different
fiber diameters. .....................................................................................84
Table 4.9: Tensile properties of IPCBT composites with different laminate
thicknesses ..........................................................................................86
Table 4.10 : Process conditions and mechanical test results of X600 and X468
laminates with CoPa and PA 12 matrix..............87
Table 4.11: Tensile properties of IPCBT and PBT matrix composites89
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LIST OF FIGURES
Page
Figure 2.1 : Differences between woven and multiaxial reinforcements ................ 12

Figure 2.2 : Woven fabrics from high tenacity fibers .............................................. 12
Figure 2.3 : Basic scheme of a multiaxial structure ............................................... 13
Figure 2.4 : Non crimp multiaxials including different numbers of layers a ........... 13
Figure 2.5 : Representation of prepreg production method ................................... 19
Figure 2.6 : Representation of filament winding method........................................ 20
Figure 2.7 : Representation of hand lay-up method of prepreg ............................ 20
Figure 2.8 : Representation of RTM ...................................................................... 21
Figure 2.9 : Representation of infusion process .................................................... 21
Figure 2.10 : Representation of vacuum bagging in autoclave .............................. 22
Figure 2.11 : Impregnation of a fiber bundle by resin under an applied pressure .. 23
Figure 2.12 : Alternative processing routes for CFRTPCs ..................................... 24
Figure 2.13 : Hybrid yarn structures and corresponding production technology ... 26
Figure 2.14 : Representation of a melt impregntaion process ............................... 27
Figure 2.15 : Anionic ring-opening polymerisation of polyamides .......................... 29
Figure 2.16 : Melt viscosities and processing temperatures of various matrix
materials for both reactive and melt processing ................................. 30
Figure 2.17 : Vacuum assisted resin infusion process........................................... 31
Figure 2.18 : RTM setup for cyclic one-part resins ............................................... 31
Figure 2.19 : Liquid-Molding of laurolactam. ......................................................... 33
Figure 2.20 : Conversion of monomers to low viscosity macrocyclics (bottom)
Conventional polymerisation (top) forms viscous polymers .............. 36
Figure 2.21 : Ring-opening metathesis polymerisation of PBT .............................. 37
Figure 2.22 : Incorporation of tin into a macrocyclic structure via the cyclic
stannoxane. ..................................................................................... 38
Figure 2.23 : Rheokinetic plots of CBT one-part systems XB2 and XB3................ 40
Figure 2.24 : Left: Degree of conversion as function of time for different
temperatures; Right: Impregnation and polymerisation time of the one-
part CBT(CBT-XB3) resin. ................................................................ 40
Figure 2.25 : Crystallization kinetics of catalyzed CBT resin ................................. 42
Figure 2.26 : Typical three point bending Stress-Strain curves of pCBT and PBT . 43
Figure 2.27 : Thermograms of CBT, ISP-PBT and IM-PBT: a)first b) second heating
(heating rate: 5C/min)........................................................................43
Figure 3.1 : Representation of X600 coded 45 reinforcement ............................ 46
Figure 3.2 : Representation of X468 coded 45reinforcement.. ........................... 46
Figure 3.3 : Representation of L300 (UD) coded reinforcement. .......................... 47
Figure 3.4 : Commingled Glass/PBT hybrid biaxial 45 fabric ............................. 47
Figure 3.5 : a) Weighing machine, b) Metal screen for scattering .......................... 49
Figure 3.6 : Scattering part of scattering coating machine ..................................... 50
Figure 3.7 : Fluard machine .................................................................................. 50
Figure 3.8 : Hot press for compression molding... ................................................. 51
Figure 3.9 : Scattering of CBT powder on reinforcement on weighing machine..52
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Figure 3.10 : Pre-pregs kept in oven...................................................................... 53
Figure 3.11 : Thermo paper placed on prepreg( after applied heat). ...................... 53
Figure 3.12 : Scattering system... .......................................................................... 54
Figure 3.13 : CBT Prepreg: CBT coated X468 (left: whole fabric, right: cutted fabric)
............................................................................................................................... 54
Figure 3.14 : Vacuum bagged prepregs................................................................. 55
Figure 3.15 : Prepregs in metal mold. .................................................................... 56
Figure 3.16 : Metal mold in hot press..................................................................... 56
Figure 3.17 : IPCBT composite flat plate with 3 mm thickness............................... 57
Figure 3.18 : Fluard bath ....................................................................................... 58
Figure 3.19 : Squeezing of the excess liquid through the rollers ........................... 58
Figure 3.20 : Wet fabric placed in oven to dry... ..................................................... 58
Figure 3.21 : Scattering of PA12 on fabric impregnated with CoPA ....................... 59
Figure 3.22 : PA12 scattered fabric placed in oven for melting and fixing of the
polymer................................................................................................59
Figure 3.23 : Glass fiber prepreg placement into the mold .......................69
Figure 4.1 : DSC thermogram of IPCBT composite produced at 200C..................71
Figure 4.2 : Cooling speed after compression: Temperature-Time curve..............74
Figure 4.3 : Temperature-Time curve of compression for 160C impregnation
temperature.............................................................................................76
Figure 4.4 : Temperature-Time curve of compression for 170C impregnation
temperature.............................................................................................76
Figure 4.5 : Stress-Strain curve of IPCBT composites by vacuum consolidation ...78
Figure 4.6 : Stress-Strain curve of IPCBT composites by compression ................. 78
Figure 4.7 : Longitudinal tensile stress-strain curve of IPCBT composite. .............. 80
Figure 4.8 : Fractured IPCBT test specimens after tensile test. ............................. 80
Figure 4.9 : Typical compression Stress-Strain curve of VE laminates. ................. 81
Figure 4.10 : Typical compression Stress-Strain curve of IPCBT laminates........... 81
Figure 4.11 : Crossections of IPCBT test specimens before & after compression . 82
Figure 4.12 : Failure envelopes of IPCBT & VE composites on 2-6 spaces ....... 83
Figure 4.13 : Failure envelopes of IPCBT & VE composites on 1-2 spaces ....... 83
Figure 4.14 : Centre temperature of the laminate during compression molding......86
Figure 4.15 : Tensile Stress-Strain curve of PA laminates ..................................... 87
Figure 4.16 : Fractured test specimen of PA composite after tensile test ............... 87
Figure 4.17 : Marbled appearance on the surface of the composite laminate ........ 88
Figure 4.18 : Laminate images produced with 6 layers of X600 at 210C for 15
minutes. ............................................................................................ 88
Figure 4.19 : Prepared PA foam before compression molding ............................... 90
Figure 4.20 : Placement of foam and the prepregs into mold ................................. 90
Figure 4.21 : Compression conditions for sandwich production out of CBT prepregs
....................................................................................................................... 91
Figure 4.22 : Compression conditions for sandwich production out of CBT prepregs
....................................................................................................................... 91
Figure 4.23 : Sandwich laminate with IPCBT skin and PA foam core .................... 92
Figure 4.24 : Sandwich laminate with PA skin and PA foam core .......................... 92
Figure A.1 : Tensile and flexural properties of IPCBTs: Hand scattering temperature
..................................................................................................................... 104
Figure A.2 : Tensile and flexural properties of IPCBTs: Scattering coating
temperature ..................................................................................... 105
Figure A.3 : Tensile and flexural properties of IPCBTs: Compression molding
pressure ........................................................................................... 106
Figure A.4 : Tensile and impact properties of IPCBT composites: Compression
molding temperature ........................................................................ 107
Figure A.5 : SEM images of IPCBT composites with different compression
temperatures: a)210C, b)200C, c)190C ....................................... 108
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Figure A.6 : Tensile and impact properties of IPCBTs with different compression
times ................................................................................................109
Figure A.7 : SEM images of IBT composites with different compression time: a)30,
b)20, c)10 .......................................................................................110
Figure A.8 : SEM image of the peeled surface of IPCBT composite laminate ......111
Figure A.9 : Tensile and flexural properties of IPCBT composites with different
demolding temperatures ...................................................................112
process cycles ...............................................................................113
Figure A.11 : Stereo microscope images of IPCBT composites produced with
different preimpregnation temperatures: a) 160C b)170C ............114
Figure A.12 : Stereo microscope images of IPCBT composite produced with 160C
preimpregnation temperature for 20 minutes compression time .....114
Figure A.13: Tensile strength and tensile modulus variations of IPCBT composites
with different volume fractions ........................................................115
Figure A.14 : Impact strength variation of IPCBT composites with different volume
fractions .........................................................................................116
Figure A.15 : SEM Image of cross sectional area of IPCBT composite (Vf: 63%) 116
Figure A.16 : SEM images of cross sectional area of the composites with 6 mm(a)
and 10 mm(b) thickness .................................................................117
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SUMMARY
In structural polymeric composite applications, textiles (e.g., unidirectional, woven

fabrics) are commonly used for reinforcement because of two reasons: high fiber
volume fraction and the possibility to tailor the load bearing capacity through the
fiber lay-up. The thermoset resins are predominantly in use as matrix materials in
textile reinforced composites due to their easy processability and enhanced fiber
wetting capability. Although they can be processed easily, they contain organic
volatiles that damage environment and human health. Furthermore, recycling of
thermoset resins are not possible because they cannot be melted upon application
of heat for re-molding.
The use of thermoplastic (TP) polymers as matrix materials offers a solution to these
particular problems since they are recyclable and environment friendly. They have
also high toughness and impact resistance. However, manufacturing high quality
thermoplastic composite parts still remain as a problem because of inherent high
melt viscosity of many of TP polymers which causes poor fiber impregnation.
Conventional thermoplastic processing methods like extrusion and injection molding
enables the use of chopped fiber reinforcements from usual blend-process-cast
point of view to manufacture composite parts with low fiber volume fractions
efficiently. The main limitation for processing however occurs in the case of
structural continuous fiber (textile) reinforced composite manufacturing processes
where the high melt viscosity problem usually necessitates high pressure
applications in order to have good fiber wetting and high fiber volume fractions.
Such applications automatically cause increased manufacturing costs.
Fiber impregnation problem may be handled either using methods which decrease
the polymer viscosity or reducing the required flow length of polymer matrix. Another
approach that is specifically applicable for thermoplastic polymers is the reactive
processing of textile fiber-reinforced thermoplastics based on impregnation of the
fibers with a low viscosity oligomeric precursor, followed by in situ polymerization.
Cyclic butylene terephtalate (CBT), as precursor, has well been studied for this
manufacturing approach due to its low melt viscosity. In all applications of this
manufacturing approach, the precursor impregnation has been handled via
conventional manufacturing techniques such as resin transfer moulding (RTM)
which is followed by an isothermal heating. This leads to entropically driven ring
opening polymerization resulting in linear high molecular weight matrix polymer.
Although TP composite materials may be manufactured using that approach, on an
industrial scale, it requires lots of time and poses process difficulties necessitating
special equipments.
Yet, it has also been shown that these problems may be eliminated by using
properly prepared prepreg materials which also enables the manufacturing of
complex shaped end products rather than laminates. Based on this idea, this thesis
focuses on the manufacturing of textile reinforced TP composites with new
manufacturing methods. Non-crimped E-glass fiber (NCGF) textiles were used as
the textile reinforcement. Cyclic butyleneterephtalate (CBT) which is the oligomer of
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polybutyleneterephtalate (PBT) was one of the resins used as the matrix of
composite. NCGF textiles were coated with CBT/polymerization catalyst mixture via
powder scattering method to obtain prepregs. For the preparation of prepregs, first
NCGF textile was impregnated with the CoPA suspension and was coated by
sprinkling PA12 powder. In situ polymerized CBT (IPCBT) composites and PA
matrix composites were produced from prepregs by compression molding in hot
press. Composite laminates obtained were subjected to tensile, flexural and impact
tests. Optimum process parameters which have to be used in hot press were
determined for all types of the matrix resins.
The efficiency of the new manufacturing method for IPCBT composites was sought
via performance comparisons with reported literature values and with effective
microscopic investigation by scanning electron microscopy (SEM) and stereo
microscope. Conventional PBT matrix composites out of commingled PBT/Glass
NCGF fabric were also produced by compression molding and compared with
IPCBT composites. Moreover, IPCBT composites were produced via vacuum
molding out of CBT prepregs and compared with IPCBT composites produced by
compression molding.
Detailed performance investigation was carried out by determining the Tsai-Wu
strength parameters (X, X, Y, Y, S) of unidirectional IPCBT composite laminates
through tensile and compressive tests at longitudinal and transverse directions as
well as tensile test of (+45/-45)6s laminates. Test results were compared with the
results of simultaneously manufactured and tested NCGF reinforced vinylester (VE)
laminates. Failure envelopes of both IPCBT and VE composites were evaluated.
Overall, the pros and cons of IPCBT composites manufactured via newly initiated
manufacturing method was evaluated and reported.
Figure 1 and 2 corresponds to the first ply failure envelopes of UD laminates where
the competitive design space of IPCBT composite laminates was demonstrated in
the shaded region. Investigation of the test results and failure modes in accordance
with the failure envelopes suggested that the IPCBT based laminates considered in
this study can be strong alternatives to the VE based laminates especially under
uniaxial compressive loading conditions as well as under impact loadings.
Figure 1 : Failure envelopes of IPCBT and VE Composites on 2-6 spaces.
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Figure 2 : Failure envelopes of IPCBT and VE Composites on 1-2 spaces.
In conclusion, NCGF reinforced IPCBT composites were successfully produced.

First of all, optimum prepreg and composite production conditions of IPCBT
composites were identified. It was shown that biaxial NCGF reinforced IPCBT
composites gave better flexural and tensile properties when it was compared with
reported results of IPCBT composites produced by RTM technique and the
composites produced by compression molding of conventional PBT in the literature.
It was seen that the new method provided reduction in processing time and energy
consumption as compared to conventional TP composite manufacturing methods. It
was also observed that IPCBT composites can be produced not only by
compression molding but also by vacuum molding with an enhancement of both
tensile and flexural strengths.
PA matrix composites were successfully produced by compression molding as well.
It was observed that the tensile properties of IPCBT composites are higher than
those of PA composites.
Sandwich structures of IPCBT composite skin and PA matrix composite skin using
PA foam as core material were successfully produced. However, bond strength
between skin and core was not enough for both PA and IPCBT. It was concluded
that the compression molding in hot press is not a proper method for one-shot
sandwich composite production.
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ELYAF TAKVYEL TERMOPLASTK KOMPOZTLERN RETM
ZET
Polimerler hayatmzda ok nemli bir rol oynamaktadrlar. Son kullanm

zelliklerine gore farkl polimerler birbirleri ile kartrlabilir veya farkl yapdaki
malzemelerle birletirilebilirler. Yapsal polimerik kompozit paralarn retiminde
yk tama kapasitelerinin yksek olmas ve yksek elyaf hacim orann
salayabilmelerinden dolay tekstiller (dokumalar, tek ynller vb.) en ok tercih
edilen takviye malzemeleridir. Tekstil takviyeli kompozitlerin retiminde matris
olarak ounlukla tercih edilen termoset polimerlerin (polyester, epoksi vb.) en
byk avantaj dk viskoziteye sahip olmalar ve bundan dolay elyaf takviyeli
kompozit retiminde dk basnlarda elyafa kolay tatbik edilebilmeleridir.
Termoset reineler kolay ilenmelerine ramen insan salna ve evreye zararl
stiren gibi kolay uucu zc ve apraz balayclar iermektedir. Is ile tekrar
eritilip ekil verilemedii iin termoset kompozit paralarn geri dnm de
mmkn deildir.
Termoplastik (TP) polimerler ise syla tekrar ekil verilebildii iin termosetlerin
aksine geri dntrlebildikleri gibi insan ve evreye zarar verecek zclerle
almay da gerektirmemektedirler. Ayrca darbe dayanmlar da termosetlere gre
daha yksek olduundan kompozit uygulamalarnda termosetlere alternatif olarak
gsterilmektedirler. Ancak, TP polimerlerin eriyik viskozitesi ok yksek olduundan
iyi bir elyaf emprenyesiyle salanabilecek kaliteli bir TP kompozit retimi hala
zlememi bir problemdir. Enjeksiyon ve ekstrzyon yntemiyle krplm elyaf
takviyesi ieren TP kompozitler kolayca retilebilirken bu kompozitlerin zellikleri
birok kullanm alannda yetersiz kalmaktadr. ok daha yksek mukavemete sahip
srekli elyaf (tekstil) takviyeli TP kompozitlerin retim yntemleri snrl kalmtr.
nk iyi bir elyaf emprenyesi ve yksek elyaf oranlar elde etmek iin gerekli
yksek scaklk ve basnlar proses zorluklarna ve maliyet artna neden
olmaktadr.
Elyafn TP polimerle slatlma problemi polimer viskozitesinin azaltlmas veya
polimerin ak mesafesinin ksaltlmas gibi yntemlerle zlebilmektedir. Dier
yntem ise elyafn dk viskoziteli oligomerik (veya monomerik) balang maddesi
ile emprenye edilip yerinde polimerizasyona tabi tutumasna dayal reaktif
termoplastik polimerizasyon prosesidir ve bu yntem termoplastik polimerler iin
uygulanabilen bir yntemdir. Dk viskozitesinden dolay poli btilen teraftalat
(PBT) oligomeri olan halkal btilen teraftalat (CBT) bu retim ynteminde
kullanlarak allmtr. Elyafn oligomerle emprenyesi termoset polimerler iin
kullanlan geleneksel reine transferiyle kalplama (RTM) tekniiyle
gerekletirilmitir. Burada RTM sistemi stlarak izotermal bir prosesle CBT nin
polimerleip lineer ve yksek molekl arlkl matris polimer olmas salanmtr. TP
kompozitler bu yntemle retiliyor olsa bile endstriyel boyutta bakldnda bu
sistemin baz proses zorluklar ve zel ekipmanlara ihtiya duymas gibi problemleri
ortaya kmaktadr. Bahsi geen problemlerin nceden oligomer (veya monomer) ile
emprenye edilmi tekstillerden (prepreg) kompozit retilmesiyle zlebilecei
grlmtr.
xxv
Bu alma da bu dnceyi takip ederek yeni yntemlerle TP kompozit retimi
zerine yrtlmtr. Kompozit takviye tekstili olarak kvrmsz E-cam elyafndan
(NCGF) tekstiller kullanlmtr. Kompozit matris polimeri olarak kullanlan
polimerlerden biri CBTdir. Prepreg retimi, NCGF tekstilinin polimerizasyon
katalizrn de ieren CBT ile toz serpme yntemiyle kaplanmasyla
gerekletirilmitir. Matris olarak kullanlan dier reine poliamiddir (PA). Prepreg
eldesi iin NCGF tekstili nce kopoliamid (CoPA) sspansiyonuyla emprenye
edilmi, zerine PA12 tozu serpilerek kaplanmtr. Yerinde polimerletirilmi CBT
(IPCBT) ve PA kompozitleri, hazrlanan prepreglerin scak preste baskyla
kalplanmas metoduyIa retilmitir. Elde edilen kompozitler ekme, eme ve darbe
testlerine tabi tutulmutur. Baskyla kalplamada kullanlacak uygun proses
deikenleri her iki matris tipi iin de belirlenmitir.
IPCBT kompozitlerinin yeni retim tekniinin baars literatrdeki mekanik
deerlerle karlatrma yaplarak ve taramal elektron mikroskobunda (SEM)
yaplan incelemelerle aratrlmtr. Bilinen PBT matrisli kompozitler PBT/E-cam
elyaflarnn karmndan oluan NCGF tekstilinin baskyla kalplanmas ile elde
edilmitir ve bu kompozitler IPCBT kompozitleriyle kyaslanmtr. Ayrca IPCBT
kompozitler prepreglerden vakum kalplama yntemiyle de retilerek scak preste
retilen IPCBT kompozitlerin mekanik zellikleri ile karlatrlmtr.
Daha detayl performans incelemesi baskyla kalplama yntemiyle retilen tek ynl
(UD) IPCBT kompozitlerinin Tsai-Wu dayanm parametrelerinin (X, X, Y, Y, S)
ekme ve basma testleriyle tespit edilmesiyle yrtlmtr. Test sonular e
zamanl olarak retilen ayn tr NCGF ieren doymam vinilester (VE)
kompozitlerinin test sonularyla kyaslanmtr. IPCBT ve VE kompozitlerinin krlma
zarflar ve IPCBT kompozitlerinin olumlu ve olumsuz ynleri deerlendirilmitir. ekil
1 ve 2 UD kompozitlerin krlma zarflarn gstermektedir. IPCBT kompozitin VE
muadiliyle rekabet edebilir tasarm blgesi koyu renkli olarak belirtilmitir.
Krlma zarflarna gre yaplan incelemelerde IPCBT kompozitlerinin zellikle tek
ynl bask yklemelerinde VE tabanl kompozitlere gl bir alternatif olabilecei
de anlalmtr. Darbe dayanmnn ise VE kompozitlerin dayanmndan 2 kat daha
fazla olduu saptanmtr.
ekil 1 : IPCBT ve VE kompozitlerinin 2-6 blgesindeki krlma zarflar
xxvi
ekil 2 : IPCBT ve VE kompozitlerinin 1-2 blgesindeki krlma zarflar
Sonu olarak, NCGF tekstili takviyeli IPCBT kompozitleri barl olarak retilmitir.
ncelikle IPCBT kompozitlerinde prepreg retimi ve kompozit retimi iin en uygun
proses deikenleri belirlenmitir. Literatr sonularyla kyaslandnda
prepgreglerden retilen IPCBT kompozitlerinin RTM le retilen ve bilinen PBT
matrisli kompozitlere gre daha iyi eme ve ekme zellikleri gsterdii grlmtr.
RTM teknii ve bilinen PBT kompozit retim yntemleriyle kyaslandnda bu yeni
yntemle proses sresi ve enerji tketiminin de drlebilecei gzlenmitir. Ayrca
yaplan almalarda, IPCBT kompozitlerinin prepreglerinden sadece baskyla
kalplama yntemiyle deil kompozitin ekme ve eme dayanmnda art
salayabilen vakumla kalplama ytemiyle de retilebilecei de grlmtr.
PA matrisli NCGF takviyeli kompozitler de prepreglerden baskyla kalplama
yntemiyle baaryla retilmitir. IPCBT kompozitlerinin ekme dayanmlarnn PA
kompozitlerinin ekme dayanmlardan daha yksek olduu tespit edilmitir.
IPCBT ve PA prepregleri kullanlarak PA kpk ara malzemesi ieren sandvi yapl
kompozit plakalar da baaryla retilmitir. Ancak yaplan lmlerde TP kompozit
yzeyi ile ara malzemenin arasndaki balanma mukavemetinin dk olduu
saptanm ve baskyla kalplamann tek admda sandvi plaka retimine uygun
olmad grne varlmtr.
xxvii
xxviii
1. INTRODUCTION
The polymers play very important role in our daily life. They can be combined with
different materials to achieve special properties according to end use applications.
Since the combinaton of them with the fibers improves their mechanical properties,
fiber reinforced polymers are used in many applicaiton areas. In structural polimeric
composite applications, textiles (e.g., unidirectional, woven fabrics) are commonly
applied as reinforcement because of the high fiber volume fractions that can be
obtained and because of the possibility to tailor the load bearing capacity through
the fiber lay-up. Thermoset resins are used in textile reinforced composite industry
as the matrix over 90% because of their easy process ability. Although,
thermoplastic resins are used in niche market, mainly due to their difficulties in
processing, they started to be an increasingly important issue in composite market
[1-3]. The investigations on manufacturing of TP composites increased in recently
years because of their advantages over thermoset composites such as ease of
recycling, high toughness, impact resistance and the restrictions of health and
environment rules [4-6]. Chopped fiber reinforced TP composites can be easily
produced with extrusion and injection process but they are limited to non-structural
applications because there is little control over ber orientations due to the use of
short bers that ow with the matrix during processing and the relatively low ber
contents (i.e. less than 40% by weight). Continuous fiber reinforced TP composites
have higher mechanical properties but they have limited production methods [7-11].
Traditionally, textile fiber-reinforced TP composites are processed by stacking
alternating layers of fiber textiles and polymer sheets in a hot-press. After heating
the package above the polymer melting point, the press is closed to obtain the
required product shape. In a subsequent cooling step the product solidification takes
place followed by demolding. Traditional melt processing, however, limits
thermoplastic composite parts in size and thickness. The main problem in using
thermoplastic resins is their high melt viscosity, which causes the poor impregnation
of the fibrous reinforcement and the processing difficulties, necessitates higher
pressures and adds expense [12]. In order to facilitate the fiber impregnation,
reducing the required flow length of the polymer matrix by, e.g. using commingled
yarns [13], or decreasing the viscosity during impregnation [14] are the main
1
methods investigated up today. One approach is the reactive processing of textile
fiber-reinforced thermoplastics based on impregnation of the fibers with a low
viscosity oligomeric precursor, followed by in situ polymerisation [15]. This approach
has been studied recently with the using of cyclic oligomers, such as cyclic butylene
terephthalate (CBT), have a low processing viscosity which can be called as water-
like [16-18]. Because cyclic oligoesters can be transformed into linear high
molecular weight thermoplastics with entropically driven ring-opening polymerisation
in a short time, they can be processed under isothermal conditions. Therefore, the
viscosity of the CBT matrix is sufficiently low and the processes which are currently
associated to manufacturing of thermoset composites like resin transfer molding
(RTM), vacuum infusion and resin film infusion, might be used for manufacturing of
thermoplastic composite parts [19]. There are some records on reactive
thermoplastic RTM, where the continuous reinforcement is impregnated with
polymeric precursors following that a chemical reaction takes place to form
thermoplastic matrix [15, 20]. Although RTM is useful process for production of
continuous glass fiber reinforced composites, narrow impregnation time needed for
complete wetting of the fibers, necessity of special equipment, time waste during
resin mixing and infusion can be eliminate, the cost can be reduced by using pre-
pregs [21-23]. Since the application of CBT for continuous fiber reinforced
thermoplastic composites was concerned there is no a published work on the
production of non-crimp glass fiber reinforced in situ polymerised CBT (IPCBT-
NCGF) composites out of CBT coated prepregs.
1.1 Purpose of the Thesis
The current study focuses on the manufacturing of non-crimp glass fiber reinforced
(NCGF) thermoplastic (TP) matrix composites. For this purpose, two kinds of TP
resin were used as IPCBT and PA12 seperately. NCGF reinforced composite
laminates were produced out of CBT/catalyst coated NCGF fabrics and PA12
coated NCGF fabrics via compression molding method. In this context, firstly pre-
pregs (Prepreg is defined as a semi product composite material which is a fiber
reinforcement impregnated with a resin) were manufactured by scattering of powder
resin onto NCGF. All powder was fixed on fibers by heating and melting of the resin
at its melting temperature. Afterwards, various composite laminates were produced
with these prepregs by compression moldig in hot press. Several layers of pre-pregs
were placed into a metal mold and compressed under pressure at a temperature
higher then melting point of the resin. The effects of prepreg manufaturing
2
parameters such as temperature, time, production rate and the prepreg conditioning
on end composites were investigated. Moreover, compression molding parameters
such as temperature, time, pressure, and composite properties such as
reinforcement type, fiber content and laminate thickness were investigated in order
to determine most suitable composite production method considering the effects of
them on mechanical properties and the processability of these pre-pregs. The
analysis results of these composites were compared with those of composites
produced by other methods in the literature.
1.2 Hypothesis
This study provided a new manufacturing method to produce thermoplastic

composites including continuous glass fiber with various advantages such as time
and energy saving, easy process ability, better composite properties when it is
compared with other TP composites produced with different production methods.
Moreover, newly initiated method provides recyclability, health and environment
advantages when it is compared with its thermoset counter parts.
3
4
2. LITERATURE REVIEW
A composite, in general, is defined as a combination of two or more component

differing in form or composition on a macro scale, with two or more distinct phases
having recognizable interfaces between them [24]. Polymeric composites consist of
a polymer as the matrix and reinfrocement which gives a specific property apart
from matrix. The polymer matrix acts to hold the reinforcement material together and
protect them, and to transfer the load to the reinforcement in the fabricated
composite part. The reinforcing fibers, which are generally used in polymeric
composites, impart strength and other required properties to the composite.
Polymeric composites can be produced with two kinds of matrix polymer known as
thermoplastic and thermoset. The common feature of thermoset polymeric
composite processes is the combining of a resin, a curing agent (initiator), some
type of reinforcing fiber, and in some cases a solvent. The curing agent, also known
as hardener, acts as a catalyst and helps in curing the resin to a hard plastic. In the
production of reinforced thermoplastic composites, heat and pressure are used to
shape the mixture into a finished part. Reinforcement fibers can be found in several
forms such as chopped, uni directional continuous, woven etc. The polymeric
composites including chopped fiber can be produced by injection and extrusion of
thermoplastic polymers. There are several methods to produce composites including
continuous fiber reinforcement for both thermoset and thermoplastic matrices.
These methods will be explained detailed in Section 2.4.
2.1 Continuous Fiber Reinforced Polymeric Composites (CFRPCs)
Fiber reinforced plastics are a subdivision of composites field in which the matrix is a
polymer (or plastic) and the reinforcement is always a fiber. CFRPCs are typically
organized in a laminate structure, such that each lamina (or flat layer) contains an
arrangement of unidirectional fibres or woven fibre fabrics embedded within a thin
layer of light polymer matrix material. The fibres, typically composed of carbon,
glass or aramid, provide the strength and stiffness. The matrix, commonly made of
thermosets such as polyester, vinylester, epoxy or thermoplastics such as PP, PA,
PET, PBT binds and protects the fibers from damage, and transfers the stresses
between fibers [25].
5
2.2 Reinforcement Materials Used in FRPCs
Fiber reinforcement materials are added to the resin system to provide strength to
the finished part. The selection of reinforcement material is based on the properties
desired in the finished product. These materials do not react with the resin but are
an integral part of the advanced composite system.
2.2.1 Type of fibers
Three basic types of fiber reinforcement materials in use in the advanced composite
industry are carbon, aramid, glass fibers.
2.2.1.1 Carbon fiber
The most commonly prefered reinforcement materials are carbon/graphite fibers.

(The terms graphite and carbon are often used interchangeably.) This is due to the
fact that many of the desired performance characteristics such as high tensile and
compressive properties and high modulus values require the use of carbon/graphite
fibers. Currently, these fibers are produced from three types of materials known as
precursor fibers:
polyacrylonitrile (PAN)
rayon
petroleum pitch
The carbon/graphite fibers are produced by the controlled burning off of the oxygen,
nitrogen, and other noncarbon parts of the precursor fiber, leaving only carbon in the
fiber. Following this burning off (or oxidizing) step, the fibers are run through a
furnace to produce either carbon or graphite fibers. Carbon fibers are produced at
furnace temperatures of 1,000-2,000C, while graphite fibers require temperatures
of 2,000-3,000 C. At these temperatures the carbon atoms in the fibers are
rearranged to impart the required characteristics to the finished fiber. The PAN-
based fiber is the more commonly used precursor in the advanced composite
industry today. In the carbon fiber reinforced composites, the matrix polymer
preferred is most often epoxy, but other polymers, such as polyester, vinyl ester or
nylon, are sometimes used. The composite may contain other fibers, such
as Kevlar, aluminium, or glass fibers, as well as carbon fiber. Although carbon fiber
can be relatively expensive, it has many applications in aerospace and automotive
fields, such as Formula One. The compound is also used in sailboats, modern
bicycles and motorcycles, where its high strength-to-weight ratio and good rigidity is
of importance.
6
2.2.1.2 Aramid fiber
Aramid fibers are another human-made product. These fibers are produced by
manufacturing the basic polymer, then spinning it into either a paper-like
configuration or into fiber. Aramid fibers have several useful characteristics such as
high strength and modulus, temperature stability, flex performance, dimensional
stability, chemical resistance, textile processability [26]. Aramid fibers have very low
density and high specific tensile strength when compared to commonly available
reinforcing fibers. They are best known for their use in bullet proof vests, chainsaw
pants, safety gloves and other applications where cut resistance and damage
tolerance are required. The main advantages of aramid fibers are [28]:
Light weight
High impact damage tolerance
High tensile strength
Moderately high tensile modulus (midway between E-glass & HS carbon)
Excellent vibration damping
Low (negative) longitudinal thermal expansion
The main disadvantages of aramid are:
Very low compressive strength
Susceptibility to UV radiation
Difficult to machine
High moisture absorption
Very high transverse thermal expansion
2.2.1.3 Glass fiber
Glass fiber is an inorganic fiber which has an amorphous structure. It can

be extruded into many fibers with small diameters suitable for textile processing. The
technique consists of heating and drawing glass into fine fibers. By blending quarry
products (sand, kaolin, limestone, colemanite) at 1600C, liquid glass is formed. The
liquid is passed through micro-fine bushings and simultaneously cooled to produce
glass fibre filaments from 5-24m in diameter. The filaments are drawn together into
a strand (closely associated) or roving (loosely associated), and coated with a
coupling agent namely sizing to provide filament cohesion and protect the glass
from abrasion. However, the choice and composition of ingredients varies to some
extent depending on the end use requirements. There are different types of glass
fibers commercially available all of which have different compositions and very often
specific technical significance. AR-glass is alkali-resistant glass used in the form of
fibers for reinforcement. C-glass has a chemically-resistant glass composition used
for fiber manufacturing. E-glass has an almost universally acceptable formulation
and has become a standard for most of the uses in fiber and relted products-the
7
letter E stands for electrical, as the composition has a high electrical resistance.
HS-glass is high strength glass fiber. Over 90% of all continuous glass fibers
produced are E glass composition [27, 28].
E Glass fibre is available in the following forms:
Strand - a compactly associated bundle of filaments. Strands are rarely seen

commercially and are usually twisted together to give yarns.
Yarns - a closely associated bundle of twisted filaments or strands. Each filament

diameter in a yarn is the same, and is usually between 4-13 micron. Yarns have
varying weights described by their tex (the weight in grammes of 1000 linear
metres) or denier ( the weight in lbs of 10,000 yards), with the typical tex range
usually being between 5 and 400.
Rovings - a loosely associated bundle of untwisted filaments or strands. Each

filament diameter in a roving is the same, and is usually between 13-24 micron.
Rovings also have varying weights and the tex range is usually between 300 and
4800. Where filaments are gathered together directly after the melting process, the
resultant fibre bundle is known as a direct roving. Several strands can also be
brought together separately after manufacture of the glass, to give what is known as
an assembled roving. Assembled rovings usually have smaller filament diameters
than direct rovings, giving better wet-out and mechanical properties, but they can
suffer from catenary problems (unequal strand tension), and are usually higher in
cost because of the more involved manufacturing processes.
It is also possible to obtain long fibres of glass from short fibres by spinning them.
These spun yarn fibres have higher surface areas and are more able to absorb
resin, but they have lower structural properties than the equivalent continuously
drawn fibres.
E-glass (Electrical grade glass) is by far the most used fiber in reinforced polymer
composites. In many industries it represents over 90% of the reinforcements used.
Its main advantages are:
Low cost
High strength
Light weight (relative to steel)
High chemical resistance
The main disadvantages are:
Low modulus (relative to other reinforcing fibers)
8
Low fatigue resistance (relative to carbon fibers)
High weight (relative to other reinforcing fibers)
Highly abrasive when machined
Susceptibility to stress corrosion
Because of its widespread use, the advantages have a tendency to outweigh the
disadvantages. Almost all glass fibers are sold in strands of grouped fibers, or
rovings, associated with a particular yield. The yield is the number of yards of roving
per pound. The metric unit of measure is TEX which is the weight in grams per
kilometer (1,000 meters). The equation (2.1) for conversion between TEX and yield
(YPP) is:
(2.1)
For stitch bonded reinforcement fabrics, typical roving sizes used range from 1800
to 113 yield (276 to 4390 TEX). Some common glass yields and filament diameters
are given in Table 2.1 below:
Table 2.1 : Glass fiber yield points according to fiber diameter.
TEX (g/1000 m) Yield (yield/lb) Fiber diameter (m)
44390 113 24
2400 206 17
1100 450 17
735 675 13
276 1800 13
The diameter of the individual filaments can be important because it represents the
ratio of surface area of the fiber to its volume. Smaller filament diameters give
higher surface area to volume ratios, which means there is more area for resin to
bond to. Smaller filaments may give slightly better properties in some instances [27-
28].
9
2.2.2 Surface treatment of the fibers: Compatibility between fiber and polymer
For adhesion to occur it is essential that intimate contact is established between the
matrix and the fibre. The ability of the matrix to wet the fibre during processing
depends on the relative surface tension between the fibre and the matrix. If the
matrix surface tension is lower than that of the fibre, spontaneous wetting may occur
as long as the viscosity of the matrix is favourable [5]. However, to ensure good
interfacial adhesion and stress transfer across the interface, chemical or physical
interactions between the matrix and the fibre need also to be formed. Coupling
agents are used to provide a stable bond between two otherwise nonbonding and
incompatible surfaces. They are molecules which have one end that is compatible
the silane structure of the glass and the other end that is compatible with the matrix.
They can be thought of as bridges connecting the reinforcement and the matrix [25].
In reinforced and filled plastics, the improved bond between the fibrous or particulate
inorganic component and the organic matrix polymer results in greater composite
strength and longer service life. Organofunctional silanes are the best known
coupling agents for glass fiber, and their effect is based on their typical special
chemical structure. Y-Si(OR)3 is the main formula where OR is a hydrolyzable group
such as methoxy, ethoxy, or acetoxy, and XY is an organofunctional group such as
amino, methacryloxy, epoxy, etc. These two type of groups exhibit different reactivity
and allow sequential reactions. In the crosslinking process, the first step is generally
the grafting of the silane the polymer backbone the linking of the polymer chains via
condensation of silanols. An amino or chloropropyl functional silane on the surface
of the glass lends itself to coordination with the amidegroups and possibly coupling
of polyamides to the glass surface. For aramid fibers non-ionic emulsifiers
containing ethylene oxide and propylene oxide tails are the most common process
aids during fiber spining process as a coupling agent [30].
2.2.3 Forms of reinforcements
Fibers used in advanced composite manufacture come in various forms, including

yarns, rovings, chopped strands, woven fabric, mats. Each of these has its own
special application. When prepreg materials are used in parts manufacture, woven
fabric or mats are required. In processes such as filament wet winding or pultrusion,
yarns and rovings are used [26]. Table 2.2 demonstrates different reinforcement
forms and their application areas with the advantages [24].
10
Table 2.2 : Reinforcement forms and application areas with advantages.
Reinforcement Advantages Applications
Sports goods
Tape High stregth and stiffness in one direction
Aircraft primary structures
Prsessure vessels
Suitabe for filament winding
Drive shafts
Single Tow Very narrow width for accurate fiber
Tubes
placement (1mm)
High strength and stiffness in one
Yact masts
direction
Strips Leaf springs
High fiber weights=1000g/m2
Skis
Economic processing
For composnents requiring predominant Aerospace
Fabrics>80%
strangth and stiffness in one direction Insutrial
warp
Weights from 160-1000g/m2 Sport leisure
Strength and stiffness in two directions
Very good handling characteristics
Aerospace
Balanced Good drape
Industrial
fabrics Choice of weave styles
Sport and lesiure
Possible to mix fibers
Weight from 20 to 1000 g/m2
Strangth and stiffness in multiple
drections
Aeropspace
Control of fber orientation
Marine
Abilitiy to optimise weight distibution in
Pipe
fabric
Multiaxials Automotive
Possible to mix fibers
Wind tribuns
No crimp
Sports and lesiure
Less waste for complex lay-ups
Indusrial
Reduced processing cost
Heavy weights achievable
Continuous filament reinforcements are very important materials for high-end

applications such as aerospace; the orientation of the fibrous reinforcement is
becoming more and more important from a load-bearing point of view as well as the
need for placing the reinforcement oriented in the third dimension. In this context,
the use of textile structures made from high-performance fibers is finding increasing
importance in composites applications. In textile processes, there is direct control
over fiber placements and ease of handling of fibers. In addition to economic
advantages, textile technologies also provide homogenous distribution of matrix and
reinforcing fiber. Thus, textile preforms are considered to be the structural backbone
of composite structures [15].
Woven and non-crimp multiaxial reinforcements are most commonly used

reinforcement forms in composite structures. Multiaxial (non-crimp) reinforcements
provide many advantages over woven fabrics such as:
11
Increased mechanical properties of end-product
Reduced weight of end-product
Design flexibility
Lower resin consumption
Faster and easier wet-out
Improved surface quality; reduction of print-through effect;
Reduced lay-up time
Reduced labor costs
Increased output
Figure 2.1 illustrates these advantages with a basic comparison of a woven fabric
and a non-crimp 0/90 reinforcement. Resin pocket and crimp effect cause higher
resin consumption, low mechanical properties and cracking. Besides, non-crimp
structure reduces the resin consumption and increases mechanical properties [29].
Figure 2.1 : Differences between woven and multiaxial reinforcements [29].
Woven fabrics can be found in different forms according to their weaving types, See
Fig. 2.2.
Figure 2.2 : Woven fabrics from high tenacity fibers [29].
Multiaxial reinforcements can consist from four layers where fiber orientations are in
all basic directions; 0/+45/90/-45. Fibers are generally stabilised by stitching using
flexible thermoplastic yarns (PET, PBT, PA etc.) to avoid any possible damage
during handling and processing of the reinforcement. Stitching pattern can vary as
12
being stiff or flexible according to requirements of composite production process.
Figure 2.3 represents a basic scheme of a multiaxial reinforcement which includes
all possible directions and the other elements.
Figure 2.3 : Basic scheme of a multiaxial structure [29].
Non crimp multiaxials can consist of fiber layers varying form uniaxial to quadriaxial.
Non crimp multiaxials including different numbers of layers can be seen in Figure
2.4.
QUADRIAXIAL BIAXIAL UNIAXIAL
Figure 2.4 : Non crimp multiaxials including different numbers of layers [29].
2.3 Polymer Systems in CFRPCs Production
The polymer systems used to manufacture advanced composites are of two basic
types: thermosetting and thermoplastic. Thermosetting polymers predominate today,
while thermoplastics have only a minor role in advanced composites manufacture
[26]. Polymer matrix material is called as the resin in composite industry.
13
2.3.1 Thermoset polymers
Thermosetting materials, or 'thermosets', are formed from a chemical reaction in

situ, where the polymer and hardener or resin and catalyst are mixed and then
undergo a non-reversible chemical reaction to form a hard, infusible product.
Thermoset resins require addition of a curing agent or hardener and impregnation
onto a reinforcing material, followed by a curing step to produce a cured or finished
part. Once cured, the part cannot be changed or reformed, except for finishing.
Although there are many different types of resin in use in the composite industry, the
majorities of structural parts are made with three main types, namely polyester,
vinylester and epoxy.
Polyester resins are the most widely used resin systems, particularly in the marine
industry. Polyester resins such as these are of the 'unsaturated' type. Unsaturated
polyester resin is a thermoset, capable of being cured from a liquid or solid state
when subject to the right conditions. Most polyester resins are viscous, pale
coloured liquids consisting of a solution of polyester in a monomer which is usually
styrene. The addition of styrene in amounts of up to 50% helps to make the resin
easier to handle by reducing its viscosity. The styrene also performs the vital
function of enabling the resin to cure from a liquid to a solid by 'cross-linking' the
molecular chains of the polyester, without the evolution of any by-products. These
resins can therefore be molded without the use of pressure and are called 'contact'
or 'low pressure' resins. Polyester resins have a limited storage life as they will set
or 'gel' on their own over a long period of time. Often small quantities of inhibitor are
added during the resin manufacture to slow this gelling action. For use in molding, a
polyester resin requires the addition of several ancillary products. These products
are generally: Catalyst, accelerator, additives [26, 28].
Vinylester resins are similar in their molecular structure to polyesters, but differ
primarily in the location of their reactive sites, these being positioned only at the
ends of the molecular chains. With the reduced number of ester groups in a
vinylester when compared to a polyester, the resin is less prone to damage by
hydrolysis. The material is therefore sometimes used as a barrier or 'skin' coat for a
polyester laminate that is to be immersed in water, such as in a boat hull. The cured
molecular structure of the vinylester also means that it tends to be tougher than
polyester, although to really achieve these properties the resin usually needs to
have an elevated temperature postcure [28].
14
Epoxy resins have been in use in the industry for over 40 years. The basic epoxy
compounds most commonly used in industry are the reaction product of
epichlorohydrin and bisphenol-A. Epoxies differ from polyester resins in that they are
cured by a 'hardener' rather than a catalyst. The hardener, often an amine, is used
to cure the epoxy by an 'addition reaction' where both materials take place in the
chemical reaction. The chemistry of this reaction means that there are usually two
epoxy sites binding to each amine site. This forms a complex three-dimensional
molecular structure. Usually identifiable by their characteristic amber or brown
colouring, epoxy resins have a number of useful properties. Both the liquid resin and
the curing agents form low viscosity easily processed systems. Epoxy resins are
easily and quickly cured at any temperature from 5C to 150C, depending on the
choice of curing agent. One of the most advantageous properties of epoxies is their
low shrinkage during cure which minimizes fabric 'print-through' and internal
stresses. High adhesive strength and high mechanical properties are also enhanced
by high electrical insulation and good chemical resistance.
The second of the essential ingredients of an advanced composite system is the

curing agent or hardener. These compounds are very important because they
control the reaction rate and determine the performance characteristics of the
finished part. Since these compounds act as catalysts for the reaction, they must
contain active sites on their molecules [24].
2.3.2 Thermoplastic polymers
Thermoplastics currently represent a relatively small part of the PMC industry. They
are typically supplied as nonreactive solids (no chemical reaction occurs during
processing) and require only heat and pressure to form the finished part. Unlike the
thermosets, the thermoplastics can usually be reheated and reformed into another
shape, if desired.
Thermoplastic polymers can be divided into two classes, high temperature

thermoplastics and the engineering thermoplastics. The classification is based on
the maximum service temperature of the polymers, which in turn is based on the
Glass Transition (Tg) temperature. Thermoset polymers may not usefully carry
mechanic loads above Tg, but semi-crystalline thermoplastic polymers may carry
load above Tg, as only the amorphous phase of the polymer has become rubbery.
The crystalline portion of the polymer remains solid until the melt temperature, Tm.
[31].
15
Table 2.3 shows the most commonly used high temperature thermoplastic polymers
for thermoplastic composites. Table 2.4 shows the engineering thermoplastic
polymers used in composites.
Table 2.3 : High temperature thermoplastics.
Matrix Morphology Tg (C) Process Temp (C) Cost (Relative)
PEEK SC 143 390 $$$
PEI A 217 330 $$
PPS SC 89 325 $
PEKK SC 156 340 $$
Table 2.4 : Engineering thermoplastics.
Matrix Morphology Tg (C) Process Temp (C) Cost (Relative)
PBT SC 56 190 $$
PA-6 SC 48 220 $
PA-12 SC 52 190 $
PP SC -20 190 $
The vast number of thermoplastic resins used in composite materials can

conveniently be separated into two categories:
1. The traditional industrial (engineering) thermoplastics which have been used with
short fiber reinforcements for many years.
2. A new set of high-performance thermoplastics which have been developed
specifically for use in advanced composites.
The conventional or industrial plastics which are common in our everyday lives
(polyethylene, nylon, polystyrene, polyester, polycarbonate, acrylic etc.) can also be
reinforced to improve their strength and rigidity. The choice of which conventional
resin to use is often dictated by properties associated with the resin, such as cost,
environmental resistance, processability, lubricity, resistance to creep, or many
others [25].
16
2.3.3 Advantages and disadvantages of thermoplastic & thermoset matrices
The inherent differences between thermoplastics and thermosets give each type of
resin some distinct advantages over the other. Thermoplastics do not require
reactive cure cycles, but are supplied as essentially nonreactive solids which require
only heat and pressure with subsequent cooling to form them. This has obvious
savings in processing time and equipment costs, but for some processes requires
that the resin diffuse quickly to coat the reinforcement during the relatively short
period of time that the resin has low viscosity. On the other hand, cured thermosets
have much higher molecular weights (since all the polymer chains are tied into one
large network), and this results in improved strength and modulus, but diminished
elongation and toughness. Furthermore, fibrous sheets already impregnated with
resin (prepregs) which are made from thermoplastics have an infinite shelf life,
compared to the limited life of thermoset prepregs. The thermoplastic prepregs are
stiff and without drape or tack which are present in the thermosets before curing. It
is obvious, therefore, that in the choice of thermoplastic versus thermoset resin,
several tradeoffs and compromises must be made. A summary of these trade-offs is
given in Table 2.5 [25].
Table 2.5 : Comparison of typical thermoset versus thermoplastic.
THERMOSET THERMOPLASTIC
(FIBERITE 931 EPOXV) (ICI APC-2 PEEK)
Melt Viscosity Low High
Fiber mpregnation Easy Difficult
Prepreg Tack Good None
Prepreg drape Good Poor
Prepreg Stability at 0F 6 mos.-1 yr. Indefinite
Processing Cycle 1-6 hrs. 15 Sec.-6 hrs.
Processing Temperature 350F 700F
Mechanical Properties Good Good
Environmental Durability Good Exceptional
Damage Tolerance Average Good
Database Large Average
17
The single biggest advantage of thermoset polymers is that they have a very low
viscosity and can thus be introduced into fibres at low pressures. Impregnation of
the fibres is followed by chemical curing to give a solid structure, which can usually
be carried out isothermally. An advantage of thermoplastics is that the molding can
be carried out non-isothermally, i.e. a hot melt into a cold mold, in order to achieve
fast cycle times. However, polymerised thermoplastics tend to have melt viscosities
between 500 and 1000 times that of thermosets, which necessitates higher
pressures, causes processing difficulties and adds expense.
Thermoplastic composite polymers can, however, be readily recycled, an

increasingly important issue in many markets, but especially in the automotive
sector. For instance, an advanced thermoplastic composite component can be
chopped to pellet-size and injection-molded to yield long-fibre reinforced moldings,
which can in turn be recycled at the end of their life. Thermoset composite materials,
on the other hand, can only be ground and used as filler, a process which decreases
the value of the composite enormously.
Another advantage of thermoplastic composites are their superior impact and

damage resistance properties. Over 90% of polymers used in composites are
thermosets, with thermoplastic composites still a niche market, mainly due to the
difficulties in processing.
There are also significant environmental issues associated with thermoset

processing, as a chemical reaction is necessary to form the solid structure of the
polymer. Approximately 65% of thermoset matrices used in structural composites
are unsaturated polyesters. Environmental regulations regarding the styrene
emissions of unsaturated polyester are affecting the total cost associated with using
them. Because of this, many people are willing to consider a substitute for
unsaturated polyester at a higher price.
In summary, thermoplastic composites to date have needed high processing

pressures, and hence expensive product tooling, as well as significant energy input
in heating and cooling the tooling. These disadvantages have in many areas
outweighed the advantages of these materials such as ease of recycling and high
toughness, and limited their applications. On the other hand, thermoset composites
are easier to process, requiring less energy and pressure, but are inherently brittle
and cannot be usefully recycled [25, 31].
18
2.4. CFRPCs Manufacturing Methods
2.4.1. Manufacturing with thermoset resins
2.4.1.1 Prepregging
Prepregging involves the application of formulated resin products, in solution or

molten form, to reinforcement such as carbon, fiberglass or aramid fiber or cloth.
The reinforcement is saturated by dipping through the liquid resin (Figure 2.5). In an
alternate method called a hot melt process the resin is impregnated through heat
and pressure. The hot melt system uses resins with a very low percentage
of solvents.
Figure 2.5 : Representation of prepreg production method [26].
2.4.1.2 Wet filament winding
In the filament wet winding process, continuous fiber reinforcement materials are
drawn through a container of resin mixture and formed onto a rotating mandrel to
achieve the desired shape (Figure 2.6.). After winding, the part is cured in an oven.
This process can also used preimpregnated fiber tows called towpregs.
19
Figure 2.6 : Representation of filament winding method [26].
2.4.1.3 Hand lay-up of prepreg
The prepreg product is trimmed and laid down over a mold where it is formed to the
desired shape. Several layers may be required. After forming, a vacuum bag is
sealed around the lay-up (2.7). Vacuum is pulled on the raw prepreg to remove air,
compact the part and serve as a barrier when the assembly is placed in an
autoclave for cure under heat and pressure. Oven cures (under vacuum only) may
be used for non-structural parts.
Figure 2.7 : Representation of hand lay-up method of prepreg [26].
2.4.1.4 Resin transfer molding (RTM)
RTM is used when parts with two smooth surfaces are required or when a low-
pressure molding process is advantageous. Fiber reinforcement fabric or mat is laid
by hand into a mold and resin mixture is poured or injected into the mold cavity
(Figure 2.8). The part is then cured under heat and pressure.
20
Figure 2.8 : Representation of RTM [26].
2.4.1.5 Infusion process
Fabrics are laid up as a dry stack of materials as in RTM. The fibre stack is then
covered with a peel ply fabric and a knitted type of non-structural fabric. The whole
dry stack is then vacuum bagged, and once bag leaks have been eliminated, resin is
allowed to flow into the laminate. The resin distribution over the whole laminate is
aided by resin flowing easily through the non-structural fabric, and wetting the fabric
out from above (Figure 2.9.) Fibres: Any conventional fabrics. Stitched materials
work well in this process since the gaps allow rapid resin transport [32].
Figure 2.9 : Representation of infusion process [29].
2.4.1.6 Vacuum bagging, autoclave cure
Most parts made by hand lay-up or automated tape lay-up must be cured by a
combination of heat, pressure, vacuum, and inert atmosphere. To achieve proper
cure, the part is placed into a plastic bag inside an autoclave (Figure 2.10). A
vacuum is applied to the bag to remove air and volatile products. Heat and pressure
are applied for curing. Usually an inert atmosphere is provided inside the autoclave
21
through the introduction of nitrogen or carbon dioxide. Exotherms may occur if the
curing step is not done properly.
Figure 2.10 : Representation of vacuum bagging in autoclave [26].
2.4.2 Manufacturing with thermoplastic resins
The short fiber reinforced thermoplastics are more commonly used in composite
manufacturing because using discontinuous (or chopped, short etc.) fibers shows
less problems. The mixing fibers and matrix in an extruder or injection can solve the
processing problems due to the high melt viscosity of the matrix by introducing high
shear forces that allow the fibers to be distributed evenly into the matrix. However, in
structural composite applications short fiber reinforced thermoplastics do not meet
the needs of applications. Therefore, textiles are commonly applied as
reinforcement because of the high fiber volume fractions that can be obtained and
because of the possibility to tailor the load bearing capacity through the fiber lay-up.
There are important two stages which have to done to achieve of well wetted
CFRPC with TP matrix. First stage is to provide intimate mechanical mingling of the
fiber and the matrix. Second stage is impregnation and consolidation using a
combination of heat and pressure. The first stage is critical as it brings together the
resin and reinforcement in such away that it minimises the subsequent flow length
required to achieve impregnation and creats the reinforcing synergy in the final
structure. Figure 2.11 represents impregnation of fibre bundle by resin under
pressure.
22
Figure 2.11 : Impregnation of a fiber bundle by resin under an applied pressure[21].
A flow length, X, can be used to describe the distance that the resin must flow to
achieve the required impregnation level at the end of stage 1. For stage 2 a simple
model relates the flow velocity (U) of the resin in the fiber bundle from Equation 2.2.
where S is the permability of the fiber bundle, is the matrix viscosity and P is to
applied pressure.
= = (2.2)
By integrating this equation and assumng a constant permeability during the

impregnation process, the time required to fully impregnate fibers bundle, timp can be
estimated by Equatin 2.3.,
= (2.3)
Equation 2.3 demonstrates the main parameters that influence the impregnation
process. The obvious objective when processing composites is to minimise the
impregnation time and it is demonstrated from equation that this can be achieved by
minmising the required flow length, X. As the viscosity of thermoplastic resins is
much higher than those of thermosets, it follows from the equation that
thermoplastic systems can not be processed using the same techniques. The
23
impregnation process can be accelerated by increasing the applied pressure, but
the maximum that can be applied is limited by the compression resistance of the
fibers. It can be seen that particular processing techniques need to be aplied to
manufacture these high viscosity resin composites at intermadiate pressure. A
number of different techniques have been developed, yet they can be grouped into
two principal areas; a process which aims to reduce the viscosity in orde to achieve
rapid impregnation, the pre-impregnation process, and the process that aims to
reduce the distance that the resin is required to flow which involve intimate mixing of
constitutents prior to melting, the mingling process. Figure 2.12 shows alternative
process routes of CFRPCs with TP matrix.
Fiber+resin
Pre-impregnation Process Intimate Mingling Techniques

-Melt impregnation -Film Stacking
-Solution impregnation -Fiber Hybridisation
-Powder impregnation
Pre-pregs Pre-pregs
-Tape, -Woven /NCF from commingled yarns
-Woven -Powder coated woven /NCF
-NCF -Film Coated woven /NCF
Figure 2.12 : Alternative processing routes for CFRTPCs [21].
2.4.2.1 Film stacking
Film stacking of textiles is melt processed by stacking alternating layers of fiber

textiles and polymer sheets in a hot-press. After heating the package above the
polymer melting point, the press is closed to obtain the required product shape. In a
subsequent cooling step the product solidification takes place followed by
demolding. Although this process is simple and less expensive than the others, it
has disadvantages.It is difficult to achieve complex shapes because the stacks are
not very drapeable. Moreover, the mingling intimacy is rather low and therefore this
technique is not suited for very dense fabrics and high fiber volume fractions [21].
24
2.4.2.2. Hybrid yarns and fabrics
Hybridisation of thermoplastic fibers and reinforcing fibers is another method for

intimate mingling techniques. A hybrid yarn consists of a blended combination of
reinforcing filament yarn and filament yarn spun from thermoplastic polymers. The
multifilament yarns are distributed amongst one another at filament level. Hybrid
yarns can be manufactured by various means, including co-wrapping, core spinning
and commingling, aiming to give uniform distribution of matrix and reinforcement
fibers as well as to reduce the damage to reinforcing fibers.
In co-wrapping, thermoplastic fibers are wrapped around a core of reinforcing fibers.

This provides better protection for the reinforcing fibers during further processing,
such as weaving or braiding. However, inhomogeneous distribution of the
reinforcing and matrix yarns may lead to poor impregnation and does require higher
processing temperatures and pressures. In friction spinning or core spinning, short
thermoplastic fibers are spun around a core of continuous reinforcing fibers.
In commingling, the reinforcing and matrix fibers are intimately mixed in a nozzle by
means of compressed air. Among these hybrid yarns, commingled yarns provide
high potential for thorough blending of matrix-forming filaments and high-
performance fibers [9, 11].
Another commingling method namely online commingling was developed to avoid

fiber damage during air pressure application. In this method commingling is made by
separate spinning of E-glass fibre (GF) and TP filaments [10]. After preforming of
hybrid yarns into the woven or NCF, hybrid preforms can be consolidated to form an
end composite by compression or vacuum consolidation [13, 33]. Figure 2.13
demonstrates various hybrid yarn types produced with different hybridisation
methods [9].
25
Figure 2.13 : Hybrid yarn structures and corresponding production technology [9].
2.4.2.3 Powder impregnation
In powder impregnation technique, thermoplastic powder particules were

incorporated into the fibres. The dry powder particles adhere electrostatically to the
fibres but since these forces are too weak, to stabilise the powder to the fibre
surface the system is subsequently heated by passing it through an oven. The
advantages of dry powder porcess over other processes can be summiresed as
follows [21, 34]. The reduction in flow length required for impregnation which takes
place paralel, rather than perpendicular to the fibres, allows for processing of low
and high viscosity matrices.
26
The process can be used with any matrix which can be provided in powder
form, and at a much lower cost than fiber spinning
There is no need to evaporate any binder, water or solvent before forming
The process is relatively simple
Highy flexible preforms can be obtaned allow the formation of complex parts
Powder impregnated preforms can be shaped using various techniques such as

rubber diaphgram forming, rubber stamping, compression by heating, vacuum
bagging in autoclave and filament winding [21, 35].
2.4.2.4 Melt impregnation
In the case of melt impregnation the fibre bundle is spread to aid melt penetration
prior to entering a crosshead extruder and die which is normally designed to
produce a thin flat tape or prepreg. The process, which is shown in figure 2.14, is
capable of offering desired tape widths and thicknesses [36].
Figure 2.14 : Representation of a melt impregntaion process [36].
2.4.2.5 Solvent impregnation
In this method polymer has to be dissolved in a solvent to reduce viscosity. Solvent

impregnation requires the polymer to be dissolved in a solvent to reduce the
viscosity during impregnation. After wet-out of the fibers was completed, the solvent
must be removed. This removing can result void formation during evaporation.
Moreover, complete removel of solvent is very difficult compromising further
processing and reduces service performance [21].
27
2.4.2.6 Reactive processing of thermoplastics
Reactive processing of thermoplastics was developed as an alternative solution to

other methods mentioned above in recently years. In this process after impregnating
the fibers with a low viscosity precursor (monomer or oligomer), polymerisation of
the thermoplastic matrix is conducted in situ. Polymerisation can be initiated by heat
and requires the addition of a catalyst system, which can be added to the precursor
prior to impregnation. Due to their low molecular weight, precursors have extremely
low melt viscosities and proper fiber impregnation is therefore achieved without the
need for high processing pressures. Moreover, through reactive processing, textile
fiber reinforced TP composites can be even manufactured through lowpressure
infusion processes such as RTM and vacuum infusion [15].
Reactive thermoplastic materials
For reactive processing of thermoplastic composites, in situ polymerisation of the

matrix basically has to meet the following requirements: a high molecular weight
linear polymer has to be formed at sufficiently high conversions without the
generation of unwanted by-products. Suitable polymerisation types are
consequently narrowed down to addition polymerisations of mono- and difunctional
species, of which vinyl polymerisation and ring-opening polymerisation are most
common.
Caprolactam and laurolactam can be anionically copolymerised to tailor polymer

properties. Polyamide-12 is anionically polymerised from -laurolactam (Tm=154
C) with activators and initiators. When processing at 180240 C, an additional
cooling step is required prior to demolding. The molten monomer has an initial
viscosity of 23 mPa s. Anionic ROP of e-caprolactam (Tm = 69 C) into high
molecular weight polyamide-6 (PA-6), see Fig. 2.15, is a catalyzed reaction
performed at 130170 C. Final conversions of up to 99.3% can be obtained in 360
min., depending on the type and amount of activator and catalyst added. The
process difficulites of polyamides is that precursor/catalyst mixing has to be kept in
nitrogen protective environment to prevent initiator deactivation [15, 37, 38].
28
Figure 2.15 : Anionic ring-opening polymerisation of polyamides [15].
Synthesis of macrocyclic polyesters and the ring-opening metathesis polymerisation

(ROMP) there of was initially developed by D.J. Brunelle and his research group at
the General Electrics Corporation, USA, in the late 1980s and early 1990s.
Macrocyclic oligomers can be obtained through cyclodepolymerisation (CDP) of
linear PET and subsequently repolymerised through ROMP into high molecular
weight PET. Up to 100% conversion at 250325 C are obtained in several hours
without a catalyst, whereas addition of a catalyst reduces the reaction time to 315
min at 225 C. The initial melt viscosity of the cyclic precursors is 30 mPa s [39, 40].
Depolymerisation of linear PBT yields a macrocyclic oligomer mixture namely CBT,
which can be repolymerised directly into solid high molecular weight (Mw = 445,000)
semi-crystalline PBT at 180200 C by addition of a titanium initiator [41]. CBT
resins are available in two forms as with and without polymerisation catalyst. CBT
will be explianed in section 2.6 detailed.
There are various thermoplastic researched which can be polymerised from their
precursors. Figure 2.16 summurizes thermoplastics plastics with their melt viscosity
and process temperatures comparing with thermosets and each other [15].
29
Figure 2.16 : Melt viscosities and processing temperatures of various matrix
materials for both reactive and melt processing [15].
Processing of reactive thermoplastics
Three reactive thermoplastic materials in particular are known to be developed

which can be processed to produce composites, caprolactam, APLC-12 and Cyclic
PBT. In both cases, the resin is a pre-activated monomer melt with low viscosities,
which polymerises in-situ to form tough, solvent-resistant, semi-crystalline polymer
matrices. Fiber reinforced composite production by liquid molding of these
thermoplastics has received renewed attention due to the development of both the
liquid activator system for the APLC and the commercialisation of cyclic oligoesters.
The biggest difference with thermoset RTM is the higher processing temperatures
above the precursors melting point.
An important advantage of the reactive TP method is that the processing can be

carried out at near-isothermal conditions, i.e. the material solidifies and crystallises
at the processing temperature. It is not, therefore, necessary to cool the tool in order
to de-mold the component, which is an important economic consideration, leading to
energy savings and shorter cycle times. The combination of low viscosity and rapid
polymerisation of CBT resin allows for fast processing in many different applications.
In addition, the initial water-like viscosity allows rapid and excellent wet-out of filler
30
reinforcements and high filler loadings can be achieved at large scale component
processing. This behavior is due to the fact that the Cyclics resins polymerise at
temperatures below both the melt temperature and the crystallization temperature of
the PBT polymer [15, 16]. For application of cyclic resins infusion system including,
heatable mold, vacuum pump and resin and activator infusion pump as shown
Figure 2.17 can be used [15, 42].
Figure 2.17 : Vacuum assisted resin infusion process [15].
J. Lohmiller and S. J. Winckler worked on RTM processing of one part CBT system
where the catalyst is pre-combined with the resin since there are few processes that
can effectively mix a reactive catalyst at ratios approaching 200:1 by volume. The
basic idea is similar to that of a hot glue gun, as shown in Figure 2.18, where solid
resin is placed in a warm cylinder(140C), and a piston is used to move the resin
and force it against the heated end plug, which is much higher in temperature
(230C).
Figure 2.18 : RTM setup for cyclic one-part resins [43].
31
In this process the mold temperature is an important parameter. Increasing the mold
temperature will speed polymerisation, but as the melt point of PBT is approached
the subsequent crystallization will be slowed. At the melt point of PBT (225C) and
above, the polymerisation will be rapid but the material will never crystallize and
solidify until it is cooled below 225C. As a baseline, the optimum (fastest)
isothermal temperature is in the 190C range as a compromise between
polymerisation and crystallization. This goes for both the fast titanium base catalyst
system as well as the slower stannoxane based catalyst system; with de-mold times
in the 10 and 30 minute range respectively. Cycling the mold temperature up to
225C for example, to promote rapid polymerisation, followed by cooling to 190C to
promote rapid crystallization, solidification, and de-molding, can improve the molding
time of titanium catalyst from 30 minutes down to the 10-15 minute range, a
substantial reduction. In all part production, the system (mold and enjector) has to
be covered with a mold release and has to be cleaned before start to molding [43].
In the liquid molding processes (e.g. RTM, Vacuum inf.) of CBT, the main issue is
the time window (time to reach 1 Pa.s.) for successfull impregnation of the fibers.
CBT oligomer mixture has a melt viscosity of 150 mPa s at 150C, which drops to 30
mPa s at 190C. When processed at 190C in protective atmosphere, the viscosity
reaches 1 Pa.s after approximately 5 minutes and final conversions of 9599% are
obtained within 30 min. The impregnation time varies from seven (180C) to two
minutes (220C) depending on the polymerisation and thus mold temperature. Due
to the narrow impregnation time processing parameters have to be controlled to
achieve fully impragnated final part [23, 42, 43].
Both nylon 6 and 12 can be polymerised through two processes, condensation

polymerisation and anionic ring-opening polymerisation. The condensation
polymerisation of Nylon 6 and 12 are common commercial methods to produce the
polymer, but both have byproducts, such as water, that make them unacceptable for
RTM applications. On the other hand, anionic polymerisation of lactams 6 and 12 (2)
can produce nylon 6 and 12 respectively, with no byproducts, and within times
acceptable to the RTM process. Anionically polymerised lactam 12 (APLC-12) is
currently marketed by EMS Chemie A.G., Switzerland, who also developed a one
part activatorinitiator solution called Grilonit that can be stored indefinitely in inert
atmosphere. APLC-12 materials are processed at molding temperatures between
180 C and 240 C, and the polymerisation time varies from seconds to minutes,
depending on the percentage of activator used, and is shorter at higher
temperatures. Viscosities less that 0.1 Pa.sec can be achieved with APLC-12
32
molding, and as a result, infiltration of high fibre volume-fractions under gravity
forces only has been demonstrated. The polymerised composite must be cooled to
below 100 C before de-molding, See Fig. 2.19.
Figure 2.19 : Liquid-Molding of laurolactam [31].
Liquid molding process can also be used for anionic polymerisation of polyamide-6
(PA-6), no longer requires pre-mixing of two separate material batches that slowly
polymerise over time (60 minutes at 180C). A vacuum infusion process for
manufacturing of polyamide-6 (Nylon 6) composite wind turbine blades is currently
being developed at The Delft University of Technology. The difficulties of processing
of anionically polimerized amides is the sensitivity of the polymerisation process to
moisture and oxygen which can cause poor matrix properties due to low
conversions and possibly a relatively high void content (15%). In this process to
avoid moisture, a well equipped tooling is necessery as follows: a heated tank
storing monomer above its melting temperature under a nitrogen environment which
is connected to a gear pump which injects the monomer to the mixing head via a oil-
heated hose; a second tank storing the liquid activating system connected to
another gear pump, injecting the liquid system to the mixing head via a water cooled
hose. Tanks and hoses ensure a perfect insulation of both materials to ambient air,
preventing any reaction pollution. The monomer and the liquid activating system are
brought in contact in the mixing head thus initiating the polymerisation just prior to
injection [37, 38].
33
The drawbacks to both nylon systems include material properties and processing
complications. The processing both systems are very sensitive to water and
impurities (including fiber sizing) during the polymerisation process. Small amounts
of water (in the few ppm range) can have adverse effects on polymerisation and few
standard fiber-sizing packages are compatible. In structural composites, one of the
important properties for structural applications is the modulus of the matrix material,
needed to properly support fibers in compression. Micromechanics models and test
data both show lower compression strength with lower modulus. The modulus of
nylon 6, in the range of 2.8 GPa, approaches some epoxies, but this is the dry as-
molded modulus. After conditioning at room temperature in 50% relative humidity,
the modulus will drop to less than half of the dry value. Such a variable modulus is
difficult to deal with from a design point of view, and leads to a wide specification
with additional weight and cost. The moisture absorption of nylon 6, which can go
above 5% by weight, also causes dimensional stability problems, including warping
and interference problems of components during operation. Nylon 12 in comparison
has very low moisture absorption and will be stable in a varying humidity
environment, but it does have a lower modulus than nylon 6 to start with. A more
attractive thermoplastic material would combine the low moisture absorption of nylon
12 with the modulus of dry nylon 6 [43].
2.5 Cyclic Butylene Terephthalate
2.5.1 Production of cyclic oligoesters
Polyester is typically manufactured by two routes: transesterification of dimethylester

with diol to form an intermediate diester and oligomers, followed by
polycondensation to form the polymer; or direct esterification of the diacid with the
diol, followed by polycondensation. Conventionally Produced polyesters contain
small amounts (%4-5) of cyclic low molecular weight oligomers. These oligomers
can create problems during PET fiber processing, such as spinning and dyeing.
They can usually be extracted from the polymer product by the Soxhlet extraction
method using several solvents like chloroform, dioxane, dichloromethane or xylene
[44-45]. They can also be removed with dissolution methods. The polyester is
dissolved in a solvent, such as phenol and tetrachloroethane mixture, dimethyl
formamide, or 1,1,1,3,3,3-hexafluoro-2-propanol. The solution is filtered off and
evaporated to obtain dry oligomers. Cyclic oligomers removal is not currently
practiced in industry [46]. Usually only small amounts of cyclic oligomers are formed
during bulk condensation polymerisations, but cyclic oligoesters can be prepared as
34
major products by using very high dilution conditions, polymer-supported
techniques, and cyclo-depolymerisations (ring-chain equilibrium reactions). The
synthetically produced cyclic oligoesters have been reported to have physical
properties similar to the cyclic oligomers extracted from condensation polymers.
These cyclic oligomers can be used as feedstock for ring-opening polymerisation
[47].
2.5.1.1 Direct synthesis
Cyclic oligomers have been prepared by a classical high dilution technique. It is a

simple reaction at high dilution of: (a) diol and diacid, (b) diacid and diester, or (c)
diester only. A novel pseudo-high dilution condensation reaction has been
developed for preparing cyclic oligomeric alkylene phthalates and. The pseudo-high
dilution condensation reaction allows high product concentrations and produces
larger quantities, since large volumes of solvent are not necessary. The reaction is
carried out by using a diol (HOAOH) or one bis-(hydroxyalkyl) ester with one
diacid chloride (ClCOBCOCl) in the presence of highly sterically unhindered
amines such as 1,4-diazabicyclo[2,2,2]octane (DABCO) or a mixture thereof with a
tertiary amine, such as triethylamine or pyridine [47].
2.5.1.2 Polymer-supported method
Cyclic oligomers can be prepared by using polymer-supported reagents. It was

reported that cyclic polyester was prepared by the utilization of an intramolecular
alkylation reaction of a -bromocarboxylic acid using an anion-exchange resin [48].
2.5.1.3 Cyclo-depolymerisation (ring-chain reaction)

Cyclic oligomers can be obtained by the cyclo-depolymerisation (CDP) of linear
polyesters, and this technique is also useful for recycling of polyesters. A typical
depolymerisation is carried out by refluxing in dilute solution for many hours in the
presence of metal catalysts, such as organotin or titanate compounds. Different
solvents and catalysts were used for the depolymerisation at low concentrations. At
the end of the reaction, the solution is cooled down to a certain temperature at which
point the polymer is precipitated [49-51].
2.5.1.4 Production of CBT oligomers
Brunelle and his co-workers found a route to making cyclic form of PBT. Using
conventional PBT production techniques, a small equilibrium concentration of low
molecular weight cyclic oligomers are formed within the predominantly linear
polymer. Interestingly the cyclic form, when isolated and melted, has a viscosity as
low as 17 m-Pascal-seconds (17 centipoise), a water-like viscosity. This equilibrium
35
between linear and cyclic forms of PBT is driven by entropy, and is concentration
dependent. The equilibrium can be driven to favor cyclic formations by lowering the
overall concentration in a solvent. The basics of the cyclic technology are to use
high dilution of normal PBT with a catalyst to drive the conversion to the cyclic form,
then isolating the cyclic oligomers by removing the solvent. The resulting cyclic form
of PBT (CBT) is solid at room temperature, white in color, with a melting range of
120-160C. Cyclics Corporation produces commercial cyclic oligomers of butylene
terephthalate (CBT), as a mixture of dimer, trimer, and tetramer via the degradation
of PBT [42, 52].
2.5.2 Polymerisation of cyclic oligoesters
Many studies on conversion of cyclic oligomers to high molecular weight linear

polymer via ring opening polymerisations have been presented. It was concluded
that the ring-opening polymerisation offers potential advantages relative to the
conventional polymerisation process. Higher polymer molecular weights can be
more easily achieved. Molecular weights as high as 100,000300,000 g/mol were
reported for ring-opening polymerisations, while the highest molecular weights
achieved by step polymerisation are 40,00060,000 g/mol. Additionally, there is no
by-product in the ring opening polymerisations. The low melt viscosity of the cyclic
oligomers also allows processing by various techniques, such as pultrusion, resin-
transfer molding, melt filtration, or reaction injection molding, either concurrent with
or just prior to polymerisation (Fig 2.20). Low viscosities are thought to be very
useful for producing polyesters with high melting points and high melt viscosities,
such as PEN or poly(butylene 2,6-naphthalate) (PBN) [15, 52].
Figure 2.20 : Conversion of monomers to low viscosity macrocyclics (bottom)

conventional polymerisation (top) forms viscous polymers [52].
36
Brunelle and his coworkers, reported that the PBT cyclics melted at much lower
temperatures, softening at 140 C and being completely molten at 160190 C.
Again, the advantage of a mixture was seen, since pure cyclic dimer melts at 196C.
The molten cyclics had a very low viscosity (about 30 cP at 190 C), and could be
easily stirred in a flask with a magnetic stirrer, making melt polymerisation studies
facile. Ideally, they tried to polymerise the PBT cyclics below the melting point of the
final polymer ( 225 C), so that thermal cycling during processing would not be
necessary. Initially, some difficulties with low temperature polymerisaton (< 200 C)
were encountered, with either slow or incomplete polymerisation being observed for
the cyclics prepared at large scale. After careful analysis, they found that the
presence of either carboxylic acids or carboxylic anhydrides could inhibit the
polymerisation at low temperatures. The high levels of water that had plagued us
during synthesis also affected polymerisation. Polymerisation at higher temperatures
(250 C) was possible, but not as desirable, especially since these impurities would
also limit the ultimate molecular weight achievable. Ultimately, they found that
stirring CH2Cl2 solutions of the cyclics with silica gel adsorbed the undesirable
imprutities, and gave PBT cyclics which polymerised normally [42,52].
Many catalysts have been used for polymerisation of polyesters via condensation,
and many of these worked quite well for cyclics polymerisation (Table 2.6). The two
classes of catalysts that proved most efficient were titanium alkoxides and cyclic
stannoxanes, both of which work by a coordination-ligand exchange mechanism.
The mechanism of the polymerisation is similar to conventional ROP, with initiation
and propagation steps [Figure 2.21]. However, because the large oligocyclic rings
have essentially no ring strain, there is no detectable exotherm upon polymerisation.
Figure 2.21 : Ring-opening metathesis polymerisation of PBT[15].
37
Table 2.6 : Catalysts (initiators) used in polymerisation of CBT.
b 3c
Initiator (mol %) Temperature Time (min) Polymerisation Mw 10 Mw/Mn
(C) (%)
Bu2SnO 275 10 97 58.9 2.5

Ti(O-i-Pr)4 (0.2) 190 6 98 115 2.1
TOT (0.1) 190 20 99 352 2.1
TOT (0.2) 190 20 98 117 2.25
TOT (0.3) 190 6 96 95 2.8
d
TOT (0.3) + 1.0% linear 190 106 95 61.2 2.8
Stannoxane 1 (0.05) 190 20 91 401 1.3
Stannoxane 1 (0.4) 190 20 95 330 1.9
NaOEt (1.0) 225 10 41 5.3 ND
Sn(OMe)2 (1.0) 250 10 54 36 ND
e
Comm PBT NA NA 98 111 2.3
a Polymerisations were carried out by adding initiator in minimum solvent to molten cyclic PBT at the
temperature shown.
b Mol % relative to monomer units.
c By GPC versus polystyrene standards.
d Bis(4-hydroxybutyl) terephthalate was added as linear.
e Sample of commercial Valox 315.
Since the polymerisation is thermo neutral, chain-transfer reactions take place at the
same rate as ring-opening reactions, and thermodynamic equilibrium is achieved,
affording polyester with polydispersivity of about 2.0. Because the end groups are
provided only from the initiator, the ultimate molecular weight depends on the
initiator level; alternatively, molecular weight can be controlled with added alcohol.
The cyclic stannoxane initiator is interesting, in that it provides no end groups. The
tin alkoxide functionality becomes built into the polymer, which is a very high-
molecular-weight macrocycle (Figure 2.22) [42, 47, 52].
Figure 2.22 : Incorporation of tin into a macrocyclic structure via cyclic

stannoxane [52].
38
In order to drive the polymerisation of CBT into PBT, catalysts based on tin or
titanium are used with concentrations in the range of 0.1 to 0.5 molar percent.
Titanium based catalysts (e.g. tetrakis (2-ethylhexyl) titanate TOT) are among the
fastest but can be very moisture sensitive, while tin based catalysts (e.g.
stannoxane) tend to be somewhat slower but can be insensitive to moisture before
polymerisation. All CBT/catalyst combinations need to be dry before the
polymerisation. The processing temperature can be from the melt point of 160C up
to 250C where PBT begins to degrade, with polymerisation rate increasing with
temperature. Of the three main process variables controlling the rate of
polymerisation (temperature, catalyst type, and catalyst concentration), catalyst
concentration is least often used because increasing the catalyst concentration
leads to lower molecular weight PBT (more sites for polymerisation lead to smaller
molecules), and lowering the concentration starts to effect the robustness of the
process. Therefore the catalyst concentration is often fixed for each particular
catalyst, and process optimization focused around temperature and catalyst type.
Temperature can have a very strong effect where, for example, a slow catalyst that
takes 30 minutes for polymerisation at 190C may take only 1 minute at 250C [43,
47].
Isothermal polymerisation
If the CBT resin is polymerised at 190C, for example, then the material will melt,
polymerise, and then crystallize and solidify without cooling. This is because the
process temperature, 190C, is below the melt point of the PBT polymer created,
which is in the range of 225C. This is a very important attribute of the CBT system
that can allow for rapid processing in a thermoset-like manner.
2.5.3 Properties of CBT and IPCBT
2.5.3.1 Viscosity
Commercial CBT pre-combined with catalyst in the ratio of 200:1 by volume, namely
one-part CBT systems, is stable at room temperature in solid form, and will begin to
polymerise upon melting. Two systems that rely on tin based catalysts are XB3
which uses a transeterification catalyst from Autofina, FASCAT 4101, and XB2
which is based on stannoxane.
The complex viscosity of the cyclic PBT can be observed through the entire
polymerisation process using an oscillating parallel plate test [43]. Figure 2.23
represents rheokinetic data for both systems, XB and XB2. The comparison of XB3
at 170 and 190C shows the strong effect of temperature, with the 190C curve
39
reaching 1 Pa-s viscosity in 140 seconds compared to 500 seconds at 170C. The
comparison of catalyst types, in one-part resins XB2 and XB3, at 190C show
dramatic differences, with the XB2 curve reaching 1 Pa-s viscosity in 50 seconds
compared to 140 seconds for the XB3 system.
Viscosity Evolution
10,00
Complex Viscosity (Pa-s)
1,00
XB3 @ 170C
0,10
XB3 @ 190C
XB2 @ 190C
0,01
0 100 200 300 400 500 600 700 800
Time (sec)
Figure 2.23 : Rheokinetic plots of CBT one-part systems XB2 and XB3 [43].
It is clear that at higher temperatures, the reaction, and hence the viscosity rise,
proceeds more rapidly. This causes decreasing in needed time for impregnation of
the fibers. (time to reach 1 Pa.s). This needed time range can enlarge by keeping
the process temperature low. However, low process temperatures increase the
polymerisation time (see Figure 2.24).
Figure 2.24 : Left: Degree of conversion as function of time for different

temperatures; Right: Impregnation and polymerisation time of the one-
part CBT(CBT-XB3) resin [23].
40
2.5.3.2 Morphology
PBT is well known to be among the easiest of the semi-crystalline polymers to
crystallise. This makes PBT difficult to produce amorphous structures unless
specimens are very thin and quenching is very rapid. PBT has a triclinic unit cell for
both known polymorphs, being the predominant polymorph, whereas the
polymorph is only observed in drawn and spun fibers [53]. It was observed that there
is an increase in amount of usual type spherulites when the cooling rate decreased
and the melt temperature increased [54].
At a low rate of crystallisation and small degree of under-cooling (where

crystallisation takes place at temperatures above 180C), the crystallisation of linear
PBT resulted in the usual spherulites. While, below the temperature of 180C, at
which the highest rate of crystallisation occurred, unusual 18 spherulites will be
formed. However, it is found that cyclic PBT, produced by isothermal polymerisation
and crystallisation at 190 C, is composed only of the usual spherulites [55]. They
are small (approximately 2-3 m diameter) and appear to be produced by very rapid
crystallisation. This suggests that cyclic PBT crystallises easily and there are clear
differences in kinetics compared with linear PBT. This behaviour is not fully
understood and is further complicated by the fact that for the cyclic PBT,
crystallisation and polymerisation are taking place at the same time. Together with
the increasing amount of usual type spherulites, PBT became more brittle, reducing
the strain at failure from more than 30 to less than 4% [54, 55].
Depending on the degree of supercooling and the reaction speed, isothermal

processing of CBT may result in simultaneous polymerisation and crystallization.
Simultaneous polymerisation and crystallization can lead to a very different crystal
morphology ranging from a fully extended chain conformation to a folded chain
conformation, which is the typical conformation for crystallization from the melt [56].
Fig. 2.25 shows the degree of crystallinity as function of time for catalyzed CBT
oligomers. Before crystallization can commence, these oligomers need to convert to
polymer of sufficiently high molecular weight.
41
Figure 2.25 : Crystallization kinetics of catalyzed CBT resin [19].
Crystallization curves of melt crystallized PBT usually show a decrease in

crystallinity and an increase in crystallization speed when the degree of
supercooling increases [57, 58]. If polymerisation and crystallization were
consecutive, meaning that molecular weight build-up was completed before the start
of crystallization, the crystallization kinetics would not differ from meltcrystallized
PBT, except for a time-shift equal to the time needed for polymerisation. Since the
crystallization curves presented here clearly differ from melt crystallized PBT, it can
be concluded that for temperatures below 200C, where polymerisation is relatively
slow, polymerisation and crystallization are simultaneous. As mentioned before, this
simultaneity can affect the crystal structure, the final degree of crystallinity and
hence the mechanical properties.
Typical stressstrain curves are depicted in Figure 2.26. which represents the
flexural tests performed on pCBT, isothermally processed at 190C, pCBT
polymerised at 230C and crystallized at 190C and classically produced PBT (rapid
cooling from the melt). It is clear that the pCBT behaves differently from PBT. Apart
from the higher modulus, pCBT breaks in a brittle manner whereas the PBT
samples do not break at all in this three point bending test, but show a yield point.
The difference between simultaneous (at 190C) and consecutive (at 230C)
polymerisation and crystallization is smaller but still obvious. Although both samples
are brittle, breaking at small strain levels, the samples prepared by consecutive
42
polymerisation and crystallization at 230C do exhibit higher strain to failure and
higher strength of sufficiently high molecular weight [19].
Figure 2.26 : Typical three point bending Stress-Strain curve of pCBT and PBT[19].
DSC diagrams show that thermal behaviour of CBT, polymerised CBT(ISP-PBT),

and injection molded commercial PBT (IM-PBT) [18].
Heat Flow (W/t)
Temperature( C)
Heat Flow (W/t)
Temperature( C)
Figure 2.27 : Thermograms of CBT, ISP-PBT and IM-PBT: a)first b) second heating
(heating rate: 5C/min) [18].
43
It can be seen that CBT melts in a broad range (from about 120 to 170C). The
broadening of the shoulder may be ascribed to the different melting temperatures of
the oligomers present in the CBT. It was reported that the heating rates play an
important role in detecting the exothermic process (mostly related with the
crystallization) during the first heating of CBT. The slower heating rate allows the
polymerised CBT to crystallize and melt subsequently inside the DSC pan. So, high
DSC heating rates hinder the crystallization of the PBT produced and as a
consequence its melting peak is missing, too [18]. In another study, modulated DSC
(MDSC) was used to study the polymerisation of a CBT as a function of the end
temperature (T = 200 and 260C) and holding time. The melting behavior of the PBT
was strongly affected by the polymerisation mode (performed below or above the
melting temperature of the PBT) [59].
2.5.3.3 Mechanical properties
Table 2.7 shows the tensile and flexural properties of commercial injection molded
PBT (PBT) and polymerised CBT (IPCBT) at 190C for 30 minutes. It can be seen
that both types of PBT possess similar values of strength and stiffness. However,
the relatively low tensile strain of ISP-PBT indicates its brittle nature.
Table 2.7 : Mechanical properties of PBT and IPCBT [18].
Tensile Tensile Flexural Flexural

Density Stregnth Modulus Tesnile Strength Modulus
(g/m3) (MPa) (GPa) Strain(%) (MPa) (GPa)
PBT 1.30 56 2.4 8.0 112 2.3
IPCBT 1.32 59 2.3 2.3 104 2.4
In another work, it was reported that reprocessed polymerised CBT, injection

molded CBT and PBT gaved close strength and modulus values, but different
strains indicating its high crystalline nature, represented in Table 2.8.
Table 2.8 : Properties of reporcessed PBT and polymerised CBT compared to

injection molded polymerised CBT [19].
Tensile Tensile
Tensile
Stregnth Modulus
Strain(%)
(MPa) (GPa)
RP-pCBT 46 2.3 3-70
RP-PBT 50 2.5 16-225
IM-pCBT 55 2.4 160
44
3. MATERIALS AND METHODS
3.1 Materials
The main focus of this chapter is to develop prepregs and to produce their
composites. For this purpose all materials and the all prepreg and composite
production methods were described detailed.
3.1.1 Reinforcing materials
E-Glass fibers in different yarn numbers (tex) were received from iecam Cam
Elyaf San. A.. Chemical structure is E-Glass composition consisting principally
oxides of; silicon, aluminum, calcium, boron, including sizing compound on surface
such as complex mixture based on silanes, polymers and polyester resins as a
coupling agent. Used fibers are compatible with unsaturated polyester resin for
thermoset composite applications. Properties;
Melting Point: 840C(pertains to bare glass)
Specific gravity: 2.6 g/cm (pertains to bare glass)
Number of tex ( g/1000 meter), used are 300 tex, 600 tex and 68 tex.
Diameter of fibers:14 m for 300 tex, 15 m for 600 tex
Reinforcements were provided by Metyx Composites. For manufacturing of pre-
pregs, 2 types of biaxial 1 type of unidirectional non-non-crimp reinforcement were
used. Glass fiber biaxial reinforcements have been produced on 2 axes consisting
two layers on +45/-45. The biaxial coded as X600 (Figure 3.1) has 600 g/m areal
weight and includes 2 layers of fiber on +45/-45 axes. 1 layer is consisting 50% of
300 tex, 50% of 600 tex glass fiber with 300 g/m areal weight. Fiber mixing was
preferred to eliminate the gap formation between fibers and to take advantage of
different fiber diameters such as high tensile strength of 600 tex, high flexural
strength of 300 tex due to the increased surface area. The biaxial coded as X468
has areal weight of 468 g/m (Figure 3.2) and includes 2 layers of fiber on +45/-45
axes consisting 300 tex fibers with 234 g/m areal weight for each layer.
45
Figure 3.1 : Representation of X600 coded 45 reinforcement.
Figure 3.2 : Representation of X468 coded 45 reinforcement.
Unidirectional reinforcement coded L300 (Figure 3.3) consists of 600 tex glass fiber
on 0 axis. Glass fibers in all reinforcements were hold together by means of
stitching with a polyester yarn.
46
Figure 3.3 : Representation of L300 (UD) coded reinforcement.
Figure 3.4 : Commingled Glass/PBT hybrid biaxial (45) fabric.
Commingled Glass-PBT hybrid fabric was provided by Metyx Composites (Figure

3.4). The fabric in weight of 750 g/m is coded as TPX750 PBT in which each layer
of +45/-45 includes 100% of 300 tex glass fiber. The Glass/PBT weight ratio is
60/40.
47
3.1.2 Matrix resins
3.1.2.1 Cyclic butylene teraphthalate

CBT (Cyclic poly(1,4-butylene teraphthalate) including stannoxane as a
polymerisation catalyst was obtained from Cyclics Corporation (CBT160).
Properties of the resin;
Polymerisation Molecular Weight: >100,000 g/mol
Bulk Density (as pellets): 0.7 g/cm
Specific gravity 20C (solid): 1.3 g/cm
Melting Range: 120200 C
Viscosity (200C): 20mPas
3.1.2.2 Polyamide 12
Polyamide 12 was obtained from EMS Chemie AG in powder form (EMS Griltex D
1428A).
Properties of the resin;
Viscosity (230 C/2.16 kg): 210 Pas
3.1.2.3 Copolyamide (CoPA) suspension
Copolyamide suspension was is obtained from EMS Chemie AG in suspension form

(CoPA suspension 2A)
Properties
Viscosity (160C/2.16kg/dried): 600 Pas
Particle size distribution;
D (v, 10%) m 0.4
D (v, 50%) m 0.6
D (v, 90%) m 0.9
Properties of this polymeric suspension in water;
Solid content of 40% by weight
Average particle size < 1 m
Benefits of the suspension is;
Good penetration into dense fabrics and yarns
Increase of chemical resistance
Increase of impact resistance
48
3.1.2.4 Unsaturated vinyl ester
Unsaturated vinyl ester resin namely Crystic VE-676-03 was supplied by Scott
Bader Co. Ltd. The resin solution includes 50% of styrene giving a viscosity 175
25 mPa.s with Brookfield viscosimeter at 25C.
3.1.3 Other chemicals
3.1.3.1 Semi permanent mold release agent

Release agent was obtained from AXEL Plastics. Agent is a proprietary resin
solution comprising modified siloxane-based polymers which crosslink and form a
release film upon evaporation of the solvent carrier. Application temperature is up to
60, use temperature is up to 210C.
3.1.3.2 Dicumyl hydroperoxide (DCP)

DCP was used as catalyst for curing of unsaturated vinyl ester resin.
3.2 Equipments
3.2.1 Weighing machine for hand scattering
TEM- NT3 model balance which has 3000 gr weighing range, 0,1 g readability (was
used to prepare pre-pregs scattering of powder with hand by means of a metal
screen in Figure 3.5.
Figure 3.5 : Weighing machine (left) and metal screen for scattering (right).
3.2.2 Scattering coating machine
Scatter coating machine was used for scattering CBT powder on reinforcement and
fixing CBT onto fiber surfaces by heating and melting. This machinery system has a
scattering unit and 2 m long oven heated by infrared beams. The conveyor band a
maximum rate of 60 m/min. and it can be heated to a maximum temperature of
250C (Figure 3.6).
49
Figure 3.6 : Scattering part of scattering coating machine.
3.2.3 Fluard machine
Laboratory scale fluard was used to impregnate the suspension CoPA to glass
reinforcement. The machine has a liquid bath with 1000 ml capacity and the
squezzing rubber rollers of the excess of the liquid. The rollers have max. 4 bar
pressure and max. 10 rpm turning speed (See Fig. 3.7.).
Figure 3.7 : Fluard machine.
3.2.4 Oven
Nve FN400 model laboratory oven was used to prepare hand scattered prepregs
and to remove moisture of prepregs. Heating capacity is maximum 250C.
3.2.5 Hot press
Carver 3856CE Model laboratory type hot press was used for composite part
manufacturing out of prepregs by compression molding. Press has a maximum 22
ton pressure, 300C temperature capacity (Figure 3.8).
50
Figure 3.8 : Hot press for compression molding.
3.2.6 Metal molds
The molds used for compression molding is stainless steel. Dimensions of the molds
are 250 mm X 250 mm with a thickness varying as 3 mm, 6 mm and 10 mm.
3.2.7 Infusion system
Vinyl ester matrix composites were produced by means of sealed vacuum film on a
glass surface via application of vacuum by a vacuum pump with 1 bar pressure
capacity. A vacuum film with 250C heat resisance was used to produce ISPCBP
composites out of CBT prerpegs.
3.2.8 Mechanical test device 100 kN
Tensile, flexural and compression analyses were performed on Zwick Z100 model
universal test machine with load cell of 100kN. Tensile grips have 100 kN capacity.
A micro-extensometer was used for displacement measurement.
3.2.9 Mechanical test device 2 kN
The bond strength of the skin to the core material of sandwichs was measured by
using Zwick Z2 model universal test machine with 2 kN of load cell.
3.2.10 Impact test equipment
Charpy impact test machine (Ceast Resil Impactor) was used to determine
toughness of the composites. The apparatus consists of a pendulum axe swinging
toward the v-notch in the test specimen.
51
3.2.11 Microscopes
Scanning electron and optical microscopy were performed on the peeled surface of
the composites in order to investigate the effect of sizing on the interface bonding.
Also the effects of process conditions on consolidation quality, void formation and
fiber orientation were investigated. For this purpose Philips XL 30SFEG model SEM
and Leica APO8 Model stereo microscope were used.
3.2.12 Furnace
Protherm PLF 110/10 model furnace has maximum working temperature of 1100C.
The furnace was used to determine fiber volume fraction of composites.
3.2.13 DSC
Differential scanning calorimeter (DSC) was performed on IPCBT-NCGF with DSC

6200 device, (SII NanoTechnology EXSTAR).
3.3 Production Methods
3.3.1 Production of IPCBT matrix composites
3.3.1.1 Preparation of pre-pregs with CBT powder

CBT prepregs are classified in two categories according to their preparation
technique as hand scattered and machine scattered. Hand scattered pre-pregs were
prepared with hand scattering method dispersing powder on weighing machine (Fig.
3.9). After scattering of powder onto the glass reinforcement, the pre-pregs were
heated and the powder was melted at a temperature, which is higher than CBTs
melting point, in drying oven. Prepreg was kept in the oven for 30 seconds after
oven reached to target temperature (Figure 3.10). Thermopapers were used to see
the temperature which prepreg surface reached (See Figure 3.11).
Figure 3.9 : Scattering of CBT powder on reinforcement on weighing machine.
52
Figure 3.10 : Pre-pregs kept in oven.
Figure 3.11 : Thermo paper placed on prepreg (after applied heat).
Machine scattered pre-pregs were prepared via scattering system using a scatter
roller to sprinkle loose, coarser powder with a typical particle size of 0-500 micron or
200-300 micron, which is then firmly fixed on the substrate in an infra-red field as
seen Figure 3.12. The thermoplastic powder is drawn from a powder funnel by a
sprinkle roller. The powder is brushed out of this roller, falls through an oscillating
sieve onto the base material. Subsequently the powdered material is fed through a
sintering chamber. The adhesive is then heated with infra-red heaters and bonded
to the base material and flattened by pressing rollers.
Fiber/Resin weight ratio was hold in a value of 70/30. This ratio was arranged with
the speed of conveyor band of the system and the mechanic variator that provides
controlling of scattered powder amount. Mechanic variator was hold in 1. Scattered
reinforcement has been got through oven, which has a 2 meter distance, at suitable
temperature determined in preliminary studies with hand-scattering method.
53
Powder
Oven
Base material Conveyor
Figure 3.12 : Scattering system.
Temperature of the oven and the speed of conveyor band were arranged to achieve
holding the substrate at 160C for 15 sn application temperature and time. Prepregs
which have 70/30 fiber/resion weight ratio successfully achieved, See Figure 3.13.
Figure 3.13 : CBT Prepreg: CBT coated X468 (left: whole fabric, right:cutted fabric).
3.3.1.2 Conditioning methods of pre-pregs before composite production
Before hot pressing process, pre-pregs were conditioned in an oven at 80C for 12
hours to remove moisture on fibers and resin. Too see the moisture removing effect
on composite laminates two kinds of wait time were compared after conditioning.
In first method the prepregs were processed in hot press as soon as they were
taken off from the oven. In second method prepregs were subjected to heating at
80C for 12 hours in the oven. Vacuum bagging was applied to take off the air from
pre-pregs as soon as they were removed from the oven (See Figure 3.14).
54
Figure 3.14 : Vacuum bagged prepregs.
3.3.1.3 Production of IPCBT composites in hot press

The number of the layers needed was calculated by formulation 3.1.
(Fiber density X Fiber ratio) + (Resin density X Resin ratio) = Composite density
Composite density X Mold depth= Total composite weight /m (3.1)
Total composite weight /m X Fiber ratio = Fiber amount to use
Fiber amount to use/ Fiber weight per m = Number of layers
Table 3.1 presents the laminates weights and calculated thiskness values of the
laminates according to fiber areal weights by using formulation 3.1. This table can
be used for 70/30 fiber resin ratio. The calculated number of layers from the
information above is given Table 3.2 for different fiber reinforcements and mold
depth used in this study for 70/30 fiber/resin weight ratio.
The composites were produced using number of layers mentioned in Table 3.2.
Beforethe prepregs were placed into the mold, all surface of the metal mold was
coated with semi permanent mold release agent to achieve easy demolding
preventing sticking the part on mold surface. Pre-pregs were placed into the mold as
in Figure 3.15. It was covered with a heated metal plate and placed to center of the
pre heated hot press to desired temperature, See Figure 3.16.
55
Table 3.1 : Calculated thickness chart according to fiber weights.
Fiber areal weights for several layers, g/m2
Fabric
areal weights 5 layers 10 layers 15 layers 3 layers 6 layers 9 layers
450 2250 4500 6750 1350 2700 4050
600 3000 6000 9000 1800 3600 5400
850 4250 8500 12750 2550 5100 7650
2
Laminate areal weights for several layers, g/m
Fabric
450 3000 6000 9000 1800 3600 5400
600 4000 8000 12000 2400 4800 7200
850 5667 11333 17000 3400 6800 10200
Calculated Thickness, mm
Fabric
450 1.8 3.6 5.4 1.1 2.1 3.2
600 2.4 4.8 7.2 1.4 2.9 4.3
850 3.4 6.8 10.1 2.0 4.1 6.1
Table 3.2 : Number of layers for prepregs with 70/30 fiber resin ratio.
Reinforcement Code Mold depth, mm Number of layers, pcs

X600 3 6
X600 6 12
X600 10 20
X468 3 8
X468 6 16
X468 10 26
L600 3 12
Figure 3.15 : Prepregs in metal mold. Figure 3.16: Metal mold in hot press.
56
A constant pressure was applied to hot press for desired period. After the time was
completed metal mold was removed from press to demold the part. Sucessful
composite plates were achieved after demolding, See Figure 3.17.
Figure 3.17 : IPCBT composite flat plate with 3 mm thickness.
3.3.1.4 Production of IPCBT composites by vacuum consolidation
5 layers of CBT prepregs consisting of X600 were vacuumed with the vacuum film
by vacuum pump on a heatable metal plate. The plate was subjected to heating at
200C for 1.5 hours. After the time was completed the plate was removed from oven
and left to cool at ambient temperature.
3.3.2 Production of PBT matrix composites from commingled fabric
TPX750 coded Glass/PBT commingled fabric was produced using hybrid yarn
commingled in air jet texturing system. +45/-45 non crimp fabric has the same
structure as X600. 8 layers of TPX750 were placed into hot press. Placement of the
fabic layers was done between two teflon films into heating plates, which has 200C
temperature, for easy demolding. Then the press was heated to 260C.
Compression runs at 260C with a constant pressure of 1.5 MPa for 30 minutes.
Press was cooled to 200C before removing of composite plate after 30 minutes
compression time was completed. The part was left to cool at ambient temperature.
57
3.3.3 Production of PA matrix composites
Firstly the glass fabric (X600) was dipped into CoPA suspension in the fluard bath.
Excess of the liquid was removed by squeezing with the rollers. Pressure of the
rollers was hold in 4 bar, and speed of rollers was 5.5 rpm, See Fig. 3.18 and 3.19
Figure 3.18: Fluard bath. Figure 3.19. Squeezing of the excess liquid
through the rollers.
After impregnation of the glass fabric with suspension, the wet fabric was placed into
the oven to leave it for drying. 130C, 2 minutes was enough for evaporation of the
water and drying (Fig. 3.20).
Figure 3.20: Wet fabric placed in oven to dry.
58
Dry fabric was weighed to analyse resin content in the fabric. For 4 bar roller
pressure was achieved % 7.6 resin weight ratio. To increase CoPA content roller
pressure was decreased to 1 bar. The resin content which is 7.58 % with 4 bar roller
pressure was increased up to 10.9 % with 1 bar roller pressure.
Dried impregnated fabrics with CoPA were cutted to the dimensions of 25 cm X 25

cm. PA12 powder was scattered by hand onto impregnated fabric on weighing
machine to catch 70/30 fiber/resin weight ratio for both X600 and X468 coded
multiaxials (Fig. 3.21). Here, total resin content of CoPa and PA 12 were hold as
30% weight ratio. After scattering the fabric was placed into oven to melt and fix
PA12 to the fabric at 190C for 3 minutes (Fig. 3.22).
Figure 3.21: Scattering of PA12 on Figure 3.22: PA12 scattered fabric placed in
fabric impregnated with oven for melting and fixing of the
CoPA . polymer.
6 layers of pre-pregs were placed into 3 mm metal mold (Fig. 3.23). Hot press
temperature was hold at 200C and 210C for 15-20 minutes with a 22 ton pressure
(See Figure 3.16). As soon as compression period was completed, the metal mold
removed from press. The part was left to cool at ambient temperature in the mold.
Figure 3.23 : Glass fiber pre-preg placement into the mold.
59
3.3.4 Production of VE matrix composites
VE composite laminates having 8 layers of L300 were manufactured via vacuum
assisted resin transfer molding process. 2% cumyl hydroperoxide was mixed with
the resin prior to impregnation as curing agent. Vacuum bagging was done at the
room temperature and under 0.9 bar pressure applied by means of vacuum pump.
Cured parts were subjected to post curing at 80C for 3 hours.
3.4 Characterization Methods
3.4.1 Fiber ratio and void content analysis
The fiber volume fractions (Vf) of the composite panels were determined using the
matrix burn out method. In this method, composite laminates were burned in a high
temperature furnace at about 600C. The remaining fibers were weighed and the
volume of the fibers was calculated based on the mass and the density of the fibers
and the matrix. The void content of the samples was determined by carrying out
density measurements according to ASTM D2734, followed by burn-out tests.
3.4.2 Mechanical characterization
At least five specimens were tested for each test case for the derivation of average
test values. Since direct comparisons may not be valid if test specimens with
different fiber volume contents are tested, mechanical analysis results were
normalized according to fiber volume fraction for a good comparison. Normalization
is a procedure for adjusting raw test values to single (specified) fiber volume
content.
Since fiber-dominated strength and stiffness properties vary linearly with fiber
volume fraction, an obvious first approach would be to determine the actual fiber
volume fractions of the test specimens by an appropriate method and to adjust raw
data values by the ratio of a common fiber volume fraction (chosen or specified) to
the actuals as shown in Equation 3.2 [60].
Normalized value = Test Value X (3.2)
Where Vfnormalizing is the chosen fiber content (volume fraction or %) and Vfspecimen is
the actual fiber content (volume fraction or %). All analysis results were normalized
to 55% volume fraction because this ratio is the closest value to average one.
60
3.4.2.1 Tensile analysis
Tensile tests of composite specimens were performed as described in ASTM D3039

test standard. Test specimens were subjected to uniaxial tension with a constant
displacement rate of 5 mm/min and corresponding stress-strain values were
recorded for maximum tensile strength and elastic modulus determination both in
transverse and longitudinal directions with respect to fiber orientation. A micro-
extensometer was used for displacement measurement. Tensile analysis was also
performed to determine bond strength between skin and core material in sandwich
laminates.
3.4.2.2 Flexural analysis
Flexural strength and modulus of the laminates were determined via 3-point bending
tests done according to ASTM D790. Span to depth ratio was hold as 16:1.
3.4.2.3 Compression analysis
ASTM D695 test standard was considered for compression tests. Constant
displacement rate was set to 1.3 mm/min. Compressive strength and modulus of
the laminates were recorded.
3.4.2.4 Impact analysis
The impact resistance of the composite specimens was determined via Charpy
impact tests done according to EN ISO 179-2 test standard. Test specimens were
notched as being 2 mm notch size according to the standard.
3.4.3 Optical analysis
Scanning electron microscopy was used for the cross sectional area and surface
characterization aiming to show the fiber wetting, compatibility of the resin and micro
void formation. Sputter deposition of thin conductive gold coating was applied onto
the sample surfaces.
Stereo microscope was used for crossectional area analysis and determination of
macro void and defects formation in composites.
3.4.4 DSC analysis
Differential scanning calorimeter (DSC) was performed on IPCBT composites.

Analysis was carried out with 14 mg sample under nitrogen to prevent moisture and
oxidative degradation. The heating and cooling rates were hold as 5 C/min. Melting
temperature (Tm) was taken as the maximum of the endothermic melting peak from
61
the heating scans, whereas the crystallization temperature (Tc) was considered to
be the maximum of the exothermic peak of crystallization from the cooling scans.
The crystallinity ratios were calculated from the determination of the melting
enthalpy of the samples. The degree of crystallinity was then defined as follows
(Equation 3.3):

(wt%) = (3.3)

where Hm is the area under the melting peak of the polymer, and H is the
melting enthalpy of the fully perfect crystal of PBT. H was accepted as 142 J/g
according to the literature [17].
62
4. RESULTS AND DISCUSSION
In this study, firstly prepregs were prepared and the composites were produced from
these prepregs. For this purpose, CBT, PA and PBT matrix prepregs were produced
using X600, X468, L300 and TPX750 coded fabrics. In order to identify optimum
conditions of CBT prepreg production, X600 coded fabric and CBT matrix were
used. Table 4.1 summarizes the process conditions of prepregs produced by hand
scattering in laboratory and scatter coating machine and composite production
conditions by compression molding.
Table 4.1 : Prepreg and composite production conditions.
Prepreg Production Composite Production

Temperature, Time, Pressure,
Temperature, Time,
Method
C s C min. MPa
Hand Scattering 160 30 200 30 1.6
Scatter Machine 145 10 200 30 1.6
According to the mechanical test results of these composites, it was concluded that
the most proper temperature for both hand scattering and machine scattering
system is 160C. Twenty seven kinds of composite were prepared from five kinds of
X600-CBT prepregs by using these optimized conditions. During the composite
production from these prepregs different compression molding parameters such as
temperature, pressure, time, different processing cycles and vacuum bagging
method were tried. Considering the thickness and fiber volume fractions of the
composites, the effects of the production parameters and methods on composite
properties were evaluated by mechanical and optical analyses. In the optimization
trials of compression molding temperature, pressure, and time, two parameters were
held constant when one parameter was tried. Composite samples with 55% volume
fraction were produced using five different pressures between 0.9-2.8 MPa, three
63
temperatures between 190-210C, five different time periods between 10-30
minutes. In order to investigate the influence of demolding temperature on
composite properties, three kinds of composite were produced at 200C, 1.6 MPa,
30 minutes compression conditions demoulding at different temperatures such as
200C, 180C, 160C. Moreover, five composites with different Vf values between
55-65% were produced at 200C with 1.6 MPa pressure for 30 minutes and
investigated. The composites with different thicknesses as 3, 6, 10 mm were
produced at 200C and 1.6 MPa for 30 minutes. The effects of pre-impregnation
time on composite properties during compression molding were investigated with
the trials of different process cycles. For this purpose, four different composites were
prepared at 160C and 170C pre-impregnation temperatures and 5 and 10 minutes
pre-impregnation periods. The prepregs of composites mentioned above were kept
in the oven for 12 h at 80C. Some prepregs were subjected to four different kinds of
conditioning. The composites of these prepregs were produced at 200C and 1.6
MPa for 30 minutes and the conditioning effects on composite properties were
investigated by mechanical and optical analysis.
PA matrix prepregs were prepared with the method mentioned in Section 3.3.3
different than that of CBT prepregs. Two kinds of PA prepreg with X600 were used
to produce four kinds of composites at temperatures between 200-210C with 3.0
MPa for 15-30 minutes.
Two kinds of prepreg including X468 and CBT with 55% Vf were produced using the
optimization conditions achieved from the trials of X600-CBT with hand scattering
and scatter coating mechine methods. Two composites with 3 mm thickness were
produced from these prepregs at 200C, with 1.6 MPa pressure for 30 minutes after
the prepreg was conditioned at 80 C for 12 hours. Demolding temperature was
200C for both composites. One PA matrix prepreg including X468 with 50% Vf was
produced as mentioned in Section 3.3.3, and then it was subjected to compression
molding to achieve 3 mm thickness composite at 210C with 3.0 MPa pressure for
20 minutes.
One kind of prepreg with 54% Vf was prepared with L300 code fabric and CBT to
produce UD and 45 composites. Moreover, VE matrix composites including L300
were produced by vacuum infusion method without preparing prepregs. VE matrix
composites in 3 mm thickness were prepared at ambient temperature and 1 atm
pressure for 24 hours.
64
For comparison of conventional PBT and IPCBT, the composite with conventional
PBT matrix was produced using TPX750 coded prepreg including commingled glass
fibers and PBT fibers supplied from Metyx Composites. Composite production was
carried out by compression molding at 260C, with 1.5 MPa pressure for 30 minutes
demolding at 200C.
Sandwich structure composites from CBT prepregs and PA prepregs were done
using PA foam as core material by compression molding. Two kinds of X600-CBT
skin sandwich were produced using two different process conditions in compression
molding. One kind of X600-PA skin sandwich was produced by compression
molding.
4.1 Optimisation of Production Conditions of CBT Prepregs
Since CBT is polymerised in situ, the processing method of IPCBT is different

significantly from conventional thermoplastic processing. It is mentioned in previous
sections that the main reason of using reactive thermoplastic resins is the
requirement of a complete impregnation to achieve good composite properties. The
continuous and rapid increase in the viscosity during processing of CBT with in situ
polymerisation, limits the time needed for the impregnation of fibers. Here, the
impregnation time is defined as the time when the reactive polymer system reaches
a viscosity of 1 Pa.s. Available impregnation time with low viscosity can change
between 2-8 minutes depending on temperature and polymerisation catalyst [42,
43]. Although, the fiber bundles in the prepreg were pre-impregnated with CBT, still
the inner fibers have to be wetted with the resin during composite production
process. In order to hold available impregnation time as much as longer to ensure
complete wetting of all fibers, the prepreg preparation temperature has to be lower
than polymerisation temperature of CBT/catalyst mixing. CBT resin does not have
an exact melting point since it consists of a mixture of oligomers, but it has a melting
range which lies between 120 and 160C and the polymerisation starts at 180C. In
order to see the influence of the pre-preg preparation temperature applied after
scattering of CBT powder precombined with its catalyst, the different temperatures
were tried. The trial temperatures were arranged in such a way that the temperature
will be lower than 180C, but will also allow for melting of CBT and sticking onto the
glass fibers. The general production parameters have been discussed detailed in
Section 3.3.1.
65
4.1.1 Laboratory scale trials
Laboratory oven adjusted to 160C, 170C and 180C. Application time at the target
temperature was chosen as 30 minutes. The composite parts were produced from
these prepregs by compression molding in hot press as explained in Section 3.3.1.2
and subjected to the tensile and flexural tests to determine most appropriate prepreg
production temperature. Hot press parameters are 200C press temperature, 1.6
MPa pressure, 30 minutes compression time. The flat composite plates were
produced with 3 mm thickness consisting 6 layers of X600 coded reinforcement.
They were demolded as soon as 30 minutes hot pressing period was completed and
allowed for cooling at ambient temperature in the mold. The tensile and flexural
strength comparison can be seen in Figure A.1 (a). According to the results
normalized to 55% volume fraction, it can be seen that 160C oven temperature
gave the highest tensile and flexural strength. Tensile and flexural modulus values
showed the same tendency as well, Fig. A.1 (b). The significant decrease in strength
and modulus with increasing prepreg production temperature like 180C may be
attributed that the polymerisation starts during prepreg production prior to
compression process resulting a viscosity rise which can affect the impregnation of
the resin.
4.1.2 Scatter coating machine trials
The hand scattering method was a laboratory scale prior study for prepreg
production to identify optimum production parameters of the real scattering system.
A crosscheck had to be done in the real scattering system using similar parameters
used in hand scattering method comparing the end composite properties. For this
purpose, the trial temperature and time of the real scattering system were arranged
as the prepreg surface can reach up to 160C. However, to reduce the process time
for saving the time during real prepreg production, the temperature was increased
and the process time was decreased in the production line. Here, the important point
is to reach up to 160C on coated surface of the pre-preg. Therefore, machine
temperature was arranged to 160C and 170C separately and the time was
changed. The scattered sample passed through the oven for 20 seconds and 15
seconds. The temperatures which the prepreg surface reached were measured by
using thermopapers as described in Section 3.3.1. See the Table 4.2 for different
machine and prepreg temperatures.
66
Table 4.2 : Prepreg production conditions in scatter coating machine.
Reached temperature Temperature of

Time,
on prepreg surface, the machine,
s
C C
160 170 20
150 160 15
145 160 10
Flat composite plates were manufactured using the prepregs produced with different
temperature and time described in Table 4.1. Composites were subjected to tensile
and flexural tests. Figure A.2 (a) represents tensile and flexural strength change with
the prepreg production temperature. Figure A.2 (b) represents the tensile and
flexural modulus change with the prepreg production temerature as well. It can be
clearly seen that the highest prepreg temperature of 160C which prepreg sample
reached showed the highest tensile strength and there is significant decreasing in
tensile strength of the samples produced at the temperature below 160C. The
temperatures 150C and 145C which prepreg sample reached gave fairly low
tensile and flexural strength as well as modulus values.
4.1.3 Conditioning of prepregs before compression

In fact, it is well known that drying is important for proper polymerisation of the CBT
resin into PBT. If the moisture content is too high, the material will not polymerise
properly (See section 2.6.2). For this reason, to obtain maximum molecular weight
build besides drying CBT resin, fibers/fillers, additives and molds should also be
dried and free of moisture before polymerisation of CBT resin takes places. All the
materials must be dried and maintained in a dry condition throughout the melting
and polymerisation stages [61]. Taking into account this information, to avoid any
risk of moisture the prepared prepregs were dried overnight at 80C kept in an oven
for the preliminary studies. In fact, if it is looked at the commercial side, drying
process causes energy consumption and time loss. Therefore, in this section
different conditioning methods were applied to save energy and time for commercial
viability. Composite parts were produced using the prepregs conditioned with
different methods and tensile tests were performed for comparison.
In the oven method the pre-pregs were hold in the oven at 80C for 12h and
they were molded in hot-press by taking quickly from the oven to the mold to
not allow for exposure air.
67
In the vacuum bagging method, firstly pre-pregs were hold in oven at 80C,
12h and they were quickly vacuumed by using a vacuum film by means of
vacuum motor to take air. These prepregs were left to wait for 2 days in
vacuum bag at ambient temperature. They were molded in hot press as soon
as the vacuum film was removed.
Another sample was conditioned with the same method of vacuum bagging.
However, the prepregs were kept in the oven at 80C for 10 minutes after
vacuum bag was removed, then pressed in press taking from the oven.
One composite sample was prepared with the prepregs which were not
conditioned allowing for exposure to ambient temperature.
Table 4.3 presents the tensile properties of the composites produced from the
prepregs which were conditioned with different methods. If we look at the tensile
properties of the unconditioned sample, we can see that significantly lower strength
and modulus values as compared to that of the sample conditioned in the oven
clearly support the claim of removing moisture obtained from literature. It is clear
that the vacuum bagging in both cases causes tensile strength and Young Modulus
reducing more than 50%. A low tensile strength and modulus are, therefore, an
indication of poor matrix properties because the proper polymerisation couldnt
achieve. If we compare the properties of the unconditioned sample and vacuumed
samples, their close strength values and remarkable modulus decreasing show that
the vacuum bagging is not a kind of suitable method to remove moisture from the
prepregs.
Table 4.3: Tensile properties of IPCBT composites conditioned with different

methods.
Conditioning Max.Tensile Modulus E, Max.Strain,

Vf, %
method Str, MPa GPa %
53 No conditioning 16311.8 16.71.4 3.50.8
51 Oven 39411.3 20.80.8 2.10.1
50 Vacuum 1594.6 13.50.3 1.80.1
Vacuum
50 177 2.5 12.70.3 3.81.2
10 min.@80C
68
4.2 Optimisation of IPCBT Composites Production by Compression Molding
In this section, the effect of composite production conditions in compression molding

on composite properties is clarified. For this purpose, + 45/-45 biaxial X600-CBT
prepregs were used for the manufacturing of composite test samples in hot press as
described in section 3.3.1.2. The composites were characterised by tensile and
impact tests. These tests were performed to determine the most suitable hot press
parameters to achieve IPCBT composites with the proper mechanical properties.
All the mechanical analyses were done only on main fiber axis as if the longitudinal
axis since the glass fiber reinforcement has balanced fiber distribution on two
directions of +45 and -45. The impregnation quality was investigated by SEM and
stereo microscope. The determination of the overall void content was done as
mentioned in Section 3.4.1.
4.2.1 Compression molding pressure
We assume that the application of pressure facilitates the flow of the low viscosity
CBT to penetrate into the fiber bundles and ensuring the complete wetting of them.
In order to clarify the effect of the pressing pressure on properties of CBT
composites, 5 different pressures were applied varying from 0.9 to 2.8 MPa. In these
trials, hot press temperature was hold at 200C for 30 minutes. Demolding of the
composite parts was done applying rapid cooling at ambient temperature described
in Section 4.1.
Figure A.3 (a) demonstrates the effect of pressure on tensile and flexural strengths
of IPCBT composites. It is clear that the composite produced with 0,9 MPa pressure
gave the lowest strength values for both tensile and flexural showing a big difference
in respect with the other composites produced with higher pressures. It can be seen
that the tensile strength doesnt show a significant difference for pressures between
1.6-2.8 MPa. If flexural strengths are taken into account it can be seen that higher
pressures than 1.6 MPa give lower strength values. Figure A.3 (b) shows tensile and
flexural modulus varying with different pressures. 1.6 MPa pressure gave the
highest tensile and flexural modulus values while other pressures do not show
significant difference between modulus values.
The void content measurement gave a result of 10.122.0% for the sample
produced with 0.9 MPa pressure. This decreasing may be attributed to the micro
voids formation due to the poor impregnation with insufficient pressure.
69
4.2.2 Compression molding temperature
In order to identify the most appropriate compression temperature three trials were
carried out at 190, 200 and 210C temperatures. Compression time and pressure
were hold as 30 minutes and 1.6 MPa respectively. Demolding of the composite
parts was done applying rapid cooling at ambient temperature as described in
section 4.2.1. Figure A.4(a) shows how to change of the tensile and impact
strengths of IPCBT composites at different compression temperatures. It is clear
that there is not considerable difference between the tensile strengths at different
temperatures. However the impact strength of the IPCBT composite increased by
the application of 200C compression temperature. On the other hand, it is obvious
that the pressing temperature affected tensile modulus of the composites. It can be
seen that the composite produced at 200C gave the highest tensile modulus
showing a big difference in respect with the other composites produced at 190C
and 210C, see Figure A.4 (b). Low impact resistance of the composites can be
caused by poor fibre-matrix interface properties as well as brittle behaviour of the
matrix. SEM images of the composites show that there is good fibre-matrix interface
property and there are no much micro voids which can act as stress concentration
sites and leads to premature failure of the composites, See Figure A.5 (a, b, c).
Thermal characterization by DSC was done to the matrix of IPCBT composite
produced at 200 C. Table 4.4 summarizes the melting temperatures and enthalpies
associated with the first and second DSC heating, as well as the crystallization
temperatures and crystallization enthalpies, deduced from the cooling regime. Fig.
4.1 shows typical DSC thermograms of IPCBT for the first and second heating at
5oC/min from 0 to 260oC. Crystallization degree (Xc) was calculated as 23.5%
according to Equation 3.3 given in section 3.4.4.
Table 4.4 : Melting temperature and enthalpies of IPCBT composite.
1st Melting Crystallization 2nd Melting

o
Tm, I ( C) - 193.2 215.8
Tm, II (oC) 223.7 - 223.7
H (J/g) 45.7 33.4 31.2
The existence of the melting peak indicates that complete polymerization and
crystallization processes have taken place. The double melting peak results from the
melting and recrystallization of imperfect crystals [63]. The appearance of double
melting peaks would therefore be an indication of poor crystal quality in the
composite part related to the time window for crystallization.
70
DSC, mW/min
DSC, mW
Temperature,C
Figure 4.1 : DSC thermogram of IPCBT composite produced at 200C.
If the polymerisation temperature is hold below the polymer melting point, and
allowed sufficient time to cold crystallize at this temperature crystal quality can be
increase [19]. However, high Xc is not desirable property for IPCBT composites
since the high crystallinity decreases toughness correspondingly the impact
strength.
In earlier studies it was recorded that when this resin is used under RTM-processing
conditions, the matrix material is much more brittle than normal PBT [18]. This
brittleness is induced by the isothermal RTM-production process, where rapid
cooling is difficult [23, 56]. Brunelle et al. [52] indicated that polymers synthesized
from cyclic oligomers displayed higher enthalpies of melting (6080 J/g) hence,
higher Xc as compared to the conventional PBT with enthalpies of melting ranging
from 3550 J/g. Therefore, toughening of IPCBT by adding comonomers is an
aspect which is now under investigation [64].
Consequence, it can be said that achieved Xc as 23% which is lower than recorded
values up today indicates that the compression molding of CBT prepregs is a
suitable process to have composites with proper toughness and impact resisstance.
4.2.3 Compression molding time
It is already known from the prior studies that CBT can polymerise between 180-
260C. According to this information the trials were done to examine process time
at 200C compression temperature to carry out the trials in an isothermal way since
this temperature is lower than expected melting temperature of the end polymer.
Press pressure was hold stable at 1.6 MPa. After compression period was
71
completed, the composite part was removed from the press with the metal mold and
left to cooling rapidly at ambient temperature. All parts were subjected to tensile and
impact tests and compared with each other.
Figure A.6 (a) demonstrates tensile and impact strength variation of composites
molded with different pressing periods varying from 10 to 30 minutes. The
composite produced with 30 minutes gave the highest tensile and impact strength
values. Although, there is not significant differences between tensile strengths of the
composites produced with 20, 25, 30 minutes, the Young Modulus value of the
composite molded for 30 minutes is quite high than those of the others, see Figure
A.6 (b).
The longest pressing time resulted in a significant enhancement of both stiffness

and strength. These differences in stiffness may be attributed to the higher
molecular weight or higher crystallinity degree of the matrix.
It is clear that the sufficient tensile strength and impact resistance values can be
achieved with 25 and 20 minutes when they were compared with 30 minutes. The
composites pressed with the pressing time lower than 20 minutes showed big
decreasing in tensile and impact properties. This result shows that the pressing time
below 20 minutes is not sufficient to produce composites from CBT prepregs. This
significant decreasing may be attributed to the uncompleted polymerisation in an
insufficient polymerisation time resulting low molecular weight and oligomer impurity
in the matrix.
The quality of the CBT impregnation was investigated by polishing the cross-section
area of the composites and viewed under SEM. Figure A.7(a, b, c) shows cross-
sectional area images of the composites for different pressing time. It can be seen
that the image of composite produced in 10 minutes has a damaged and rough
surface appearance. This rough looking of the matrix and broken fibers indicate the
weak matrix property due to probably uncompleted polymerisation. However SEM
images reveal that the composite laminates have well-impregnated area with only a
few micro voids resulting in an overall void content of 3.70.9% according to burn
out tests. Micro voids formation probably caused by the trapped air during the hot
press moulding. However, any macro void which is possible to be formed between
the glass bundles was not observed in the cross section of IPCBT composites.
The results reveal that a good impregnation was achieved in IPCBT composites in
fact. Furthermore, the void content value obtained in this study is within the range of
void content reported by other workers for noncrimp glass fabric composites. Parton
72
[19] quoted void content value of 4.21.7% and large inter bundle voids for UD
IPCBT composites with 0.54 of Vf produced by RTM method. Another study by
Vendramini et al. [13] reported a void content value as 3% for UD glass fiber
reinforced PBT composites with 0.50 of Vf produced from commingled PBT/Glass
fiber by hot compression at 240C under pressure.
When the SEM images and void content calculations were compared with the
reported data of different production methods of PBT composites it can be said that
the pre-impregnation of fibers with CBT named as prepreg can improve wetting
ability and eliminate the big void formations.
Figure A.8 represents SEM micrograph of the peeled out surface of IPCBT
composite. The Image confirms that there is a good interfacial bonding between the
fiber and resin, IPCBT matrix strongly adhered to the fiber surfaces.
4.2.4 Demolding temperature: Rapid and slow cooling
Isothermal processing is an obvious advantage for the composite production in hot

compression process, see Section 2.6.2. Since the melting and molding temperature
of the resin are both the same, isothermal processing is possible for CBT resin. This
means that both polymerisation and crystallisation take place at the same
temperature. However, to allow the part for cooling at ambient temperature after
demolding at 200C can be assumed as a rapid cooling. If the part is cooled down
slower in the mold before demolding, this allows for crystallisation of the matrix.
It is well known that the crystallisation degree of the matrix can affect the
mechanical properties of the composites significantly. Therefore, to observe the
influence of demolding temperature on mechanical properties, 3 composite parts
were produced at different demolding temperatures. After hot-press period was
completed at 200C, the press was cooled slowly to demolding temperature which is
aimed to reach. The composite part was removed from the press at demolding
temperature and allowed for cooling at ambient temperature in the metal mold.
The mechanical properties of the parts demolded at different temperatures were

compared with those of the composite part demolded at 200C. Compression
conditions of the composites were hold as 200C, 1.6 MPa, 30 minutes for all
samples. Different cooling rates can be observed on temperature-time curve of
cooled laminates after compression, see Figure 4.2.
73
200
180
160
140
Temperature, C
120
200C
100
180C
80 160C
60
40
20
0 30 50 60 80 90
Time, Min.
Figure 4.2 : Cooling speed after compression: Temperature-Time curve.
Figure A.9 (a) shows the tensile and flexural strengths of IPCBT composites
demolded at different temperatures. The flexural strength of 701 MPa and tensile
strength of 504 MPa recorded for the part demolded at 180C were quite high
values considering strengths of the part demolded at 200C, 546 MPa for flexural,
424 MPa for tensile strength. Although the tensile and flexural strengths of the part
demolded at 160 C are lower than those of the 180C demolding temperature, but
160C demolding temperature still have quite higher values than those of 200C.
If tensile and flexural modulus values (Figure A.9 (b)) are compared each other, it
can be seen that while felxural modulus of 180C is higher than those of the others,
there is no considerable difference between the tensile modulus.
From microstructural point of view, there are some possible reasons for this
improvement. Apart from the presence of defects and micro voids high degree of
crystallinity can substantially increase the strength of a polymeric material.
Moreover, if the impact properties of the same laminates are observed, it is clear
that the composite part demolded at 200C has the highest impact resistance (See
Table 4.5). The lower impact values of slow cooled parts as compared to that of
rapid cooled part clearly support the idea indicating that the slow cooling can
increase the crystallinity degree of IPCBT matrix.
74
Table 4.5 : Impact strengths of IPCBT composites at different molding
temperatures.
Vf, Demolding Temperature, Impact strength,

% C kJ/m2
52 200 191.948.1
53 180 160.1410.5
52 160 148.015.8
4.3 Development of TP Composites: Various Matrices, Reinforcing Materials

and Production Methods
4.3.1 Production methods
4.3.1.1 Production of IPCBT composites with different processing cycle

For reactive processing of thermoplastics, the processing time is very important. An
important aspect of the composite producing process is to ensure that the all fibers
are impregnated by the resin completely before the propagation step of the
polymerisation, which involves a rapid viscosity rise, starts.
Rheological properties of CBT have been discussed in more detailed in Section

2.6.3. According to the data it is clear that at the polymerisation temperature of CBT
although the initial viscosity is very low, the reaction, and hence the viscosity rise,
proceeds rapidly. Reaching to the high viscosities in short time causes to decrease
in the time for impregnation (time to reach 1 Pa s).
In this section, in the beginning of compression process the prepregs were hold for a
specific time at the temperatures below CBTs polymerisation temperature to
achieve completely impregnation before polymerisation starts. For this purpose,
several composite parts were produced with X600 prepregs.
The beginning temperatures were choose as 160C and 170C taking into account
this melting range which the polymerisation does not occur yet. The pre-
impregnation times were hold as 5 minutes and then temperature was increasedup
to 200C and hold for 30 minutes. The press load was kept stable in 1.6 MPa during
whole process. Temperature and time variation curves describing processing routes
of the compression with pre-impregnation are depicted in Figure 4.3 and 4.4.
75
210
200 202 200
Temperature, C
190
180
Top plate
170
Bottom plate
160 162
150
0 5 10 15 20 25 30 35 40 45 50 55 60
Time, Min.
Figure 4.3 : Temp.-Time curve of compression for 160C impregnation temp.
210
200 201 200

Temperature, C
190
180
Top plate
170 171
Bottom plate
160
150
0 5 10 15 20 25 30 35 40 45 50 55 60
Time, Min.
Figure 4.4 : Temp.-Time curve of compression for 170C impregnation temp.
In order to assess the mechanical properties of the IPCBT composites produced

with pre-impregnation route, tensile and flexural tests were performed and the
properties of these composites were compared with those of the samples produced
with the isothermal process at 200C for 30 minutes. Comparison of the tensile and
flexural strengths is shown in Figure A.10 (a). Tensile and flexural modulus values of
different processing routes for 160, 170 and 200C impregnation temperatures can
be seen in Figure A.10 (b) as well. From the results presented in figures, it can be
seen that composite produced without pre-impregnation has higher tensile strength
and tensile modulus. It is clear that the influence of the pre-impregnation on the
longitudinal tensile strength and modulus doesnt improve the tensile properties of
IPCBT composites. The flexural strength on the other hand is affected more by the
pre-impregnation route. Since the matrix strength dominates the transverse
strength, good matrix properties can increase the transverse strength significantly
76
(10%). Increasing in flexural strengths with pre-impregnation application indicates
that this route improve the matrix properties effecting the impregnation of fibers.
However, higher modulus values both flexural and tensile of the composite
produced without pre-impregnation sign that the different temperature routes
decreases the stiffness of the matrix. This result can be attributed to influence of
pre-impregnation temperature on crystallinity of IPCBT. Stereo microscope images
of the composites prepared with pre impregnation at 160 and 170C are depicted in
Figure A.11(a) and Figure A.11(b) respectively. Cross-sectional are images of these
composites show that the impregnation quality is good. Same pre-impregnation
route was performed by taking the pre-impregnation time 10 minutes, and
compression time 20 minutes instead of 30. This route was applied with 160C and
170C pre-impregnation temperatures. Recorded tensile strengths were 283 MPa
for 160C and 104 MPa for 170C. Tensile modulus values were 18 GPa and 19
GPa respectively. In the cross sectional area images taken by stereo microscope of
the composites, the raw appearances of the matrix indicate that it couldnt complete
its polymerisation, see Figure A.12 (a) and A.12 (b). Quite low tensile strength and
modulus values support this assumption. On the other hand, 10 minutes pre-
impregnation period caused macro voids in the composites which can be easily
seen in the stereo microscope images. These voids are probably caused by the air
bubbles formation in the matrix during resin flow period due to the prolonged flowing
time. After solidification of the matrix, the trapped air formed like macro voids which
decrease the tensile strength.
4.3.1.2 Production of IPCBT composites by vacuum consolidation
Compression molding is a process which is useful for the fast production cycles and
high pressures can be applied. However, its high tooling expenses limit to produce
large composite parts due to the necessity of large mold dimensions and high
pressures. For the large composite part production vacuum molding is preferable
option in composite industry. In order to identify if IPCBT composites can be
produced in vacuum consolidation process, CBT-X600 prepregs produced in
machine scattering (160C, 12) were subjected to vacuum molding as described in
Section 3.3.1.3. Mechanical properties of the composites were identified by tensile
and flexural analyses. Table 4.6 summarizes the tensile and flexural properties of
the laminates produced with different two process routes. Apart from the flexural
modulus, it can be said that vacuum consolidation gives better properties both in
tensile and flexural tests.
77
Table 4.6 : Comparison of tensile and flexural properties of IPCBT composites after
different process routes.
Max. Tensile Tensile Max. Flexural Flexural

Process route Modulus, GPa
Strength, MPa Modulus, GPa Strength, MPa
Vacuum Cons. 30812 221 54214 171
Compression 2877 221 48416 221
Figure 4.5 and 4.6 represents typical load-elongation curves recorded in three point
bending mode.
Stress, MPa
Strain,%
Figure 4.5 : Stress-Strain curve of IPCBT composites by vacuum consolidation.
1600
1400
1200
Stress, MPa
1000
F o r c e (N )
800
600
400
200
0
0 0.5 1 1.5 2 2.5 3 3.5 4
Stroke (mm)
Strain,%
Figure 4.6 : Stress-Strain curve of IPCBT composites by compression.
Tendency of the characteristic flexural property curves indicates that IPCBT

composites produced with compression and vacuum molding behave same.
78
4.3.2 Production of different structures of IPCBT composites
4.3.2.1 UD IPCBT composites and comparison with UD VE composites
To investigate mechanical properties of UD IPCBT composites, the pre-pregs were
prepared using unidirectional glass fiber reinforcements (L300) as described in
Section 3.1.1. Prepreg production was carried out using hand scattering method at
temperature 160C for 30 minutes. The fiber ratio of IPCBT composites were hold
as 70% (w/w) which gives approximately 54% (v/v) fiber volume fraction (Vf). For the
composite production from UD prepregs, the hot press conditions which have given
best mechanical properties in preliminary studies were used. All composites were
produced at 200C pressing temperature with 1.6 MPa pressure for 30 minutes
demolding at 180C. The composites which include 12 layers of L300
reinforcements were subjected to tensile, compression on transverse and
longitudinal load directions. In addition, one sample was prepared as that it consists
of 12 layers glass fibers on +45/-45 directions and subjected to tensile test. In
Section 2.3.3 it was mentioned detailed about the advantages and disadvantages of
thermoset resins and their important role in composite applications. It is known that
vinylester resin is the preferred one because of its advantages and the lower price.
Therefore, in this section the composites produced with vinyl ester resin using the
same reinforcement L300 were compared with IPCBT composites. Production
method was described detailed in Section 3.2.7. The fiber ratio of VE composites
were hold as 54% fiber volume fraction (Vf). Table 4.7 summarizes the mechanical
test results done with IPCBT and VE laminates. As an overall view, the weakness of
IPCBT-NCGF laminates when compared with VE-NCGF laminates was clearly
visible.
Table 4.7 : Tensile and compressive properties of IPCBT and VE composites.

Max. Max. Max.
Tensile Compressive
Tensile Tensile Compressive
Modulus Modulus
Strength Strain Strength
(GPa) (GPa)
(MPa) (%) (MPa)
(0)12 IPCBT 76012 30.31 2.9 22013 25.71
(90)12 IPCBT 211 7.80 1.1 624 7.14
(+45/-45)6s
IPCBT 836 7.60 12.7 - -
(0)8 VE 91716 44.91 2.0 30022 25.41
(90)8 VE 443 11.60 0.6 1282 10.11
(+45/-45)4s VE 1372 15.30 17.5 - -
79
The main problem that was predominantly effective in the fracture of IPCBT based
laminates was the severe and early matrix cracking. This problem was initially
identified from the transverse tensile and compression tests where matrix phase
was carrying the majority of the load. Besides, the significant strength difference
under longitudinal tensile loading may again be attributed to the occurrence of
severe matrix cracking which initiated the overall catastrophic fracture (See Figure
4.7 and. 4.8).
Figure 4.7 : Longitudinal tensile stress-strain curve of IPCBT composite.
Front view
Side view
Figure 4.8 : Fractured IPCBT test specimens after tensile test.
80
In the compression analysis, the fracture mode of VE laminates was initial plastic
fiber kinking followed by the final fiber fracture at the edge of the kink band, see
Figure 4.9.
8000
7000
6000
5000
Stress, MPa
Force (N)
4000
3000
2000
1000
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Stroke (mm)
Strain, %
Figure 4.9 : Typical compression Stress-Strain curve of VE laminates.
The fracture of IPCBT laminates was either initiated by fiber kinking and followed by
sudden delamination failure from the kinking crack tip or was directly caused by
delamination, see Figure 4.10. Crossection images of test specimens before and
after compression test supports delamination failure of IPCBT matrix assumption,
See Figure 4.11.
7000
6000
Stress, MPa
5000
Force (N)
4000
3000
2000
1000
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Stroke (mm) %
Strain,
Figure 4.10 : Typical compression Stress-Strain curve of IPCBT laminates.
81
Before compression
After compression
Figure 4.11 : Crossections of IPCBT test specimens before and after compression.
The main driving force in the occurrence of transverse matrix cracks may be
attributed to the presence of uncontrolled residual stresses appeared during
manufacturing process [65]. This behavior was initially identified from the testing of
transverse tensile and compression tests where the matrix phase was carrying the
majority of the applied load.
On the other hand longitudinal compression test results suggested a closer

performance for both type of laminates. Correspondingly, the significant strength
difference under longitudinal tensile loading was related with the initiation of
transverse matrix cracks from critically stressed (residual+applied) regions. At this
point it is vital to underline that the occurring of matrix cracks may be repaired for
thermoplastic materials. Hence this defect may be altered by re-processing.
Further analysis was done to seek the failure envelopes of laminates on 1-2 and
2-6 stress spaces. Failure envelopes were created by a simple progressive
damage failure analysis done by MICMAC software offered by Stanford University.
The progressive damage analysis enable the creation of predictive points on the
failure envelopes out of the anchor points provided by experimental results. In the
scope of this analysis, Tsai-Wu failure criterion was taken as bases in the
mechanical behaviour prediction of each laminate under different loading conditions.
Figure 4.12 and 4.13 corresponds to the first ply failure envelopes of UD laminates
where the competitive design space of IPCBT composite laminates was
demonstrated in the shaded region.
82
Figure 4.12 : Failure envelopes of IPCBT and VE Composites on 2-6 spaces.
Figure 4.13 : Failure envelopes of IPCBT and VE Composites on 1-2 spaces.
The impact strength of the biaxial IPCBT laminates was determined to be 169 kJ/m
produced with semi-isothermal, 190 kJ/m produced with isothermal route through
notched Charpy impact testing. Since there exist no published work examining the
impact performance of IPCBT based composite materials, the comparison was done
with respect to its thermoset equal. VE based composites having L300 coded NCGF
reinforcement with a lamination sequence of (0/90)4s was manufactured by vacuum
infusion and tested subsequently. The notched Charpy impact strength of biaxial VE
83
laminates was found to be 81 kJ/m. This remarkable difference in the impact
strength can be attributed to the inherent impact absorbing capability of
thermoplastics with respect to thermoset based resins.
4.3.2.2 IPCBT Composites produced with different reinforcements

The diameter of the individual filaments can be important because smaller filament
diameters give higher surface area to volume ratios, which means there is more
area for resin to bond to. Bonding to large area may give slightly better properties in
some instances, see Section 2.2.1.3. Therefore, composite laminates were
produced using X468 coded reinforcement which have smaller diameter of fibers
and compared with the composites of X600 coded reinforcement which have bigger
diameter of fibers. Properties of these reinforcements were explained detailed in
Section 3.1.1.1. Table 4.8 summarizes tensile and flexural properties of the IPCBT
composites of X600 and X468 coded reinforcements. Tensile properties show that
X600 has higher tensile strength and modulus values. Higher strength and modulus
of the composites with X600 can be caused by the higher strength of 600 tex fibers
which have higher fiber diameter than those of 300 tex fibers since the tensile
analysis gives opportunity to test more fiber dominant property. On the other hand,
flexural strength of the composite with X468 resulted higher value in respect with the
flexural strength of X600. Higher strength of the composite with X468 may be
attributed that there is more contact between fiber and resin since the fibers with
lower fiber diameter have large surface area. More contact in a large area between
fiber and resin means that the resin can bond stronger on fiber surface, so this
strong bond prevents the premature failure. Because the flexural properties are
more composite dominant, it can be said that the reinforcement X468 which has 300
tex fibers gives better composite property when we compare with the composite
including X600 in contrast the fiber property.
Table 4.8 : Comparison of mechanical properties of IPCBT composites with different

fiber diameters.
Fiber Max.Tensile Tensile Max. Flexural Flexural
Reinforcement Diameter, Strength, Modulus, Strength, Modulus,
m MPa GPa MPa GPa
50% of 14
X600 42411 221 5467 251
50% of 15
X468 14 3904 201 5784 261
84
4.3.2.3 Production of IPCBT composites with different fiber volume fractions
An important aspect in continuous fiber reinforced composite production is to
achieve the highest fiber ratio with good composite properties. This study was
carried out to obtain high fiber ratio with good mechanical properties. To observe the
effect of fiber content on the properties of end composite different fiber volume
fractions varies between 55-65% were tried. For this purpose, the prepregs including
different amounts of CBT resin were produced by compression in hot press at 200C
for 30 minutes with 1.6 MPa pressure. Produced composite parts were subjected to
the tensile and impact tests. Figure A.13 (a) and Figure A.13 (b) represent tensile
strength and tensile modulus variations with different volume fraction respectively. It
is clear that the higher fiber ratios than approximately 63% cause significant
decreasing in tensile strength and Young modulus. Figure A.14 demonstrates
impact resistances variation in different fiber volume fractions. Recorded values are
nearly between 190-210 kj/m giving not quite remarkable differences. From the
micro structural point of view, it can be said that low resin volumes allow to
formation of voidsa and resin poor places, which cause strength decreasing, due to
the insufficient impregnation of fiber. SEM image of the composite with 63% Vf can
support this assumption (See Figure A.15).
4.3.2.4 Production of IPCBT composites in different thicknesses

In order to identify influences of end laminate thickness on properties of IPCBT
composites, several laminates were produced by compression in different thickness
as 6 and 10 mm with X600 pre-pregs at 200C for 30 minutes. Press load was kept
in 1.6 MPa. Metal molds with 6 mm and 10 mm dept were used for the trials. For 10
mm laminates, a thin probe was placed into the centre of laminate through a drilled
hole on one side of the mold to measure the temperature in the middle of the
laminate during compression. Heating plates of the hot press were set up to 205C
for both upper and bottom. Figure 4.14 shows the centre temperature which the
laminate reached during compression in 30 minutes. IPCBT laminates with 6mm
and 10 mm thicknesses were successfully produced with a 54% fiber volume
fraction.
Table 4.9 summarizes the tensile properties of IPCBT composites with different
thicknesses. It can be seen that while Young Modulus values dont change too
much, tensile strength shows a decreasing. Figure A.16 (a) and A.16 (b) show SEM
images of cross sectional area of the composites with 6 mm and 10 mm thickness
respectively. Macro void formations between the fiber bundles can be attributed to in
sufficient impregnation due to the large cross section area of composites. These
85
voids can give lower tensile strengths causing stress concentration which starts
premature failure.
208
206
Centre Temperature, C
204
202
200
198
196
194
192
190
188
186
184
0 2 4 6 8 10 12 14 16 18 20 22 24 26 28 30
Compression Time, Min.
Figure 4.14 : Centre temperature of the laminate during compression molding.
Table 4.9 : Tensile properties of IPCBT composites with different laminate

thicknesses.
Laminate Thickness, mm Tensile Strength, MPa Tensile Modulus, GPa
3 39411 211
6 3063 201
10 3266 201
4.3.3 PA matrix composites

Nylons 6 and 12 have been used to produce thermoplastic composites through in-
situ polymerisation, See Section 2.5.1. Anionic polymerisation of lactams 6 and 12
can produce nylon 6 and 12 respectively, with no byproducts, and within times
acceptable to the RTM process. The drawbacks to both nylon systems include
material properties and processing complications. The processing both systems are
very sensitive to water and impurities (including fiber sizing) during the
polymerisation process. Small amounts of water (in the few ppm range) can have
adverse effects on polymerisation. There are several records on in situ
polymerisation of PA matrix composites. However, some process difficulties couldnt
be solved. In this section, a new method to prepare PA matrix composites is
suggested. For this purpose PA matrix composites produced by suspension
impregnation and powder scattering of PA 12 (see section 3.3.1.5) were analysed
and compared with literature values.
86
Several laminates were produced with X600 and X468 coded reinforcements. The
process conditions and laminate properties can be seen in Table 4.10. The pressure
was hold as 3 MPa for all samples.
Table 4.10 : Process conditions and mechanical test results of X600 and X468
laminates with CoPa and PA 12 matrix.
Process Max. Max.
Fabric Vf, Number Process Modulus,
Time, Tensile Strain,
Code % of layers Temp., C GPa
min. Str, MPa %
X600 54 6 15 210 317 17 1.93
X600 54 6 15 200 - - -
X600 54 7 20 210 - - -
X468 50 8 20 210 - - -
200C for 15
X600 50 6 30 228 16 1.62
185C in 15
Failure of the laminates have occurred after maximum tensile strength was achieved
and was differentiated by the sudden load drop observed at the end of testing, See
Figure 4.15. The fracture mode of laminate can be seen in fractured test specimen
image indicating sudden load drop of final fiber fracture without delamination, see
Figure 4.16.
Stress, MPa
Strain, %
Figure 4.15 : Tensile Stress-Strain curve of PA laminates.
Figure 4.16 : Fractured test specimen of PA composite after tensile test.
The first problem was the marbled surface appearance, see Figure 4.17. Although
first sample (Fig. 4.18) gave enough mechanical result to solve surface appearance
problem, the process temperature was decreased to 200C. Lower temperature
caused worse appearance on the surface. Increasing of the number of the layers,
87
temperature and the time didnt improve the surface appearances. In order to
improve surface and mechanical properties the idea is to hold temperature at 210C
and change the pressure for further trials.
Figure 4.17 : Marbled appearance on the surface of the composite laminate.
Figure 4.18 : Laminate images produced with 6 layers of X600 at 210C for 15
minutes.
Since anionic polymerisation of PA is very sensitive to moisture, due to the nature of

glass fiber many studies were done with carbon fiber. Moeginger and his co-workers
reported that 390 MPa tensile strength, 26 GPa tensile modulus for glass woven
reinforced anionically polymerised composite (Vf=60%) in RTM. It is clear that the
tensile strength and stiffness of PA 12 composites are less than those of anionacally
polymerised PA composites.
4.3.4 Composites out of commingled PBT/Glass fabric

In this section, IPCBT matrix composite was compared with the composite which
has a conventional PBT matrix. PBT composites were produced by compression
molding in hot press using commingled PBT/Glass fabric. Producing method has
been explained in section 3.3.2 detailed. Table 4.11 summarizes the tensile
88
properties of IPCBT and PBT matrix composites. It can be seen that both types of
PBT possess similar values of strength. However, the relatively high tensile modulus
IPCBT indicates its brittle nature.
Table 4.11 : Tensile properties of IPCBT and PBT matrix composites.
Types of Compression Max. Tensile Tensile

Matrix Used in Conditions Stregth, MPa Modulus, GPa
Composite
200C, 30, 1.6 MPa
IPCBT 424 22
Demolding @200C
200C, 30, 1.6 MPa
IPCBT 504 22
Demolding @180C
260C, 30, 1.5 MPa
PBT 425 14
Demolding @200C
There are several possible reasons for this brittleness. Presence of voids, low
molecular weight, high degree of crystallinity can substantially reduce the ductility of
a polymeric material [19]. It was recorded that IPCBT shows much higher degree of
crystallinity than commerical PBT which is polymerised by conventionally as
explained in Section 2.6.1 [18, 58, 59]. Relatively low strain and low moduli of
commercial PBT can be attributed to its low crystallinity when it is compared with
IPCBT.
4.3.5 Production of sandwich structures with CBT and PA prepregs
There are many applications to produce structural composite sandwich laminates

consisting a core material as foam of polymer etc. and fiber reinforced skins on each
side of the core. Main required property in a sandwichs is the high bond strength
between skin and core to have proper mechanical properties. Generally sandwichs
are produced using structural adhesives such as epoxy, urethane-acrylte etc. to
bond composite skins and core to each other. However, this bonding application is a
second step which causes time waste in industrial scale. In this study, the purpose
is to produce sandwich in one step including skin production and skin-core bonding
at the same time namely called one-shot production. Therefore, core foam and
several layers of prepregs were palced into metal mold in the sequence of prepregs
+ foam + skins then molded in hot press. CBT and PA prepregs were used as the
skin and PA foam was used as core material. Before molding, PA foam was drilled,
sanded and cut to make resin flow easier and increase the surface area to make
bond between core and skins stronger. See Figure 4.19.
89
Figure 4.19 : Prepared PA foam before compression molding.
Foam was placed between 3 layers of X600-CBT prepreg on each side then into the
mold with 10 mm dept, See Figure 4.20.
Figure 4.20 : Placement of foam and the prepregs into mold.
First trial was done with a temperature range starting from 160C increasing to
200C. The compression temperature, time and pressure can be observed detailed
on Figure 4.21. When the system reached up to 200C, the resin immigrated out the
mold because of higher volume of the foam than the mold cavity and very low
viscosity of CBT.
The best way to hold the resin in the mold was to hold pressure low until the
viscosity of the resin reachs up sufficient values. Therefore, second trial was done
starting with 200C press temperature keeping the pressure as 0 MPa. Then
pressure was increased at the point where the viscosity increased. Application route
of this process can be seen in Figure 4.22.
90
210
200
2.9 MPa
Temperature, C
190
180
Top plate
170 Bottom plate
160
150
0 20 40 60 80
0 MPa
Time, Min.
Figure 4.21 : Compression conditions for sandwich production out of CBT prepregs.
210
0 MPa
200 201
199 2.9 MPa
194
190 190
Temperature, C
188
180
170
163
160 159
150
0 20 40 60 80
Time, Min.
Figure 4.22 : Compression conditions for sandwich production out of CBT prepregs.
IPCBT skin PA core sandwich laminate was successfully produced by this route.
See Fig. 4.23.
91
Figure 4.23 : Sandwich laminate with IPCBT skin and PA foam core.
Sandwich laminate with PA skin was produced by using 2 layers of X-600-PA

prepregs and PA foam in hot press. Molding was carried out with temperature range
starting from 200C and cooling to 170C in 25 minutes. The pressure was hold in
2.5 MPa. Sandwich laminates were successfully produced by this route, See Figure
4.24.
Figure 4.24 : Sandwich laminate with PA skin and PA foam core.
Bond strengths between skin and foam were measured by peeling test. Bond
strength of IPCBT and PA sandwichs are 2 N/5cm, 10 N/5cm respectively. However,
bond strength between skin and core was not enough for both PA and IPCBT. This
low strength can be result of insufficient impregnation of foam with resin by closed
cell structure of the foam. As a consequence, it is clear that the compression
molding in hot press is not a proper method for one-shot TP sandwich composite
production.
92
5. CONCLUSION AND RECOMMENDATIONS
The objective of this research is to develop a manufacturing technique for glass fiber
reinforced thermoplastic matrix composites having superior properties while costs
are low. This makes process and material suitable for mass production. The major
purpose is mentioned in the first section.
5.1 Application of The Work
In this thesis, a new process was developed to produce NCGF reinforced PBT
matrix composites. Isothermal and semi-isothermal processing of NCGF reinforced
IPCBT composites via in-situ polymerisation of CBT/Glass fiber prepregs has been
successfully performed by means of compression molding technique.
First of all, the prepreg production temperature which gives highest mechanical
property was identified as 160C. The optimum compression parameters which give
highest mechanical properties were identified as 200C compression temperature,
30 minutes compression time and 1.6 MPa compression pressure for isothermal
process. Semi-isothermal process with 180C demolding temperature gives higher
tensile and flexural properties than isothermal process. However, impact strength of
IPCBT composite produced with isothermal process is higher than that of the
composites produced with semi-isothermal process. Although preimpregnation at
temperatures below 200C during compression slightly increases flexural strength,
longer process period and energy lost make this route useless. It is also concluded
that IPCBT composites can be produced not only by compression molding but also
vacuum molding with a strength enhancement for both tensile and flexural.
Biaxial NCGF reinforced IPCBT composites gave better flexural and tensile
properties when it was compared with reported results of IPCBT composites
produced by RTM technique and the composites produced by compression molding
of Glass/PBT commingled woven fabric in the literature. SEM analysis revealed that
there is good interfacial bonding between IPCBT matrix and NCGF. If more so, the
micro void formation, probably caused by trapped air during compression, was
reduced in respect of the composites produced by RTM. Thus, it can be concluded
93
that the decreased distance between resin and fiber surface by pre-impregnation
before compression process, which is namely called prepreg, facilitates good
penetration of the resin through inner fibers. Moreover, if the processing time of
RTM technique is taken into account, the processing time can be reduced
eliminating resin-catalyst heating and mixing period with prepreg compression
method proposed. Moreover, suggested method eliminates the narrow impregnation
time problem which can cause uncomplete impregnation resulting dry fibers in RTM
system. For the composite production out of conventional PBT/Glass commingled
fibers, it can be said that the higher process temperatures and cooling necessity
during the compression molding of commingled fabric shows the advantages of
suggested method in this study reducing time and cost and increasing wetting ability
of the fibers. Comparison of IPCBT composites and PBT composites out of
commingled PBT/Glass fibers showed that while the tensile strength doesnt
change, IPCBT matrix has higher stiffness with high tensile modulus. It must be
considered that PBT matrix composites can be produced at temperatures which is
higher than 250C and, isothermal process is not possible.
Additionally, a detailed mechanical testing effort was done on the unidirectional

laminates of IPCBT and was consecutively discussed with vinyl ester based
laminates. Investigation of the test results and failure modes in accordance with the
failure envelopes suggested that the IPCBT based laminates considered in this
study can be strong alternatives to the VE based laminates especially under uniaxial
compressive loading conditions as well as impact loadings. However, the
performance of UD IPCBT laminates was found to be lower under tensile and in-
plane shear modes due to high susceptibility to matrix crack formation.
In the literature, the composites fiber reinforced, sizing removed by burning off fiber
reinforced and without fiber were produced using IPCBT as the matrix by RTM and
hot press processes. In these studies, changing of molecular weight of IPCBT matrix
with used processes and the applied temperatures were also investigated. It was
found that, the achieved molecular weights with RTM at 190C and 230C are
Mw=85 kg/mol Mn=39 kg/mol, and Mw=73 kg/mol Mn=35 kg/mol respectively.
Recorded molecular weights with hot press are Mw=78 kg/mol Mn=34 kg/mol for
190C, Mw=79 kg/mol Mn=36 kg/mol for 240C. According to the results it is clear
that process type and process temperature do not affect significantly molecular
weight of IPCBT [20, 23].
94
PA matrix composites were successfully produced by compression molding as well.
IPCBT composites gave higher tensile properties when they were compared with
each other.
Sandwich structures of IPCBT and PA skin using PA foam were successfully

produced. However, bond strength between skin and core was not enough for both
PA and IPCBT. It was concluded that the compression molding in hot press is not a
proper method for one-shot sandwich composite production.
95
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102
APPENDICES
APPENDIX A : FIGURES OF EXPERIMENTAL RESULTS
103
APPENDIX A : FIGURES OF EXPERIMENTAL RESULTS
600
Tensile Strength
Flexural Strength
500
400
Strength (MPa)
300
200
100
0
160 170 180
Temperature (C)
(a)
30
Tensile Modulus
Flexural Modulus
25
20
Modulus(GPa)
15
10
0
160 170 180
Temperature (C)
( b)
Figure A.1 : Tensile and flexural properties of IPCBTs: Hand scattering
temperature.
104
600 Tensile Strength
Flexural Strength
500
400
Strength (MPa)
300
200
100
0
140 145 150 155 160
Temperature (C)
(a)
Tensile Modulus
Flexural Modulus
25
20
Modulus (GPa)
15
10
0
140 145 150 155 160 165
Temperature (C)
(b)
Figure A.2 : Tensile and flexural properties of IPCBTs: Scattering coating
temperature.
105
Flexural Strength
500
400
Strength (MPa)
300
200
100
0
0,5 1,0 1,5 2,0 2,5 3,0 3,5
Pressure (MPa)
(a)
30 Tensile Modulus
Flexural Modulus
25
20
Modulus (GPa)
15
10
0
0,5 1,0 1,5 2,0 2,5 3,0 3,5
Pressure (MPa)
(b)
Figure A.3 : Tensile and flexural properties of IPCBTs: Compression
molding pressure.
106
500 Tensile Str.(MPa)
Impact Str.(kJ/m)
400
300
Strength
200
100
0
190 200 210
Temperature (C)
(a)
30
25
Tensile Modulus (GPa)
20
15
10
0
190 200 210
Temperature (C)
(b)
Figure A.4 : Tensile and impact properties of IPCBT composites:
Compression molding temperature.
107
(a)
(b)
(c)
Figure A.5 : SEM images of IPCBT composites with different compression

temperatures: a)210C, b)200C, c)190C.
108
500 Tensile Sterngth (MPa)
Impact Strength (kJ/m)
400
300
Strength
200
100
0
5 10 15 20 25 30 35
Time (Min.)
(a)
25
20
15
10
0
10 15 20 25 30 35
Time (Min.)
(b)
Figure A.6 : Tensile and impact properties of IPCBTs with differerent
compression time.
109
(a)
(b)
(c)
Figure A.7 : SEM images of IBT composites with different compression time:
a)30, b)20, c)10.
110
Figure A.8 : SEM image of the peeled surface of IPCBT composite laminate.
111
800
Tensile Strength
Flexural Strength
700
600
500
Strength (MPa)
400
300
200
100
0
160 180 200
Demolding Temp. (C)
(a)
35 Tensile Modulus
Flexural Modulus
30
25
Modulus (GPa)
20
15
10
0
160 180 200
Demolding Temp. (C)
(b)
demolding temperatures.
112
Flexural Strength
600
500
Strength (MPa)
400
300
200
100
0
150 160 170 180 190 200 210
Temperature (C)
(a)
Tensile Modulus
Flexural Modulus
26
24
22
20
18
Modulus (GPa)
16
14
12
10
8
6
4
2
0
150 160 170 180 190 200 210
Temperature (C)
(b)
process cycles.
113
(a)
(b)
Figure A.11 : Stereo microscope images of IPCBT composites produced with

different preimpregnation temperatures: a) 160C b)170C.
Figure A.12 : Stereo microscope images of IPCBT composite produced with 160C
preimpregnation temperature for 20 minutes compression time.
114
450
400
Tensile Strength (MPa)
350
300
250
46 48 50 52 54 56 58 60 62 64
Volume Fraction (%)
(a)
24
22
20
18
16
14
12
10
50 55 60 65
Volume Fraction (%)
(b)
Figure A.13 : Tensile strength and tensile modulus variations of IPCBT composites
with different volume fractions.
115
220
200
Impact Strength (kJ/m)
180
160
140
120
100
55 60 65
Volume Fraction (%)
Figure A.14 : Impact strength variation of IPCBT composites with different volume
fractions.
Figure A.15 : SEM Image of cross sectional area of IPCBT composite (Vf: 63%).
116
(a)
(b)
Figure A.16 : SEM images of cross sectional area of the composites with 6 mm(a)
and 10 mm(b) thickness.
117
118
CURRICULUM VITAE
Candidates full name: Glnur Baer
Place and date of birth: Rize/11.11.1979
e-mail: [email protected]
Universities and Colleges attended:
Baclar Lisesi-Fen Matematik-1993-1996
stanbul niveristesi-B.Sc.Kimya Mhendislii Blm-1996-2001
stanbul Teknik niversitesi-M.Sc. Polymer Sci. & Technology-2004-2006
stanbul Teknik niversitesi-Ph.D. Polymer Sci. & Technology-2006- -
Publications:
Baer, G., Bilge, K., Papila, M., Uyank, N. 2012: Investigation of the strength and
failure envelopes of non-crimp glass fiber reinforced thermoplastic composites
based on in-situ polymerized cyclic oligomers. ECCM15-15th European Conference
On Composite Materials Congress June 24-28, 2012 Venice, Italy.
Baer, G., Uyank, N. 2010: Manufacturing of multiaxial non-crimp form glass fiber
reinforced thermoplastic composites. PPS-26 Regional Meeting, 2024 October,
Istanbul, 2010, Turkey.
Baer, G., Uyank, N. 2010: Multiaxial continuous glass fiber reinforced
thermoplastik composites manufacturing. National Polymer Science and Technology
Congress, May 12, 2010, Kocaeli, Turkey.
Baer, G., Uyank, N. 2010: Thermal and rheological characterization of polyolefin
compatibilizers grafted with itaconic acid and its monoesters for nanocomposites.
ECCM14-14th European Conference On Composite Materials, June 7-10, 2010
Budapest, Hungary.
Baer, G., Uyank, N., Eriman, B. 2006: Itakonik asit monoesterleri ile polietilen
a kopolimerlerinin sentezi, karakterizasyonlar ve teorik olarak incelenmesi. XX.
National Chemistry Congress, September 4-8, 2006, Kayseri, Turkey.
Baer, G., Uyank, N. 2006: Itakonik asit ve mono esterleriyle alanm AYPE ve
i-PP nin thermal ve reolojik zelliklerinin incelenmesi. I. International (participated)
Polymeric Composites Symposium, November 17-19, 2006, zmir, Turkey.
119
120

Sayfa 51

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Sayfa 51

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ISTANBUL TECHNICAL UNIVERSITY GRADUATE SCHOOL OF SCIENCE

ENGINEERING AND TECHNOLOGY

PRODUCTION OF FIBER REINFORCED THERMOPLASTIC COMPOSITES

Department of Polymer Science and Technology

Polymer Science and Technology Programme

PRODUCTION OF FIBER REINFORCED THERMOPLASTIC COMPOSITES

Department of Polymer Science and Technology

Polymer Science and Technology Programme

Thesis Advisor: Prof. Dr. Nurseli UYANIK

ELYAF TAKVYEL TERMOPLASTK KOMPOZTLERN RETM

Polimer Bilim ve Teknolojisi Anabilim Dal

Polimer Bilim ve Teknolojisi Program

Tez Danman: Prof. Dr. Nurseli UYANIK

Thesis Advisor : Prof. Dr. Nurseli UYANIK ..............................

Jury Members : Prof. Dr. Hulusi ZKUL ..............................

Prof. Dr. Hseyin YILDIRIM ..............................

Prof. Dr. Ahmet AKAR .............................

Prof. Dr. Ayfer SARA .............................

Date of Submission : 21 June 2012

This work is supported by ITU Graduate School of Science Engineering and

October 2012 Glnur BAER

Figure 2.1 : Differences between woven and multiaxial reinforcements ................ 12

In structural polymeric composite applications, textiles (e.g., unidirectional, woven

Figure 1 : Failure envelopes of IPCBT and VE Composites on 2-6 spaces.

In conclusion, NCGF reinforced IPCBT composites were successfully produced.

Polimerler hayatmzda ok nemli bir rol oynamaktadrlar. Son kullanm

ekil 1 : IPCBT ve VE kompozitlerinin 2-6 blgesindeki krlma zarflar

1.1 Purpose of the Thesis

This study provided a new manufacturing method to produce thermoplastic

A composite, in general, is defined as a combination of two or more component

2.1 Continuous Fiber Reinforced Polymeric Composites (CFRPCs)

2.2.1 Type of fibers

2.2.1.1 Carbon fiber

The most commonly prefered reinforcement materials are carbon/graphite fibers.

2.2.1.3 Glass fiber

Glass fiber is an inorganic fiber which has an amorphous structure. It can

E Glass fibre is available in the following forms:

Strand - a compactly associated bundle of filaments. Strands are rarely seen

Yarns - a closely associated bundle of twisted filaments or strands. Each filament

Rovings - a loosely associated bundle of untwisted filaments or strands. Each

Table 2.1 : Glass fiber yield points according to fiber diameter.

TEX (g/1000 m) Yield (yield/lb) Fiber diameter (m)

2.2.3 Forms of reinforcements

Fibers used in advanced composite manufacture come in various forms, including

Reinforcement Advantages Applications

Continuous filament reinforcements are very important materials for high-end

Woven and non-crimp multiaxial reinforcements are most commonly used

Figure 2.1 : Differences between woven and multiaxial reinforcements [29].

Figure 2.2 : Woven fabrics from high tenacity fibers [29].

Figure 2.3 : Basic scheme of a multiaxial structure [29].

QUADRIAXIAL BIAXIAL UNIAXIAL

2.3 Polymer Systems in CFRPCs Production

Thermosetting materials, or 'thermosets', are formed from a chemical reaction in

The second of the essential ingredients of an advanced composite system is the

2.3.2 Thermoplastic polymers

Thermoplastic polymers can be divided into two classes, high temperature

Table 2.3 : High temperature thermoplastics.

Matrix Morphology Tg (C) Process Temp (C) Cost (Relative)

PEEK SC 143 390 $$$

PEI A 217 330 $$

PEKK SC 156 340 $$

Table 2.4 : Engineering thermoplastics.

Matrix Morphology Tg (C) Process Temp (C) Cost (Relative)

The vast number of thermoplastic resins used in composite materials can

Table 2.5 : Comparison of typical thermoset versus thermoplastic.

Melt Viscosity Low High

Fiber mpregnation Easy Difficult

Prepreg Tack Good None

Prepreg drape Good Poor

Prepreg Stability at 0F 6 mos.-1 yr. Indefinite

Processing Cycle 1-6 hrs. 15 Sec.-6 hrs.

Processing Temperature 350F 700F

Mechanical Properties Good Good

Environmental Durability Good Exceptional

Damage Tolerance Average Good

Database Large Average